CN108565301B

CN108565301B - Photoelectric detector based on metal surface plasma induction dual-band response and preparation method thereof

Info

Publication number: CN108565301B
Application number: CN201810305675.5A
Authority: CN
Inventors: 胡平安; 戴明金; 陈洪宇
Original assignee: Harbin Institute of Technology Shenzhen
Current assignee: Harbin Institute of Technology Shenzhen
Priority date: 2018-04-08
Filing date: 2018-04-08
Publication date: 2020-04-17
Anticipated expiration: 2038-04-08
Also published as: CN108565301A

Abstract

The invention provides a photodetector based on metal surface plasma-induced dual-band response and a preparation method, and belongs to the technical field of sensors. The detector of the invention comprises: a substrate, an indium selenide nanosheet, a gold nanoarray and two metal electrodes. The light-sensitive material used in the present invention is indium selenide. At present, the working range of indium selenide-based photodetectors is mostly concentrated in the ultraviolet waveband, and its responsivity begins to decay seriously from the visible light waveband, making it unable to work normally in the long waveband. In order to solve this problem, the method of metal surface plasmon resonance induction in the present invention improves the quantum efficiency of the indium selenide photodetector in the visible light region, and further realizes that it has dual wavebands in the wide spectral range of ultraviolet-visible-near-infrared detection function. In addition, this novel dual-band detector has the characteristics of simple structure, small size, and easy coupling to the focal plane readout circuit, which is beneficial to the development of next-generation multifunctional, multivariable detection photodetectors.

Description

Photoelectric detector based on metal surface plasma induction dual-band response and preparation method thereof

Technical Field

The invention relates to a photoelectric detector based on metal surface plasma induction dual-band response and a preparation method thereof, belonging to the technical field of sensors.

Background

At present, the semiconductor photoelectric detector has wide application in a plurality of fields of military affairs and national economy. For example, it plays an increasingly important role in optical imaging, optical communication, remote sensing, and other technologies. In recent years, with the continuous development and updating of scientific technology, people have higher and higher requirements on photoelectric detectors, and the requirements on some photoelectric detectors with special functions are more and more urgent. For example, the newly developed "sky eye" in Tiangong No. two is a special photoelectric sensor, and the "forward sky eye" can realize the multiband detection function of ultraviolet-visible-near infrared atmospheric edge imaging spectrum. This also means that the development of photosensors from single-function, single-detection-object to multi-function and multi-variable tests is a necessary trend. At present, for a photoelectric detector based on a traditional semiconductor material, methods such as adding a filter, constructing a superlattice, a quantum well structure and a heterojunction composite material are mainly used for realizing the response of the detector in a dual-band or multi-band (Infrared,2006,27 and 35; Infrared,2006,27 and 44-48; Infrared Laser and Engineering,2009,38 and 211-. These methods not only require extremely complicated production processes, but also have high requirements on production equipment; in addition, conventional bulk and thin film semiconductor materials have limitations in achieving device miniaturization and portability.

In order to solve the above problems, with the continuous development of the material field, two-dimensional semiconductor nanomaterials are becoming hot and popular targets for researchers to pay attention to due to their characteristics of ultra-high mobility, flexibility, adjustable band gap, etc. (Materials Science & Technology,2017,25, 1-7). For example, an indium selenide semiconductor material has higher mobility, a suitable band gap and better room temperature stability, and becomes a novel photodetector material (advanced material,2014,26, 6587-. However, due to the optical characteristics of the indium selenide semiconductor material, although it has a high responsivity in the ultraviolet region, the responsivity attenuation from the visible region is very severe, so that its optical detection function in the long wavelength band is not well developed and utilized (Nano Letter,2014,14, 2800) -2806).

