CN110459548A - A kind of photodetector and preparation method thereof based on Van der Waals hetero-junctions - Google Patents
A kind of photodetector and preparation method thereof based on Van der Waals hetero-junctions Download PDFInfo
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Abstract
The invention discloses a kind of photodetector and preparation method thereof based on Van der Waals hetero-junctions.The photodetector includes that optical fiber, Van der Waals heterojunction structure, a pair of of fiber sidewall metal electrode and a pair of of fiber end face metal electrode, fiber sidewall metal electrode are connected with fiber end face metal electrode；Van der Waals heterojunction structure is located at the end face of optical fiber, is followed successively by tungsten disulfide film, molybdenum disulfide film and graphene film from top to bottom；A pair of of fiber end face metal electrode is separately connected the graphene film at Van der Waals heterojunction structure both ends.Visible near infrared band weak light detection function and full wave strong optical detection function may be implemented in photodetector prepared by the present invention, while having preferable stability and anti-interference ability, has wide application prospect in optical communication, light sensing field.
Description
Technical field
The present invention relates to photoelectron technical fields, and in particular to field of photodetectors.More specifically, it is related to a kind of complete
New superelevation responsiveness, high-speed response, ultra-wideband-light electric explorer and preparation method thereof.
Background technique
Photodetector is the device for converting optical signal into electric signal, when photodetector is irradiated by light, can be drawn
The variation of its conductivity is played to detected using electrical method.Photodetector is in military and national economy each neck
There is extensive utilization in domain, and wherein the photodetector of hypersensitivity is in modern optical communication, environment measuring, biomedical research
Etc. research fields have outstanding contributions.Photodetector can be divided into two types, one is photon type detector, in detector
Semiconductor material directly absorbs the variation that photon generates conductivity, this is a kind of sensitive detection parts of selective response wave length, than
Such as photoelectric tube, photoconductive detector, photovoltaic detector；One is thermal detector, the detecting element in detector absorbs light
The energy of radiation and the raising for causing temperature, cause the change of physical parameter and are detected, this is a kind of no wavelength selection
The sensitive detection parts, such as pyroelectric detector, thermistor etc. of property.Photon type detector has high detectivity and photoresponse
Degree has unique advantage for the incident light of low light intensity, but the wave-length coverage of its detection is due to by semiconductor material
The limitation of band gap is usually relatively narrow.Thermal detector has wide spectral response range, but its detectivity and responsiveness are lower, therefore
It is suitable for the detection of the incident light of highlight intensity.But it due to the difference of photon type detector and thermal detector Physical Mechanism, passes
System detector is difficult to take into account high responsiveness and wide response wave length scope.
Grapheme two-dimension material has obtained worldwide extensive as a kind of zero gap semiconductor material since its discovery
Concern.Intrinsic single-layer graphene has up to 200000cm2The electron mobility of/(Vs), the up to thermal conductivity of 5300W/mK,
Much higher than traditional semiconductor material.Furthermore graphene also there is high mechanical strength, good bending property, be easy to and other
Material combines, and graphene is integrated well with many structures.In terms of photodetector, graphene can be used
In the wideband photodetectors of preparation high speed, good thermal conductivity and electron mobility make the response speed of detector very
Fastly, the wave-length coverage that the property of zero band gap responds detector is very wide, but very due to the absorptivity of intrinsic graphene
Small (single-layer graphene only has 2.3% absorptivity for visible, near infrared band vertical incidence light), and electron-hole recombinations
Rate is high, the service life is low, its optical gain very little is resulted in, to strongly limit the optical responsivity of device；In addition, the zero of graphene
Band gap causes it that can not have the state of on or off, therefore limits its application.The transition metal of band gap with one fixed width
The classes grapheme two-dimension materials such as disulphide (TMDCs), black phosphorus (BP) are found that they are good with it from after graphene successively
Photoelectric properties, be widely used in the field of photodiode, phototransistor, photodetector.In photodetector
Aspect, these class grapheme two-dimension material photodetectors have good switch performance.But, on the one hand, it is limited to electronics
The influence of mobility and defect, responsiveness be often difficult to it is high, response speed also more slowly；On the other hand, by
It is limited to the limitation of two-dimensional semiconductor material band gap itself, detection wave-length coverage is often smaller, is confined to visible light wave range.
