CN116666487A - GaN/Ga with self-powered working mode 2 O 3 pn junction ultraviolet photoelectric detector and its preparing method - Google Patents
GaN/Ga with self-powered working mode 2 O 3 pn junction ultraviolet photoelectric detector and its preparing method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims abstract description 44
- 239000002127 nanobelt Substances 0.000 claims abstract description 31
- 230000004044 response Effects 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000010408 film Substances 0.000 claims description 64
- 238000000137 annealing Methods 0.000 claims description 42
- 239000002074 nanoribbon Substances 0.000 claims description 14
- 238000000059 patterning Methods 0.000 claims description 13
- 238000005566 electron beam evaporation Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000000609 electron-beam lithography Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000001039 wet etching Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 238000002955 isolation Methods 0.000 claims description 5
- 229920002120 photoresistant polymer Polymers 0.000 claims description 5
- 238000000231 atomic layer deposition Methods 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001459 lithography Methods 0.000 claims description 4
- 229910052594 sapphire Inorganic materials 0.000 claims description 4
- 239000010980 sapphire Substances 0.000 claims description 4
- 238000004857 zone melting Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000000233 ultraviolet lithography Methods 0.000 claims 2
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 230000004298 light response Effects 0.000 abstract description 8
- 238000004891 communication Methods 0.000 abstract description 3
- 238000004151 rapid thermal annealing Methods 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 2
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- 238000012544 monitoring process Methods 0.000 abstract description 2
- 229910002601 GaN Inorganic materials 0.000 description 73
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 6
- 238000001259 photo etching Methods 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- RNQKDQAVIXDKAG-UHFFFAOYSA-N aluminum gallium Chemical compound [Al].[Ga] RNQKDQAVIXDKAG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 229910001751 gemstone Inorganic materials 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- 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 potential barriers, e.g. phototransistors
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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Abstract
The invention discloses a GaN/Ga device with a self-powered working mode 2 O 3 A pn junction ultraviolet photoelectric detector and a preparation method thereof. The invention adopts the epitaxial growth method to firstly and thenGrowing p-GaN on a substrate, and then doping the element with n-Ga 2 O 3 The nanobelt is transferred to the p-GaN film to form pn junction, and then GaN/Ta: ga is respectively added 2 O 3 preparing p-type and n-type contact electrodes on two sides of the pn junction, and respectively performing rapid thermal annealing on the prepared electrodes to form ohmic contact so as to obtain GaN/Ga 2 O 3 The pn junction is a self-powered ultraviolet photodetector. The self-powered ultraviolet photoelectric detector has extremely low dark current, extremely high rectification ratio, excellent light response and extremely fast response time, and has wide application prospect in the fields of human health, environmental monitoring, military, safety communication and space detection.
Description
Technical Field
The invention relates to the technical field of semiconductors and ultraviolet photodetectors, in particular to GaN/Ga with a self-powered working mode 2 O 3 A pn junction ultraviolet photoelectric detector and a preparation method thereof.
Background
Gallium oxide (Ga) compared with conventional semiconductor silicon (Si) and various wide bandgap semiconductor materials such as diamond, aluminum nitride (AlN), boron Nitride (BN), zinc oxide (ZnO) and aluminum gallium nitride (AlGaN) 2 O 3 ) The material has proper direct wide band gap (about 4.9 eV), high breakdown strength (about 9 MV/cm), high adsorption coefficient and good chemical stability, and Ga 2 O 3 Is representative of fourth generation semiconductor materials. Ga 2 O 3 The base photodetector is considered the most desirable and excellent Ultraviolet (UV) photodetector candidate. In recent years, ga 2 O 3 UV-based photodetectors are becoming an increasing trend in the military and civilian fields. Ga of various structures for improving device performance 2 O 3 The base device is designed and fabricated.
