CN113328004B - Indium selenide photoelectric detector for surface modification by utilizing stannous selenide nanocrystals and preparation method thereof - Google Patents
Indium selenide photoelectric detector for surface modification by utilizing stannous selenide nanocrystals and preparation method thereof Download PDFInfo
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- CN113328004B CN113328004B CN202110442127.9A CN202110442127A CN113328004B CN 113328004 B CN113328004 B CN 113328004B CN 202110442127 A CN202110442127 A CN 202110442127A CN 113328004 B CN113328004 B CN 113328004B
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- AKUCEXGLFUSJCD-UHFFFAOYSA-N indium(3+);selenium(2-) Chemical compound [Se-2].[Se-2].[Se-2].[In+3].[In+3] AKUCEXGLFUSJCD-UHFFFAOYSA-N 0.000 title claims abstract description 120
- LYZMBUYUNBCSMW-UHFFFAOYSA-N selenium(2-);tin(2+) Chemical compound [Se-2].[Sn+2] LYZMBUYUNBCSMW-UHFFFAOYSA-N 0.000 title claims abstract description 86
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Abstract
The invention discloses an indium selenide photoelectric detector for surface modification by utilizing stannous selenide nanocrystals and a preparation method thereof, wherein the indium selenide photoelectric detector comprises a substrate, an n-type indium selenide film layer arranged on the substrate, a p-type stannous selenide nanocrystal arranged on the n-type indium selenide film layer, and a first electrode and a second electrode which are arranged on the substrate and are respectively connected with two ends of the n-type indium selenide film layer. According to the invention, on the premise of not changing the microstructure of the indium selenide film layer, the p-type stannous selenide nanocrystals are modified on the surface of the indium selenide film layer to form a local heterojunction, under illumination, the heterojunction can enable a large number of electrons and holes to be generated at the interface of the n-type indium selenide film layer and the p-type stannous selenide nanocrystals, and the photo-generated electron holes can be rapidly separated at the heterojunction formed by the stannous selenide nanocrystals and the indium selenide film layer, so that the light-dark current ratio, the light responsivity and the specific detectivity of the prepared photoelectric detector can be effectively improved.
Description
Technical Field
The invention relates to the field of photoelectric detection, in particular to an indium selenide photoelectric detector for surface modification by utilizing stannous selenide nanocrystals and a preparation method thereof.
Background
A photodetector is a kind of photodetector device made by using the photoconductive effect of semiconductor materials. The semiconductor photoelectric detector can excite non-equilibrium carriers in a semiconductor material through photons to cause the change of electrical properties, and has the characteristics of small volume, integration, high response speed, high sensitivity and the like. The photoelectric detector has wide application, covers various fields of military and national economy, and promotes the development of the fields of aerospace, night vision and medical imaging, solar cells, wide-spectrum switches, optical communication, biological identification and the like. At present, efficient photoelectric detectors formed by using novel two-dimensional material semiconductors are rapidly developing in the fields of scientific research and industrial production.
Indium selenide (InSe) is a layered III-VI semiconductor having a graphene-like honeycomb lattice, each layer consisting of closely packed Se-In-Se sheets. Indium selenide has four different layered structures (β -, e-, γ -, and δ -) based on the arrangement of the superimposed sequences. Among them, β -and γ -are the two most studied phase structures in InSe. Natural indium selenide is an n-type semiconductor material, has a direct band gap of 1.3eV, and the size of the band gap changes with the decrease of the number of layers. Because the interlayer interaction of the indium selenide is weak, single-layer or few-layer indium selenide can be obtained by a mechanical stripping method.
Indium selenide has high carrier mobility, low effective electron mass, and broad band light absorption, making it of great interest in the electronic and optoelectronic fields. However, few studies on indium selenide photodetectors modified with nanocrystals have been reported in the prior art.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, an object of the present invention is to provide an indium selenide photodetector with better photoelectric properties and a method for manufacturing the same.
The technical scheme of the disclosure is as follows:
the utility model provides an utilize stannous selenide nanocrystalline to carry out surface modification's indium selenide photoelectric detector, wherein, is in including base, setting n type indium selenide rete, setting on the base are in p type stannous selenide nanocrystalline on the n type indium selenide rete, and the setting is in on the base and with first electrode and second electrode that n type indium selenide rete both ends are connected respectively.
The indium selenide photoelectric detector is characterized in that the p-type stannous selenide nanocrystals are arranged on the n-type indium selenide film layer.
The indium selenide photoelectric detector is characterized in that the thickness of the n-type indium selenide film layer is 0.8nm-80nm.
