CN106549077B - A kind of photoelectric diode device and a kind of method for producing rectifying effect - Google Patents
A kind of photoelectric diode device and a kind of method for producing rectifying effect Download PDFInfo
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- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by at least one potential-jump barrier or surface barrier, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier
Abstract
A kind of photoelectric diode device, including light source and rectifier structure, the rectifier structure includes high resistance light gain semi-conductor substrate, graphene layer on the high resistance light gain semi-conductor substrate, the first ITO electrode and second electrode on the high resistance light gain semi-conductor substrate and the graphene layer, wherein, first ITO electrode and the second electrode distinguish a part of and high resistance light gain semi-conductor substrate contact, another part contacts with the graphene layer, and wherein：I) energy of the light of the light source transmitting is more than the band gap of the high resistance light gain semi-conductor substrate, and the light source only irradiates the first ITO electrode；Ii) area of first ITO electrode is more than the facula area of the source emissioning light.The photoelectric diode device of the present invention is planar structure, and photoelectric response speed is high, has potential application in Planar integration and micro-nano device field.
Description
Technical field
The invention belongs to technical field of semiconductors, more particularly to a kind of photoelectric diode device and a kind of generation rectification effect
The method answered.
Background technology
Graphene is a kind of New Two Dimensional material being made up of the carbon atom of honeycomb arrangement, and it has unique linear energy
Band structure, excellent electric property, big specific surface area, mechanical strength and good chemical stability.Graphene and tradition
Semiconductor (particularly semiconductor silicon material), which combines to prepare schottky junction device and largely report, [sees arXiv：
1505.07686(2015)].Schottky junction as modem semi-conductor devices essential building blocks in modern semiconductors photoelectricity group
It is widely applied in part and system.The existing solar cell based on graphene/semiconductor Schottky knot, the pole of photoelectricity two
Pipe etc. all employs the vertical structure type device of graphene/semiconductor (doping), and (i.e. the electrode of diode is prepared in graphite respectively
On alkene and semiconductor), the graphene layer of the vertical structure type device is as transparency electrode and carrier-collecting layer, and semiconductor material
The bed of material is both the response layer of optical signal, and the transport layer of photo-generated carrier.Due to the migration of carrier in a semiconductor material
The limitation of speed, the photoelectric response speed of this graphene/semiconductor Schottky p n junction photodiode is compared to commercial silicon substrate light
Electric diode has no improvement, still in musec order；In addition, its vertical stratification is limited in the side such as Planar integration and micro-nano device
The application in face.
The content of the invention
The defects of it is an object of the invention to overcome above-mentioned prior art, there is provided a kind of photoelectric diode device, including light
Source and rectifier structure, the rectifier structure include high resistance light gain semi-conductor substrate, are served as a contrast positioned at the high resistance light gain semi-conductor
Graphene layer on bottom, the first ITO (a kind of band gap on the high resistance light gain semi-conductor substrate and the graphene layer
For 4.0eV indium tin oxide) electrode and second electrode, wherein, a part and the high resistant of first ITO electrode
Gain of light Semiconductor substrate contacts, and another part contacts with the graphene layer, a part for the second electrode and the height
Light blocking gain semi-conductor substrate contact, another part contact with the graphene layer, and wherein：
I) energy of the light of the light source transmitting is more than the band gap of the high resistance light gain semi-conductor substrate, and the light source
Only irradiate the first ITO electrode；
Ii) area of first ITO electrode is more than the facula area of the source emissioning light.
According to the photoelectric diode device of the present invention, it is preferable that the light source only irradiates the close of first ITO electrode
The region of the graphene layer.
According to the photoelectric diode device of the present invention, it is preferable that the area of first ITO electrode is launched for the light source
At least 10 times of the facula area of light.
According to the photoelectric diode device of the present invention, it is preferable that the high resistance light gain semi-conductor substrate is that high resistant is organic
Semiconductor or high resistant inorganic semiconductor.
