CN113097315A - MSM multi-quantum well photoelectric detector using MXene-GaN Schottky junction and preparation method thereof - Google Patents
MSM multi-quantum well photoelectric detector using MXene-GaN Schottky junction and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an MSM multi-quantum well photoelectric detector utilizing an MXene-GaN Schottky junction and a preparation method thereof, belongs to the technical field of photoelectric detectors, and solves the problems of large dark current and low responsivity of an MSM type photoelectric detector in the prior art. The MXene material and the graphical sapphire substrate are combined, so that dark current is reduced, responsivity is improved, and the method can be used in the fields of underwater optical detection, underwater communication and the like.
Description
Technical Field
The invention belongs to the technical field of photoelectric detectors, and particularly relates to an MSM multi-quantum well photoelectric detector utilizing an MXene-GaN Schottky junction and a preparation method thereof.
Background
Photodetectors are an important class of devices widely used in the sensing and detection fields, and typical device structures of photodetectors include schottky type, metal-semiconductor-metal (MSM) type, p-i-n (pin) type, and avalanche type (APD) at present. MSM photodetectors, which consist of two back-to-back schottky contacts, are of interest to researchers for their high response speed. Furthermore, since Field Effect Transistor (FET) technology can share the same schottky contact of the FET gate and does not require bipolar doping, it is easy to manufacture and can be integrated with Field Effect Transistor (FET) technology. However, such detectors still have many challenges to be solved. The first problem is the large dark current, which causes a large amount of reverse tunneling current due to chemical disorder and more defect states caused by the deposition of metal on the metal-semiconductor surface. Secondly, the responsivity of the MSM photodetector is low because the interdigital design of the opaque metal electrode causes the part of the vertically incident light to be reflected, and the high cost and brittleness of the transparent metal electrode, which are combined to cause the responsivity of the detector to be low. Therefore, how to effectively reduce the interface defects, reduce the dark current, and improve the detector response rate becomes an urgent problem to be solved in the MSM type photodetector.
MXene material is a new type of two-dimensional (2D) material, and this unique 2D material has many properties such as metal conductivity, mechanical flexibility, hydrophilicity, good transmittance and chemical stability. In addition, different surface termination functional groups will affect the electrostatic potential and electronic structure of MXene, making its work function variable between 1.6eV and 6.2eV, and the widely adjustable work function makes MXene an ideal choice for forming ohmic or schottky contacts with various semiconductor materials required by different devices, or can solve the problems of high dark current and low responsivity faced by MSM-type detectors.
Disclosure of Invention
The invention aims to:
in order to solve the problems of large dark current and low responsivity of an MSM type photoelectric detector in the prior art, the MSM multi-quantum well photoelectric detector utilizing an MXene-GaN Schottky junction and the preparation method thereof are provided, so that the photoelectric detector can be applied to the fields of underwater optical detection, underwater communication and the like.
The technical scheme adopted by the invention is as follows:
the MSM multi-quantum well photoelectric detector utilizing the MXene-GaN Schottky junction comprises a growth substrate, wherein the growth substrate is of a graphical sapphire substrate structure, and a GaN thin film layer, an n-type GaN thin film layer, a GaN-InGaN combination layer and an MXene material layer are connected to the surface of the growth substrate from bottom to top.
Further, the GaN-InGaN combination layer is provided with a plurality of layers, and each GaN-InGaN combination layer is composed of an upper GaN layer and a lower InGaN layer which are connected with each other.
Further, the GaN thin film layer is composed of undoped GaN, and the thickness of the GaN thin film layer is 2.2-2.6 microns.
Further, the thickness of the n-type GaN thin film layer is 1.4-1.6 μm.
A method for preparing an MSM multi-quantum well photoelectric detector by using MXene-GaN Schottky junction is characterized by comprising the following steps:
a. taking the patterned sapphire substrate structure as a detector growth substrate;
b. growing a GaN film on the growth substrate in the step a;
c. growing an n-type GaN film on the GaN film in the step b;
d. c, growing a plurality of GaN-InGaN combination layers on the n-type GaN thin film in the step c;
e. preparing MXene material, and covering Ti on the surface of the multilayer GaN-InGaN combined layer in the step d3C2TxMXene film.