Ga 2 O 3 The basic UV photodetectors are largely divided into five main categories: photoconductive types, metal-semiconductor-metal (MSM) types, schottky (Schottky) diodes, pn junctions, and phototransistors. Photoconductive types have a slower response due to the presence of a sustained photoconductive effect; the MSM type of light response is relatively small; the preparation process of the phototransistor is complex and does not have a self-power supply function; the preparation process of the Schottky diode and the pn junction device is relatively simple, has small dark current and has the advantage of self power supply. The self-powered detector also includes a heterojunction structure. Various self-powered photodetectors present the challenge of relatively low optical response. In recent years, various studies for improving the light response have been widely attempted. Chen et al [1] Au/beta-Ga is reported 2 O 3 Self-powered UV photodetector with Schottky junction, au and Ga 2 O 3 Forming a metal/semiconductor Schottky contact at the contact interface to form a Schottky potential due to the work functions of the metal and semiconductorBarrier by Au/beta-Ga 2 O 3 The presence of a built-in electric field in the depletion region formed by the interface enables a self-powered mode of operation. However, the difference of work functions of the metal and the semiconductor in the device is not large, so that the dark current of the device is large, the light response is small, and the response time is slow. Zhao et al [2] ZnO/beta-Ga is reported 2 O 3 Heterojunction self-powered UV photodetector with ZnO and Ga 2 O 3 The contact interface of (2) forms a heterojunction barrier due to the difference of work functions of the two materials, and the heterojunction barrier is formed by ZnO/beta-Ga 2 O 3 The heterojunction interface forms a depletion region to realize a self-powered working mode. Although the work functions of the two materials of the device are greatly different, the enhanced device performance is realized, including dark current reduction and response time increase, the difference of the work functions of the n-n heterojunction is relatively not large, and meanwhile, the Ga is prepared 2 O 3 This results in a device with a still lower photo-response. Guo et al [3] GaN/Sn Ga is reported 2 O 3 pn junction self-powered UV photodetector through p-type GaN and n-type Ga 2 O 3 And the contact is carried out, and a pn junction depletion region and a built-in electric field are formed at a contact interface due to the difference of work functions of the two materials, so that a self-powered working mode is realized. Since the difference of work functions of two materials of the device is larger than that of an n-n heterojunction, high-quality Ga is prepared by Pulse Laser Deposition (PLD) and Sn doping 2 O 3 Further enhancements in device performance are achieved, including increased dark response, reduced current and faster response times. However, since Sn-Ga is prepared 2 O 3 The film is large in size (several hundred μm 2 Even larger) and the work function difference from GaN is still small, resulting in Ga 2 O 3 Miniaturization of the photoelectric performance and device size of the base UV photodetector is limited.
To give full play to Ga 2 O 3 Device advantage, ga 2 O 3 The basic self-powered UV photodetector needs to meet the following characteristics: 1. the self-powered working mode is provided to realize working without an external power supply; ga 2 2 O 3 The work function difference with the p-type material is large, and the darkness is realizedThe current is small and the response is fast; 3. ga prepared 2 O 3 High monocrystals and small size. However, ga having the above characteristics 2 O 3 The development of special device technology for the base UV photodetector is required, and has not been reported at present.
Disclosure of Invention
The invention aims to provide GaN/Ga with self-powered working mode 2 O 3 The invention relates to a pn junction ultraviolet photoelectric detector and a preparation method thereof, which comprises the steps of doping n-Ga 2 O 3 The nanobelt is transferred to a specific position on the epitaxially grown p-GaN film to form a pn junction, thereby obtaining GaN/Ga-based film 2 O 3 Self-powered ultraviolet photodetectors of pn junctions. The self-powered ultraviolet photoelectric detector has extremely low dark current, extremely high rectification ratio, excellent light response and extremely fast response time, and has wide application prospect in the fields of human health, environmental monitoring, military, safety communication and space detection.
The invention adopts an epitaxial growth method to grow p-GaN on the substrate, and then doped n-Ga 2 O 3 The nanobelt is transferred to the p-GaN film to form a pn junction, and then GaN/Ga is respectively arranged on the pn junction 2 O 3 preparing p-type and n-type contact electrodes on two sides of the pn junction, and respectively performing rapid thermal annealing on the prepared electrodes to form ohmic contact so as to obtain GaN/Ga 2 O 3 The pn junction is a self-powered ultraviolet photodetector. The aim of the invention is achieved by the following technical scheme.