Graphene is formed into Van der Waals hetero-junctions in conjunction with a type grapheme two-dimension material, class graphite can be enhanced
The carrier mobility of alkene two-dimensional material, so that the optical responsivity of detector is greatly improved, but response speed is still relatively slow, visits
It is still smaller to survey wave-length coverage.A variety of different class grapheme two-dimension materials are combined and form Van der Waals hetero-junctions, due to
They have different work functions, a built-in electric field can be formed accelerate electronics, hole separation and compound speed, from
And improve response speed and optical responsivity；Due between them there are the electron transition of the interlayer of different two-dimensional materials, can be with
Energy needed for reducing incident photon, so that detection wave-length coverage is extended, but its optical responsivity is still relatively small.
Summary of the invention
It is an object of the invention to graphene is formed Robert Van de Walle in conjunction with a variety of different class grapheme two-dimension materials
This hetero-junctions provides a kind of high-responsivity based on Van der Waals hetero-junctions, high-speed response, wideband photodetectors.This hair
Another bright purpose is to provide a kind of preparation method of photodetector.
Photodetector of the invention the technical solution adopted is that:
A kind of photodetector based on Van der Waals hetero-junctions, including optical fiber, Van der Waals heterojunction structure, one
To fiber sidewall metal electrode and a pair of of fiber end face metal electrode, fiber sidewall metal electrode and fiber end face metal electrode
It is connected；The Van der Waals heterojunction structure is located at the end face of optical fiber, is followed successively by tungsten disulfide film, curing from top to bottom
Molybdenum film and graphene film；The pair of fiber end face metal electrode is separately connected Van der Waals heterojunction structure both ends
Graphene film.
Further, the pair of fiber sidewall metal electrode and a pair of of fiber end face metal electrode are relative to optical fiber
Axisymmetrical distribution.
Preferably, the material of metal electrode is gold, with a thickness of 40nm.
Preferably, the spacing between the pair of fiber end face metal electrode is 5-15 μm.
Preferably, the graphene film is 3-10 layers, and the molybdenum disulfide film is 3-10 layers, and the tungsten disulfide is thin
Film is 3-10 layers.
The method that the present invention prepares above-mentioned photodetector, the specific steps are as follows:
(1) graphene film is grown in copper foil surface using chemical vapour deposition technique, it is raw in sapphire or mica surface
Long molybdenum disulfide film and tungsten disulfide film；Spin coating is carried out to above-mentioned three kinds of films with PMMA solution, and to empty sapphire
Substrate carries out spin coating and forms PMMA film, then corrodes copper foil with ferric chloride aqueous solutions, is corroded with sodium hydrate aqueous solution blue precious
Stone or mica；Later by the graphene film of acquisition, molybdenum disulfide film, tungsten disulfide film and PMMA film be transferred to from
It is cleaned in sub- water for several times, heat drying after being taken out all films with sheet glass or silicon wafer；
(2) fiber coating layer is removed, and for several times with alcohol solvent ultrasonic cleaning, is then cut flat with fiber end face；
(3) optical fiber probe of drawing or sharp metal probe are placed on D translation platform, it under the microscope will step
Suddenly film made from (1) cuts small pieces into strips and is provoked with probe, according to tungsten disulfide film, molybdenum disulfide film, graphite
The sequence of alkene film be placed sequentially in step (2) preparation fiber end face on, formed Van der Waals heterojunction structure, then plus
Structure and optical fiber is firmly combined in heat；Finally PMMA film is provoked with probe, is covered on Van der Waals heterojunction structure
And it is vertical with the film direction of structure；
(4) physical vaporous deposition is utilized, one layer of metal of uniform deposition on the fiber end face and side wall that step (3) obtain
Then the PMMA film of covering is removed with probe, regrinds the part metals film on fiber sidewall and fiber end face by film,
A pair of fiber sidewall metal electrode and a pair of of fiber end face metal electrode, and fiber sidewall metal electrode and fiber end face gold is made
Belong to electrode to be connected.