The indium selenide photoelectric detector is characterized in that the thickness of the p-type stannous selenide nanocrystal is 0.5nm-50nm.
The indium selenide photodetector includes a base, a substrate, and an insulating substrate disposed on the substrate.
The indium selenide photodetector is characterized in that the insulating substrate is made of silicon dioxide.
The indium selenide photodetector is characterized in that the first electrode and the second electrode are made of one of gold, titanium, chromium and tungsten.
A method for preparing an indium selenide photoelectric detector by utilizing stannous selenide nanocrystals for surface modification comprises the following steps:
preparing a p-type stannous selenide nanocrystalline suspension and an n-type indium selenide film layer in advance;
directionally transferring the n-type indium selenide film layer onto a substrate through a micro-mechanical transfer platform;
manufacturing an electrode pattern on the substrate, and preparing a first electrode and a second electrode in an evaporation mode, wherein the first electrode and the second electrode are respectively connected with two ends of the n-type indium selenide film layer;
and dripping the p-type stannous selenide nanocrystalline suspension on the n-type indium selenide film layer to generate p-type stannous selenide nanocrystals on the n-type indium selenide film layer, thus preparing the indium selenide photoelectric detector.
The preparation method of the indium selenide photoelectric detector comprises the following steps of:
SnCl2·2H2Dissolving O in deionized water, carrying out ultrasonic treatment at room temperature, adding NaOH, and continuing to carry out ultrasonic treatment to obtain a first mixtureMixing the liquid;
adding selenium powder into the first mixed solution, and carrying out heating treatment under a vacuum condition to react to obtain a second mixed solution;
cleaning the second mixed solution, and then carrying out vacuum drying treatment to obtain p-type stannous selenide nanocrystalline powder;
dispersing the p-type stannous selenide nanocrystalline powder in absolute ethyl alcohol, sequentially performing ultrasonic treatment and centrifugal treatment, and extracting supernatant to obtain the p-type stannous selenide nanocrystalline suspension.
The preparation method of the indium selenide photoelectric detector comprises the steps of carrying out heating treatment under the vacuum condition at the temperature of 400-450K for 20-40h.
Has the advantages that: compared with the prior art, the p-type stannous selenide nanocrystals are modified on the surface of the n-type indium selenide photoelectric detector to form the pn photoelectric heterojunction of the local interface, so that the prepared indium selenide photoelectric detector modified by the stannous selenide nanocrystals has the advantages of large light-dark current ratio, high light responsivity and high specific detection rate.
Drawings
Fig. 1 is a schematic structural diagram of an indium selenide photodetector with a surface modified by a stannous selenide nanocrystal.
Fig. 2 is a flowchart of a preferred embodiment of a method for preparing an indium selenide photodetector with surface modification by using stannous selenide nanocrystals.
Fig. 3 is an I-V curve diagram of the indium selenide photodetector provided by the present invention before and after surface modification by stannous selenide nanocrystals.
Fig. 4 is an I-t curve diagram of the indium selenide photodetector provided by the present invention before surface modification by the stannous selenide nanocrystal.
Fig. 5 is an I-t curve diagram of the indium selenide photodetector provided by the present invention after surface modification by stannous selenide nanocrystals.
Fig. 6 is a photo-responsivity diagram of the indium selenide photodetector provided by the present invention before and after surface modification by the stannous selenide nanocrystal.
Fig. 7 is a graph of specific detectivity of the indium selenide photodetector before and after surface modification by stannous selenide nanocrystals.
Detailed Description
The invention provides an indium selenide photoelectric detector for surface modification by utilizing stannous selenide nanocrystals and a preparation method thereof, and the invention is further explained in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As used herein, the singular forms "a", "an", "the" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. It will be understood that when an element is referred to as being "connected" or "coupled" to another element, it can be directly connected or coupled to the other element or intervening elements may also be present. Further, "connected" or "coupled" as used herein may include wirelessly connected or wirelessly coupled. As used herein, the term "and/or" includes all or any element and all combinations of one or more of the associated listed items.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Referring to fig. 1, fig. 1 is a schematic structural diagram of an indium selenide photodetector with a surface modified by a stannous selenide nanocrystal, as shown in the figure, the indium selenide photodetector includes a substrate 1, an n-type indium selenide film layer 2 disposed on the substrate 1, a p-type stannous selenide nanocrystal 3 disposed on the n-type indium selenide film layer 2, and a first electrode 4 and a second electrode 5 disposed on the substrate 1 and respectively connected to two ends of the n-type indium selenide film layer 2.