The invention provides a GaN/Ga device with a self-powered working mode 2 O 3 A pn junction ultraviolet photodetector comprising a substrate, a p-GaN film layer, an isolation layer, and doped Ga 2 O 3 A nanobelt, a p-type contact electrode and an n-type contact electrode; the upper surface of the p-GaN film layer is divided into a left part and a right part, wherein Al is arranged above one part 2 O 3 Thin film as isolation layer, doped Ga 2 O 3 One end of the nanometer belt layer is arranged on the surface of the isolating layer, the other end is arranged on the surface of the exposed p-GaN film layer to form a pn junction, and the n-type contact electrode is arranged on the G doped on the isolating layera 2 O 3 An n-type ohmic contact is formed above the nanoribbon layer, and a p-type contact electrode is arranged above the exposed p-GaN thin film layer to form a p-type ohmic contact.
In the present invention, doped n-Ga 2 O 3 In the nanobelt, the doping element is selected from any one of Ta, sn, zn, mg, nb, al, in, C, si, ge, N and B, and the doping amount of the doping element is 0.01-1mol%.
In the invention, the substrate is sapphire, the thickness of the p-GaN film layer is 50-1000nm, and the doped n-Ga 2 O 3 The length, width and thickness of the nano-belt are 5-30 μm, 1-5 μm and 100-500nm respectively, and the thickness of the isolation layer is 20-50nm.
In the invention, the p-type contact electrode is Ni/Au, the thickness of Ni is 30-80nm, and the thickness of Au is 50-100nm.
In the invention, the n-type contact electrode is Ti/Al/Ni/Au, the thickness of Ti is 5-30nm, the thickness of Al is 50-150nm, the thickness of Ni is 20-70nm, and the thickness of Au is 30-80nm.
The invention further provides GaN/Ga with self-powered working mode 2 O 3 The preparation method of the pn junction ultraviolet photoelectric detector comprises the following steps:
(1) And (3) epitaxially growing a magnesium (Mg) -doped GaN film on the substrate by adopting Metal Organic Chemical Vapor Deposition (MOCVD) to obtain the high-quality monocrystalline GaN epitaxial wafer. Carrying out rapid annealing on the GaN epitaxial wafer under a specific gas environment and temperature for a set time to form p-GaN;
(2) Growing Al on the surface of the p-GaN film obtained in the step (1) by adopting Plasma Enhanced Atomic Layer Deposition (PEALD) 2 O 3 Film as p-GaN film and part of n-Ga 2 O 3 Is a barrier layer of (a);
(3) Al obtained in the step (2) 2 O 3 Patterning the surface of the film by Ultraviolet (UV) lithography to form a region to be etched, and then performing wet etching on the lithography patterning window by using hydrofluoric acid (HF) solution to remove part of Al 2 O 3 Sequentially ultrasonically cleaning the film by adopting acetone, isopropanol and deionized water to remove photoresist of the obtained structure;
(4) p-GaN and part of Al obtained in step (3) 2 O 3 Patterning an alignment mark and a p-GaN contact electrode area on the surface of the film by adopting UV lithography, and preparing a corresponding mark and a p-type contact electrode on the surface of the film by an Electron Beam Evaporation (EBE) and peeling off liftoff process;
(5) Carrying out rapid annealing on the p-type contact electrode obtained in the step (4) for a set time under a specific gas environment and temperature to form p-type ohmic contact;
(6) Ga to be doped 2 O 3 Nanoribbon (Ga) 2 O 3 ) Mechanically stripping and transferring to the p-GaN and Al obtained in step (5) 2 O 3 Film surface, ga 2 O 3 Part of the nano belt is arranged on the surface of the p-GaN film, and the other part of the nano belt is arranged on Al 2 O 3 A film surface;
(7) Patterning the doped Ga on the surface of the structure obtained in step (6) by Electron Beam Lithography (EBL) 2 O 3 The contact electrode region of the nanoribbon and is grown on Ga by Electron Beam Evaporation (EBE), lift-off process 2 O 3 Preparing an opposite n-type contact electrode on the surface of the nano belt;
(8) And (3) carrying out rapid annealing on the n-type contact electrode obtained in the step (7) for a set time under a specific gas environment and temperature to form n-type ohmic contact.
In the step (1), the substrate is sapphire, the thickness of the GaN film is 50-1000nm, and the rapid annealing atmosphere is nitrogen (N) 2 ) Or argon (Ar), the annealing temperature is 700-800 ℃ and the annealing time is 2-4min.
In the step (2), al 2 O 3 The thickness of the film is 20-50nm.
In the step (3), the wet etching time of the HF solution is 50-200s, and the ultrasonic time of the acetone is 2-5min.
