CN111048620B - Ultraviolet photoelectric detector based on titanium dioxide nanotube and graphene heterojunction and preparation method thereof - Google Patents
Ultraviolet photoelectric detector based on titanium dioxide nanotube and graphene heterojunction and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a heterojunction ultraviolet photoelectric detector based on a titanium dioxide nanotube and graphene and a preparation method thereof. According to the invention, the titanium dioxide film is plated on the titanium dioxide nanotube, so that the heterojunction defects and the recombination probability of current carriers are reduced, the contact between the titanium dioxide film and graphene is optimized, the dark current is inhibited, and the photocurrent is improved, thereby achieving the purpose of improving the responsivity and the responsivity of the detector.
Description
Technical Field
The invention belongs to the field of semiconductor thin film photoelectric detectors, and particularly relates to a titanium dioxide nanotube and graphene heterojunction-based ultraviolet photoelectric detector and a preparation method thereof.
Background
With the continuous development and deepening of the photoelectric detection technology, the measurement spectrum range is also continuously expanded, and the measurement spectrum range is expanded to the ultraviolet light region with the wavelength of 10nm to 400 nm. Correspondingly, the development and measurement technology of the ultraviolet intensity testing instrument is also rapidly improved. The ultraviolet photoelectric detector is a novel photoelectric detection technology with wide application range, has wide application fields, and has wide application prospects in national defense, combustion engineering, ultraviolet alarm systems and medical fields. In military aspect, the ultraviolet tracking system is mainly used for an ultraviolet alarm system and an ultraviolet tracking system; in the civil aspect, the ultraviolet radiation detector is mainly used for measuring the radiation intensity of ultraviolet rays, and can be used for detecting cancerous cells, hemoglobin, white blood cells, red blood cells and the like in medicine. With the rapid development of ultraviolet alarm and ultraviolet tracking technology, ultraviolet photodetectors have become one of the very valuable research directions in the field of photodetection. Following infrared detection, ultraviolet detection has been developed as a dual-purpose photoelectric detection technology for military and civilian use and has rapidly developed.
The ultraviolet detector which is put into commercial use at present mainly takes a silicon-based ultraviolet photoelectric tube and an ultraviolet photomultiplier as main components, and although the ultraviolet detector has the advantage of high sensitivity, the ultraviolet detector also has the defects of needing an additional optical filter, being large in size, easy to damage, needing to work at higher voltage and lower temperature and the like, so that the further application of the ultraviolet detector is greatly restricted. In recent years, the preparation process and characteristic research of wide bandgap semiconductor materials have been greatly developed, and some wide bandgap semiconductor materials, which only absorb ultraviolet light, are resistant to high temperature and suitable for use in severe environments, are gradually hot spots of research due to their excellent photoelectric properties. The titanium dioxide not only has moderate forbidden band width and strong anti-interference capability, is suitable for detecting the ultraviolet intensity under the infrared or visible light background, but also has excellent thermal conductivity, thermal stability and chemical inertness, wherein because of the TiO2The nanotube has large specific area and high depth-to-width ratio, and is very suitable for the research and manufacture of ultraviolet detecting devices. Therefore, the development of a novel wide bandgap semiconductor ultraviolet detector shows unique application prospects, and research work for replacing the traditional semiconductor ultraviolet detector with the novel wide bandgap semiconductor ultraviolet detector is widely concerned.
Based on the research of ultraviolet detectors prepared by semiconductor thin film heterojunction, the ultraviolet detectors with titanium dioxide nanotube-graphene heterojunction structures have been researched by people at present. Deng-Yue Zhang et al [ Applied Surface Science387(2016): 1162-]The ultraviolet detector of the prepared titanium dioxide nanotube-graphene heterojunction is 365nm and 7.16mW/cm2The measured responsivity was 0.126A/W and the responsivity was 3.3X 1011Jones, whose responsivity is too low; suttinart nootkown kaew et al Materials Letters 218(2018) 274-279]The ultraviolet detector of the prepared titanium dioxide nanotube-graphene heterojunction is at 365nm and 350 mu W/cm2The measured responsivity was 20A/W and the responsivity was 1.9X 1010Jones, response rate is also low.