In this embodiment, the overlapping region between the p-type stannous selenide nanocrystal 3 and the n-type indium selenide film layer 2 forms a heterojunction, and since the conduction band and the valence band of the stannous selenide and the indium selenide are located between the conduction band and the valence band of the stannous selenide due to different positions of the conduction band and the valence band, the overlapping region between the p-type stannous selenide nanocrystal 3 and the n-type indium selenide film layer 2 forms a heterostructure.
In this embodiment, a trap state exists at the interface between the n-type indium selenide film layer 2 and the p-type stannous selenide nanocrystal 3, and the grating effect is derived from the capture and localization of long-life carriers on the surface or interface, especially for a nanocrystal two-dimensional material with a high specific surface area. In the dark, the interface between the n-type indium selenide film layer and the p-type stannous selenide nanocrystals forms depletion regions, their fermi levels (E)F) Aligned under equilibrium conditions. Under the illumination, photo-generated electron-hole pairs are generated at the contact interface of the n-type indium selenide film layer and the p-type stannous selenide nanocrystals and are separated by a formed built-in electric field, and a large amount of photo-generated electrons are transferred from the p-type stannous selenide nanocrystals and circulated to one side of the n-type indium selenide film layer. On the other hand, the photo-generated holes in the p-type stannous selenide nanocrystal can be reserved, and the holes accumulated in the p-type stannous selenide nanocrystal can play a role of a local grid and induce a strong grating effect, so that the photocurrent of the n-type indium selenide film layer is increased, and the photoelectric performance of the indium selenide photoelectric detector is improved. That is to say, in the embodiment, the p-type stannous selenide nanocrystal 3 and the n-type indium selenide film layer 2 construct the heterostructure, and under the illumination condition, electrons and holes generated by the p-type stannous selenide nanocrystal and the n-type indium selenide film layer can be rapidly separated at the heterojunction, so that the light darkness of the prepared photoelectric detector can be effectively improvedCurrent ratio, photoresponse, and specific detectivity.
In some embodiments, as shown in fig. 1, a plurality of p-type stannous selenide nanocrystals arranged in a matrix are disposed on the n-type indium selenide film layer. In the embodiment, the plurality of p-type stannous selenide nanocrystals are arranged on the n-type indium selenide film layer, so that a plurality of distributed heterogeneous structures are formed, and the optical dark current ratio, the optical responsivity and the ratio detection rate of the photoelectric detector are improved exponentially. By way of example, the
In some embodiments, the thickness of the n-type indium selenide film layer is from 0.8nm to 80nm, but is not limited thereto. For example, the number of the n-type indium selenide film layers may be 1 to 100.
In some embodiments, the p-type stannous selenide nanocrystals have a thickness of 0.5nm to 50nm, but are not limited thereto. For example, the number of p-type stannous selenide nanocrystals can be 1-100.
In some embodiments, the base includes a silicon substrate and an insulating substrate disposed on the silicon substrate. In this embodiment, the material of the insulating substrate is silicon dioxide, but is not limited thereto.
In some embodiments, the material of the first electrode and the second electrode is independently selected from one of gold, titanium, chromium, and tungsten, but is not limited thereto. In this embodiment, the first electrode is a source electrode, and the second electrode is a drain electrode. Alternatively, the first electrode is a drain electrode and the second electrode is a source electrode.
In some embodiments, there is also provided a method for preparing an indium selenide photodetector with surface modification by using stannous selenide nanocrystals, as shown in fig. 2, which includes the steps of:
s10, preparing a p-type stannous selenide nanocrystalline suspension and an n-type indium selenide film layer in advance;
s20, directionally transferring the n-type indium selenide film layer to a substrate through a micro-mechanical transfer platform;
s30, manufacturing an electrode pattern on the substrate, and preparing a first electrode and a second electrode in an evaporation mode, wherein the first electrode and the second electrode are respectively connected with two ends of the n-type indium selenide film layer;
and S40, dripping the p-type stannous selenide nanocrystalline suspension on the n-type indium selenide film layer, and generating p-type stannous selenide nanocrystals on the n-type indium selenide film layer to prepare the indium selenide photoelectric detector.
The preparation method of the indium selenide photodetector provided by the embodiment is simple and easy to operate, and in the embodiment, the substrate is cleaned by acetone, ethanol and deionized water in advance.
