CN115295677A - High responsivity beta-Ga 2 O 3 Base heterojunction self-powered ultraviolet detector and preparation method and application thereof - Google Patents
High responsivity beta-Ga 2 O 3 Base heterojunction self-powered ultraviolet detector and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses beta-Ga with high responsivity 2 O 3 A base heterojunction self-powered ultraviolet detector and a preparation method and application thereof belong to the field of semiconductor photoelectric devices. The ultraviolet detector comprises a substrate, a first electrode, a p-type wide bandgap conductive film and intrinsic beta-Ga which are sequentially stacked from bottom to top 2 O 3 Thin film depletion layer, n-beta-Ga 2 O 3 Sn conductive film, n + ‑β‑Ga 2 O 3 Sn electron collecting layer, mgO Na or MgO K film passivating layer and second electrode, and the forbidden band width of p forbidden band conducting film is more than 3.0eV. The high-responsivity beta-Ga is obtained by utilizing vacuum film-making methods such as chemical vapor deposition, metal organic vapor phase epitaxy, pulse laser deposition and the like 2 O 3 The radical heterojunction self-powered ultraviolet detector effectively improves beta-Ga 2 O 3 The basic heterojunction film ultraviolet detector has responsivity and wide application prospect in solar blind waveband detection.
Description
Technical Field
The invention belongs to the field of semiconductor photoelectric devices, and particularly relates to high-responsivity beta-Ga 2 O 3 A base heterojunction self-powered ultraviolet detector, a preparation method and application thereof are provided.
Background
This band is called the "solar blind" band because of the complete absorption by the ozone layer of the ultraviolet radiation in the 200-280nm band, which is almost absent from the atmosphere. The ultraviolet detector based on the wave band has the advantages of low background noise, low false alarm rate and the like, so the ultraviolet detector has wide application prospects in military fields of ultraviolet guidance, ultraviolet space early warning, missile early warning and the like, and in civil fields of high-response fire early warning, corona detection, atmospheric environment monitoring and the like, and is widely concerned by researchers.
Although traditional semiconductor materials such as Si and Ge have the advantages of low cost and mature technology, the defects of large equipment volume, unstable performance under high-temperature, high-pressure and other environments and the like caused by the fact that a cooling device is usually required to be added due to the narrow forbidden band width, and a high-quality optical filter is required in the solar-blind band detection aspect, so that the responsivity of the high-quality optical filter is limited. The wide band gap semiconductor ultraviolet detector directly responds to ultraviolet photons without complex and expensive optical elements, and has the advantages of small size, flexibility, high stability, integration, high quantum efficiency and the like. beta-Ga 2 O 3 The band gap of the material is 4.90eV, the material is in a solar blind waveband, has extremely high chemical stability and thermal stability, and is a natural solar blind ultraviolet detection material. beta-Ga 2 O 3 The ultraviolet detector has remarkable photoelectric performance, has good spectral selectivity and small dark current (Zou R, zhang Z, liu Q, et altemperature deep-ultraviolet photodetector based on multi-layered(l00)facet-orientedβ-Ga 2 O 3 nanobelts[J].Small:2014,10(9):1848-56.]。
Currently, n-type beta-Ga 2 O 3 This can be achieved by elemental doping of Sn, si etc. and can be cited in the literature [ s.c.siah, r.e.brandt, k.lim, l.t.schelhas, r.jamamilo, m.d.heinemann, d.chua, j.wright, j.d.perkins, c.u.segre, r.g.gordon, m.f.toney, and t.bulonasi.dot activation in Sn-doped Ga 2 O 3 investigated by X-ray absorption spectroscopy.APPLIED PHYSICS LETTERS 107,252103(2015)]. p-type beta-Ga 2 O 3 Is difficult to obtain, resulting in beta-Ga 2 O 3 The base junction type photoelectric detector mainly comprises heterojunction, and beta-Ga is known at present 2 O 3 The following disadvantages may exist in the base heterojunction detector: 1) The response value is low, and the open-circuit voltage is small; 2) There is a persistent photoconductive phenomenon resulting in a photoresponse speed on the order of seconds.
Disclosure of Invention
To solve the existing beta-Ga 2 O 3 The invention aims to provide a high-responsivity beta-Ga material with low responsivity for a base heterojunction film ultraviolet detector 2 O 3 The base heterojunction self-powered ultraviolet detector.
