CN109648095B - Antimony nanosheet and stripping method thereof, and flexible photodetector and preparation method thereof - Google Patents

Antimony nanosheet and stripping method thereof, and flexible photodetector and preparation method thereof Download PDF

Info

Publication number
CN109648095B
CN109648095B CN201811528364.1A CN201811528364A CN109648095B CN 109648095 B CN109648095 B CN 109648095B CN 201811528364 A CN201811528364 A CN 201811528364A CN 109648095 B CN109648095 B CN 109648095B
Authority
CN
China
Prior art keywords
antimony
nanosheets
vpim
nanosheet
stripping
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811528364.1A
Other languages
Chinese (zh)
Other versions
CN109648095A (en
Inventor
张浩力
肖琪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanzhou University
Original Assignee
Lanzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanzhou University filed Critical Lanzhou University
Priority to CN201811528364.1A priority Critical patent/CN109648095B/en
Publication of CN109648095A publication Critical patent/CN109648095A/en
Application granted granted Critical
Publication of CN109648095B publication Critical patent/CN109648095B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0551—Flake form nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01L31/0248—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
    • 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
    • H01L31/0264—Inorganic materials
    • 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
    • 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
    • H01L31/0248—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
    • 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
    • H01L31/0264—Inorganic materials
    • H01L31/0328—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
    • H01L31/0336—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032 in different semiconductor regions, e.g. Cu2X/CdX hetero-junctions, X being an element of Group VI of the Periodic System
    • 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
    • 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
    • H01L31/109—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier the potential barrier being of the PN heterojunction type
    • 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses an antimony nanosheet and a stripping method thereof, and a flexible photodetector and a preparation method thereof, and relates to the technical field of photoelectric materials. The method for peeling the nanosheet comprises the following steps: mixing antimony powder with liquid-phase stripping liquid, and performing ultrasonic treatment for 2-4 h; wherein the liquid phase stripping solution is a mixture of a diluent and a high polymer ionic liquid, the diluent is an oily solvent, and the high polymer ionic liquid is poly (1-vinyl-3-propylimidazole hexafluorophosphate) and/or poly (1-vinyl-3-propylimidazole bistrifluoromethanesulfonylimide). Prepared by the stripping method of the antimony nanosheet, wherein the antimony nanosheet is Sb/P ([ VPIm)]PF6) Nanosheets or Sb/P ([ VPIm)]TFSI) nanosheets, which can be applied to the preparation of photodetectors. The preparation method of the detector comprises the steps of firstly preparing the nano sheets by the stripping method of the antimony nano sheets, and then compounding the nano sheets and the cadmium sulfide quantum dots to form the photodetector, and the photodetector is a flexible photoelectric detector.

Description

Antimony nanosheet and stripping method thereof, and flexible photodetector and preparation method thereof
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to an antimony nanosheet and a stripping method thereof, and a flexible photodetector and a preparation method thereof.
Background
Antimonene is a recently reported two-dimensional material of the same family as black phosphorus. Theoretical prediction shows that stibene has better stability, higher mobility and adjustable band gap than black phosphorus, and has been applied to various fields such as photoelectric devices, electrocatalysis, energy storage, cancer treatment and the like.
Its narrow interlayer spacing and strong bonding energy make the preparation of antimonenes challenging. Only a few articles have reported the successful preparation of antimonenes, such as mechanical exfoliation, liquid phase exfoliation and epitaxial growth. Mechanical stripping can give large sheets of stibene but has the disadvantages of land yield and time consuming; the epitaxial growth can obtain the nanosheet with a good crystal form and controllable size and thickness, and has the disadvantages that a high-temperature and high-vacuum environment is usually used in the preparation process, the preparation of the nanomaterial needs to be completed on a specific substrate, and how to transfer the nanomaterial from the substrate to further research and application is a big problem.
Disclosure of Invention
The invention aims to provide a stripping method of antimony nanosheets, which has the advantage of high yield of antimony nanosheets by adopting two high polymer ionic liquids provided by the invention to carry out liquid phase stripping.