The above analysis is combined to consider that: (1) when the traditional bulk semiconductor material is used as an effective light absorption layer, because of the huge volume, the lightness and the miniaturization of the device can not be realized; (2) when the two-dimensional semiconductor material is used as an effective light absorption layer, the thickness of the two-dimensional semiconductor material is small, so that the absorption efficiency of incident light is low, and the sensitivity and the responsiveness of the device are difficult to improve again; (3) due to the limitation of the light absorption characteristics of the indium selenide semiconductor, the detector based on indium selenide can only have higher response in a narrower ultraviolet spectrum range, and cannot realize dual-band or multi-band detection in a wider spectrum range. Aiming at the problems, the invention adopts a metal surface plasma resonance induction mode in the indium selenide semiconductor nano material to realize a photoelectric detector with dual-band spectral response, high sensitivity, high responsivity and miniaturization.

Disclosure of Invention

The invention aims to provide a method for selectively enhancing responsivity by metal surface plasma resonance, and finally a photoelectric detector with high performance and small volume and dual-band response is obtained.

The invention aims to provide a novel dual-band response photoelectric detector as shown in the attached figure 1, which comprises: the device comprises a substrate 1, indium selenide semiconductor nanosheets 2, a gold nano array 3, a metal electrode 4 and a metal electrode 5.

The invention also aims to provide a preparation method of the novel dual-band response photoelectric detector.

The purpose of the invention is realized by the following technical scheme, as shown in the attached figure 2, the invention comprises the following steps:

the method comprises the following steps: cleaning a substrate 1, wherein the substrate 1 can be selected from silicon oxide wafers, mica, PET and polyimide according to needs, selecting a corresponding cleaning solvent comprising a mixed solution of sulfuric acid and hydrogen peroxide, ethanol, isopropanol, acetone, deionized water and the like according to the selected substrate, carrying out ultrasonic treatment for 20-40 min, and drying by using a nitrogen gun for later use;

step two: preparing a few layers of indium selenide semiconductor nanosheets 2 on a clean substrate 1, wherein the indium selenide semiconductor nanosheets 2 can be prepared by a mechanical stripping method, chemical vapor deposition, physical vapor deposition, molecular beam epitaxy and the like, and the thickness is 20-50 nm;

step three: the gold nano array is prepared by using the self-assembled silicon oxide pellet thin film as a mask, and the gold nano array 3 is arranged on the upper surface of the indium selenide semiconductor nano sheet 2 and has the thickness of 20-30 nm. The gold nano-arrays are arranged in a close-packed hexagonal manner, the gold nano-particles are triangular, the size of the gold nano-particles is 80-150 nm, and the size of the gold nano-particles can be adjusted by adjusting the size of the silicon dioxide pellets according to requirements;

step four: the method for transferring the gold nano array to the indium selenide semiconductor nano sheet by using a polymer-assisted method comprises the following steps: spin-coating a layer of polymethyl methacrylate film on the surface of a gold nano array, drying at 120-150 ℃, soaking in hydrofluoric acid aqueous solution with the concentration of 10-20%, separating the gold nano array from a substrate by removing an oxide layer on the upper layer of an oxide silicon wafer substrate, suspending the gold nano array and the polymethyl methacrylate film on the liquid surface, washing with water for at least 3 times, transferring to an indium selenide semiconductor nano sheet, drying, and soaking with acetone to remove the polymethyl methacrylate, thereby obtaining a composite structure of the indium selenide semiconductor nano sheet and the gold nano array;

step five: and respectively preparing metal electrodes at two ends of the indium selenide semiconductor nanosheet to finish the preparation of the device. The metal electrode 4 and the metal electrode 5 can be independently selected from Au, Ag, Al, In and Cu electrodes according to requirements, and the thickness is 20-50 nm. The preparation method comprises the following steps: the method comprises a thermal evaporation coating technology, an electron beam evaporation coating technology and a magnetron sputtering technology, wherein a metal electrode 4 and a metal electrode 5 are in direct contact with an indium selenide semiconductor nanosheet 2, and the distance between the metal electrode 4 and the metal electrode 5 is 3-10 mu m.