In the step (4), the lateral dimension of the contact electrode region of the p-GaN is 60-100 μm, the electrode structure is Ni (30-80 nm)/Au (50-100 nm), and the marking metal is any one of Ti/Au, cr/Au and Ni/Au, au, W, pt.
In the step (5), the p-GaN thin film electrode junctionIs made of Ni/Au, and the atmosphere for rapid annealing is oxygen (O 2 ) The set temperature of annealing is 450-650 ℃, and the annealing time is 3-5min.
In the above step (6), ga 2 O 3 The length, width and thickness of the nano-belt are 5-30 μm, 1-5 μm and 100-500nm respectively. Doped Ga 2 O 3 In the nano-belt, the doping element is any one of Ta, sn, zn, mg, nb, al, in, C, si, ge, N and B, the doping amount of the doping element is 0.01-1mol percent, and the doping amount of the doping element is Ga 2 O 3 The nano-belt is prepared by a light zone melting method.
In the above step (7), n-Ga 2 O 3 The lateral dimension of the contact electrode area of the nano belt is 1-5 mu m, and the electrode structure is Ti (5-30 nm)/Al (50-150 nm)/Ni (20-70 nm)/Au (30-80 nm).
In the above step (8), n-Ga 2 O 3 The structure of the nano-electrode is Ti/Al/Ni/Au, and the atmosphere of rapid annealing is N 2 Or Ar, the annealing set temperature is 450-550 ℃, and the annealing time is 1-3min.
The principle of the invention is as follows:
the GaN/Ga with the self-powered working mode provided by the invention 2 O 3 When the device works under zero bias, the device works in a working mode without an external power supply; when the device is operated under an externally applied bias, the device operates in an externally applied power mode of operation. The invention is realized by doping n-Ga 2 O 3 The nanobelt is transferred to a specific position on the epitaxially grown p-GaN film to form a pn junction, and the self-powered pn junction photodetector completely passes GaN/Ga under zero bias 2 O 3 The separation of the photo-generated electron-hole pairs driven by the built-in electric field of the depletion region of the pn junction. Wherein GaN and Ga 2 O 3 The work function difference of the device is larger, so that the potential barrier of the depletion region is larger, and the dark current of the device is small and the response time is quick. At the same time due to Ga 2 O 3 Doped such that Ga 2 O 3 More effective carriers in the material, thereby promoting the photodetector to generate more photogenerated carriers, resulting in greater photoresponsivity.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention is realized by constructing GaN/Ga 2 O 3 The pn junction enables the device to have the self-powered characteristic, namely, a built-in electric field and a depletion region are formed under zero bias voltage, and the self-powered pn junction UV photoelectric detector with small dark current and ultrahigh light response is prepared.
2.Ga prepared by mechanical exfoliation 2 O 3 The size of the nano belt is small, and the miniaturization of the device can be realized.
3. By reacting Ga 2 O 3 Doping nanoribbons to Ga 2 O 3 Increasing the effective carrier concentration of Ga 2 O 3 The fermi level of (c) is moved toward the conduction band and enters the conduction band, so that the work function gap with GaN is further enlarged, the depletion region barrier of the pn junction is increased, the dark current is reduced, and the response time is increased.
4. The ohmic contact between the metal and the semiconductor is formed, so that more photo-generated carriers can form photocurrent, and the photoresponse is enhanced.
Drawings
FIG. 1 is a GaN/Al film of an embodiment of the invention 2 O 3 And (5) an epitaxial wafer structure schematic diagram.
FIG. 2 shows GaN/Al of an embodiment of the invention 2 O 3 Al grows on the surface of the epitaxial wafer 2 O 3 The structure of the insulating layer is schematically shown.
Fig. 3 is a schematic diagram of a structure of a spin-on photoresist mask layer according to an embodiment of the present invention.
FIG. 4 shows Al of the embodiment of the present invention 2 O 3 The structure of the insulating layer after wet etching is schematically shown.
Fig. 5 is a schematic view of exposure of alignment marks and GaN contact electrodes according to an embodiment of the invention.
Fig. 6 is a schematic structural diagram of a p-GaN contact electrode prepared according to an embodiment of the present invention after rapid thermal annealing (RTP) to form a p-type ohmic contact.
FIG. 7 shows a transfer Ta:Ga according to an embodiment of the invention 2 O 3 Schematic of structure after nanoribbonA drawing.