The present invention is based on the high-responsivity of Van der Waals hetero-junctions, high-speed response, the principles of wideband photodetectors are as follows:
Under low light condition, device works in photon type mode detector, and photoconductive effect plays a leading role.Under the conditions of short wavelength,
It will lead to molybdenum disulfide (MoS in light beam irradiation to Van der Waals hetero-junctions2), tungsten disulfide (WS2) in electronics, hole pair
Separation, wherein electrons and holes are since the effect of built in field is respectively to graphene layer and tungsten disulfide (WS2) move in layer.
Since graphene itself is p-type, majority carrier is hole, and the injection of electronics will lead to the reduction of hole concentration, to lead
The decline for causing its conductivity generates negative photoelectric current.At the same time, in tungsten disulfide (WS2) hole in layer will form one
The effect of similar grid is electrostatically-doped to graphene progress, further such that its conductivity declines.It is and short under the conditions of long wavelength
Wavelength condition the difference is that, when light beam irradiation is on Van der Waals hetero-junctions, molybdenum disulfide (MoS2), tungsten disulfide
(WS2) electronics, hole are influenced not separating to by band gap in layer, still, electrons are from tungsten disulfide (WS2) layer conduction band
Transit to molybdenum disulfide (MoS2) layer valence band in make electronics, hole separation, the injection and two of electronics in p-type graphene
Tungsten sulfide (WS2) grid voltage in hole influences meeting so that the reduction of its conductivity, photoelectric current are negative in layer.And under intense light conditions, device
Part works in the mixed mode of thermal detector and photon type detector, photoconductive effect and light radiation fuel factor collective effect, and
It is leading with light radiation fuel factor.With the increase of optical power, graphene gradually embodies the response for the heat that light irradiation generates
Come, so that conductivity becomes larger, generate positive photoelectric current, the negative photoelectric current generated with photoconductive effect is cancelled out each other and finally made
Photoelectric current size is obtained to be positive.In strong light and dim light, the optical responsivity and incident optical power of the sensor have excellent
Log-log linear dependence, therefore can be used for the sensor measuring of optical power.Meanwhile device to the photoresponse of different wave length not
Together, therefore it may be used as the sensor measuring of optical wavelength.
The Van der Waals being made of the present invention is based on fiber end face graphene and multiple types grapheme two-dimension materials are different
Matter knot realizes a kind of high-performance optical electrical resistivity survey of detection wave-length coverage with superelevation optical responsivity, high response speed, ultra wide band
Device is surveyed, compared with prior art, which has the advantage that (1) may be implemented visible near infrared band dim light and visit
Brake, detection accuracy are high.(2) photodetector may be implemented and full wave strong optical detection function, at the same have compared with
Good stability and anti-interference ability, has wide application prospects in optical communication, light sensing field.(3) system of the photodetector
Preparation Method is simple, low in cost, high yield rate, has applicability to a variety of two-dimensional materials.(4) substrate of the photodetector is not
It is confined to fiber end face, has good compatibility, including silicon substrate, glass, polymer, ceramics etc. for various plane systems.
Detailed description of the invention
The present invention is based on the high-responsivity of Van der Waals hetero-junctions, high-speed response, the structures of wideband photodetectors by Fig. 1
Schematic diagram and test circuit diagram.1- end electrode, 2- side-wall electrode, 3- Van der Waals hetero-junctions.
The present invention is based on the high-responsivities of Van der Waals hetero-junctions, the preparation of high-speed response, wideband photodetectors by Fig. 2
Flow chart.
Fig. 3 is that the present invention is based on the high-responsivity of Van der Waals hetero-junctions, high-speed response, wideband photodetectors are typical
Test performance figure, (a) be device electric current and photoelectric current difference be biased under response curve；It (b) is device light
The relation curve of electroresponse degree and incident optical power；It (c) is the relation curve of device photoelectric responsiveness and lambda1-wavelength.
Specific embodiment
It is elucidated further below implementation process of the present invention.
