CN110828609B - Self-excitation storable photoconductive device and preparation method thereof - Google Patents

Self-excitation storable photoconductive device and preparation method thereof Download PDF

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CN110828609B
CN110828609B CN201911061486.9A CN201911061486A CN110828609B CN 110828609 B CN110828609 B CN 110828609B CN 201911061486 A CN201911061486 A CN 201911061486A CN 110828609 B CN110828609 B CN 110828609B
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CN110828609A (en
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姜昱丞
贺安鹏
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Suzhou University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—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
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    • H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
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    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H—ELECTRICITY
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    • H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
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    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L31/00—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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
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Abstract

The invention discloses an auto-excitation storable photoconductive device and a preparation method thereof. The invention takes a single crystal STO substrate as an insulating oxide, and after ion beam bombardment, a nano conductive thin layer, namely surface electron gas SSEG, is formed on the surface layer of the single crystal STO substrate and is an N-type semiconductor; WSe2The material is a P-type two-dimensional semiconductor material, and the layers are combined together by Van der Waals force to form tungsten diselenide and strontium titanate surface electron gas and PN junction thereof, has the characteristics of simple structure, high photoelectric efficiency and storage, can realize the storage of photo-generated electron hole pairs, and obtains photo-generated carriers with unlimited service life; the working process is self-excited, the external quantum efficiency is high, the structure is simple, and the method can be used in the field of nano energy devices.

