CN112164732B - Ultraviolet photodiode and preparation method thereof - Google Patents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- H01L31/08—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 in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—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 in which radiation controls flow of current through the device, e.g. photoresistors characterised by at least one potential-jump barrier or surface barrier, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier
- H01L31/108—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier the potential barrier being of the Schottky type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
- H01L31/1852—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising a growth substrate not being an AIIIBV compound
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
- H01L31/1856—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising nitride compounds, e.g. GaN
Abstract
The invention belongs to the technical field of semiconductors and discloses an ultraviolet photodiode and a preparation method thereof. The ultraviolet photodiode comprises the following structures: a substrate; the GaN layer is arranged on the upper surface of the substrate; ti3C2The Schottky contact layer and the ohmic contact layer are oppositely arranged on two sides of the upper surface of the GaN layer; a metal contact layer provided on the Ti3C2An upper surface of the schottky contact layer. The ultraviolet photodiode has excellent ultraviolet detection performance, high responsivity, high specific detection rate, high response speed and high current on-off ratio; the preparation method does not need a complex metal deposition or sputtering process, has no damage to the surface of a semiconductor and has a simple process.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to an ultraviolet photodiode and a preparation method thereof.
Background
Ultraviolet Photodetectors (PDs) are a basic optoelectronic device capable of converting incident short-wave (<400nm) radiation into electrical signals for photoelectric conversion processing. Based on the capture, identification and visualization of optical information by the detector, the ultraviolet detection technology is widely applied to the fields of military affairs, safety communication, imaging, biological detection, chemical analysis, daily life monitoring and the like. Currently commercial ultraviolet photodiodes are mainly based on vacuum photomultiplier tubes and ultraviolet enhanced silicon photodiodes. However, when the vacuum device uses the vacuum tube, the vacuum device has the defects of large volume, high working voltage, weak nature and the like; in addition, the fabrication of high performance silicon photodiodes (such as p-n or p-i-n junctions) typically undergo complex microfabrication processes such as high temperature diffusion and ion implantation, resulting in shortened minority carrier lifetime and severe degradation of photodetection performance, which limits the application of silicon photodetectors.
In recent decades, new materials and device structures have been increasingly studied in order to meet the requirements of the modern miniaturized electronics industry. The two-dimensional material is one of important materials for optical detection by virtue of strong light-substance interaction, wide band gap and high carrier mobility. Recently, a series of wide bandgap semiconductors (i.e., forbidden bands)>3.0eV) in uv detectors, e.g. Ga2In4S9、NiPS3BiOBr (I), perovskite Sr2Nb3O10And the like. However, the current ultraviolet detector made of two-dimensional materials still faces the problems of small photoresponse rate, low current on/off ratio (the on/off ratio is the regulation capability of the device to the current and is defined as the ratio of the on-state current to the off-state current of the device) and the like because the thin atomic layer causes weak and low light absorption.
Accordingly, it is desirable to provide an ultraviolet photodiode having high optical responsivity, on/off ratio, and detectivity.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. To this end, the present invention proposes an ultraviolet photodiode having high optical responsivity, on/off ratio and detectivity.
An ultraviolet photodiode comprising the following structure:
a substrate;
the GaN layer is arranged on the upper surface of the substrate;
Ti3C2the Schottky contact layer and the ohmic contact layer are oppositely arranged on two sides of the upper surface of the GaN layer;
a metal contact layer arranged onThe Ti3C2An upper surface of the schottky contact layer.
Using two-dimensional Ti3C2The three-dimensional GaN and the three-dimensional GaN form a multi-dimensional material, and the construction of the Van der Waals heterojunction of the material can effectively improve the photoelectric property of the ultraviolet photodiode; the two-dimensional/three-dimensional system triggers new coupling between the three-dimensional material and the two-dimensional atomic layer, the three-dimensional layer shows excellent optical absorption performance, and a van der Waals heterojunction induced local electric field can effectively separate photo-generated electron/hole pairs to generate more efficient photoelectric conversion; and the two-dimensional/three-dimensional mixed-dimensional material has high compatibility with a planar micromachining process. So that the ultraviolet photodiode has high light responsivity, on/off ratio and detectivity.