Disclosure of Invention
The invention aims to: aiming at the problems of low responsivity and low responsivity of the existing ultraviolet detector prepared based on the semiconductor thin film heterojunction, the invention provides the good titanium dioxide nanotube graphene heterojunction, and the problem of untight contact between the heterojunction and the titanium dioxide nanotube graphene heterojunction is solved by plating the titanium dioxide thin film between the heterojunction and the titanium dioxide nanotube graphene heterojunction, so that the photoelectric property of the heterojunction is improved. Therefore, the invention provides a titanium dioxide nanotube and graphene heterojunction-based ultraviolet photoelectric detector.
Another object of the present invention is to provide a method for preparing a titanium dioxide nanotube and graphene heterojunction-based ultraviolet photodetector.
The technical scheme adopted by the invention is as follows:
based on titanium dioxide nanotube and graphite alkene heterojunction ultraviolet photoelectric detector, include, titanium dioxide nanotube and graphite alkene, be provided with the titanium dioxide film between titanium dioxide nanotube and the graphite alkene. The electrode is a gold electrode. In addition, the device also comprises a motor.
The contact between the nanotube and the graphene is optimized by plating the titanium dioxide film, and the grown uneven nanotube and the graphene are in direct contact with each other to have a plurality of defects, and the titanium dioxide film is plated between the uneven nanotube and the graphene to ensure that the magnetic heterojunction can be in uniform and good contact under the influence of the same material and is regularly attached to the electronic transmission layer, so that the nonuniformity due to direct contact is reduced, the contact resistance between interfaces is reduced, the photocurrent is improved, and the large-area production is facilitated.
Preferably, the thickness of the titanium dioxide thin film is 10-100 nm. A more preferred titanium dioxide film has a thickness of 50 nm.
Preferably, the length of the titanium dioxide nanotube ranges from 10 to 100 μm.
Preferably, the graphene is single-layer graphene.
The preparation method of the ultraviolet photoelectric detector based on the titanium dioxide nanotube and the graphene heterojunction comprises an anodic oxidation method, a template method, a hydrothermal synthesis method or a microwave synthesis method.
Wherein, the anodic oxidation method comprises the following steps:
a) putting a titanium sheet and an inert electrode into an anodic oxidation device, taking the titanium sheet or a titanium foil as an anode and the inert electrode as a cathode, carrying out constant-current anodic oxidation in electrolyte at the voltage of 20-60V for 2-6h and the temperature of the electrolyte of 20-60 ℃, and cleaning and drying to obtain a titanium dioxide nanotube; wherein, ultrasonic cleaning and drying are needed to be carried out on a beaker, a platinum electrode, a titanium sheet and the like; wherein the inert electrode in the step a) is a platinum electrode or a nickel electrode;
b) preparing a titanium dioxide film on the surface of the titanium dioxide nanotube, and annealing;
c) transferring single-layer graphene on the surface of the titanium dioxide film;
d) and (3) performing gold electrode evaporation on the front surface or part of the device, and then using silver paste as a lead contact point to obtain the ultraviolet photoelectric detector.
Preferably, the electrolyte in step a) contains NH4F. Ethylene glycol and deionized water, NH4The mass percentage of F is 0.25%, the mass percentage of ethylene glycol is 90.75%, and the balance is deionized water.
Preferably, the method for preparing the titanium dioxide film with the thickness of 10-100nm on the surface of the titanium dioxide nanotube in the step b) is one or more of an electron beam deposition method, a magnetron sputtering method and an activated reactive evaporation method.
Preferably, the annealing temperature of the step b) is 400-450 ℃, and the annealing time is 2-3 h.
Preferably, single-layer graphene is transferred on the surface of the titanium dioxide film by a wet method in the step c).