The present invention is based on the high-responsivity of Van der Waals hetero-junctions, high-speed response, the structures of wideband photodetectors by Fig. 1
Schematic diagram including fiber end face electrode 1, optical fiber side electrode 2, is covered on model moral on fiber core and under end electrode
Wa Ersi hetero-junctions 3.Wherein, fiber end face electrode 1 is connected with optical fiber side electrode 2, and opposed optical fibers axle center is symmetrical, electricity
Spacing between pole is matched with fibre core diameter.In test, model is given by optical fiber side electrode 2 and fiber end face electrode 1
De Waersi hetero-junctions 3 applies external bias, when light is irradiated by fiber core to the surface of Van der Waals hetero-junctions 3,
The photoelectric current of generation can be by fiber end face electrode 1, the export of optical fiber side electrode 2, analysis.
For the device for realizing Fig. 1, detailed process manufactured in the present embodiment is as shown in Figure 2:
(1) film preparation: graphene film is grown in copper foil surface using chemical vapour deposition technique, in sapphire or cloud
Matrix is looked unfamiliar long molybdenum disulfide (MoS2), tungsten disulfide (WS2) film.Spin coating is carried out to above-mentioned film with PMMA solution, and to sky
Sapphire Substrate carry out spin coating, then with ferric chloride aqueous solutions corrode copper foil, with sodium hydrate aqueous solution corrode sapphire or
Mica.Later by the graphene of acquisition, molybdenum disulfide (MoS2), tungsten disulfide (WS2) and PMMA film be transferred in deionized water
It cleans for several times, with sheet glass (SiO2) or silicon wafer (Si) be drawn off rear heat drying.
(2) fiber coating layer is removed, and for several times with alcohol solvent ultrasonic cleaning, is cut fiber end face using optical fiber cutter
It is flat；
(3) optical fiber probe of drawing or sharp metal probe are placed on D translation platform, it under the microscope will be
Sheet glass (SiO2) or silicon wafer (Si) on film cutting small pieces and provoked into strips with optical fiber probe, according to tungsten disulfide
(WS2), molybdenum disulfide (MoS2), at the center of the sequence of the graphene fiber end face that is placed sequentially in step (2) preparation, formed
Van der Waals hetero-junctions 3, itself and optical fiber is firmly combined in heating later.Finally PMMA film is chosen with same method
It rises, is placed on end centre of optic fibre and vertical with graphene Van der Waals hetero-junction thin-film before.
(4) it is first visited with optical fiber using physical vaporous deposition in one layer of metallic film of fiber end face and side wall uniform deposition
Needle removes the PMMA film of covering；The fiber finish piece for using fine sand later, grinds off the part metals film on fiber sidewall,
A pair of metal electrodes is made；Then part metals film is struck off on fiber end face using tungsten metal probe, form a pair of of metal
Electrode is to get the photodetector for arriving the present embodiment, wherein the metal electrode phase on the metal electrode and end face on fiber sidewall
Even.
The photosensitive element of photodetector of the invention is not limited to the combination of graphene Yu molybdenum disulfide, tungsten disulfide,
There is staggered semiconductor material to all can serve as photosensitive element between energy band.
Fig. 3 is the test result of the embodiment of the present invention, and the present invention is based on the photodetectors of Van der Waals hetero-junctions
Test macro, including light source, single mode optical fiber, coupler, commercial photodetector, digital sourcemeter, electrode holder, computer and sheet
The photodetector of embodiment preparation.The light of light source output is by single mode optical fiber switch-in coupler, two light that coupler picks out
Fibre is respectively connected to photodetector manufactured in the present embodiment and commercial photodetector.By digital sourcemeter by electrode holder to light
Fine end electrode provides voltage simultaneously its size of current of real-time detection, and test result is displayed in real time and remembered by computer software
Record.In the case where difference is biased, the electric current of registering device and the response curve of photoelectric current obtain Fig. 3 (a), from linear I-V
Curve can be seen that device has good Ohmic contact；Change the power of incident light, the photoelectric current size of registering device is simultaneously counted
It calculates its optical responsivity and obtains Fig. 3 (b), it can be seen that device has high optical responsivity, and optical responsivity and power have
Log-log linear relationship；Change the wavelength of incident light, the photoelectric current size of registering device simultaneously calculates its optical responsivity and obtains Fig. 3
(c), it can be seen that device has very wide bandwidth of operation.