It is another object of the present invention to provide the above-mentioned highly responsive beta-Ga 2 O 3 A preparation method of a base heterojunction self-powered ultraviolet detector.
It is still another object of the present invention to provide the above highly responsive beta-Ga 2 O 3 The application of the base heterojunction self-powered ultraviolet detector in solar blind band detection is provided.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a highly responsive beta-Ga 2 O 3 The base heterojunction self-powered ultraviolet detector comprises a substrate, a first electrode, a p-type wide bandgap conductive film and intrinsic beta-Ga which are sequentially stacked from bottom to top 2 O 3 Thin film depletion layer, n-beta-Ga 2 O 3 Sn conductive film, n + -β-Ga 2 O 3 A Sn electron collecting layer, a MgO Na or MgO K film passivation layer and a second electrode; wherein:
the forbidden band width of the p-type wide forbidden band conductive film is more than 3.0eV;
the intrinsic beta-Ga 2 O 3 A thin film depletion layer is arranged between the p-type wide bandgap conductive thin film and the n-beta-Ga 2 O 3 Between Sn conductive films;
the MgO: na or MgO: K thin film passivation layer covers the n-beta-Ga 2 O 3 On the Sn conductive film;
n is said + -β-Ga 2 O 3 An Sn electron collecting layer is located on the n-beta-Ga 2 O 3 Between the Sn conductive film and the second electrode.
Preferably, the substrate is selected from sapphire, silicon or metal materials with flat and smooth surfaces.
Preferably, the first electrode is a Ru/Ni/Ag/Pt/Au laminated alloy thin film, wherein the thickness of Ru is 5-50nm, the thickness of Ni is 10-100nm, the thickness of Ag is 10-100nm, the thickness of Pt is 10-100nm, and the thickness of Au is 50-1000nm.
Preferably, the second electrode is a Ti/Au laminated alloy thin film, the thickness of Ti is 10-500nm, and the thickness of Au is 50-1000nm.
Preferably, the intrinsic β -Ga 2 O 3 The thickness of the thin film depletion layer is 5-50nm.
Preferably, the n-beta-Ga 2 O 3 The Sn atom percentage content in the Sn conductive film is 0.01at percent to 1at percent, and the thickness is 300 nm to 2000nm.
Preferably, n is + -β-Ga 2 O 3 The Sn electron collecting layer is of a strip structure, wherein the atomic percentage of Sn is 1at percent to 10at percent, and the thickness is 50nm to 500nm.
Preferably, the p-type wide bandgap conductive film is one or more selected from p-GaN, p-SiC and p-ZnO conductive films.
Preferably, the thickness of the MgO: na or MgO: K thin film passivation layer is 50-500nm, and the content of Na or K atom percentage is 0.1at% -5at%.
The present invention also provides the highly responsive beta-Ga 2 O 3 The preparation method of the base heterojunction self-powered ultraviolet detector comprises the following steps:
s101, cleaning a substrate;
s102, preparing a Ru/Ni/Ag/Pt/Au laminated alloy film on the cleaned substrate through vacuum magnetron sputtering to serve as a first electrode;
s103, preparing a p-type wide bandgap conductive film on the first electrode by adopting a vacuum film-making method selected from Metal Organic Vapor Phase Epitaxy (MOVPE), pulsed Laser Deposition (PLD), magnetron sputtering or Molecular Beam Epitaxy (MBE);
s104, preparing intrinsic beta-Ga on the p-type wide bandgap conductive film by adopting PLD 2 O 3 A thin film depletion layer;
s105, adopting PLD to deposit intrinsic beta-Ga 2 O 3 Preparation of n-beta-Ga on thin film depletion layer 2 O 3 A Sn conductive film;
s106, covering the n-beta-Ga by using a mask plate 2 O 3 Sn conductive film formed on n-beta-Ga by PLD 2 O 3 Preparing n on Sn conductive film + -β-Ga 2 O 3 A Sn electron collecting layer;
s107, a vacuum film-making method combining a mask plate and magnetron sputtering is carried out in the step n + -β-Ga 2 O 3 Preparing a Ti/Au alloy laminated film on the Sn electron collection layer as a second electrode;
s108, covering the second electrode with a mask plate, and performing vacuum film forming on n-beta-Ga by adopting a magnetron sputtering method 2 O 3 A passivation layer of MgO, na or MgO, K film is prepared on the Sn conductive film.