Another object of the present invention is to provide an antimony nanosheet, which is prepared using the above-described exfoliation method, to give Sb/P ([ VPIm)]PF6) Nanosheets or Sb/P ([ VPIm)]TFSI) nanosheets, which can be used in the preparation of photodetectors.
The third objective of the invention is to provide a preparation method of the photodetector, wherein the antimony nanosheet prepared by the stripping method is compounded with the cadmium sulfide quantum dots, and the method is simple and easy to implement.
It is a fourth object of the present invention to provide a flexible photodetector made of Sb/P ([ VPIm)]PF6) Nanosheets or Sb/P ([ VPIm)]TFSI) nano-sheet composite cadmium sulfide quantum dots.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a stripping method of antimony nanosheets, which comprises the following steps:
mixing antimony powder with liquid-phase stripping liquid, and performing ultrasonic treatment for 2-4 h;
wherein the liquid phase stripping solution is a mixture of a diluent and a high polymer ionic liquid, the diluent is an oily solvent, and the high polymer ionic liquid is poly (1-vinyl-3-propylimidazole hexafluorophosphate) and/or poly (1-vinyl-3-propylimidazole bistrifluoromethanesulfonylimide).
The invention also provides an antimony nanosheet prepared by the stripping method of the antimony nanosheet, wherein the antimony nanosheet is Sb/P ([ VPIm)]PF6) Nanosheets orSb/P([VPIm]TFSI) nanosheets.
The invention also provides a preparation method of the optical detector, which comprises the following steps:
preparing nano-sheets to be processed according to the stripping method of the antimony nano-sheets, wherein the nano-sheets to be processed are Sb/P ([ VPIm)]PF6) Nanosheets or Sb/P ([ VPIm)]TFSI) nanoplatelets;
compounding the nano sheet to be processed with the cadmium sulfide quantum dot.
The invention also provides a flexible optical detector which is prepared by applying the preparation method of the optical detector.
The embodiment of the invention provides a stripping method of antimony nanosheets, which has the beneficial effects that: the two high polymer ionic liquids provided by the invention are diluted to be used as liquid-phase stripping liquid, and the yield of the antimony nanosheets subjected to ultrasonic treatment is high, so that the antimony nanosheets have a good market application prospect. The antimony nanosheet provided by the invention is prepared by the stripping method of the antimony nanosheet, and the antimony nanosheet is Sb/P ([ VPIm)]PF6) Nanosheets or Sb/P ([ VPIm)]TFSI) nanosheets, which can be applied to the preparation of photodetectors.
In the preparation method of the photodetector provided by the embodiment of the invention, Sb/P ([ VPIm) is prepared by the stripping method of the antimony nanosheets]PF6) Nanosheets or Sb/P ([ VPIm)]TFSI) nano-sheet, and then compounding the nano-sheet and cadmium sulfide quantum dots to form the photodetector, which is a flexible photodetector. The flexible photodetector provided by the embodiment of the invention is prepared by the preparation method of the photodetector, and is prepared by Sb/P ([ VPIm)]PF6) and CdS quantum dots remarkably improve the photocurrent density and stability of the device.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a scanning electron micrograph of antimony powder after grinding and after ball milling;
FIG. 2 is a photograph of glass antimony nanosheet suspensions in different solvents and the corresponding absorbances of the dispersions;
FIG. 3 is a diagram of the absorption spectra of antimony nanosheets in different solutions;
FIG. 4 is a concentration dependent absorption spectrum of two antimony nanoplates;
FIG. 5 shows Sb/P ([ VPIm ]]PF6) And raman plots of bulk Sb;
FIG. 6 shows the blocks Sb and Sb/P ([ VPIm ]]PF6) XRD pattern of (a), and bulk antimony and Sb/P ([ VPim [)]PF6) XPS spectroscopy of (a);
FIG. 7 is an XPS spectrum of bulk Sb crystals, Sb/P ([ VPIm ] TFSI), and antimony sonicated in water;
FIG. 8 shows Sb/P ([ VPIm ]]PF6) Transmission electron microscope, TEM and AFM test charts;
FIG. 9 shows Sb/P ([ VPIm ]]PF6) An AFM image of (1);
FIG. 10 is a schematic diagram of a photodetector, and Sb/P ([ VPIm)]PF6) /CdS, pure CdS and Sb/P ([ VPIm)]PF6) Raman spectroscopy of the device of the thin film;
FIG. 11 shows Sb/P ([ VPIm ]]PF6) A device of/CdS, pure CdS film and a cross-sectional SEM image of the device;
FIG. 12 shows a graph based on Sb/P ([ VPIm ]]PF6) Each performance test chart of the/CdS photoelectric detector;
FIG. 13 is a graph of various property tests based on a pure CdS photodetector;
FIG. 14 is a graph of performance measurements for a Sb/P ([ VPIm ] PF6) based photodetector;
FIG. 15 is a band diagram of Sb and CdS and a mechanism diagram presumed.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following describes the antimony nanosheet and the stripping method thereof, and the flexible photodetector and the preparation method thereof provided by the embodiment of the present invention.