Compared with the prior art, the invention has the beneficial effects that:
(1) by coating with TiO2The thin film layer improves the contact problem between the nanotube and the graphene, solves the problem of untight contact of the nanotube, and is beneficial to the formation of a heterojunction;
(2) according to the invention, a titanium dioxide film is plated on the titanium dioxide nanotube, so that the heterojunction defect and the recombination probability of a current carrier are reduced, the contact between the titanium dioxide nanotube and graphene is optimized, the dark current is inhibited, and the photocurrent is improved, thereby achieving the purpose of improving the responsivity and the responsivity of the detector;
(3) the length of the nanotube growing in different anodic oxidation time of the invention is different, which can cause the photoelectric performance of the device to be different, the nanotube growing in about 3 hours is most uniform and compact, the length of the nanotube is 71.0 μm, and the performance of the prepared device is best, and the nanotube can collapse due to the influence of transverse corrosion along with the increase of the length of the nanotube, and the performance of the device can be reduced.
Drawings
Fig. 1 is a schematic structural diagram of an ultraviolet light detector based on a titanium dioxide nanotube and graphene heterojunction according to the present invention;
FIG. 2 is a graph showing the length of the titanium dioxide nanotubes grown according to the present invention as a function of time;
FIG. 3 is a schematic cross-sectional view of a surface coated with a titanium dioxide film according to the present invention;
FIG. 4 shows the ultraviolet radiation (365 nm wavelength, 1mW/cm incident light power) of the ultraviolet detector prepared by the invention2) The response of (2) is along the time variation curve;
FIG. 5 shows the ultraviolet detector prepared by the present invention under ultraviolet irradiation (wavelength of 365nm, incident light power of 1 mW/cm)2) And response time profile in the off condition.
Labeled as: 1-anode, 2-graphene, 3-titanium dioxide film, 4-titanium dioxide nanotube and 5-titanium sheet.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Example 1:
as shown in fig. 1, the ultraviolet photodetector based on the titanium dioxide nanotube and graphene heterojunction includes a titanium dioxide nanotube 4 and graphene 2, and a titanium dioxide thin film 3 is disposed between the titanium dioxide nanotube 4 and the graphene 2. The ultraviolet photoelectric detector comprises a titanium sheet 5, a titanium dioxide nanotube 4, graphene 2, a titanium dioxide film 3 and a metal anode 1 from bottom to top in sequence. The thickness of the titanium dioxide film 3 is 10-100 nm. The length range of the titanium dioxide nanotube 4 is 10-100 μm. The graphene 2 is single-layer graphene 2.
Example 2:
cleaning a 2mm by 2mm titanium sheet, and drying in a drying oven after cleaning; growing a titanium dioxide nanotube by an anodic oxidation method, wherein the anodic oxidation time is 6 h; annealing the nanotube for 3h under the annealing condition of 450 ℃; performing magnetron sputtering on the surface of the nanotube to form a titanium dioxide film with the thickness of 50 nm; then transferring single-layer graphene on the surface by using a wet method; then, gold electrode (100nm) was deposited on the surface by evaporation. Anodic oxidation processThe electrolyte used contains NH4F. Ethylene glycol and deionized water, NH4The mass percentage of F is 0.25%, the mass percentage of ethylene glycol is 90.75%, and the balance is deionized water.
Example 3:
cleaning a 2mm by 2mm titanium sheet, and drying in a drying oven after cleaning; growing a titanium dioxide nanotube by an anodic oxidation method, wherein the anodic oxidation time is 4 h; annealing the nanotube for 3h under the annealing condition of 450 ℃; performing magnetron sputtering on the surface of the nanotube to form a titanium dioxide film with the thickness of 50 nm; then transferring single-layer graphene on the surface by using a wet method; then, gold electrode (100nm) was deposited on the surface by evaporation. The electrolyte used in the anodic oxidation process contains NH4F. Ethylene glycol and deionized water, NH4The mass percentage of F is 0.25%, the mass percentage of ethylene glycol is 90.75%, and the balance is deionized water.