Preferably, the intrinsic beta-Ga 2 O 3 The preparation process parameters of the thin film depletion layer comprise: introduction of O 2 Gas, growth pressure of 0.01-0.1Pa, growth temperature of 380-650 ℃, distance between the substrate and the target material of 20-50mm, and growth time of 1-10min.
Preferably, the n-beta-Ga is 2 O 3 The preparation process parameters of the Sn conductive film comprise: introduction of O 2 Gas, growth pressure of 0.01-5Pa, growth temperature of 350-950 ℃, distance between the substrate and the target of 20-50mm, and growth time of 100-240min.
Preferably, n is + -β-Ga 2 O 3 The preparation process parameters of the Sn electronic collecting layer comprise: introduction of O 2 Gas, growth pressure of 0.01-5Pa, growth temperature of 350-950 ℃, distance between the substrate and the target of 20-50mm, and growth time of 30-60min.
Preferably, the preparation process parameters of the MgO: na or MgO: K thin film passivation layer comprise: introducing Ar and O 2 Mixed gas of Ar and O 2 The volume ratio of (1).
The present invention also provides the highly responsive beta-Ga 2 O 3 The application of the base heterojunction self-powered ultraviolet detector in solar blind band detection is provided.
The invention utilizes the vacuum film-making technologies such as Chemical Vapor Deposition (CVD), metal Organic Vapor Phase Epitaxy (MOVPE), pulse Laser Deposition (PLD) and the like to prepare high-responsiveness beta-Ga on a substrate with flat and smooth surface such as sapphire, silicon, metal and the like 2 O 3 The radical heterojunction self-powered ultraviolet detector utilizes intrinsic beta-Ga 2 O 3 As depletion layer and absorption layer, mgO-Na (or K) film as passivation layer, n + -β-Ga 2 O 3 Sn film as an electron collecting layer, and beta-Ga 2 O 3 The basic heterojunction solar blind detector has higher responsivity compared with the existing beta-Ga 2 O 3 The responsivity of the basic heterojunction ultraviolet detector is improved by nearly 2 times, and the basic heterojunction ultraviolet detector has the following advantages:
1) Light injection into intrinsic beta-Ga 2 O 3 Because the film is not doped, the lattice distortion is small, and the photon-generated carriers rapidly drift to a loop under the action of an internal electric field, so that the composition of the photon-generated carriers is reduced, and the short-circuit current and the open-circuit voltage are increased.
2) The surface recombination is reduced by using the MgO: na (or K) film as a passivation layer.
3) By n + -β-Ga 2 O 3 The Sn film is used as an electron collecting layer, and the electron collecting efficiency is improved.
Drawings
The above and other objects, features and advantages of exemplary embodiments of the present invention will become readily apparent from the following detailed description, which proceeds with reference to the accompanying drawings. Several embodiments of the present invention are illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings and in which:
FIG. 1 shows high responsivity β -Ga in the examples 2 O 3 The structural schematic diagram of the base heterojunction self-powered ultraviolet detector; wherein:
1-a substrate;
2-a first electrode of Ru/Ni/Ag/Pt/Au;
3-p type wide bandgap conductive film;
4-intrinsic beta-Ga 2 O 3 A thin film depletion layer;
5——n-β-Ga 2 O 3 sn conductive film;
6——n + -β-Ga 2 O 3 a Sn electron collecting layer;
7-MgO is Na (or K) film passivation layer;
8-Ti/Au second electrode.