According to the photoelectric diode device of the present invention, it is preferable that the light source is ultraviolet source, and the high resistant gain of light is partly
Conductor substrate is SiC, or the light source is visible light source, and the high resistance light gain semi-conductor substrate is Si, GaP or GaAs.
According to the photoelectric diode device of the present invention, it is preferable that the second electrode is metal or ITO electrode.
According to the photoelectric diode device of the present invention, it is preferable that also including light tight coat, the light tight coat
Coat to the region in addition to the region of the close graphene layer of first ITO electrode of the rectifier structure.
According to the present invention photoelectric diode device, it is preferable that also include be respectively electrically connected to first ITO electrode and
The first lead and the second lead of the second electrode.
According to the photoelectric diode device of the present invention, it is preferable that also include the high resistance light gain semi-conductor substrate, institute
State the encapsulating housing that graphene layer, first and second electrode and first and second lead are packaged, wherein institute
Stating encapsulating housing has thang-kng window.
Present invention also offers a kind of method that rectifying effect is produced using above-mentioned photoelectric diode device.
According to the method for the generation rectifying effect of the present invention, wherein, when applying positive bias to first ITO electrode,
Short-circuit photocurrent is close or equal to dark current；And when applying back bias voltage to first ITO electrode, short-circuit photocurrent is with irradiation
The enhancing of light intensity and increase.
The rectification characteristic of the graphene photoelectric diode device of the planar structure of the present invention is obvious, and photoelectric transformation efficiency is high,
It can be widely applied to organic and inorganic semiconductor material system and prepare flexible, photodiode member
Device.Particularly in a short-circuit situation, under conditions of the photoelectric diode device applies forward bias on unirradiated electrode,
It is alternatively arranged as ultrafast, the sensitive photo-detector without external power source.
Brief description of the drawings
Embodiments of the invention are described further referring to the drawings, wherein：
Fig. 1 is the schematic diagram according to the cross section structure of the photoelectric diode device of the present invention；
Fig. 2 is the top view of the rectifier structure 100 in the photoelectric diode device shown in Fig. 1, and lead is not shown；
Fig. 3 is the band structure schematic diagram of the first ITO electrode and SiC heterojunction boundaries, wherein EC、EVAnd EFRepresent respectively
SiC conduction band, valence band and fermi level；
Fig. 4 be have illumination and by illumination the first ITO electrode apply back bias voltage in the case of ITO- graphenes-ITO energy
Band structure schematic diagram；
Fig. 5 be no light in the case of or by the first ITO electrode of illumination apply positive bias in the case of ITO- graphite
Alkene-ITO band structure schematic diagram；
Fig. 6 is photocurrent response curve of the photoelectric diode device of the specific example of the present invention under short circuit condition；
Fig. 7 is the relation curve that the photoelectric current in Fig. 6 subtracts the net photoelectric current after dark current and bias；
Fig. 8 is the top view of the rectifier structure in the photoelectric diode device of another specific example of the present invention；
Fig. 9 is the cross section structure schematic diagram of the rectifier structure in the photoelectric diode device of the another example of the present invention.
Embodiment
In order that the purpose of the present invention, technical scheme and advantage are more clearly understood, pass through below in conjunction with accompanying drawing specific real
Applying example, the present invention is described in more detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention,
It is not intended to limit the present invention.
In order to make full use of and excavate all works for participating in part in the photoelectric diode device based on ITO and graphene
With the present invention proposes a kind of substrate to the absorbable photoelectric diode device of exposure light.Due to backing material thickness much
More than ITO electrode or the thickness of graphene, photo-generated carrier can be in substrate/ITO circle caused by its efficient absorption to exposure light
It is quickly transferred in ITO electrode or graphene, causes by irradiation ITO in the presence of face electric field and substrate/graphene Interface electric field
The change of electrode or graphene fermi level.By using the light irradiation to ITO electrode, photoelectric diode device of the invention exists
Under the irradiation of the absorbable exposure light of substrate, voltage difference quickly is set up between the electrode at graphene both ends, so as to irradiated
When applying positive bias in ITO electrode, short-circuit photocurrent is close or equal to dark current；And work as and applied negative bias by irradiation ITO electrode
During pressure, short-circuit photocurrent increases with the enhancing of irradiation light intensity, so as to produce rectifying effect under positive back bias voltage.The rectifying effect
Realization, without opening the band gap of graphene, realized simply by the regulation and control of grating pressure and the particular attribute of ITO electrode.