In this embodiment, the n-type indium selenide film layer is transferred onto a PDMS substrate in advance, the PDMS (polydimethylsiloxane) substrate is a flexible substrate with viscosity, the n-type indium selenide film layer can be bonded by using the viscosity of the PDMS substrate, and then the n-type indium selenide film layer is transferred from the PDMS substrate to the surface of a base through a micromechanical transfer platform.
In some embodiments, the preparation of the p-type stannous selenide nanocrystal suspension comprises the steps of: snCl2·2H2Dissolving O in deionized water, carrying out ultrasonic treatment at room temperature, adding NaOH, and continuing to carry out ultrasonic treatment to obtain a first mixed solution; adding selenium powder into the first mixed solution, and carrying out heating treatment under a vacuum condition, wherein the heating treatment temperature is 400-450K, and the heating treatment time is 20-40h, so as to obtain a second mixed solution; cleaning the second mixed solution, and then carrying out vacuum drying treatment to obtain p-type stannous selenide nanocrystalline powder; dispersing the p-type stannous selenide nanocrystalline powder in absolute ethyl alcohol, sequentially performing ultrasonic treatment and centrifugal treatment, and extracting supernatant to obtain the p-type stannous selenide nanocrystalline suspension.
In some embodiments, the preparation of the p-type stannous selenide nanocrystal suspension comprises the steps of: weighing SnCl2·2H2O (1.4 g) was dissolved in 50ml of deionized water, sonicated at room temperature for 30min, then 90mmol of NaOH was added and sonication continued for 30min. The mixed solution was transferred to a polytetrafluoroethylene liner having a capacity of 100ml, and then 0.24g of selenium powder was added, sealed in a reaction vessel, and then heated in a vacuum drying oven at 403K for 36 hours. Sample reactionAfter completion, the reaction product was cooled to room temperature, collected, washed with absolute ethanol and deionized water 3 times or more, and then the washed sample was placed in a vacuum oven and dried at 333K for 4 hours. And after drying, obtaining the stannous selenide powder. Then, the prepared stannous selenide powder (5 mg) is put into 10mL of absolute ethyl alcohol and is subjected to ultrasonic treatment for 300min. Centrifuging the solution after ultrasonic treatment at 3000rpm for 1h, and extracting supernatant to obtain the p-type stannous selenide nanocrystal suspension.
The following further explains the indium selenide photodetector surface-modified by stannous selenide nanocrystals and the preparation method thereof by specific embodiments:
example 1
The preparation method of the indium selenide photoelectric detector for surface modification by utilizing the stannous selenide nanocrystal comprises the following steps:
preparing p-type stannous selenide nanocrystalline by adopting a liquid phase stripping method, preparing n-type indium selenide thin-sheet layer by adopting a mechanical stripping method, and then, preparing SiO by adopting acetone, ethanol and deionized water2Cleaning the Si substrate, blowing the substrate with nitrogen, transferring the n-type indium selenide thin sheet layer on the PDMS substrate, and transferring the n-type indium selenide thin sheet layer on the PDMS substrate to SiO through a micro-mechanical transfer platform2The surface of the substrate is/Si, and furthermore, the standard photoetching process is adopted to form the SiO2Manufacturing an electrode pattern on a Si substrate, preparing gold electrodes at two ends of an n-type indium selenide thin sheet layer in an evaporation mode, removing residual photoresist and redundant gold powder in the photoetching process by using an organic solvent, modifying p-type stannous selenide nanocrystals to the surface of the n-type indium selenide thin sheet layer by using a rubber head dropper, and overlapping with part of an interface region of the n-type indium selenide thin sheet layer to form a pn photoelectric heterojunction, thus obtaining the indium selenide photoelectric detector with the modified surface of the stannous selenide nanocrystals, wherein the thickness of the prepared n-type indium selenide thin sheet layer is 70nm, and the thickness of the prepared p-type stannous selenide nanocrystals is 5-20nm.
The photoelectric performance of the indium selenide photodetector surface-modified by the stannous selenide nanocrystal prepared in the embodiment 1 is detected, fig. 3 is an I-V curve diagram of the indium selenide photodetector surface-modified by the stannous selenide nanocrystal prepared in the embodiment 1 before and after modification, and data in the graph shows that the photocurrent of the indium selenide photodetector surface-modified by the stannous selenide nanocrystal prepared is remarkably improved after modification. Fig. 4 and 5 are I-t graphs of the stannous selenide nanocrystal-modified indium selenide photodetector prepared in embodiment 1 before and after modification, respectively, and it can be known from data in the graphs that the modified indium selenide photodetector prepared in embodiment 1 of the present invention has a very significant improvement in photocurrent after modification, and is stable in response to light and has a large photocurrent gain. Fig. 6 and 7 are a graph of the optical responsivity of the indium selenide photodetector prepared by the present invention before and after modification by the stannous selenide nanocrystal and a graph of the specific detectivity, respectively, and it can be known that the maximum optical responsivity of the prepared indium selenide photodetector modified by the stannous selenide nanocrystal after modification is 21.5A/W and the optical responsivity before modification is 0.7A/W, which are calculated by using the test data in fig. 3, and the performance is improved by 30 times compared with that before modification.