FIG. 8 shows a Ta:Ga phase of an embodiment of the invention 2 O 3 Is a schematic diagram of contact electrode electron beam exposure.
Fig. 9 is a schematic diagram of the structure of a contact electrode for preparing p-GaN before RTP according to the embodiment of the invention.
Fig. 10 is a schematic diagram of the final device structure of the p-GaN prepared contact electrode of the embodiment of the present invention after RTP to form a p-type ohmic contact.
Fig. 11 is a current-voltage curve for a device of an embodiment of the invention in the dark state.
Fig. 12 is a graph of the light response of a device of an embodiment of the invention.
Fig. 13 is a response time curve of a device of an embodiment of the invention.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement of the purpose and the effect of the present invention easy to understand, the present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
GaN/Ta: ga in self-powered working mode 2 O 3 The preparation method of the pn junction ultraviolet photoelectric detector comprises the following steps:
(1) Metal Organic Chemical Vapor Deposition (MOCVD) on 4inch sapphire (Al 2 O 3 ) And (0001) epitaxially growing a 100nm magnesium (Mg) -doped GaN film on the substrate to obtain a high-quality single crystal GaN epitaxial wafer. Carrying out rapid annealing on the GaN epitaxial wafer under a specific gas environment and temperature for a set time to form p-GaN, wherein N is adopted for annealing 2 The annealing temperature and time were 700℃and 3min, respectively. The resulting epitaxial structure is shown in fig. 1.
(2) Growing 30nm Al on the surface of the p-GaN film obtained in the step (1) by adopting Plasma Enhanced Atomic Layer Deposition (PEALD) 2 O 3 Film as p-GaN film and part of n-Ga 2 O 3 The resulting wafer structure is shown in figure 2.
(3) Al obtained in the step (2) 2 O 3 Film surface by means of violetPatterning the region to be etched by external (UV) photoetching, and then carrying out wet etching on the photoetching patterned window by adopting hydrofluoric acid solution (HF: water volume ratio is 1:100) to remove part of Al 2 O 3 Etching the film for 100s, sequentially ultrasonically cleaning with acetone, isopropanol and deionized water for 2min to remove photoresist of the obtained structure, and obtaining Al 2 O 3 The thin film etched structure is shown in fig. 3 and 4.
(4) p-GaN and part of Al obtained in step (3) 2 O 3 And patterning an alignment mark and a p-GaN contact electrode area by adopting UV photoetching on the surface of the film, wherein the transverse dimension of the electrode area is 60nm, preparing a corresponding mark and a p-type contact electrode on the surface of the film by adopting an Electron Beam Evaporation (EBE) and liftoff process, and the electrode structure is Ni (30 nm)/Au (50 nm), wherein the obtained structure is shown in figure 5.
(5) Performing rapid annealing on the p-type contact electrode obtained in the step (4) under a specific gas environment and temperature for a set time to form p-type ohmic contact, wherein the annealing adopts O 2 The annealing temperature and time were 500 ℃ and 4min, respectively, and the resulting structure is shown in fig. 6.
(6) Tantalum (Ta) -doped Ga prepared by optical zone melting method 2 O 3 Nanoribbon (Ta: ga) 2 O 3 ) [4][5] Mechanically stripping and transferring to the p-GaN and Al obtained in step (5) 2 O 3 Film surface, ga 2 O 3 Part of the nano belt is arranged on the surface of the p-GaN film, and the other part of the nano belt is arranged on Al 2 O 3 Film surface, ta, ga 2 O 3 The length, width and height of the nanoribbon were 10 μm, 2 μm and 200nm, respectively, and the resulting structure was shown in FIG. 7.
(7) Patterning Ta-doped Ga on the surface of the structure obtained in step (6) using Electron Beam Lithography (EBL) 2 O 3 A nanoribbon contact electrode region having a lateral dimension of 2 μm and being grown by an EBE, liftoff process in Ta: ga 2 O 3 The nanoribbon surface was prepared for n-type contact electrode with the electrode structure Ti (15 nm)/Al (80 nm)/Ni (30 nm)/Au (50 nm) as shown in FIGS. 8 and 9.