FIG. 2 shows high responsivity β -Ga in example 2 O 3 Base heterojunction self-powered ultraviolet detector (1) and traditional beta-Ga 2 O 3 And the wavelength and responsivity relation diagram of the base heterojunction self-powered ultraviolet detector (2).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It should be apparent that the described embodiments are only some of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
As shown in FIG. 1, a highly responsive beta-Ga is exemplarily described 2 O 3 The base heterojunction self-powered ultraviolet detector comprises a substrate 1, a first electrode 2, a p-type wide bandgap conductive film 3, and intrinsic beta-Ga 2 O 3 Thin film depletion layer 4, n-beta-Ga 2 O 3 Sn conductive film 5, n + -β-Ga 2 O 3 A Sn electron collecting layer 6, a MgO Na (or K) film passivation layer 7 and a second electrode 8; wherein: a first electrode 2 disposed on the substrate 1, a p-type wide bandgap conductive film 3 disposed on the first electrode 2, and intrinsic beta-Ga 2 O 3 A thin film depletion layer 4 arranged on the p-type wide bandgap conductive thin film 3, n-beta-Ga 2 O 3 A Sn conductive film 5 is provided on intrinsic beta-Ga 2 O 3 N on the thin film depletion layer 4 + -β-Ga 2 O 3 The Sn electron collecting layer 6 is a strip structure and is crossed with the MgO Na (or K) thin film passivation layer 7 on the n-beta-Ga 2 O 3 A second electrode 8 disposed on the Sn conductive film 5 + -β-Ga 2 O 3 A substrate/a first electrode/a p-type wide bandgap conductive film/intrinsic beta-Ga is formed on the Sn electron collecting layer 6 2 O 3 Thin film depletion layer/n-beta-Ga 2 O 3 Sn conductive film/n + -β-Ga 2 O 3 An Sn electron collecting layer (MgO: na (or K) film passivation layer)/a second electrode ".
In some embodiments, the material of the substrate 1 may be sapphire, quartz, metal, etc. with a smooth surface.
In some embodiments, the p-type wide bandgap conductive film 3 has a bandgap greater than 3.0eV and a thickness of 50-200nm; intrinsic beta-Ga 2 O 3 The thin film depletion layer 4 is high-quality beta-Ga 2 O 3 The film does not contain any other impurities, and the thickness of the film is 5-50nm; n-beta-Ga 2 O 3 The Sn atom percentage content of the Sn conductive film 5 is 0.01at percent to 1at percent, and the thickness is 300 nm to 2000nm; n is + -β-Ga 2 O 3 The Sn electron collection layer 6 contains 1at percent to 10at percent of Sn atoms, and the thickness of the Sn electron collection layer is 50nm to 500nm; mgO Na (or K) film passivation layer 7 contains Na or K atoms in an amount of 0.1at%-5at%, and a thickness of 50-500nm.
In some embodiments, if the p-type wide bandgap conductive film 3 is a p-GaN film, it is prepared by MOVPE and is a Mg-doped p-GaN film (p-GaN: mg); if the p-type wide bandgap conductive film 3 is a p-ZnO film, the film is prepared by magnetron sputtering and is an N-doped p-ZnO film (p-ZnO: N); n-beta-Ga 2 O 3 Sn conductive film 5 or n + -β-Ga 2 O 3 The Sn electronic collection layer 6 is prepared by adopting PLD; the MgO: na (or K) thin film passivation layer 7 is prepared by magnetron sputtering.
In some embodiments, the first electrode 2 is a Ru/Ni/Ag/Pt/Au alloy stack, the Ru having a thickness of 5-50nm; the thickness of Ni is 10-100nm; the thickness of Ag is 10-100nm; the thickness of Pt is 10-100nm; the thickness of Au is 50-1000nm; the second electrode 8 is Ti/Au alloy, the thickness of Ti is 10-500nm, and the thickness of Au is 50-1000nm.
In some embodiments, the first electrode 2Ti/Au, ru/Ni/Ag/Pt/Au alloy stack is prepared by using vacuum techniques such as electron beam, magnetron sputtering, and the like, in combination with a mask plate technique.
The following preparation methods were used in the following examples to prepare highly responsive beta-Ga 2 O 3 The self-powered ultraviolet detector of the base heterojunction comprises the following steps:
a) Substrate cleaning: cleaning the substrate with ethanol, acetone and deionized water in sequence at the time t1, and drying with nitrogen;
b) Putting the cleaned substrate into a growth chamber of a magnetron sputtering device, setting technological parameters such as atmosphere, vacuum degree and the like, and preparing a Ru/Ni/Ag/Pt/Au alloy lamination as a first electrode;
c) Putting the substrate/first electrode deposited with the first electrode into an MOVPE reaction chamber or a magnetron sputtering growth chamber, setting technological parameters such as growth temperature, atmosphere, vacuum degree and the like, and preparing a p-GaN or p-ZnO conductive film;
d) Putting the substrate/first electrode/p-GaN (or p-ZnO) film into Pulsed Laser Deposition (PLD) to perform intrinsic n-beta-Ga 2 O 3 Thin film and n-beta-Ga 2 O 3 Preparing a Sn conducting layer film;
e) Covering n-beta by using mask technique-Ga 2 O 3 Sn conductive layer film, and n is deposited by using PLD equipment + -β-Ga 2 O 3 A Sn electron collecting layer;
f) On the basis of the step e), utilizing a mask plate technology and adopting a magnetron sputtering device at n + -β-Ga 2 O 3 Depositing a second electrode on the Sn electron collecting layer;
g) Covering the second electrode film by using a mask plate technology, and depositing a MgO: na (or K) film passivation layer by using a magnetron sputtering device.