The invention has the beneficial effects that:

1. the photosensitive material adopted by the invention is indium selenide, and has a proper direct optical band gap and high mobility. The prepared material has high crystallization quality, and provides a foundation for preparing a miniaturized and high-performance photoelectric detector;

2. the invention applies the surface plasma effect of the gold nano array, effectively improves the absorption efficiency of the semiconductor material to incident light, and provides a foundation for preparing a photoelectric detector with high responsivity;

3. the invention applies the surface plasma effect of the gold nano array, realizes that the responsivity of the indium selenide photoelectric detector is obviously improved in a visible light region by adjusting the position of a resonance absorption peak, achieves the aim of dual-band detection, and can further realize the aim of multi-band detection by adjusting the resonance wavelength of a metal surface plasmon polariton;

4. the preparation process disclosed by the invention is simple to implement, good in operability, mature in process technology and good in repeatability, avoids the use of a complex photoetching technology, and provides a reference case for the preparation of a self-driven optoelectronic device based on a semiconductor nano material.

Drawings

FIG. 1 is a schematic structural diagram of a metal surface plasmon-induced dual-band response-based photodetector according to the present invention.

FIG. 2 is a schematic diagram of a process for preparing a metal surface plasma-induced dual-band response photodetector according to the present invention.

FIG. 3 is an extinction spectrum of a gold nano-array.

FIG. 4 is a graph of the spectral response of a photodetector based on a metal surface plasmon induced two-band response.

Reference numeral 1 in fig. 1, a substrate; 2 is an indium selenide semiconductor nano sheet; 3 is a gold nano-array; 4 is a metal electrode; and 5, a metal electrode.

Detailed Description

The invention will be described in further detail below with reference to the accompanying drawings: the present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation is given, but the scope of the present invention is not limited to the following embodiments.

Examples

Firstly, selecting silicon oxide wafer as substrate 1, cutting the substrate into 1cm x 1cm square, firstly using H₂SO₄:H₂O₂The mixed solution is cleaned for 30min at 85 ℃, then ultrasonic cleaned for 10min by acetone, isopropanol, ethanol and deionized water respectively, and finally the silicon oxide wafer is dried by nitrogen for standby (fig. 2 a).

And (3) stripping the silicon oxide wafer substrate by a mechanical stripping method to obtain an indium selenide semiconductor nanosheet 2 (fig. 2 b). The specific method comprises the following steps: placing a little block indium selenide on a Sigao adhesive tape, folding the adhesive tape, repeatedly sticking the adhesive tape for 6-10 times, sticking the adhesive tape with the indium selenide on a cleaned silicon oxide wafer substrate, placing the substrate for 10 hours, tearing the adhesive tape, and leaving indium selenide nanosheets 2 on the substrate.

The preparation method of the gold nano array 3 comprises the following steps: at the interface of water and air, a layer of film is self-assembled by using small silicon dioxide balls, a small silicon dioxide ball film is selected from a silicon oxide wafer which is fished up on the water surface, the silicon oxide ball film is dried and then placed into a cavity of a thermal evaporation coating machine, a layer of gold film with the thickness of 20-50 nm, more preferably 25nm, is evaporated, and after the silicon oxide film on a substrate is removed by using an adhesive tape, so that a gold nano array 3 is obtained on the substrate, the size of the gold nano array is 80-150 nm, the thickness of the gold nano array is 25nm, the size of the gold nano array can be accurately regulated and controlled by the size of the small silicon dioxide balls, and the.