Description

Self-excitation storable photoconductive device and preparation method thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a storable photoconductive device.
Background
The photovoltaic effect, the photoconductive effect, often occurs when light is incident on the PN junction. Efficient photoelectric devices often have excellent external quantum efficiency, and the rapid recombination of photo-generated electron hole pairs greatly shortens the service life of carriers, thereby limiting the external quantum efficiency of the photoelectric devices. In order to obtain excellent optoelectronic devices, researchers have tried various strategies, such as using novel P-type and N-type semiconductor materials or designing new functional interfaces. Currently, the improvement of external quantum efficiency is mainly achieved by improving the absorption of photons by the device, and relatively little research is done on the improvement of the lifetime of carriers. In recent years, the van der waals heterojunction based on the two-dimensional material is different from the military projection in the aspect of environment-friendly and efficient nanometer energy devices, and a large number of researches show that the van der waals heterojunction has huge application prospects in the aspects of photovoltaic cells, photoelectric detection and the like. One great advantage of van der waals junctions is that the band gap structure that is relied upon between layers allows us to manipulate the physical properties of PN junctions without introducing additional disorder. The heterojunction plays an important role in capturing electron-hole pairs, prolonging the service life of photogenerated electron-hole pairs and separating the photogenerated electron-hole pairs. However, most of the current van der waals heterojunction structures are composed of two-dimensional P-type and N-type materials, and other two-dimensional systems, such as two-dimensional electron gas, are widely concerned due to the singular physical properties thereof, but no van der waals heterojunction structure about electron gas is reported at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the self-excitation storable photoconductive device which has a simple structure and high photoelectric efficiency and can be stored and the preparation method thereof.
The technical scheme for realizing the aim of the invention is to provide a preparation method of the self-excitation storable photoconductive device, which comprises the following steps:
(1) WSe (tungsten diselenide) with few layers2Slave block WSe2Up-transfer to single-crystal strontium titanate SrTiO3A substrate STO surface;
(2) covering photoresist on one side of the sample obtained in the step (1) by adopting a photoetching process, wherein the coverage area of the photoresist accounts for the WSe of the substrate 21/2-2/3 of the surface area, and the rest area of the other side of the substrate is WSe2And an STO surface exposed state;
(3) depositing gold on the surface of the sample obtained in the step (2) by adopting a magnetron sputtering process, removing the photoresist by using acetone, covering the region in the exposed state in the step (2) with the gold, and covering the photoresist with a WSe part2And an STO exposed condition;
(4) and covering photoresist on one side covered by the gold by adopting a photoetching process, wherein the photoresist covers the whole area covered by the gold and the exposed WSe2Covering 1/2-2/3 of the surface area;
(5) exposing WSe by ion beam etching process2And STO etch, WSe to be exposed2After all etching is carried out, continuing to etch the STO substrate in a proper amount until the surface of the STO substrate etched by the ion beams forms an STO surface electron gas SSEG;
(6) sequentially cleaning a sample by acetone, alcohol and deionized water to obtain the WSe2The self-excited storable photoconduction device of PN junction of SSEG.
The technical scheme of the invention also comprises a WSe obtained by the preparation method2The self-excited storable photoconduction device of the/SSEG PN junction.
The invention provides tungsten diselenide (WSe)2) Strontium titanate (SrTiO)3STO) Surface Electron Gas (SSEG) (WSe)2SSEG) PN junction, which is a storable photoconductive device. The device has simple structure, high external quantum efficiency and long storage timeAnd the like.
In the technical scheme of the invention, a single crystal STO substrate is used as an insulating oxide, and after ion beam bombardment, a nano conductive thin layer, namely surface electron gas SSEG, is formed on the surface layer of the single crystal STO substrate and is an N-type semiconductor; WSe2The invention is a P-type two-dimensional semiconductor material, the layers are combined together by Van der Waals force, the invention uses a micro-mechanical stripping method to remove WSe with few layers2Sticking on the surface of the single crystal STO; gold electrode, WSe obtained using micromechanical lift-off process2The small size is not beneficial to the preparation of the electrode, so the invention is applied to WSe2One side is plated with a gold electrode.
Experiments show that the ratio of the current after the optical storage to the current before the optical storage of the storable photoconductive device provided by the invention is more than 10 under the bias of 5V9Its external quantum efficiency is up to 4410000%. Firstly testing the discharge IV curve of the device after being fully charged for 2 minutes, then fully charging again, testing the discharge IV curve after being charged for 7 days, and comparing the two IV curves to find that the difference is small, which shows that the difference of the charge quantity after being stored for 2 minutes and 7 days is small, and the side surface reflects the long storage time of the device on photo-generated carriers.
Compared with the prior art, the storable photoconductive device provided by the invention takes the single crystal STO as the substrate, SSEG as the N pole and WSe as the N pole2As the P pole, the photoelectric device has the characteristics of simple structure, high photoelectric efficiency and storage. The invention provides a van der Waals heterojunction based on strontium titanate surface electron gas, which can realize the storage of photo-generated electron hole pairs and obtain photo-generated carriers with unlimited service life; the working process is self-excited, the external quantum efficiency is high, the structure is simple, and the method can be used in the field of nano energy devices.
Drawings
Fig. 1 is a schematic flow chart of a preparation process of a self-excited storable photoconductive PN junction according to an embodiment of the present invention.
Fig. 2 is an atomic force microscope and optical microscope image of a self-excited storable photoconductive PN junction provided by an embodiment of the present invention.
Fig. 3 is a schematic structural diagram of a self-excited storable photoconductive device according to an embodiment of the present invention.
Fig. 4 is an IV curve in the dark 2 minutes after the self-excited storable photoconductive PN junction is charged and 7 days after the charge is charged according to an embodiment of the present invention, and the inset is an IV curve in the dark after the uncharged junction and the charged junction.
Fig. 5 is a graph of the amount of stored charge (the amount of stored charge within 0-4 v) of the self-excited storable photoconductive PN junction under different power densities of 405 nm light irradiation versus the illumination time according to the embodiment of the present invention.
Fig. 6 is an IV curve of a self-excited storable photoconductive PN junction in the dark after being charged under irradiation with light of different wavelengths according to an embodiment of the present invention.
Detailed Description
In order to make the objects and advantages of the present invention more clear, the technical solution of the present invention is further described below with reference to the accompanying drawings and examples.
Example 1
Referring to FIG. 1, there is provided a WSe in accordance with the present embodiment2A schematic diagram of a PN junction preparation process of the SSEG; the method comprises the following specific steps:
s1: using adhesive tape to reduce the number of layers of WSe2Slave block WSe2Transferred to the surface of the single-crystal STO substrate and the resulting sample structure is shown in fig. S1;
s2: using photolithographic techniques to expose WSe on one side of a sample2The surface of area 2/3 and the STO substrate on that side were covered with photoresist, the rest was exposed, and the structure of the sample obtained was as shown in fig. S2;
s3: depositing gold on the surface of the sample obtained in the previous step by adopting a magnetron sputtering technology, and removing the photoresist by using acetone, wherein the area in the exposed state in the graph S2 is covered by the gold, and the rest part is WSe2Exposed state, the structure of the sample obtained is shown in fig. S3;
s4: again using photolithographic technique to cover the gold on one side of the WSe 22/3 of the area and the gold-covered surface of the side are covered with photoresist, and the structure of the obtained sample is shown in S4;
s5: use of ion beam to etch exposed WSe2And STO, WSe to be exposed2Is completely etched away and then is followed byEtching the STO substrate in a proper amount until an SSEG (STO surface electron gas) is formed on the surface of the STO substrate etched by the ion beam, wherein the structure of the obtained sample is shown as S5;
s6: the sample was washed with acetone, alcohol and deionized water in sequence, and WSe was completed2The PN junction preparation of the/SSEG is a photoconductive PN junction with a self-excitation storable function, and the obtained sample structure is shown as a graph S6.
Referring to fig. 2, it is an atomic force microscope and optical microscope image of the self-excited storable photoconductive PN junction provided in this embodiment, where the atomic force microscope image is measured at a dashed box in the optical microscope image; the simple structure can be seen from fig. 2.
WSe obtained by the above preparation method2The PN junction of SSEG is connected with a wire between two metal electrodes, and a voltage is applied to the two ends of the PN junction to prepare the self-excited storable photoconductive device, and the structural schematic diagram of the self-excited storable photoconductive device is shown in the attached figure 3.
Referring to fig. 4, the self-excited storable photoconductive device provided in this example is shown as the IV curve in the dark 2 minutes after charge-up and 7 days after charge-up. The test is carried out after the same light radiation intensity and irradiation time (the light radiation time is long enough to ensure that the stored charge amount of the PN junction reaches saturation), the IV curve of the PN junction is measured after the light source is turned off for 2 minutes and 7 days, the difference of the IV curves measured in the previous and subsequent times is small, the voltage step used in the previous and subsequent measurements is consistent (the measurement time is consistent), therefore, the difference of the number of photo-generated carriers after the photo-generated carriers are stored for 7 days and 2 minutes is small, and the WSe is shown2the/SSEG can stably store photo-generated electron-hole pairs for a long time.
The stored charge was measured against the time of illumination at different power densities of 405 nm light, as shown in figure 5. It can be known from the figure that as the optical power density increases, the time required for the stored charge of the PN junction to reach saturation is shorter and shorter, and the PN junction irradiated under different optical power densities has similar stored charge saturation values, which indicates that the charge storage capacity of the PN junction is independent of the optical power density.
Referring to fig. 6, in the discharge IV curve of the self-excited storable photoconductive PN junction provided in this embodiment after being fully charged under the irradiation of light with different wavelengths, the PN junction is subjected to charge depletion and long-time irradiation of light with corresponding wavelengths before the test, so as to ensure that the stored charge is excited by the wavelength and the charge storage is saturated. In the figure, x 2 and x 5 indicate that the ordinate of the curve is uniformly multiplied by 2 or 5, for better comparison and for distinguishing different wavelengths. The shorter the radiation wavelength, the stronger the charge storage capacity of the PN junction, and at long wavelength radiation (532 nm, 655 nm, 808 nm), the PN junction can only store charge at 21V, indicating that photon energy at long wavelength is insufficient to excite charge storage behavior in the region above 21V.
The self-excited storable photoconductive PN junction provided by the invention has the advantages of excellent external quantum efficiency, long storage time, simple structure and strong stability, and has an application prospect in the field of nano energy devices.