In the step a), ethanol and acetone are firstly used for ultrasonic treatment for 15 minutes respectively, then deionized water is used for cleaning, and finally nitrogen is used for blowing clean.
In steps e) and f), n + -β-Ga 2 O 3 The Sn electron collection layer and the second electrode mask plate covered on the Sn electron collection layer have the same shape and are both rectangular.
In the step g), the MgO, na (or K) film passivation layer mask plate is rectangular.
In steps e), f) and g), n + -β-Ga 2 O 3 The ratio of the widths of the Sn electron collection layer and the second electrode mask plate to the widths of the MgO: na (or K) film passivation layer adopted masks is 1.
The manufacturing process further comprises the following steps:
(A) PLD preparation of intrinsic beta-Ga 2 O 3 The technological parameters of the thin film depletion layer are as follows: introduction of O 2 Gas, the growth pressure is 0.01-0.1Pa, the growth temperature is 380-650 ℃, the distance between the substrate and the target material is 20-50mm, and the growth time is 1-10min;
(B) PLD preparation of n-beta-Ga 2 O 3 The process parameters of the Sn conductive film are as follows: introduction of O 2 Gas, the growth pressure is 0.01-5Pa, the growth temperature is 350-950 ℃, the distance between the substrate and the target material is 20-50mm, and the growth time is 100-240min;
(C) Preparation of n by PLD + -β-Ga 2 O 3 The technological parameters of the Sn electron collection layer are as follows: introduction of O 2 Gas, growth pressure of 0.01-5Pa, growth temperature of 350-950 ℃, distance between the substrate and the target of 20-50mm, and growth time of 30–60min；
(D) The technological parameters for preparing the MgO to Na (or K) film passivation layer by magnetron sputtering are as follows: introducing Ar and O 2 Mixed gas of Ar: O 2 The value range is 0-10, the growth pressure is 0.5-5Pa, the sputtering power is 10-80W, the growth temperature is 200-600 ℃, and the growth time is 20-120min.
Against beta-Ga 2 O 3 The invention solves the problems of low responsivity, small open-circuit voltage and the like of the basic heterojunction thin-film solar blind detector, and prepares the beta-Ga with high responsivity 2 O 3 A radical heterojunction self-powered ultraviolet detector in n-beta-Ga 2 O 3 In a Sn/p-wide bandgap conductive thin film heterojunction, intrinsic high-quality beta-Ga is used 2 O 3 The thin film improves the width of a depletion layer and improves the absorptivity and the utilization rate of light; by adding MgO to Na (or K) film passivation layer to n-beta-Ga 2 O 3 Carrying out surface passivation and field passivation on the Sn conducting layer; by increasing n + -β-Ga 2 O 3 Sn electron collection reduces current and voltage loss between the electrode and the conductive layer. By the method, beta-Ga is improved 2 O 3 The heterojunction film ultraviolet light detector has open-circuit voltage and short-circuit current, and accordingly improves responsivity.
Example 1
This example prepares highly responsive beta-Ga 2 O 3 The base heterojunction self-powered ultraviolet detector comprises the following steps:
s201, cleaning the sapphire substrate. Ultrasonic treating with ethanol and acetone for 15 min, soaking in 80 deg.C diluted hydrochloric acid for 10min, and treating with H 3 PO 4 :H 2 SO 4 And the mixed acid solution of = 1.
S202, putting the cleaned substrate into a growth chamber of a magnetron sputtering device, setting process parameters such as atmosphere, vacuum degree and the like, and preparing a Ru/Ni/Ag/Pt/Au laminated first electrode;
s203, placing the substrate deposited with the first electrode into an MOVPE reaction chamber, trimethyl gallium (TMGa) and magnesium dicocene (Cp) 2 Mg) and high purity ammonia (NH) 3 ) As Ga, mg and N sources, respectively. High purity hydrogen (H) 2 ) As a carrier gas. Subjecting a sapphire substrate to H at 1050 DEG C 2 Baking under atmosphere, H 2 /NH 3 Nitriding in the atmosphere, growing at 550 ℃ for 180min, and preparing the p-GaN-Mg conducting layer.