The gold nanoarrays 3 prepared in advance are transferred onto the silicon oxide wafer substrate 1 with indium selenide nanosheets 2 by a polymer assisted method (fig. 2 c). The specific method comprises the following steps: spin-coating a layer of polymethyl methacrylate film on the surface of a gold nano array, drying at 120-150 ℃, soaking in hydrofluoric acid aqueous solution with the concentration of 10% -20%, soaking for 20-40 s, suspending the gold nano array and the polymethyl methacrylate film on the liquid surface, washing for 5-10 times, transferring to an indium selenide semiconductor nano sheet, drying, soaking with acetone to remove the polymethyl methacrylate, and obtaining the composite structure of the indium selenide semiconductor nano sheet and the gold nano array.

The method for manufacturing the metal electrode comprises the following steps: selecting a carbon fiber with the diameter of 8 microns as a mask plate, placing the mask plate in the middle of the indium selenide nanosheets, exposing two ends of the mask plate, and evaporating a metal electrode 4 and a metal electrode 5 by thermal evaporation (shown in figure 2d), wherein the metal electrode 4 and the metal electrode 5 are both selected from Au electrodes, the thickness of the Au electrodes is 30nm, and the distance between the two electrodes is 5 microns, so that the preparation of the device is completed.

Comparative example

Firstly, selecting silicon oxide wafer as substrate 1, cutting the substrate into 1cm x 1cm square, firstly using H₂SO₄:H₂O₂Cleaning the mixed solution at 85 ℃ for 30min, then respectively ultrasonically cleaning the mixed solution with acetone, isopropanol, ethanol and deionized water for 10min, and finally blowing the silicon oxide wafer by nitrogen for later use.

And stripping the silicon oxide wafer substrate 1 by a mechanical stripping method to obtain the indium selenide semiconductor nanosheet 2. The specific method comprises the following steps: placing a little block indium selenide on a Sigao adhesive tape, folding the adhesive tape, repeatedly sticking the adhesive tape for 6-10 times, sticking the adhesive tape with the indium selenide on a cleaned silicon oxide wafer substrate, placing the substrate for 10 hours, tearing the adhesive tape, and leaving indium selenide nanosheets 2 on the substrate.

This comparative example is the same as example 1 except for the following features: after the indium selenide nanosheets 2 are prepared, and before the

metal electrodes

4 and 5 are prepared, the steps of preparing and transferring the gold nanoarrays 2 are omitted.

As shown in fig. 3, the extinction spectrum of gold nanoarray. As can be seen from the extinction spectrogram, the gold nano-array has two obvious extinction peaks at 664nm of a visible light region and 1080nm of a near infrared light region. The prepared gold nano array can generate surface plasma resonance in visible light and near infrared light regions, which provides a foundation for further application to a dual-band response photoelectric detector.

As shown in fig. 4, in order to test the performance of the photodetector based on the metal surface plasmon induced dual-band response, the prepared device was tested for its responsivity under uv-vis-nir irradiation (example 1). From the test results, it can be seen that the device exhibits very good photodetection capability. Wherein, the responsivity of the optical fiber is over 100mA/W in two wave bands of 320-400 nm and 650-750 nm.

As shown in fig. 4, in order to further illustrate that the gold nano-array can effectively realize a dual-band photodetector, the spectral response (comparative example) of the indium selenide photodetector without the gold nano-array is tested and compared, and as can be seen from the responsivity enhancement proportion spectrogram, the responsivity enhancement proportion is larger in the range of 650-750 nm.

Within the range of 650-750 nm, the maximum value of the responsivity enhancement ratio of the photoelectric detector exceeds 1200%, which is quite consistent with the extinction spectrum of the gold nano array, and fully proves that the gold nano particles play a fundamental role in inducing the photoelectric detector with dual-band response. The above results fully demonstrate that the photoelectric detector based on metal surface plasma induced dual-band response prepared by the invention has excellent performance. Meanwhile, a novel idea is provided for further developing a new generation of dual-band photoelectric detector, and the method has important reference value.

While the foregoing is directed to the preferred embodiments of the present invention, other embodiments and modes of operation may be devised without departing from the basic scope thereof, and the scope thereof is not limited by the claims that follow.