Example 4:
cleaning a 2mm by 2mm titanium sheet, and drying in a drying oven after cleaning; growing a titanium dioxide nanotube by an anodic oxidation method, wherein the anodic oxidation time is 3 h; annealing the nanotube for 3h under the annealing condition of 450 ℃; performing magnetron sputtering on the surface of the nanotube to form a titanium dioxide film with the thickness of 50 nm; then transferring single-layer graphene on the surface by using a wet method; then, gold electrode (100nm) was deposited on the surface by evaporation. The electrolyte used in the anodic oxidation process contains NH4F. Ethylene glycol and deionized water, NH4The mass percentage of F is 0.25%, the mass percentage of ethylene glycol is 90.75%, and the balance is deionized water.
Comparative example 1:
cleaning a 2mm by 2mm titanium sheet, and drying in a drying oven after cleaning; growing a titanium dioxide nanotube by an anodic oxidation method, wherein the anodic oxidation time is 6 h; annealing the nanotube for 3h under the annealing condition of 450 ℃; transferring single-layer graphene on the surface of the nanotube; gold electrodes (100nm) were vapor deposited on the surface. The electrolyte used in the anodic oxidation process contains NH4F. Ethylene glycol and deionized water, NH4The mass percentage of F is 0.25%, the mass percentage of ethylene glycol is 90.75%, and the balance is deionized water.
Comparative example 2:
cleaning a 2mm by 2mm titanium sheet, and drying in a drying oven after cleaning; growing a titanium dioxide nanotube by an anodic oxidation method, wherein the anodic oxidation time is 4 h; annealing the nanotube for 3h under the annealing condition of 450 ℃; transferring single-layer graphene on the surface of the nanotube; gold electrodes (100nm) were vapor deposited on the surface. The electrolyte used in the anodic oxidation process contains NH4F. Ethylene glycol and deionized water, NH4The mass percentage of F is 0.25%, the mass percentage of ethylene glycol is 90.75%, and the balance is deionized water.
Comparative example 3:
cleaning a 2mm by 2mm titanium sheet, and drying in a drying oven after cleaning; growing a titanium dioxide nanotube by an anodic oxidation method, wherein the anodic oxidation time is 3 h; annealing the nanotube for 3h under the annealing condition of 450 ℃; transferring single-layer graphene on the surface of the nanotube; gold electrodes (100nm) were vapor deposited on the surface. The electrolyte used in the anodic oxidation process contains NH4F. Ethylene glycol and deionized water, NH4The mass percentage of F is 0.25%, the mass percentage of ethylene glycol is 90.75%, and the balance is deionized water.
And (3) detecting an experimental result:
under standard test, the ultraviolet wavelength is 365nm, and the power is 1mW/cm2The dark current Jd, the photocurrent Jph, the photoresponse R, the specific detectivity D, and the response time of the devices prepared in comparative examples 1, 2, 3 and examples 2, 3, 4 were measured and the results are shown in table 1:
table 1 uv photodetector performance parameters
As can be seen from table 1: compared with the ultraviolet photodetectors which are not plated with the titanium dioxide film (namely the ultraviolet photodetectors prepared in the comparative examples 1 to 3), the ultraviolet photodetectors which are plated with the titanium dioxide film through magnetron sputtering (namely the ultraviolet photodetectors prepared in the examples 2 to 4) have the advantages that the photocurrent is increased, the dark current ratio is increased, the responsivity is obviously increased, and the response time is about 1ms (as shown in figures 4 and 5). The reason is that the contact between the nanotube and the graphene is optimized by plating the titanium dioxide film, and the uneven nanotube grown by anodic oxidation has many defects when being directly contacted with the graphene, and the titanium dioxide film is plated between the nanotube and the graphene, so that the magnetic heterojunction can be uniformly and well contacted under the influence of the same material (as shown in figure 3), and is regularly attached to the electron transmission layer, thereby reducing the nonuniformity due to direct contact, reducing the contact resistance between interfaces, improving the photocurrent, and being more beneficial to large-area production.