S204, putting the substrate/the first alloy metal film electrode/the p-GaN conductive film into a growth chamber of PLD equipment, and introducing O 2 Gas, growth pressure of 0.085Pa, growth temperature of 480 ℃, distance between the substrate and the target of 40mm, and high-purity (99.999%) Ga as the target 2 O 3 Growth time of 3min, preparation of intrinsic beta-Ga 2 O 3 A thin film depletion layer.
S205, on the basis of the step S204, changing the growth process. Introduction of O 2 Gas, growth pressure of 1Pa, growth temperature of 500 ℃, distance between the substrate and the target material of 45mm, and the target material of Ga with 0.5at% of Sn atom percentage 2 O 3 Growth time of 120min, preparation of n-beta-Ga 2 O 3 A Sn conductive film.
S206, covering the n-beta-Ga by using a mask technology 2 O 3 Placing the Sn conducting layer film into a growth chamber of PLD equipment, and introducing O 2 Gas, growth pressure of 0.85Pa, growth temperature of 500 ℃, and target material of Ga with 3at% of Sn atom percentage 2 O 3 The distance between the substrate and the target material is 40mm, the growth time is 40min, and n is prepared + -β-Ga 2 O 3 Sn electron collection layer.
S207, on the basis of the step S206, utilizing a mask plate technology and a magnetron sputtering device to perform sputtering on n + -β-Ga 2 O 3 A second electrode is prepared on the Sn electron collecting layer.
S208, utilizing a mask plate technology, using a magnetron sputtering device, and introducing Ar: O 2 1, the growth pressure is 0.8Pa, the target material is MgO with the Na atom percentage content of 1at%, the sputtering power is 15W, the growth temperature is 450 ℃, the growth time is 40min, and in the case of n, the mixed gas is prepared by mixing the following raw materials in percentage by mass + -β-Ga 2 O 3 Preparing a passivation layer of MgO-Na film on the Sn electron collecting layer to obtain a sapphire substrate/(Ru/Ni/Ag/Pt/Au) laminated first electrode/p-GaN-Mg conductive layer/intrinsic beta-Ga 2 O 3 Thin film depletion layer/n-beta-Ga 2 O 3 Sn conductive film/n + -β-Ga 2 O 3 An Sn electron collection layer/MgO Na film passivation layer/(Ti/Au) laminated second electrode ultraviolet light detector.
For the above-mentioned beta-Ga 2 O 3 The photoelectric performance test is carried out on the p-n heterojunction ultraviolet detector, the result shows that the device has the maximum responsivity near the wavelength 254nm under the bias voltage of 0V, and the responsivity value is obviously reduced when the wavelength is larger than 270nm, as shown in figure 2, the ultraviolet detector obtained by the invention has solar blind characteristics.
Example 2
In this example, "sapphire substrate/(Ru/Ni/Ag/Pt/Au) laminated first electrode/p-GaN: mg conductive layer/n-beta-Ga) was prepared under the same process conditions as in example 1 2 O 3 The Sn conductive film/(Ti/Au) laminated second electrode ultraviolet detector comprises the following specific processes:
s301, cleaning the sapphire substrate. Firstly, using ethanol and acetone to make ultrasonic treatment for 15 min, then using dilute hydrochloric acid with 80 deg.C to make digestion for 10min, finally using H 3 PO 4 :H 2 SO 4 And the mixed acid solution of = 1.
S302, putting the cleaned substrate into a growth chamber of a magnetron sputtering device, setting process parameters such as atmosphere, vacuum degree and the like, and preparing a Ru/Ni/Ag/Pt/Au laminated first electrode;
s303, placing the substrate deposited with the first electrode into an MOVPE reaction chamber, trimethyl gallium (TMGa) and magnesium dicocene (Cp) 2 Mg) and high purity ammonia (NH) 3 ) As Ga, mg and N sources, respectively. High purity hydrogen (H) 2 ) As a carrier gas. Subjecting a sapphire substrate to H at 1050 DEG C 2 Baking under atmosphere, H 2 /NH 3 Nitriding in the atmosphere, growing at 550 ℃ for 180min, and preparing the p-GaN-Mg conducting layer.