Claims

1. a photodetector based on metal surface plasma-induced dual-band response, is characterized in that, comprising: substrate, indium selenide (InSe) semiconductor nanosheet, gold nanoarray, two metal electrodes;

Among them, the substrate provides support; the thickness of the two metal electrodes is 20-50 nm, the distance is 3-10 μm, and the two metal electrodes directly contact both ends of the indium selenide semiconductor nanosheet; the thickness of the indium selenide semiconductor nanosheet is 20-10 μm. 50nm; the gold nanoarray is on the upper surface of the indium selenide semiconductor nanosheet, and the indium selenide photodetector is induced by metal surface plasmon resonance to have high response and sensitivity in the visible light region.

2 . The photodetector based on metal surface plasmon-induced dual-band response according to claim 1 , wherein the substrate is selected from silicon oxide wafers, mica, PET and polyimide according to requirements. 3 .

3 . The photodetector based on metal surface plasmon-induced dual-band response according to claim 1 , wherein the two metal electrodes are selected from Au, Al, Ag, Cu and In electrodes. 4 .

4 . The photodetector based on metal surface plasmon-induced dual-band response according to claim 1 , wherein the gold nanoarrays are arranged in a close-packed hexagonal arrangement, with a size of 80-150 nm and a thickness of 20-30 nm; 5 . The size of the gold nanoarray is precisely regulated by the size of the mask, and the thickness is precisely regulated by the coating time.

5. A preparation method of a photodetector based on metal surface plasma-induced dual-band response as claimed in claim 1, wherein the specific preparation process comprises the following steps:

①Choose a suitable substrate and clean it. The cleaning process of the silicon oxide wafer is as follows: soaking in a sulfuric acid hydrogen peroxide solution with a concentration of 75% at 85°C for 30min, and then ultrasonicating with acetone, isopropanol, ethanol and deionized water for 10min respectively. ;Finally, dry with nitrogen gas and wait for use; the mica substrate does not need to be cleaned; the cleaning process of the PET and polyimide substrates is as follows: acetone, isopropanol, ethanol and deionized water are used for each ultrasonic wave for 10min, and nitrogen is used to blow dry, ready to use;

② Preparation of indium selenide semiconductor nanosheets on a clean substrate;

(3) Preparation of gold nanoarrays, another piece of silicon oxide substrate was taken, and a layer of gold film was prepared on the substrate by using the self-assembled silicon oxide ball film as a mask. After removing the silicon dioxide film with adhesive tape, gold nanometers were obtained. Array, the preparation method of gold film includes: thermal evaporation coating technology, electron beam evaporation technology or magnetron sputtering technology;

④ Transfer the gold nanoarrays to the surface of the indium selenide semiconductor nanosheets, and use the polymer-assisted method to transfer the gold nanoarrays to the indium selenide semiconductor nanosheets;

⑤ Metal electrodes are respectively prepared at both ends of the indium selenide semiconductor nanosheet, and the two metal electrodes are selected from Au, Al, Ag, Cu and In electrodes; the electrode preparation methods include: thermal evaporation coating technology, electron beam evaporation technology or magnetic Controlled sputtering technology.

6 . The method for preparing a photodetector based on metal surface plasma-induced dual-band response according to claim 5 , wherein the method for preparing indium selenide semiconductor nanosheets is mechanical exfoliation, chemical vapor deposition, physical vapor deposition or molecular beam epitaxy.

7 . The preparation method of a photodetector based on metal surface plasma-induced dual-band response according to claim 5 , wherein the gold nanoarray adopts thermal evaporation coating technology and electron beam evaporation technology in the preparation process. 8 . Or one of the magnetron sputtering techniques.

8. The preparation method of a photodetector based on metal surface plasma-induced dual-band response according to claim 5, wherein the preparation method of the two metal electrodes is thermal evaporation coating technology, electron beam evaporation technology Or one of the magnetron sputtering techniques.