Preferably, the Ti is3C2The Schottky contact layer is Ti3C2A semi-transparent schottky contact layer.
Preferably, the substrate is a sapphire substrate.
Preferably, the GaN layer has a carrier concentration at room temperature (23-28 deg.C) in the range of 1X 1015cm-3To 5X 1017m-3. The GaN layer is made of an unintentionally doped GaN thin film.
Preferably, the Ti is3C2The thickness of the Schottky contact layer is 5-30 nm.
Preferably, the ohmic contact layer is an InGa alloy.
Preferably, the metal contact layer is Ag.
A preparation method of an ultraviolet photodiode comprises the following steps:
(1) preparing a GaN layer on a substrate;
(2) coating Ti on one side of the upper surface of the GaN layer3C2Colloidal solution, drying to form Ti3C2A Schottky contact layer; with Ti3C2The Schottky contact layer is separated by a certain distance, the other side of the upper surface of the GaN layer is coated with the InGa alloy, and the InGa alloy is dried to form an ohmic contact layer;
(3) at Ti3C2Coating silver glue on the upper surface of the Schottky contact layer, and dryingAnd drying to form a metal contact layer, thus obtaining the ultraviolet photodiode.
Preferably, the GaN layer in step (1) is trimethyl gallium, trimethyl aluminum and NH3As a source, nitrogen was produced as a carrier gas.
Preferably, the GaN layer in step (1) comprises a GaN nucleation layer, a GaN buffer layer and an intrinsic GaN layer, wherein the GaN nucleation layer has a thickness of 20-60nm, the GaN buffer layer has a thickness of 150-250nm, and the intrinsic GaN layer has a thickness of 1-5 μm.
Preferably, said Ti in step (2)3C2The colloidal solution is washed and diluted before spraying. The washing process is carried out at Ti3C2Adding deionized water into the colloidal fluid, centrifuging, and taking supernatant; this was repeated three times. The diluting process is to add deionized water for dilution to prepare Ti3C2The pH value of the colloidal solution is 5.5-6.5. To protect the Ti produced3C2The colloidal solution is not oxidized, and is stored in an argon-filled liquid storage bottle and is placed in a refrigerator for standby.
Preferably, Ti is sprayed in the step (2)3C2Before the colloidal solution, it is earlier right the GaN layer washes, the washing process is for washing the GaN layer with acetone, ethanol, water and dilute hydrochloric acid in proper order, gets rid of surperficial organic matter and oxide layer to before spouting, soak the GaN layer in the piranha solution, carry out surface hydrophilic treatment, weather.
Preferably, the GaN layer in step (2) is a preheated GaN layer, and the heating temperature is 70-90 ℃.
Specifically, the preparation method of the ultraviolet photodiode comprises the following steps:
(1) putting the clean-free sapphire substrate into an MOCVD (metal organic chemical vapor deposition) growth chamber, and adding trimethyl gallium, trimethyl aluminum and NH on the sapphire substrate3As a source, nitrogen gas was used as a carrier gas, and a 50nm GaN nucleation layer, a 200nm GaN buffer layer, and a 3 μm intrinsic GaN layer were sequentially epitaxially formed to form the GaN layer.
(2) At Ti3C2Adding ice water into the colloidal solution, and separatingHearts (3500rpm, 20min), followed by supernatant, the above washing process was repeated 3 times. Deionized water was used to mix 1: 1 to prepare Ti3C2Colloidal solution, pH 6. To protect the Ti produced3C2The colloidal solution is not oxidized, and is stored in an argon-filled liquid storage bottle and is placed in a refrigerator for standby. And (3) washing the GaN layer for 2 times by using acetone, ethanol, deionized water and dilute hydrochloric acid in sequence to remove organic matters and an oxide layer on the surface. In the process of spraying Ti3C2Before the colloid solution, the GaN layer is soaked in the piranha solution for 5 minutes for surface hydrophilic treatment, and then is dried by nitrogen. Mixing Ti3C2Spraying colloidal solution on one side of the upper surface of the GaN layer at 80 deg.C with a spray gun, spraying for 20S, placing a mask plate between the spray gun and GaN to control Ti3C2The shape and size of the layer, then moved to N2Further drying in a glove box; and coating the other side of the upper surface of the GaN layer with the InGa alloy, and drying to form an ohmic contact layer.