Further, the growth method of the GaN-InGaN combination layer structure in the step d includes: heteroepitaxial growth of GaN-InGaN multiple quantum wells on patterned sapphire substrates by metal organic compound vapor deposition, comprising the steps of:
growing an InGaN quantum well layer with indium content of about 25% and thickness of 3 nm;
raising the temperature to 100 ℃ within 60 seconds under the condition of the step I, and growing a 10nm high-temperature GaN barrier;
taking the grown material as a base, repeating the steps of the first step and the second step, and finally forming the GaN-InGaN multi-quantum well structure with a plurality of periods.
Further, the preparation method of the MXene material in the step e comprises the following steps:
s1 preparation of Ti3C2TxMXene aqueous solution;
s2 preparation of Ti3C2TxMXene film layer.
Further, the step S1 is to prepare Ti3C2TxThe MXene aqueous solution comprises the following steps:
(1) 0.67g of LiF was dissolved in 6 mol/L10 mL of HCl solution over a period of 5 minutes with constant stirring;
(2) mixing 1g of Ti3AlC2Adding MAX powder into an etchant, and then magnetically stirring for 24 hours at room temperature;
(3) transferring the obtained acidic mixture to a centrifugal tube under the condition of the step (2) and centrifuging at the rotating speed of 3500 rpm;
(4) repeatedly washing the obtained suspension with deionized water, and centrifuging until neutral pH is reached;
(5) under the condition of the step (4), collecting the precipitate, re-dispersing the precipitate in deionized water, and carrying out ultrasonic treatment for 3 hours under an argon atmosphere;
(6) centrifuging the solution at 3500rpm for 1h to obtain supernatant, i.e. desired Ti3C2TxMXene aqueous solution;
further, the step S2 is to prepare Ti3C2TxThe MXene film layer comprises the following steps:
1) washing the wafer with deionized water;
2) when the wafer is still wet, a polyvinyl chloride electrostatic film with electrode hole is pasted on the wafer;
3) drying the deionized water, and then adding the Ti prepared in the step S13C2TxDropping MXene solution on the mask to cover the holes and waiting for MXene solutionNaturally drying the liquid;
4) forming Ti in the hole3C2TxAfter MXene film, removing the PVC electrostatic film, putting the detector device in argon atmosphere, and annealing at 300 ℃ to obtain Ti3C2TxMXene film.
The MQW is a multiple quantum well, and refers to a system in which multiple quantum wells are combined together.
PSS (Patterned sapphire substrate), namely Patterned sapphire substrate, growing a mask for dry etching on the sapphire substrate, etching the mask to form a pattern by using a standard photoetching process, etching the sapphire by using an ICP (inductively coupled plasma) etching technology, removing the mask, and growing a GaN material on the mask, wherein the longitudinal epitaxy of the GaN material can be changed into the transverse epitaxy.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the invention is greatly improved on the basis of the traditional detector: MXene material is used as an electrode, and MXene-GaN Van der Waals metal-semiconductor junctions are formed to reduce the problems of possible defects, chemical disorder and the like on the material interface, obviously reduce the noise of a detector and achieve the aim of inhibiting dark current.
2. Compared with the traditional Cr/Au-GaN-Cr/Au MSM detector, the dark current of the MX-GaN-MX MQW detector is reduced by three orders of magnitude on the basis of the former.
3. According to the invention, the GaN material grown on the patterned sapphire substrate provides local photon extraction and photocurrent collection, meanwhile, the MXene material has certain light transmittance, the substrate nano pattern locally improves the responsivity by scattering normal incident light to different directions, and the substrate nano pattern is beneficial to subsequent development.
Drawings
FIG. 1 is a diagram of a photodetector and detector quantum well structure of the present invention;
FIG. 2 is a top view of a photodetector embodiment of the present invention;
fig. 3 is a microscopic enlarged view of the patterned sapphire substrate.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The MSM multi-quantum well photoelectric detector utilizing the MXene-GaN Schottky junction comprises a growth substrate, wherein the growth substrate is of a graphical sapphire substrate structure, and a GaN thin film layer, an n-type GaN thin film layer, a GaN-InGaN combination layer and an MXene material layer are connected to the surface of the growth substrate from bottom to top.
Further, the GaN-InGaN combination layer is provided with a plurality of layers, preferably eight layers, each of which is composed of an upper GaN layer and a lower InGaN layer connected to each other.