(8) For the n-type contact electrode obtained in the step (7),performing rapid annealing under specific gas environment and temperature for a set time to form N-type ohmic contact, wherein the rapid annealing atmosphere is N 2 The temperature was set at 450℃and the annealing time was 3min, to obtain GaN/Ta: ga as shown in FIG. 10 2 O 3 Self-powered pn junction UV photodetectors.
GaN/Ta: ga with self-powered mode of operation prepared in this example 2 O 3 The pn junction ultraviolet photodetector is based on a built pn junction. The current-voltage curve of the device without illumination is shown in FIG. 11, in which the rectification ratio of the pn junction is 0.6-1.0X10 7 (I 2.5 V /I -0.5V ) Dark current in self-powered mode (zero bias) is-1 pA, which is quite competitive in self-powered UV photodetectors that have been reported. The light response curves of the device under different light intensities are shown in FIG. 12, and the light intensity is 40mW/cm 2 The light responsivity of the device reaches 7 multiplied by 10 under 254nm light 3 a/W, which is large in all reported self-powered UV photodetectors. GaN/Ta: ga of the present example 2 O 3 The response time diagram of the self-powered pn junction uv photodetector is shown in fig. 13. Rise time (τ) r ) And fall time (τ) f ) 9.9 and 30.1ms respectively. Response times are a considerable advantage in reported self-powered UV photodetectors. Such GaN/Ta: ga with self-powered mode of operation 2 O 3 The pn junction ultraviolet photoelectric detector can realize the unification of small dark current, large light responsivity and quick response and gives Ga 2 O 3 The design of the photoelectric device and the communication device brings new possibility, and the device has good rectifying effect and is suitable for preparing high-performance Ga 2 O 3 Rectifier, ga 2 O 3 Logic device. In addition, the device has good breakdown resistance and thermal stability, and is suitable for preparing high-performance Ga 2 O 3 A power device.
Example 2
GaN/Ta: ga in self-powered working mode 2 O 3 The preparation method of the pn junction ultraviolet photoelectric detector comprises the following steps:
(1) At 4inch blue using Metal Organic Chemical Vapor Deposition (MOCVD)Gem (Al) 2 O 3 ) And (0001) epitaxially growing a 100nm magnesium (Mg) -doped GaN film on the substrate to obtain a high-quality single crystal GaN epitaxial wafer. Carrying out rapid annealing on the GaN epitaxial wafer under a specific gas environment and temperature for a set time to form p-GaN, wherein N is adopted for annealing 2 The annealing temperature and time were 750 ℃ and 2min, respectively. The resulting epitaxial structure is shown in fig. 1.
(2) Growing 40nm Al on the surface of the p-GaN film obtained in the step (1) by adopting Plasma Enhanced Atomic Layer Deposition (PEALD) 2 O 3 Film as p-GaN film and part of n-Ga 2 O 3 The resulting wafer structure is shown in figure 2.
(3) Al obtained in the step (2) 2 O 3 Patterning the surface of the film by Ultraviolet (UV) photoetching to form a region to be etched, and then carrying out wet etching on the photoetched window by adopting hydrofluoric acid solution (HF: water volume ratio is 1:100) to remove part of Al 2 O 3 Etching the film for 150s, sequentially ultrasonically cleaning the film for 3min by adopting acetone, isopropanol and deionized water to remove photoresist of the obtained structure, and obtaining Al 2 O 3 The thin film etched structure is shown in fig. 3 and 4.
(4) p-GaN and part of Al obtained in step (3) 2 O 3 And patterning an alignment mark and a p-GaN contact electrode area by adopting UV photoetching on the surface of the film, wherein the transverse dimension of the electrode area is 100nm, preparing a corresponding mark and a p-type contact electrode on the surface of the film by adopting an Electron Beam Evaporation (EBE) and liftoff process, and the electrode structure is Ni (50 nm)/Au (80 nm), wherein the obtained structure is shown in figure 5.
(5) Performing rapid annealing on the p-type contact electrode obtained in the step (4) under a specific gas environment and temperature for a set time to form p-type ohmic contact, wherein the annealing adopts O 2 The annealing temperature and time were 550℃and 3min, respectively, and the resulting structure was shown in FIG. 6.