In summary, the p-type stannous selenide nanocrystals are modified on the surface of the n-type indium selenide photoelectric detector to form the pn photoelectric heterojunction with the local interface, so that the prepared indium selenide photoelectric detector modified by the stannous selenide nanocrystals has the advantages of large light-dark current ratio, high light responsivity and high specific detection rate.
It is to be understood that the application of the present disclosure is not limited to the examples described above, and that modifications and variations may be made by persons skilled in the art in light of the above teachings, and all such modifications and variations are intended to fall within the scope of the appended claims.
Claims (8)
1. An indium selenide photoelectric detector for performing surface modification by using stannous selenide nanocrystals is characterized by comprising a substrate, an n-type indium selenide film layer arranged on the substrate, p-type stannous selenide nanocrystals arranged on the n-type indium selenide film layer, and a first electrode and a second electrode which are arranged on the substrate and are respectively connected with two ends of the n-type indium selenide film layer, wherein the thickness of the n-type indium selenide film layer is 0.8nm-80nm, and the thickness of the p-type stannous selenide nanocrystals is 0.5nm-50nm;
the preparation method of the p-type stannous selenide nanocrystal comprises the following steps:
SnCl2·2H2Dissolving O in deionized water, carrying out ultrasonic treatment at room temperature, adding NaOH, and continuing to carry out ultrasonic treatment to obtain a first mixed solution; adding selenium powder into the first mixed solution, and carrying out heating treatment under a vacuum condition, wherein the heating treatment temperature is 400-450K, and the heating treatment time is 20-40h, so as to obtain a second mixed solution; and cleaning the second mixed solution, and then carrying out vacuum drying treatment to obtain the p-type stannous selenide nanocrystal.
2. The indium selenide photodetector of claim 1, wherein the p-type stannous selenide nanocrystals are disposed on the n-type indium selenide film layer.
3. The indium selenide photodetector of claim 1, wherein the base includes a silicon substrate and an insulating substrate disposed on the silicon substrate.
4. The indium selenide photodetector of claim 3, wherein the insulating substrate is silicon dioxide.
5. The indium selenide photodetector of claim 1, wherein the material of the first electrode and the second electrode is selected from one of gold, titanium, chromium, and tungsten.
6. A method for preparing an indium selenide photoelectric detector by utilizing stannous selenide nanocrystals for surface modification is characterized by comprising the following steps:
preparing a p-type stannous selenide nanocrystalline suspension and an n-type indium selenide film layer in advance;
directionally transferring the n-type indium selenide film layer onto a substrate through a micro-mechanical transfer platform;
manufacturing an electrode pattern on the substrate, and preparing a first electrode and a second electrode in an evaporation mode, wherein the first electrode and the second electrode are respectively connected with two ends of the n-type indium selenide film layer;
and dripping the p-type stannous selenide nanocrystalline suspension on the n-type indium selenide film layer to generate p-type stannous selenide nanocrystals on the n-type indium selenide film layer, thus preparing the indium selenide photoelectric detector.
7. The method for preparing an indium selenide photodetector as claimed in claim 6, wherein the preparation of the p-type stannous selenide nanocrystal suspension comprises the steps of:
SnCl2·2H2Dissolving O in deionized water, carrying out ultrasonic treatment at room temperature, adding NaOH, and continuing to carry out ultrasonic treatment to obtain a first mixed solution;
adding selenium powder into the first mixed solution, and performing heating treatment under a vacuum condition to obtain a second mixed solution through reaction;
cleaning the second mixed solution, and then carrying out vacuum drying treatment to obtain p-type stannous selenide nanocrystalline powder;
dispersing the p-type stannous selenide nanocrystalline powder in absolute ethyl alcohol, sequentially performing ultrasonic treatment and centrifugal treatment, and extracting supernatant to obtain the p-type stannous selenide nanocrystalline suspension.
8. The method for preparing an indium selenide photodetector as claimed in claim 7, wherein the temperature of the heat treatment under vacuum is 400-450K, and the time of the heat treatment is 20-40h.
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