(3) Finally at Ti3C2And coating a silver colloid solution on the upper surface of the Schottky contact layer, naturally drying to form a metal contact layer, and thus obtaining the ultraviolet photodiode.
Compared with the prior art, the invention has the following beneficial effects:
(1) the ultraviolet photodiode adopts two-dimensional Ti3C2The GaN ultraviolet absorption layer is used as a top electrode of the photodiode, has good light transmission and higher work function, and has excellent ultraviolet detection performance by being combined with the GaN ultraviolet absorption layer; the ultraviolet photodiode has good photoelectric property, high responsivity, high specific detectivity, high response speed and high current switching ratio, and can realize self-driven work.
(2) The ultraviolet photodiode adopts two-dimensional Ti3C2And the GaN form a Van der Waals heterostructure, different from the traditional metal-semiconductor Schottky photodiode, the complex metal deposition or sputtering process is not needed, and the damage to the surface of the semiconductor is avoided.
(3) The ultraviolet photodiode adopts two-dimensional Ti3C2AsThe photodiode top electrode is simple in process, and a large-area ultraviolet photodiode array can be realized through simple spin coating, spraying, printing and other technologies.
Drawings
FIG. 1 is a schematic structural diagram of an ultraviolet photodiode according to example 1;
FIG. 2 is a graph of current-voltage curves for the UV photodiode of example 1 in the dark state and UV light;
FIG. 3 is a diagram of the optical switch of the UV photodiode of example 1 at 355 nm;
fig. 4 is a graph of the uv response characteristics of the uv photodiode described in example 1.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
An ultraviolet photodiode comprising the structure shown in figure 1: a substrate 100; a GaN layer 200 disposed on an upper surface of the substrate 100; ti3C2The schottky contact layer 300 and the ohmic contact layer 400 are oppositely arranged on two sides of the upper surface of the GaN layer 200; a metal contact layer 500 disposed on the Ti3C2The upper surface of the schottky contact 300.
The preparation method of the ultraviolet photodiode comprises the following steps:
(1) putting the clean-free sapphire substrate into an MOCVD (metal organic chemical vapor deposition) growth chamber, and adding trimethyl gallium, trimethyl aluminum and NH on the sapphire substrate3As a source, nitrogen gas was used as a carrier gas, and a 50nm GaN nucleation layer, a 200nm GaN buffer layer, and a 3 μm intrinsic GaN layer were sequentially epitaxially formed to form the GaN layer.
(2) At Ti3C2Adding ice water into the colloidal solution, and separatingHearts (3500rpm, 20min), followed by removal of supernatant, the above washing process was repeated 3 times. Deionized water was used to mix 1: 1 to prepare Ti3C2Colloidal solution, pH 6. To protect the Ti produced3C2The colloidal solution is not oxidized, and is stored in an argon-filled liquid storage bottle and is placed in a refrigerator for standby. And (3) washing the GaN layer for 2 times by using acetone, ethanol, deionized water and dilute hydrochloric acid in sequence to remove organic matters and an oxide layer on the surface. In the process of spraying Ti3C2Before the colloid solution, the GaN layer is soaked in the piranha solution for 5 minutes for surface hydrophilic treatment, and then is dried by nitrogen. Mixing Ti3C2Spraying colloidal solution on one side of the upper surface of the GaN layer at 80 deg.C with a spray gun, spraying for 20S, placing a mask plate between the spray gun and GaN to control Ti3C2The shape and size of the layer, then moved to N2Further drying in a glove box; and coating the other side of the upper surface of the GaN layer with the InGa alloy, and drying to form an ohmic contact layer.
(3) Finally at Ti3C2And coating a silver colloid solution on the upper surface of the Schottky contact layer, naturally drying to form a metal contact layer, and thus obtaining the ultraviolet photodiode.
Example 2
An ultraviolet photodiode comprising the following structure: a substrate; the GaN layer is arranged on the upper surface of the substrate; ti3C2The Schottky contact layer and the ohmic contact layer are oppositely arranged on two sides of the upper surface of the GaN layer; a metal contact layer provided on the Ti3C2An upper surface of the schottky contact layer.