Preferably, the GaN thin film layer is composed of undoped GaN, and the thickness of the GaN thin film layer is 2.4 μm.
Preferably, the thickness of the n-type GaN thin film layer is 1.5 μm.
Example 2
A method for preparing an MSM multi-quantum well photoelectric detector by using MXene-GaN Schottky junction comprises the following steps:
a. taking the patterned sapphire substrate structure as a detector growth substrate;
b. growing a GaN film on the growth substrate in the step a;
c. growing an n-type GaN film on the GaN film in the step b;
d. c, growing a plurality of GaN-InGaN combination layers on the n-type GaN thin film in the step c;
e. preparing MXene material, and covering Ti on the surface of the multilayer GaN-InGaN combined layer in the step d3C2TxMXene film.
Further, the growth method of the GaN-InGaN combination layer structure in the step d includes: heteroepitaxially growing a GaN-InGaN multiple quantum well on a patterned sapphire substrate by atmospheric pressure metal organic chemical vapor deposition, comprising the steps of:
growing an InGaN quantum well layer with indium content of about 25% and indium content of 3 nm;
raising the temperature to 100 ℃ within 60 seconds under the condition of the step I, and growing a 10nm high-temperature GaN barrier;
taking the grown material as a base, repeating the steps of the first step and the second step, and finally forming the GaN-InGaN multi-quantum well structure with a plurality of periods. Preferably, eight periods of GaN-InGaN multi-quantum well structures are formed.
Further, the preparation method of the MXene material in the step e comprises the following steps:
s1 preparation of Ti3C2TxMXene aqueous solution;
s2 preparation of Ti3C2TxMXene film layer.
Further, the step S1 is to prepare Ti3C2TxThe MXene aqueous solution comprises the following steps:
(1) 0.67g of LiF was dissolved in 6 mol/L10 mL of HCl solution over a period of 5 minutes with constant stirring;
(2) mixing 1g of Ti3AlC2Adding MAX powder into an etchant, and then magnetically stirring for 24 hours at room temperature;
(3) transferring the obtained acidic mixture to a centrifugal tube under the condition of the step (2) and centrifuging at the rotating speed of 3500 rpm;
(4) repeatedly washing the obtained suspension with deionized water, and centrifuging until neutral pH is reached;
(5) under the condition of the step (4), collecting the precipitate, re-dispersing the precipitate in deionized water, and carrying out ultrasonic treatment for 3 hours under an argon atmosphere;
(6) centrifuging the solution at 3500rpm for 1h to obtain supernatant, i.e. desired Ti3C2TxMXene aqueous solution;
further, the step S2 is to prepare Ti3C2TxThe MXene film layer comprises the following steps:
1) washing the wafer with deionized water;
2) when the wafer is still wet, a polyvinyl chloride electrostatic film with electrode hole is pasted on the wafer;
3) drying the deionized water, and then adding the Ti prepared in the step S13C2TxDropping MXene solution on the mask to cover the holes, and waiting for the MXene solution to dry naturally;
4) forming Ti in the hole3C2TxAfter MXene film, removing the PVC electrostatic film, putting the detector device in argon atmosphere, and annealing at 300 ℃ to obtain Ti3C2TxMXene film.
The working principle of the invention is as follows: packaging the detector in a chip or a specific device, and respectively connecting electrodes to MXene materials on the left side and the right side; and then, incident light is emitted from the right above the detector, and the incident light is directly emitted to the surface of the patterned sapphire after entering the detector, reflected light with different emergent direction angles is formed through reflection, so that the reflected light with the angle larger than the total reflection angle is reflected for multiple times in the detector, the light absorption of the quantum well structure is enhanced, the responsivity of the detector is improved, and meanwhile, noise and dark current can be remarkably reduced through a Schottky junction formed by the Mxene and the GaN.
Test data show that under the illumination with the wavelength of 405nm, the responsivity and the external quantum efficiency of the detector respectively reach 64.6A/W and 19783.6 percent, and the huge potential and advantages of the detector in the aspects of underwater optical detection and communication are reflected.