The stripping method of the antimony nanosheet provided by the embodiment of the invention comprises the following steps: mixing antimony powder with liquid-phase stripping liquid, and performing ultrasonic treatment for 2-4 h; wherein the liquid phase stripping solution is a mixture of a diluent and a high polymer ionic liquid, the diluent is an oily solvent, and the high polymer ionic liquid is poly (1-vinyl-3-propylimidazole hexafluorophosphate) and/or poly (1-vinyl-3-propylimidazole bistrifluoromethanesulfonylimide).
It is noted that the liquid phase stripping is carried out after the two high polymer ionic liquids provided by the embodiment of the invention are diluted, and the yield of the antimony nanosheet after ultrasonic treatment is high, so that the antimony nanosheet has a good market application prospect. Poly 1-vinyl-3-propylimidazolium hexafluorophosphate (P ([ VPIm ] PF6)) and poly 1-vinyl-3-propylimidazolium bistrifluoromethanesulfonylimide (P ([ VPIm ] TFSI)) are in solid state and have the specific structures:
Figure BDA0001905040330000061
the synthesis principle of two high polymer ionic liquids can be expressed as follows:
Figure BDA0001905040330000064
reference may be made in particular to the document "Advanced applications of ionic liquids in polymer science".
Specifically, the diluent is selected from at least one of N-methylpyrrolidone, dichloromethane, ethyl acetate, petroleum ether and N, N-dimethylformamide, preferably N, N-Dimethylformamide (DMF). Common oily solvents can be used for diluting the high polymer ionic liquid, and the N, N-dimethylformamide is adopted, so that the dispersing performance is better, and the yield of the antimony nanosheets is further improved.
Specifically, the amount of antimony powder is 0.5-2mg, preferably 0.7-1.2mg, per ml of liquid-phase stripping solution. The concentration of the poly-1-vinyl-3-propylimidazole hexafluorophosphate in the diluent is 12-14mg/mL, and the concentration of the poly-1-vinyl-3-propylimidazole bistrifluoromethanesulfonimide in the diluent is 7-8 mg/mL. In order to achieve better yield, the concentration of the liquid-phase stripping solution and the using amount of antimony powder need to be strictly controlled, the yield of antimony nanosheets can be reduced when the using amount of antimony powder is too small, and raw material waste is caused by too large using amount of antimony powder.
Preferably, the antimony powder is prepared by grinding antimony crystals for 5-15min and then ball-milling for 2-4 h; wherein, the rotating speed in the ball milling process is 450-550 rpm. The inventor finds that the ball milling mode is favorable for further improving the utilization rate of raw materials, probably because the pretreatment process of the low-rotation-speed ball milling enables the large antimony crystals to be almost reduced, so that the utilization rate of the raw materials in the subsequent ultrasonic process is greatly improved, and the high-polymer ionic liquid has good dispersion effect, so that the yield of the antimony nanosheets is high.