The preparation method of the ultraviolet photodiode comprises the following steps:
(1) putting the clean-free sapphire substrate into an MOCVD (metal organic chemical vapor deposition) growth chamber, and adding trimethyl gallium, trimethyl aluminum and NH on the sapphire substrate3As a source, nitrogen gas was used as a carrier gas, and a 30nm GaN nucleation layer, a 150nm GaN buffer layer, and a 5 μm intrinsic GaN layer were sequentially epitaxially formed to form the GaN layer.
(2) At Ti3C2Adding ice water into the colloidal solution, centrifuging (3500rpm, 20min), and collectingSupernatant liquid is discharged; the above washing process was repeated 3 times. Deionized water was used to mix 1: 1 to prepare Ti3C2Colloidal solution, pH 6. To protect the Ti produced3C2The colloidal solution is not oxidized, and the colloidal solution is stored in an argon-filled liquid storage bottle and is placed in a refrigerator for standby. And (3) washing the GaN layer for 2 times by using acetone, ethanol, deionized water and dilute hydrochloric acid in sequence to remove organic matters and an oxide layer on the surface. In the process of spraying Ti3C2Before the colloid solution, the GaN layer is soaked in the piranha solution for 5 minutes for surface hydrophilic treatment, and then is dried by nitrogen. Deionized water was used in a volume ratio of 1:3 to Ti3C2Further dilution of the colloidal solution, followed by Ti3C2Spraying colloidal solution on one side of the upper surface of the GaN layer at 85 deg.C with a spray gun, spraying for 20S, placing a mask plate between the spray gun and GaN to control Ti3C2The shape and size of the layer, then moved to N2Further drying in a glove box; and coating the other side of the upper surface of the GaN layer with the InGa alloy, and drying to form an ohmic contact layer.
(3) Finally at Ti3C2And coating a silver colloid solution on the upper surface of the Schottky contact layer, naturally drying to form a metal contact layer, and thus obtaining the ultraviolet photodiode.
Product effectiveness testing
The ultraviolet photodiode prepared in example 1 was subjected to performance testing, and the light-to-dark current ratios of the ultraviolet photodiode in a dark place and under irradiation of ultraviolet light of 250nm, 300nm and 355nm were measured, as shown in fig. 2, the abscissa in fig. 2 is voltage and the ordinate is current, and it can be seen from the figure that the light-to-dark current ratios of the prepared ultraviolet photodiode under irradiation of ultraviolet light of 250nm, 300nm and 355nm are all higher than 104. The current regulation and control capability of the ultraviolet photodiode is tested, and the on-state current and the off-state current of the ultraviolet photodiode are tested under 355nm, and as can be seen from fig. 3, the prepared ultraviolet photodiode has a high current on-off ratio.
Testing ultraviolet response characteristics of the prepared ultraviolet photodiode, wherein under 0V bias, the test result is shown in figure 4, the abscissa in the figure is wavelength, the left side of the ordinate is responsivity, and the ordinate is verticalThe right side of the mark is the detectivity, and the graph shows that the responsivity of the ultraviolet region is higher than 0.1A/W, the peak responsivity is as high as 0.25A/W, and the detectivity is higher than 1013Jones。
Claims (9)
1. An ultraviolet photodiode comprising the structure:
a substrate;
the GaN layer is arranged on the upper surface of the substrate;
Ti3C2the Schottky contact layer and the ohmic contact layer are oppositely arranged on two sides of the upper surface of the GaN layer;
a metal contact layer provided on the Ti3C2An upper surface of the schottky contact layer;
the preparation method of the ultraviolet photodiode comprises the following steps:
(1) preparing a GaN layer on a substrate;
(2) coating Ti on one side of the upper surface of the GaN layer3C2Colloidal solution, drying to form Ti3C2A Schottky contact layer; with Ti3C2The Schottky contact layer is separated by a certain distance, the other side of the upper surface of the GaN layer is coated with the InGa alloy, and the InGa alloy is dried to form an ohmic contact layer;
(3) at Ti3C2And coating silver glue on the upper surface of the Schottky contact layer, drying and forming a metal contact layer to obtain the ultraviolet photodiode.