Fig. 1 shows the schematic diagram of the cross section structure of the photoelectric diode device according to the present invention, including rectifier structure 100
With radiation source 200, rectifier structure 100 includes high resistance light gain semi-conductor substrate 1, positioned at high resistance light gain semi-conductor substrate 1
On graphene layer 2, the first ITO electrode 31 and second electrode on high resistance light gain semi-conductor substrate 1 and graphene layer 2
32, and first, second lead 41,42 electrically connected respectively with first, second electrode 31,32, wherein, the first ITO electrode 31
A part contacted with high resistance light gain semi-conductor substrate 1, another part contacts with graphene layer 2, one of second electrode 32
Divide and contacted with high resistance light gain semi-conductor substrate 1, another part contacts with graphene layer 2.Fig. 2 is the pole of photoelectricity two shown in Fig. 1
The top view of rectifier structure 100 in pipe device, first, second lead 41,42 not shown in it.It is well known that led in semiconductor
Domain, so-called " high resistant " refer to that resistivity is higher than 105Ω·cm。
The high resistance light gain semi-conductor substrate 1 of rectifier structure is except as graphene in the photoelectric diode device of the present invention
Outside the support substrate of layer 2 and electrode 31,32, it is often more important that using high resistance light gain semi-conductor substrate 1 as photosensitive material, work as light
Illumination of the energy that source is sent more than high resistance light gain semi-conductor substrate band gap is mapped to the first ITO on prepared rectifier structure
During electrode, the larger light absorbs volume of high resistance light gain semi-conductor substrate, which enhances, contrasts the high photon energy of its band-gap energy
Absorb, so as to produce substantial amounts of photo-generated carrier in high resistance light gain semi-conductor substrate.
The first ITO electrode 31 of rectifier structure is except the rectifying junction as the present invention in the photoelectric diode device of the present invention
Outside the electrode of structure, the photo-generated carrier shifted from high resistance light gain semi-conductor substrate 1 to electrode 31 is also received.In addition, the second electricity
Ohm contact electrode of the pole 32 only as rectifier structure, it can be ITO electrode, or metal electrode.Because fermi level exists
The balance of high resistance light gain semi-conductor material and the first ITO electrode interface requirement, in interface formed with beneficial to photoproduction current-carrying
The electric field that son drifts about from high resistance light gain semi-conductor substrate to the first ito transparent electrode.The built in field contributes to photoproduction current-carrying
Son is from high resistance light gain semi-conductor substrate to the first ito transparent electrode fast transfer.It should be understood readily by those skilled in this art, work as
When illumination causes high resistance light gain semi-conductor substrate to by irradiation ITO electrode transfer carrier, it may result in graphene layer 2
It is poor (fermi level of radiation exposed first ITO electrode is high) that fermi level is produced between two end electrodes, if the hot spot of exposure light
Area is less than the area of radiation exposed first ITO electrode, and (resistivity is generally 10 to the semiconductor conductive characteristic of ITO materials-2- several
Ω cm) such that the carrier in ITO electrode is substantially confined to be illuminated region and its surrounding, promptly can not uniformly it divide
Whole ITO electrode is distributed in, so that the fermi level difference between the two end electrodes of graphene layer 2 is higher.When to unirradiated
When second electrode applies forward voltage (applying negative voltage to radiation exposed first ITO electrode), because negative voltage suppresses to carry
Stream, so photovoltage is kept approximately constant, causes under short circuit condition and produced in the device in the migration being illuminated in ITO electrode
Raw larger photoelectric current；And apply negative voltage to unirradiated second electrode and (apply to radiation exposed first ITO electrode
Forward voltage) when, photo-generated carrier promptly redistributes in whole radiation exposed first ITO electrode, and photovoltage is with anti-
Reduce to the increase of bias, until being wholly absent, cause short-circuit photocurrent smaller, close to dark current, so as in positive reverse bias
It is lower to produce obvious rectifying effect.It is it will be appreciated by those skilled in the art that positive applying to unirradiated first ITO electrode
During voltage, although the carrier in radiation exposed first ITO electrode can leak to second electrode by graphene layer 2, by
Photo-generated carrier is constantly be generated in a steady stream in lasting light irradiation, is finally reached dynamic equilibrium and is caused residue in the first ITO electrode
The overwhelming majority of caused photo-generated carrier.