S304, putting the substrate/the first alloy metal thin film electrode/the p-GaN (or p-ZnO) thin film into a PLD (programmable logic device) equipment growth chamber, and introducing O 2 Gas, growth pressure of 1Pa, growth temperature of 500 ℃, distance between the substrate and the target of 45mm, and the target of Ga with 0.5at% of Sn atom percentage 2 O 3 The growth time is 120min, and n-beta-Ga is prepared 2 O 3 A Sn conductive film.
S305, utilizing a mask plate technology and adopting a magnetron sputtering device at n + -β-Ga 2 O 3 A second electrode is prepared on the Sn electron collecting layer. Obtaining a sapphire substrate/(Ru/Ni/Ag/Pt/Au) laminated first electrode/p-GaN: mg conductive layer/n-beta-Ga 2 O 3 An Sn conductive film/(Ti/Au) laminated second electrode ultraviolet light detector.
S306, for the beta-Ga obtained in the step S305 2 O 3 The photoelectric performance test of the base pn heterojunction ultraviolet detector shows that the device has the maximum responsivity near the wavelength of 254nm under the bias voltage of 0V, and the responsivity value is slowly reduced when the wavelength is larger than 270nm, as shown in figure 2, the ultraviolet detector obtained by the invention has solar blind characteristics.
As a result, it can be understood that the high responsivity beta-Ga of the present invention 2 O 3 The radical heterojunction self-powered ultraviolet detector utilizes intrinsic beta-Ga 2 O 3 As depletion layer and absorption layer, mgO: na (or K) film as passivation layer, n + -β-Ga 2 O 3 Sn film as an electron collecting layer, and beta-Ga 2 O 3 The basic heterojunction solar blind detector has higher responsivity compared with the existing beta-Ga 2 O 3 The responsivity of the base heterojunction ultraviolet detector is improved by nearly 2 times, and the method has the following advantages:
1) Light injection into intrinsic beta-Ga 2 O 3 Because the film is not doped, the lattice distortion is small, and the photon-generated carriers rapidly drift to a loop under the action of an internal electric field, the composition of the photon-generated carriers is reduced, and the short-circuit current and the open-circuit voltage are increased;
2) The MgO, na (or K) film is used as a passivation layer, so that the surface recombination is reduced;
3) By n + -β-Ga 2 O 3 The Sn film is used as an electron collecting layer, and the electron collecting efficiency is improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. High responsivity beta-Ga 2 O 3 The base heterojunction self-powered ultraviolet detector is characterized by comprising a substrate, a first electrode, a p-type wide bandgap conductive film and intrinsic beta-Ga which are sequentially stacked from bottom to top 2 O 3 Thin film depletion layer, n-beta-Ga 2 O 3 Sn conductive film, n + -β-Ga 2 O 3 A Sn electron collecting layer, a MgO Na or MgO K film passivation layer and a second electrode; wherein:
the forbidden band width of the p-type wide forbidden band conductive film is more than 3.0eV;
the intrinsic beta-Ga 2 O 3 A thin film depletion layer is arranged between the p-type wide bandgap conductive thin film and the n-beta-Ga 2 O 3 Sn conductive films;
the MgO: na or MgO: K film passivation layer covers the n-beta-Ga 2 O 3 On a Sn conductive film;
n is said + -β-Ga 2 O 3 An Sn electron collecting layer is located at the n-beta-Ga 2 O 3 Between the Sn conductive film and the second electrode.
2. Highly responsive beta-Ga according to claim 1 2 O 3 The base heterojunction self-powered ultraviolet detector is characterized in that the substrate is made of sapphire, silicon or metal materials with flat and smooth surfaces.
3. Highly responsive beta-Ga according to claim 1 2 O 3 A base heterojunction self-powered ultraviolet detector is characterized in that,
the first electrode is a Ru/Ni/Ag/Pt/Au laminated alloy thin film, wherein the thickness of Ru is 5-50nm, the thickness of Ni is 10-100nm, the thickness of Ag is 10-100nm, the thickness of Pt is 10-100nm, and the thickness of Au is 50-1000nm;
and/or the second electrode is a Ti/Au laminated alloy thin film, the thickness of Ti is 10-500nm, and the thickness of Au is 50-1000nm.