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 and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. The MSM multi-quantum well photoelectric detector utilizing the MXene-GaN Schottky junction is characterized by comprising a growth substrate, wherein the growth substrate is of a graphical sapphire substrate structure, and a GaN thin film layer, an n-type GaN thin film layer, a GaN-InGaN combination layer and an MXene material layer are connected to the surface of the growth substrate from bottom to top.
2. The MSM multi-quantum well photodetector using MXene-GaN Schottky junction according to claim 1, wherein the GaN-InGaN combination layer is provided with a plurality of layers, each composed of an upper GaN layer and a lower InGaN layer interconnected.
3. The MSM multi-quantum well photodetector of claim 1 using MXene-GaN Schottky junction, wherein the GaN thin film layer is composed of undoped GaN, and the thickness of the GaN thin film layer is 2.2 μm to 2.6 μm.
4. The MSM multi-quantum well photodetector using MXene-GaN Schottky junction according to claim 1, wherein the thickness of the n-type GaN thin film layer is 1.4 μm to 1.6 μm.
5. A method for preparing an MSM multi-quantum well photoelectric detector by using MXene-GaN Schottky junction is characterized by comprising the following steps:
a. taking the patterned sapphire substrate structure as a detector growth substrate;
b. growing a GaN film on the growth substrate in the step a;
c. growing an n-type GaN film on the GaN film in the step b;
d. c, growing a plurality of GaN-InGaN combination layers on the n-type GaN thin film in the step c;
e. preparing MXene material, and covering Ti on the surface of the multilayer GaN-InGaN combined layer in the step d3C2TxMXene film.
6. The method for preparing the MSM multi-quantum well photodetector using the MXene-GaN Schottky junction according to claim 5, wherein the growth method of the GaN-InGaN combined layer structure in the step d comprises: heteroepitaxial growth of GaN-InGaN multiple quantum wells on patterned sapphire substrates by metal organic compound vapor deposition, comprising the steps of:
growing an InGaN quantum well layer with indium content of about 25% and thickness of 3 nm;
raising the temperature to 100 ℃ within 60 seconds under the condition of the step I, and growing a 10nm high-temperature GaN barrier;
taking the grown material as a base, repeating the steps of the first step and the second step, and finally forming the GaN-InGaN multi-quantum well structure with a plurality of periods.
7. The method for preparing the MSM multi-quantum well photoelectric detector by using the MXene-GaN Schottky junction according to claim 5, wherein the method for preparing the MXene material in the step e comprises the following steps:
s1 preparation of Ti3C2TxMXene aqueous solution;
s2 preparation of Ti3C2TxMXene film layer.
8. The method for preparing the MSM multi-quantum well photodetector using MXene-GaN Schottky junction according to claim 7, wherein the step S1 is to prepare Ti3C2TxThe MXene aqueous solution comprises the following steps:
(1) 0.67g of LiF was dissolved in 6 mol/L10 mL of HCl solution over a period of 5 minutes with constant stirring;
(2) mixing 1g of Ti3AlC2Adding MAX powder into an etchant, and then magnetically stirring for 24 hours at room temperature;
(3) transferring the obtained acidic mixture to a centrifugal tube under the condition of the step (2) and centrifuging at the rotating speed of 3500 rpm;
(4) repeatedly washing the obtained suspension with deionized water, and centrifuging until neutral pH is reached;
(5) under the condition of the step (4), collecting the precipitate, re-dispersing the precipitate in deionized water, and carrying out ultrasonic treatment for 3 hours under an argon atmosphere;
(6) centrifuging the solution at 3500rpm for 1h to obtain supernatant, i.e. desired Ti3C2TxMXene aqueous solution.
9. The method of claim 7The method for preparing the MSM multi-quantum well photoelectric detector by using the MXene-GaN Schottky junction is characterized in that the step S2 is to prepare Ti3C2TxThe MXene film layer comprises the following steps:
1) washing the wafer with deionized water;
2) when the wafer is still wet, a polyvinyl chloride electrostatic film with electrode hole is pasted on the wafer;
3) drying the deionized water, and then adding the Ti prepared in the step S13C2TxDropping MXene solution on the mask to cover the holes, and waiting for the MXene solution to dry naturally;
4) forming Ti in the hole3C2TxAfter MXene film, removing the PVC electrostatic film, putting the detector device in argon atmosphere, and annealing at 300 ℃ to obtain Ti3C2TxMXene film.
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