Illustrate the photoelectric diode device of the present invention below by way of specific example.
Reference picture 1 illustrates the specific example of the photoelectric diode device of the present invention, and it includes rectifier structure 100 and ultraviolet light
Source 200, rectifier structure 100 include SiC substrate 1, the graphene layer 2 in SiC substrate 1, positioned at SiC substrate 1 and graphene
The first ITO electrode 31 and the second ITO electrode 32 on layer 2, a part for the first ITO electrode 31 contacts with SiC substrate 1, another
Part contacts with graphene layer 2, and the part of the second ITO electrode 32 contacts with SiC substrate 1, another part and graphene layer 2
Contact.Wherein, the size of first ITO electrode 31 is 1mm × 1mm；The thickness of SiC substrate 1 is 350 μm；Two electrodes it
Between graphene layer length × 10 μm of a width of 100 μ m；The spot diameter of the ultraviolet source is 150 μm.
Experiment is found：The ultraviolet lighting for being more than SiC band gap when energy is mapped to transparent first of prepared rectifier structure
When on the region of the close graphene layer 2 of ITO electrode, electron transition that can be in exciting irradiation area SiC valence band to conduction band.And
Caused photo-generated carrier is quickly transferred under SiC and the effect of the Interface electric field of the first ITO electrode (as shown in Figure 3) in SiC
In first ITO electrode, it is poor to cause to exist between the fermi level at the both ends that graphene contacts with electrode energy of position, so as to two
Voltage difference is produced between individual electrode, as shown in figure 4, Fig. 4 is the feelings for having illumination and being applied back bias voltage by the first ITO electrode of illumination
ITO- graphenes-ITO band structure schematic diagram under condition, wherein：V is the bias that is applied；It in photon energy is h ν that Δ E, which is,
In the case that the light of (its energy is more than the band gap of high resistance light gain semi-conductor) irradiates the first ITO electrode, produced at graphene both ends
Raw fermi level is poor.When not applied forward voltage by the second ITO electrode of ultraviolet light irradiation, short-circuit photocurrent is with ultraviolet light
Strengthen and increase；And during the second ITO electrode application reverse biased, short-circuit photocurrent changes close to dark current little with light intensity.
As a comparison, apply forward voltage feelings in the case that Fig. 5 shows no light or to the first ITO electrode by ultraviolet light irradiation
Under condition, the band structure schematic diagram of ITO- graphene-ITO devices.
In addition, at the heterojunction boundary that graphene and SiC are formed, caused photo-generated carrier equally can be with SiC
It is transferred to by SiC conduction band in graphene.The electronic work function of electronic work function and SiC yet with graphene approaches,
Band curvature at graphene and SiC heterojunction boundary is smaller, the valence-band electrons energy of electron energy and SiC in graphene
Close electrons are back to SiC valence band, cause the quantity of net carrier in graphene constant or change is smaller.Fig. 6 be
Under short circuit condition, the 325nm of different capacity ultraviolet light is only irradiated under the areas case of close graphene of the first ITO electrode
Photocurrent response curve (curve from the bottom to top corresponds respectively to 0mW (unglazed), 1mW, 3mW, 5mW, 7mW and 10mW purple
Photocurrent response rule under outer light irradiation).Fig. 7 is net after the dark current in the case of photoelectric current in Fig. 6 subtracts no light
Photo-current intensity is with ultraviolet light intensity and the changing rule of bias.The rectifying effect that can be clearly apparent under phase reverse bias, positive electricity
The ratio between net photoelectric current can reach 10 caused by pressure and backward voltage3, this embodies good rectification effect.