The embodiment of the invention also provides an antimony nanosheet prepared by the stripping method of the antimony nanosheet, wherein the antimony nanosheet is Sb/P ([ VPIm)]PF6) Nanosheets or Sb/P ([ VPIm)]TFSI) nanosheets, having a good crystal structure and micron-scale lateral dimensions, can find application in the preparation of photodetectors.
The embodiment of the invention also provides a preparation method of the optical detector, which comprises the following steps: preparing nano-sheets to be processed according to the stripping method of the antimony nano-sheets, wherein the nano-sheets to be processed are Sb/P ([ VPIm)]PF6) Nanosheets or Sb/P ([ VPIm)]TFSI) nanoplatelets; compounding the nano sheet to be processed with the cadmium sulfide quantum dot.
Specifically, the compounding method of the nanosheet to be processed and the cadmium sulfide quantum dot can be various existing compounding methods, and in order to directly synthesize the CdS quantum dot from an aqueous solution without any ligand, a Sequential Chemical Bath Deposition (SCBD) method is applied.
Further, the process of compounding the nanosheet to be processed with the cadmium sulfide quantum dot comprises the following steps: concentrating the nano-sheets to be processed to 0.1-0.3mg/mL, and then drying the nano-sheets on a substrate film to form a film so as to obtain a substrate material with a nano-sheet layer; and compounding cadmium sulfide quantum dots on the substrate material with the nanosheet layer by adopting a sequential chemical bath deposition method.
Preferably, the substrate film is an ITO/PET substrate, the film forming thickness of the nanosheet to be processed is 4-6 μm, and the electrode spacing is 90-110 nm. Meanwhile, the film formation width may be controlled to about 0.3 to 0.5cm, for example, 0.4cm, and the film formation length may be controlled to about 0.2 to 0.3 cm. The drying film-forming process can be a vacuum drying mode at normal temperature, and the drying time is about 2 hours.
Specifically, the process of compounding cadmium sulfide quantum dots on a substrate material with a nanosheet layer includes: sequentially immersing the substrate material with the nanosheet layer into four different vessels, wherein the residence time is 25-35s each time; wherein the first vessel is filled with CdCl2The aqueous solution is filled with Na in a second vessel2And the water solution of S is filled in the third vessel and the fourth vessel.
To achieve better recombination, CdCl2Aqueous solution and Na2The concentration of the S aqueous solution is 0.04-0.06 mol/L; the process of sequentially immersing the nanosheet layer of substrate material into four different vessels is repeated 8-12 times, such as 10 times. This cycle was repeated 10 times to give a yellow film. The CdS film size is controlled by adhesive tape, has a length of 0.25cm and a width of 0.4cm, and is located at Sb/P ([ VPIm)]PF6) film, slip was about 0.05 cm.
The embodiment of the invention also provides a flexible photodetector which is prepared by applying the preparation method of the photodetector, and the photocurrent density and the stability of a device are obviously improved by compounding Sb/P ([ VPIm ] PF6) and CdS quantum dots.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a stripping method of antimony nanosheets, which comprises the following steps:
and (3) uniformly grinding the bulk antimony crystals in an agate mortar for 5min in the same direction, and then putting the ground antimony powder into a ball mill to grind for 2h at the rotating speed of 450 rpm. Will be processedThe antimony powder is put into high polymer ionic liquid diluted by N-methyl pyrrolidone in an amount of 0.5mg/mL, and is put into an ultrasonic cleaner of ice bath for ultrasonic treatment for 2 hours. Wherein the high polymer ionic liquid is poly (1-vinyl-3-propylimidazole hexafluorophosphate) (P ([ VPim [ ])]PF6))，P([VPIm]PF6The concentration in the dilution was 12 mg/mL.
Example 2
The embodiment provides a stripping method of antimony nanosheets, which comprises the following steps:
and (3) uniformly grinding the bulk antimony crystals in an agate mortar for 15min in the same direction, and then putting the ground antimony powder into a ball mill to grind for 4h at the rotation speed of 550 rpm. The treated antimony powder is put into high polymer ionic liquid diluted by dichloromethane in an amount of 2mg/mL, and put into an ultrasonic cleaner of ice bath for ultrasonic treatment for 4 hours. Wherein the high polymer ionic liquid is poly (1-vinyl-3-propylimidazole hexafluorophosphate) (P ([ VPim [ ])]PF6))，P([VPIm]PF6The concentration in the dilution was 14 mg/mL.