As shown in fig. 2, the length of nanotubes grown at different anodization times is different, which results in different photoelectric properties of the device, and the nanotubes grown at 3 hours and having a length of 71.0 μm are most uniform and dense, so that the prepared device has the best performance, and as the length of the nanotubes increases, the nanotubes collapse due to the influence of lateral corrosion, and the device performance is reduced.
The graphene serving as a zero-band-gap two-dimensional Dirac material has high carrier mobility, is combined with the titanium dioxide sensitive to ultraviolet light to form a heterojunction ultraviolet photoelectric detector, has 1-2 orders of magnitude higher responsivity and responsivity than a common titanium dioxide detector, and can control the response time to be in an order of ms.
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.
Claims (9)
1. The ultraviolet photoelectric detector based on the titanium dioxide nanotube and the graphene heterojunction comprises a vertical titanium dioxide nanotube array and graphene, and is characterized in that a titanium dioxide film is arranged between the titanium dioxide nanotube array and the graphene; the thickness of the titanium dioxide film is 10-100 nm; the method for preparing the titanium dioxide film with the thickness of 10-100nm on the surface of the titanium dioxide nanotube array is one or more of an electron beam deposition method, a magnetron sputtering method and an activation reactive evaporation method.
2. The titanium dioxide nanotube and graphene heterojunction-based ultraviolet photodetector of claim 1, wherein the length of the titanium dioxide nanotube array is in the range of 10-100 μ ι η.
3. The titanium dioxide nanotube and graphene heterojunction-based ultraviolet photodetector of any one of claims 1 to 2, wherein the graphene is single-layer graphene.
4. The preparation method of the ultraviolet photodetector based on the titanium dioxide nanotube and graphene heterojunction as claimed in claim 1, wherein the preparation method of the titanium dioxide nanotube array is an anodic oxidation method.
5. The preparation method of the ultraviolet photodetector based on the titanium dioxide nanotube and graphene heterojunction as claimed in claim 4, wherein the anodic oxidation method comprises the following steps:
a) putting a titanium sheet and an inert electrode into an anodic oxidation device, taking the titanium sheet as an anode and the inert electrode as a cathode, carrying out constant-current anodic oxidation in electrolyte at the voltage of 20-60V for 2-6h and the temperature of the electrolyte of 20-60 ℃, and cleaning and drying to obtain a titanium dioxide nanotube array;
b) preparing a titanium dioxide film on the surface of the titanium dioxide nanotube array, and annealing;
c) transferring single-layer graphene on the surface of the titanium dioxide film;
d) and (3) performing gold electrode evaporation on the front surface or part of the device, and then using silver paste as a lead contact point to obtain the ultraviolet photoelectric detector.
6. The method for preparing the ultraviolet photodetector based on the titanium dioxide nanotube and graphene heterojunction as claimed in claim 5, wherein the electrolyte in the step a) contains NH4F. Ethylene glycol and deionized water, NH4The weight percentage content of F is 0.25-0.5%, the weight percentage content of glycol is 90.75-90.5%, and the rest is deionized water.
7. The method for preparing the ultraviolet photodetector based on the titanium dioxide nanotube and graphene heterojunction as claimed in claim 5, wherein the method for preparing the titanium dioxide film with the thickness of 10-100nm on the surface of the titanium dioxide nanotube array in the step b) is one or more of an electron beam deposition method, a magnetron sputtering method and an activated reactive evaporation method.
8. The method for preparing the ultraviolet photodetector based on the titanium dioxide nanotube and graphene heterojunction as claimed in claim 5, wherein the annealing temperature in the step b) is 400-450 ℃, and the annealing time is 2-3 h.
9. The preparation method of the ultraviolet photodetector based on the titanium dioxide nanotube and graphene heterojunction, according to claim 5, wherein in the step c), the single-layer graphene is transferred on the surface of the titanium dioxide film by a wet method.
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