Fig. 8 is the schematic diagram of the rectifier structure in the photoelectric diode device of another example of the present invention.In this example,
Unshowned light source is 532nm of the energy more than 2.3eV green glow, and the light source only irradiates the first ITO electrode close to graphene
Region；High resistance light gain semi-conductor substrate uses GaP single-chips；Second electrode 32 is Ti metals.Wherein, GaP single-chips
Thickness is 300 μm；The area of first ITO electrode 31 and the area equation of second electrode 32, size is 1mm × 1mm；Two electrodes it
Between graphene layer length × 3 μm of a width of 10 μ m, the spot diameter of green-light source is 200 μm.
Fig. 9 be the present invention another example photoelectric diode device in rectifier structure structural representation.In the example
In, unshowned light source is 632nm of the energy more than 1.42eV feux rouges, and the light source only irradiates the first ITO electrode close to stone
The region of black alkene；High resistance light gain semi-conductor substrate uses the Semi-insulating GaAs film of epitaxial growth on a si substrate；Second electricity
Pole 32 is Ti metals.Wherein, the thickness of GaAs films is 100nm；The size of ITO electrode is 1mm × 1mm, Ti metal electrodes
Size is 0.2mm × 0.2mm；The length of graphene layer × 3 μm of a width of 100 μ m between two electrodes；Irradiate the spot diameter of feux rouges
For 100 μm.
According to other examples of the present invention, exposure light not necessarily irradiates the area of the close graphene layer of the first ITO electrode
Domain, still, as irradiation zone can be weakened gradually away from graphene layer, optical rectification effect.
, can be by the close graphene layer of the first ITO electrode in order to limit irradiation zone according to other examples of the present invention
Region is exposed, the remainder coating light non-transmittable layers of device.At this moment the light that light source is sent is uniformly irradiated with whole device just
The device can be made to realize the rectifying effect under positive reverse bias.
, can be by graphene in order to suppress leakage of the photo-generated carrier by graphene layer according to other examples of the present invention
2 size (including length and width) between two electrodes 31,32 of layer is defined.In principle, between two electrodes 31,32
Graphene layer 2 it is longer and narrower, its rectifying effect is more prominent.But it should be understood readily by those skilled in this art, to graphene
The restriction of layer size is not essential.Detected based on short-circuit photocurrent, apply back bias voltage or not in the electrode tip for receiving light irradiation
Under the conditions of alive, the photoelectric diode device may act as ultrafast photo-detector.
According to other examples of the present invention, in order to reduce absorption of irradiated first ITO electrode to exposure light, irradiated
The shape of first ITO electrode can be prepared into hollow out electrode, such as gauze shape, strip on the premise of its electric conductivity is not influenceed
Deng.It will be understood by those skilled in the art that in the present invention, any restriction is not made to electrode size, shape and hollow out degree.
According to other examples of the present invention, the material of high resistance light gain semi-conductor substrate is organic or inorganic semiconductor material
Material, the thickness of substrate are more than 50nm.
According to other examples of the present invention, the area of radiation exposed ITO electrode is at least 10 times of irradiation facula area, excellent
Elect 20 times as.
According to other examples of the present invention, the rectifier structure of photoelectric diode device of the invention can also be included high resistant
The encapsulating housing that gain of light Semiconductor substrate, graphene layer, electrode and lead are packaged, the encapsulating housing have thang-kng window
Mouthful.
In order to embody the effect of the present invention, inventor compares experiment, and bar is tested using with the first example identical
Part, the first ITO electrode is replaced with into Ti metal electrodes, now, during with ultraviolet light irradiation, rectifying effect can not be observed.