4. Highly responsive beta-Ga according to claim 1 2 O 3 The base heterojunction self-powered ultraviolet detector is characterized in that,
the intrinsic beta-Ga 2 O 3 The thickness of the film depletion layer is 5-50nm;
and/or said n-beta-Ga 2 O 3 The Sn atom percentage content in the Sn conductive film is 0.01at percent to 1at percent, and the thickness is 300 nm to 2000nm.
5. Highly responsive beta-Ga according to claim 1 2 O 3 A base heterojunction self-powered ultraviolet detector, wherein n is + -β-Ga 2 O 3 The Sn electron collection layer is a strip-shaped structure, wherein the atomic percentage of Sn is 1at percent to 10at percent, and the thickness is 50nm to 500nm.
6. Highly responsive beta-Ga according to claim 1 2 O 3 The base heterojunction self-powered ultraviolet detector is characterized in that the p-type wide bandgap conductive film is one or more selected from p-GaN, p-SiC and p-ZnO conductive films.
7. Highly responsive beta-Ga according to claim 1 2 O 3 The base heterojunction self-powered ultraviolet detector is characterized in that the thickness of a MgO: na or MgO: K thin film passivation layer is 50-500nm, and the percentage content of Na or K atoms is 0.1at% -5at%.
8. Highly responsive beta-Ga as claimed in any one of claims 1 to 7 2 O 3 The preparation method of the base heterojunction self-powered ultraviolet detector is characterized by comprising the following steps of:
s101, cleaning a substrate;
s102, preparing a Ru/Ni/Ag/Pt/Au laminated alloy film on the cleaned substrate through vacuum magnetron sputtering to serve as a first electrode;
s103, preparing a p-type wide bandgap conductive film on the first electrode by adopting a vacuum film-making method selected from metal organic matter vapor phase epitaxy, pulse laser deposition, magnetron sputtering or molecular beam epitaxy;
s104, preparing intrinsic beta-Ga on the p-type wide bandgap conductive film by adopting pulsed laser deposition 2 O 3 A thin film depletion layer;
s105, depositing intrinsic beta-Ga on the substrate by adopting pulse laser 2 O 3 Preparation of n-beta-Ga on thin film depletion layer 2 O 3 A Sn conductive film;
s106, covering the n-beta-Ga by using a mask plate 2 O 3 Sn conductive film deposited on n-beta-Ga by pulsed laser 2 O 3 Preparing n on Sn conductive film + -β-Ga 2 O 3 A Sn electron collecting layer;
s107, a vacuum film-making method combining a mask plate and magnetron sputtering is carried out in n + -β-Ga 2 O 3 Preparing a Ti/Au alloy laminated film on the Sn electron collection layer as a second electrode;
s108, covering the second electrode with a mask plate, and forming a film on the n-beta-Ga layer by adopting a magnetron sputtering vacuum film forming method 2 O 3 A passivation layer of MgO, na or MgO, K film is prepared on the Sn conductive film.
9. Highly responsive beta-Ga according to claim 8 2 O 3 The preparation method of the base heterojunction self-powered ultraviolet detector is characterized in that the intrinsic beta-Ga 2 O 3 The preparation process parameters of the thin film depletion layer comprise: introduction of O 2 Gas, the growth pressure is 0.01-0.1Pa, the growth temperature is 380-650 ℃, the distance between the substrate and the target material is 20-50mm, and the growth time is 1-10min;
and/or said n-beta-Ga 2 O 3 The preparation process parameters of the Sn conductive film comprise: introduction of O 2 Gas, the growth pressure is 0.01-5Pa, the growth temperature is 350-950 ℃, the distance between the substrate and the target material is 20-50mm, and the growth time is 100-240min;
and/or said n + -β-Ga 2 O 3 The preparation process parameters of the Sn electronic collecting layer comprise: introduction of O 2 Gas, the growth pressure is 0.01-5Pa, the growth temperature is 350-950 ℃, the distance between the substrate and the target material is 20-50mm, and the growth time is 30-60min;
and/or the preparation process parameters of the MgO: na or MgO: K thin film passivation layer comprise: introducing Ar and O 2 Mixed gas of Ar and O 2 The volume ratio of (1).
10. Highly responsive beta-Ga as claimed in any one of claims 1 to 7 2 O 3 The application of the base heterojunction self-powered ultraviolet detector in solar blind band detection is provided.
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