Claims (2)

1. A method for preparing a self-excited storable photoconductive device, comprising the steps of:
(1) WSe (tungsten diselenide) with few layers2Slave block WSe2Up-transfer to single-crystal strontium titanate SrTiO3A substrate STO surface;
(2) covering photoresist on one side of the sample obtained in the step (1) by adopting a photoetching process, wherein the covered area of the photoresist accounts for 1/2-2/3 of the surface area of the substrate STO, and the rest area of the other side of the substrate is WSe2And an STO surface exposed state;
(3) depositing gold on the surface of the sample obtained in the step (2) by adopting a magnetron sputtering process, removing the photoresist by using acetone, covering the region in the exposed state in the step (2) with the gold, and covering the photoresist with a WSe part2And an STO exposed condition;
(4) and covering photoresist on one side covered by the gold by adopting a photoetching process, wherein the photoresist covers the whole area covered by the gold and the exposed WSe2Covering 1/2-2/3 of the surface area;
(5) exposing WSe by ion beam etching process2And STO etch, WSe to be exposed2After all etching is carried out, continuing to etch the STO substrate in a proper amount until the surface of the STO substrate etched by the ion beams forms an STO surface electron gas SSEG;
(6) sequentially cleaning a sample by acetone, alcohol and deionized water to obtain the WSe2The self-excited storable photoconduction device of PN junction of SSEG.
2. A WSe obtained by the process of claim 12The self-excited storable photoconduction device of the/SSEG PN junction.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05235382A (en) * 1992-02-18 1993-09-10 Kanegafuchi Chem Ind Co Ltd Semiconductor device
JP2004214547A (en) * 2003-01-08 2004-07-29 Zenji Hiroi Optical semiconductor element having organic-inorganic semiconductor heterojunction
CN107425081A (en) * 2017-06-28 2017-12-01 中国人民解放军国防科学技术大学 Topological insulator array type optical electric explorer based on graphene class two-dimensional material protection layer and its preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05235382A (en) * 1992-02-18 1993-09-10 Kanegafuchi Chem Ind Co Ltd Semiconductor device
JP2004214547A (en) * 2003-01-08 2004-07-29 Zenji Hiroi Optical semiconductor element having organic-inorganic semiconductor heterojunction
CN107425081A (en) * 2017-06-28 2017-12-01 中国人民解放军国防科学技术大学 Topological insulator array type optical electric explorer based on graphene class two-dimensional material protection layer and its preparation method and application

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