(6) Tantalum (Ta) -doped Ga prepared by optical zone melting method 2 O 3 Nanoribbon (Ta: ga) 2 O 3 ) [4][5] Mechanically stripping and transferring to the p-GaN and Al obtained in step (5) 2 O 3 Film surface, ga 2 O 3 Part of the nano belt is arranged on the surface of the p-GaN film, and the other part of the nano belt is arranged on Al 2 O 3 Film surface, ta, ga 2 O 3 The length, width and height of the nanoribbon were 20 μm, 3 μm and 300nm, respectively, and the resulting structure was shown in FIG. 7.
(7) Patterning Ta-doped Ga on the surface of the structure obtained in step (6) using Electron Beam Lithography (EBL) 2 O 3 A nanoribbon contact electrode region having a lateral dimension of 3 μm and being fabricated by an EBE, liftoff process at Ta: ga 2 O 3 The nanoribbon surface was prepared for n-type contact electrodes with the electrode structure Ti (30 nm)/Al (120 nm)/Ni (50 nm)/Au (70 nm) as shown in FIGS. 8 and 9.
(8) Performing rapid annealing on the N-type contact electrode obtained in the step (7) under a specific gas environment and temperature for a set time to form N-type ohmic contact, wherein the rapid annealing atmosphere is N 2 The temperature was set at 480℃and the annealing time was 2min, to obtain GaN/Ta: ga as shown in FIG. 10 2 O 3 Self-powered pn junction UV photodetectors.
GaN/Ta: ga with self-powered mode of operation prepared in this example 2 O 3 The pn junction uv photodetector has similar performance characteristics to those of embodiment 1, and will not be described again.
The above embodiments are not intended to limit the scope of the present invention, and any other modifications, alterations, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the invention should be considered as equivalent substitutions within the scope of the invention.
Claims (9)
1. GaN/Ga with self-powered working mode 2 O 3 The pn junction ultraviolet photodetector is characterized by comprising a substrate, a p-GaN film layer, an isolation layer and doped Ga 2 O 3 A nanobelt, a p-type contact electrode and an n-type contact electrode; the upper surface of the p-GaN film layer is divided into a left part and a right part, wherein Al is arranged above one part 2 O 3 Film as isolationLayer, doped Ga 2 O 3 One end of the nanometer belt layer is arranged on the surface of the isolating layer, the other end is arranged on the surface of the exposed p-GaN film layer to form a pn junction, and the n-type contact electrode is arranged on the Ga doped on the isolating layer 2 O 3 An n-type ohmic contact is formed above the nanoribbon layer, and a p-type contact electrode is arranged above the exposed p-GaN thin film layer to form a p-type ohmic contact.
2. GaN/Ga with self-powered mode of operation according to claim 1 2 O 3 The pn junction ultraviolet photodetector is characterized in that the doped n-Ga 2 O 3 In the nanobelt, the doping element is selected from any one of Ta, sn, zn, mg, nb, al, in, C, si, ge, N and B, and the doping amount of the doping element is 0.01-1mol%.
3. GaN/Ga with self-powered mode of operation according to claim 1 2 O 3 The pn junction ultraviolet photoelectric detector is characterized in that the substrate is sapphire, the thickness of the p-GaN film layer is 50-1000nm, and the doped n-Ga 2 O 3 The length, width and thickness of the nano-belt are 5-30 μm, 1-5 μm and 100-500nm respectively, and the thickness of the isolation layer is 20-50nm.
4. GaN/Ga with self-powered mode of operation according to claim 1 2 O 3 The pn junction ultraviolet photoelectric detector is characterized in that the p-type contact electrode is Ni/Au, the thickness of Ni is 30-80nm, and the thickness of Au is 50-100nm.
5. GaN/Ga with self-powered mode of operation according to claim 1 2 O 3 The pn junction ultraviolet photoelectric detector is characterized in that the n-type contact electrode is Ti/Al/Ni/Au, the thickness of Ti is 5-30nm, the thickness of Al is 50-150nm, the thickness of Ni is 20-70nm, and the thickness of Au is 30-80nm.
6. GaN/Ga with self-powered mode of operation according to claim 1 2 O 3 pn junction ultraviolet photoelectric detectionA device is characterized in that the doped n-Ga 2 O 3 The doping element in the nano-belt is Ta, and the rectification ratio I of the obtained pn junction ultraviolet photoelectric detector 2.5V /I -0.5V Up to 0.6X10 7 -1.0×10 7 The dark current in the self-powered mode is 1-8pA, and the light intensity is 40mW/cm 2 Under 254nm light, the light responsivity reaches 5 multiplied by 10 3 -7×10 3 A/W, rise time of response time τ r And a fall time τ f 8.4-9.9ms and 28.6-30.1ms, respectively.