2. The uv photodiode of claim 1, wherein the substrate is a sapphire substrate.
3. The UV photodiode of claim 1, wherein the GaN layer has a carrier concentration of 1 x 10 at 23-28 ℃15To 5X 1017m-3。
4. The UV photodiode of claim 1, wherein the Ti is3C2Thickness of Schottky contact layerIs 5-30 nm.
5. The UV photodiode of any one of claims 1-4, wherein the ohmic contact layer is an InGa alloy.
6. The UV photodiode of any one of claims 1-4, wherein the metal contact layer is Ag.
7. The UV photodiode of claim 1, wherein the GaN layer in step (1) comprises a GaN nucleation layer, a GaN buffer layer and an intrinsic GaN layer, wherein the GaN nucleation layer has a thickness of 20-60nm, the GaN buffer layer has a thickness of 150-250nm, and the intrinsic GaN layer has a thickness of 1-5 μm.
8. The UV photodiode of claim 1, wherein in step (2) Ti is coated3C2Before the colloid solution, washing the GaN layer; the washing process is to wash the GaN layer with acetone, ethanol, water and dilute hydrochloric acid in sequence.
9. The UV photodiode of claim 1, wherein the GaN layer in step (2) is a pre-heated GaN layer, and the heating temperature is 70-90 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010968434.6A CN112164732B (en) | 2020-09-15 | 2020-09-15 | Ultraviolet photodiode and preparation method thereof |
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| CN202010968434.6A CN112164732B (en) | 2020-09-15 | 2020-09-15 | Ultraviolet photodiode and preparation method thereof |
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| CN112164732A CN112164732A (en) | 2021-01-01 |
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| CN1681134A (en) * | 2004-04-07 | 2005-10-12 | 中国科学院半导体研究所 | Ultraviolet detector with gallium nitride Schottky structure and production thereof |
| CN1681135A (en) * | 2004-04-07 | 2005-10-12 | 中国科学院半导体研究所 | Barrier height reinforced ultraviolet detector with gallium nitride schottky and production thereof |
| JP2006156464A (en) * | 2004-11-25 | 2006-06-15 | National Institute For Materials Science | Diamond ultraviolet photosensor |
| CN1956227A (en) * | 2005-10-24 | 2007-05-02 | 中国科学院半导体研究所 | Back radiating gallium nitride base Schottky structure UV detector |
| CN101901850A (en) * | 2009-05-27 | 2010-12-01 | 中国科学院半导体研究所 | Ultraviolet two-color detector with new structure based on gallium nitride material |
| CN210167365U (en) * | 2019-06-17 | 2020-03-20 | 南京紫科光电科技有限公司 | Homoepitaxy GaN Schottky barrier type ultraviolet avalanche detector |
| CN111341497A (en) * | 2020-03-13 | 2020-06-26 | 浙江大学 | Preparation method of silver nanowire-MXene composite transparent conductive film |
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| CN1681134A (en) * | 2004-04-07 | 2005-10-12 | 中国科学院半导体研究所 | Ultraviolet detector with gallium nitride Schottky structure and production thereof |
| CN1681135A (en) * | 2004-04-07 | 2005-10-12 | 中国科学院半导体研究所 | Barrier height reinforced ultraviolet detector with gallium nitride schottky and production thereof |
| JP2006156464A (en) * | 2004-11-25 | 2006-06-15 | National Institute For Materials Science | Diamond ultraviolet photosensor |
| CN1956227A (en) * | 2005-10-24 | 2007-05-02 | 中国科学院半导体研究所 | Back radiating gallium nitride base Schottky structure UV detector |
| CN101901850A (en) * | 2009-05-27 | 2010-12-01 | 中国科学院半导体研究所 | Ultraviolet two-color detector with new structure based on gallium nitride material |
| CN210167365U (en) * | 2019-06-17 | 2020-03-20 | 南京紫科光电科技有限公司 | Homoepitaxy GaN Schottky barrier type ultraviolet avalanche detector |
| CN111341497A (en) * | 2020-03-13 | 2020-06-26 | 浙江大学 | Preparation method of silver nanowire-MXene composite transparent conductive film |
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