Example 3
The embodiment provides a stripping method of antimony nanosheets, which comprises the following steps:
and (3) uniformly grinding the bulk antimony crystals in an agate mortar for 10min in the same direction, and then putting the ground antimony powder into a ball mill to grind for 3h at the rotating speed of 500 rpm. The treated antimony powder was added to a high polymer ionic liquid diluted with ethyl acetate in an amount of 0.7mg/mL, and the mixture was subjected to ultrasonic treatment in an ultrasonic cleaner in an ice bath for 3 hours. Wherein the polymer ionic liquid is poly (1-vinyl-3-propylimidazole bistrifluoromethanesulfonimide) (P ([ VPIm ] TFSI)), and the concentration of the P ([ VPIm ] TFSI) in a diluent is 7 mg/mL.
Example 4
The embodiment provides a stripping method of antimony nanosheets, which comprises the following steps:
and (3) uniformly grinding the bulk antimony crystals in an agate mortar for 10min in the same direction, and then putting the ground antimony powder into a ball mill to grind for 3h at the rotating speed of 500 rpm. The treated antimony powder is put into high polymer ionic liquid diluted by petroleum ether in an amount of 1.2mg/mL, and put into an ultrasonic cleaner of ice bath for ultrasonic treatment for 3 hours. Wherein the polymer ionic liquid is poly (1-vinyl-3-propylimidazole bistrifluoromethanesulfonimide) (P ([ VPIm ] TFSI)), and the concentration of the P ([ VPIm ] TFSI) in a diluent is 7.61 mg/mL.
Example 5
The embodiment provides a stripping method of antimony nanosheets, which comprises the following steps:
and (3) uniformly grinding the bulk antimony crystals in an agate mortar for 10min in the same direction, and then putting the ground antimony powder into a ball mill to grind for 3h at the rotating speed of 500 rpm. The treated antimony powder was put into polymer ionic liquid diluted with N, N-Dimethylformamide (DMF) in an amount of 1mg/mL, and put into an ultrasonic cleaner in an ice bath for ultrasonic treatment for 3 hours. Wherein the high polymer ionic liquid is poly (1-vinyl-3-propylimidazole hexafluorophosphate) (P ([ VPim [ ])]PF6))，P([VPIm]PF6) The concentration in the dilution was 13 mg/mL.
Example 6
The embodiment provides a method for manufacturing a photodetector, which includes the following steps:
first, antimony nanosheets were prepared according to the preparation method in example 5, yielding Sb/P ([ VPIm)]PF6) Nanosheets.
Next, Sb/P ([ VPIm)]PF6) Concentrating the nanosheets to 0.1mg/mL, and then drying the nanosheets on an ITO/PET substrate to form a film to obtain a substrate material with a nanosheet layer, wherein the film forming thickness is 4 micrometers, the length is 0.2cm, and the width is 0.3 cm; and lightly scratching the flexible ITO/PET substrate by a blade with a distance of about 90nm to enable the electrodes to be spaced.
Finally, the base material with the nanosheet layer was sequentially immersed in 0.04mol/L CdCl2Aqueous solution, 0.04mol/L Na2The S aqueous solution, the ultrapure water and the ultrapure water are subjected to circulation repetition for 8 times, wherein the residence time of each time is about 25S.
Example 7
The embodiment provides a method for manufacturing a photodetector, which includes the following steps:
first, antimony nanosheets were prepared according to the preparation method in example 5, yielding Sb/P ([ VPIm)]PF6) Nanosheets.
Next, Sb/P ([ VPIm)]PF6) Concentrating the nanosheets to 0.3mg/mL, and then drying the nanosheets on an ITO/PET substrate to form a film to obtain a substrate material with a nanosheet layer, wherein the film forming thickness is 6 micrometers, the length is 0.3cm, and the width is 0.5 cm; and lightly scratching the flexible ITO/PET substrate by a blade with a knife, and controlling the spacing to be about 110nm so as to enable the electrodes to be spaced.