Under the incidence for the 400nm wavelength that incident optical power is 5fW, to the bias of device application -3V, optical responsivity can
Up to 107The magnitude of A/W, response speed is very fast, can achieve the magnitude of ms；In the 1550nm wavelength that incident optical power is 20nW
Under incidence, to the bias of device application -3V, for optical responsivity up to the magnitude of 10A/W, response speed can achieve the amount of ms
Grade.
It can be seen that the present invention using graphene and two layers of class grapheme two-dimension material from above test result, compare
In other existing Van der Waals hetero-junctions, there is higher optical responsivity, faster response time, and the wave in more broadband
Long respective range.
Claims (8)
1. a kind of photodetector based on Van der Waals hetero-junctions, which is characterized in that heterogeneous including optical fiber, Van der Waals
Junction structure, a pair of of fiber sidewall metal electrode and a pair of of fiber end face metal electrode, fiber sidewall metal electrode and optical fiber end
Face metal electrode is connected；The Van der Waals heterojunction structure is located at the end face of optical fiber, is followed successively by tungsten disulfide from top to bottom
Film, molybdenum disulfide film and graphene film；It is heterogeneous that the pair of fiber end face metal electrode is separately connected Van der Waals
The graphene film at junction structure both ends.
2. a kind of photodetector based on Van der Waals hetero-junctions according to claim 1, which is characterized in that described
A pair of of fiber sidewall metal electrode and a pair of of fiber end face metal electrode are distributed relative to the axisymmetrical of optical fiber.
3. a kind of photodetector based on Van der Waals hetero-junctions according to claim 1, which is characterized in that metal
The material of electrode is gold, with a thickness of 40nm.
4. a kind of photodetector based on Van der Waals hetero-junctions according to claim 1, which is characterized in that described
Spacing between a pair of of fiber end face metal electrode is 5-15 μm.
5. a kind of photodetector based on Van der Waals hetero-junctions according to claim 1, which is characterized in that described
Graphene film is 3-10 layers, and the molybdenum disulfide film is 3-10 layers, and the tungsten disulfide film is 3-10 layers.
6. a kind of preparation method of the photodetector based on Van der Waals hetero-junctions as described in claim 1, feature exist
In, the specific steps are as follows:
(1) graphene film is grown in copper foil surface using chemical vapour deposition technique, in sapphire or mica surface growth two
Vulcanize molybdenum film and tungsten disulfide film；Spin coating is carried out to above-mentioned three kinds of films with PMMA solution, and to empty Sapphire Substrate
Carry out spin coating formed PMMA film, then with ferric chloride aqueous solutions corrode copper foil, with sodium hydrate aqueous solution corrode sapphire or
Mica；The graphene film of acquisition, molybdenum disulfide film, tungsten disulfide film and PMMA film are transferred to deionized water later
It is middle to clean for several times, heat drying after being taken out all films with sheet glass or silicon wafer；
(2) fiber coating layer is removed, and for several times with alcohol solvent ultrasonic cleaning, is then cut flat with fiber end face；
(3) optical fiber probe of drawing or sharp metal probe are placed on D translation platform, under the microscope by step (1)
Film obtained cuts small pieces into strips and is provoked with probe, according to tungsten disulfide film, molybdenum disulfide film, graphene film
Sequence be placed sequentially in step (2) preparation fiber end face on, formed Van der Waals heterojunction structure, then heating make to tie
Structure and optical fiber are firmly combined；Finally PMMA film is provoked with probe, be covered on Van der Waals heterojunction structure and with knot
The film direction of structure is vertical；
(4) physical vaporous deposition is utilized, one layer of metal foil of uniform deposition on the fiber end face and side wall that step (3) obtain
Then the PMMA film of covering is removed with probe, regrinds the part metals film on fiber sidewall and fiber end face, made by film
Obtain a pair of of fiber sidewall metal electrode and a pair of of fiber end face metal electrode, and fiber sidewall metal electrode and fiber end face metal
Electrode is connected.
7. preparation method as claimed in claim 6, which is characterized in that in the step (1), the number of plies of graphene film is 3-
10 layers, the number of plies of molybdenum disulfide film is 3-10 layers, and the number of plies of tungsten disulfide film is 3-10 layers.
8. preparation method as claimed in claim 6, which is characterized in that in the step (4), the material of metallic film is gold,
With a thickness of 40nm.
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