7. A GaN/Ga with self-powered mode of operation according to claim 1 2 O 3 The preparation method of the pn junction ultraviolet photoelectric detector is characterized by comprising the following steps of:
(1) Epitaxially growing a magnesium-doped GaN film on a substrate by adopting MOCVD (metal organic chemical vapor deposition) to obtain a GaN epitaxial wafer, and then carrying out rapid annealing on the GaN epitaxial wafer to form a p-GaN film;
(2) Growing Al on the surface of the p-GaN film obtained in the step (1) by adopting a Plasma Enhanced Atomic Layer Deposition (PEALD) method 2 O 3 A film;
(3) Al obtained in the step (2) 2 O 3 Patterning the surface of the film by ultraviolet lithography to form a region to be etched, and then wet etching the lithography patterning window by using HF solution to remove part of Al 2 O 3 Sequentially ultrasonically cleaning the film by adopting acetone, isopropanol and deionized water to remove photoresist of the obtained structure;
(4) p-GaN and the rest of Al obtained in step (3) 2 O 3 Patterning an alignment mark and a p-GaN contact electrode area on the surface of the film by adopting ultraviolet lithography, and preparing a corresponding mark and a p-type contact electrode on the surface of the film by adopting an electron beam evaporation and stripping process;
(5) Carrying out rapid annealing on the p-type contact electrode obtained in the step (4) to form p-type ohmic contact;
(6) Ga to be doped 2 O 3 The nanoribbon is mechanically peeled off and transferred to the p-GaN and Al obtained in the step (5) 2 O 3 Film surface, ga 2 O 3 Part of the nano belt is arranged on the surface of the p-GaN film, and the other part of the nano belt is arranged on Al 2 O 3 A film surface;
(7) Patterning the doped Ga on the surface of the structure obtained in the step (6) by adopting electron beam lithography 2 O 3 The contact electrode area of the nano-belt is formed in Ga by an electron beam evaporation and stripping process 2 O 3 Preparing an opposite n-type contact electrode on the surface of the nano belt;
(8) Performing rapid annealing on the n-type contact electrode obtained in the step (7) to form n-type ohmic contact to obtain GaN/Ga with self-powered working mode 2 O 3 pn junction ultraviolet photodetectors.
8. The method according to claim 7, wherein,
the substrate in the step (1) is sapphire, the thickness of the GaN film is 50-1000nm, the atmosphere of rapid annealing is nitrogen or argon, the annealing temperature is 700-800 ℃, and the annealing time is 2-4min;
in step (2), al 2 O 3 The thickness of the film is 20-50nm;
in the step (3), the time of wet etching of the HF solution is 50-200s;
in the step (4), the lateral dimension of the contact electrode area of the p-GaN is 60-100 mu m, the electrode structure is that the thickness of Ni/Au Ni is 30-80nm, and the thickness of Au is 50-100nm; the marking metal is any one of Ti/Au, cr/Au, ni/Au, W or Pt;
in the step (5), the atmosphere of rapid annealing is oxygen, the annealing temperature is 450-650 ℃, and the annealing time is 3-5min;
in step (6), ga 2 O 3 The length, width and thickness of the nano-belt are 5-30 μm, 1-5 μm and 100-500nm respectively;
in step (7), ta-Ga 2 O 3 The lateral dimension of the contact electrode area of the nano belt is 1-5 mu m, the contact electrode is Ti/Al/Ni/Au, the thickness of Ti is 5-30nm, the thickness of Al is 50-150nm, the thickness of Ni is 20-70nm, and the thickness of Au is 30-80nm;
in the step (8), the atmosphere of the rapid annealing is nitrogen or argon, the annealing temperature is 450-550 ℃, and the annealing time is 1-3min.
9. The method according to claim 7, wherein in the step (6), ga is doped 2 O 3 In the nano-belt, the doping element is any one of Ta, sn, zn, mg, nb, al, in, C, si, ge, N and B, the doping amount of the doping element is 0.01-1mol percent, and the doping amount of the doping element is Ga 2 O 3 The nano-belt is prepared by a light zone melting method.
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