In summary, the operation principle of photoelectric diode device provided by the invention is totally different from the photoelectricity of prior art
Diode, the photoelectric diode device fully utilize high resistance light gain semi-conductor material and contrast the high photon of its band-gap energy
Photo-generated carrier is quickly transferred to ITO electrode and graphene in efficient absorption, high resistance light gain semi-conductor material, and in graphene
It is poor that fermi level is established between the electrode at both ends.The voltage difference keeps steady when applying forward voltage to unirradiated electrode
It is fixed；And when applying negative voltage to unirradiated electrode, the voltage difference gradually decreases to zero (see figure with the increase of back bias voltage
Short-circuit photocurrent is converged under back bias voltage on dark current curve in 6), so as to realize the rectifying effect of photodiode (see figure
7).The device technology of the photoelectric diode device of the present invention is simple, and size is small, and manufacturing cost is cheap, and is planar structure, can
With applied to Planar integration and micro-nano device.In addition, in the case where applying the short circuit condition of forward voltage to unirradiated electrode, due to
The excellent electrons transport property of graphene, it is possible to achieve to the super fast response and sensitive detection of exposure light.Therefore the light of the present invention
Electric diode device is also used as ultrafast, sensitive optoelectronic switch and sensitive detector.
Although the present invention be described by means of preferred embodiments, but the present invention be not limited to it is described here
Embodiment, also include made various changes and change without departing from the present invention.
Claims (11)
1. a kind of photoelectric diode device, including light source and rectifier structure, the rectifier structure includes high resistance light gain semi-conductor
Substrate, the graphene layer on the high resistance light gain semi-conductor substrate, positioned at the high resistance light gain semi-conductor substrate and
The first ITO electrode and second electrode on the graphene layer, wherein, a part and the high resistant of first ITO electrode
Gain of light Semiconductor substrate contacts, and another part contacts with the graphene layer, a part for the second electrode and the height
Light blocking gain semi-conductor substrate contact, another part contact with the graphene layer, and wherein：
I) energy of the light of the light source transmitting is more than the band gap of the high resistance light gain semi-conductor substrate, and the light source only spoke
According to the first ITO electrode；
Ii) area of first ITO electrode is more than the facula area of the source emissioning light.
2. photoelectric diode device according to claim 1, wherein, the light source only irradiates first ITO electrode
Close to the region of the graphene layer.
3. photoelectric diode device according to claim 1, wherein, the area of first ITO electrode is the light source
Launch the facula area of light at least 10 times.
4. photoelectric diode device according to claim 1, wherein, the high resistance light gain semi-conductor substrate has for high resistant
Machine semiconductor or high resistant inorganic semiconductor.
5. photoelectric diode device according to claim 1, wherein, the light source is ultraviolet source, and the high resistance light increases
Beneficial Semiconductor substrate is SiC, or the light source is visible light source, the high resistance light gain semi-conductor substrate be Si, GaP or
GaAs。
6. photoelectric diode device according to claim 1, wherein, the second electrode is metal or ITO electrode.
7. photoelectric diode device according to claim 1, wherein, in addition to light tight coat, the light tight painting
Coating is coated to the area in addition to the region of the close graphene layer of first ITO electrode of the rectifier structure
Domain.
8. photoelectric diode device according to claim 1, in addition to it is respectively electrically connected to first ITO electrode and institute
State the first lead and the second lead of second electrode.
9. photoelectric diode device according to claim 8, in addition to by the high resistance light gain semi-conductor substrate, described
The encapsulating shell that graphene layer, first ITO electrode and the second electrode and first and second lead are packaged
Body, wherein the encapsulating housing has thang-kng window.
10. a kind of method that photoelectric diode device using described in claim 1-9 produces rectifying effect.
11. the method according to claim 10 for producing rectifying effect, wherein, apply just when to first ITO electrode
During bias, short-circuit photocurrent is close or equal to dark current；And when applying back bias voltage to first ITO electrode, short-circuit photoelectricity
Stream increases with the enhancing of irradiation light intensity.
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