Finally, the base material with the nanosheet layer was sequentially immersed in 0.06mol/L CdCl2Aqueous solution, 0.06mol/L of Na2The S aqueous solution, the ultrapure water and the ultrapure water are cyclically repeated for 12 times, wherein the residence time of each time is about 35S.
Example 8
The embodiment provides a method for manufacturing a photodetector, which includes the following steps:
first, antimony nanosheets were prepared according to the preparation method in example 5, yielding Sb/P ([ VPIm)]PF6) Nanosheets.
Next, Sb/P ([ VPIm)]PF6) Concentrating the nanosheets to 0.2mg/mL, and then drying the nanosheets on an ITO/PET substrate to form a film to obtain a substrate material with a nanosheet layer, wherein the film forming thickness is 5 micrometers, the length is 0.25cm, and the width is 0.4 cm; and lightly scratching the flexible ITO/PET substrate by a blade with a distance of about 100nm to enable the electrodes to be spaced.
Finally, the base material with the nanosheet layer was sequentially immersed in 0.05mol/L CdCl2Aqueous solution, 0.05mol/L of Na2The retention time of the S aqueous solution, the ultrapure water and the ultrapure water is about 30S each time, and the cycle is repeated for 10 times.
Example 9
The embodiment provides a method for manufacturing a photodetector, which includes the following steps:
first, antimony nanosheets were prepared according to the preparation method in example 4, resulting in Sb/P ([ VPIm ] TFSI) nanosheets.
Secondly, concentrating Sb/P ([ VPIm ] TFSI) nanosheets to 0.2mg/mL, and then drying and forming a film on an ITO/PET substrate to obtain a substrate material with a nanosheet layer, wherein the film forming thickness is 5 micrometers, the length is 0.25cm, and the width is 0.4 cm; and lightly scratching the flexible ITO/PET substrate by a blade with a distance of about 100nm to enable the electrodes to be spaced.
Finally, the base material with the nanosheet layer was sequentially immersed in 0.05mol/L CdCl2Aqueous solution, 0.05mol/L of Na2The retention time of the S aqueous solution, the ultrapure water and the ultrapure water is about 30S each time, and the cycle is repeated for 10 times.
Comparative example 1
This comparative example provides a method of stripping antimony nanosheets, substantially the same as example 5, except that treatment was carried out with DMF alone, without the addition of P ([ VPIm ] PF 6).
Comparative example 2
The present comparative example provides a stripping method of antimony nanosheets, substantially the same as comparative example 1, except that DMF was replaced with 2-butanol.
Comparative example 3
The comparative example provides a stripping method of antimony nanosheets, which is substantially the same as comparative example 1, except that DMF is replaced with an aqueous isopropanol solution, and the volume ratio of isopropanol to water is 4: 1.
Comparative example 4
This comparative example provides a method of stripping antimony nanosheets, substantially the same as comparative example 1, except that DMF was replaced with isopropyl alcohol (IPA).
Comparative example 5
This comparative example provides a method for peeling antimony nanosheet, substantially the same as in example 5, except that the grinding process was carried out using only a mortar, with the total grinding time being unchanged.
Test example 1
The grinding process in the preparation method of example 5 was tested, and the state of the pretreated antimony powder was tested by means of scanning electron microscopy analysis, and the results are shown in fig. 1. In the figure, a and b are antimony powder after grinding by a mortar; c and d are antimony powder after ball milling. It can be seen that the manual grinding inevitably leaves out many large lumps of antimony exceeding 20 microns, which would greatly reduce the efficiency of liquid phase stripping if not cut; the antimony powder after ball milling at low rotation speed has relatively uniform size within about 2 microns, and massive antimony crystals can not be seen almost, so that a good material basis is provided for efficient liquid phase stripping at the back.
Test example 2
The dispersion effect of antimony in examples 4 to 5 and comparative examples 1 to 4 was measured, and the results are shown in fig. 2 and 3. Fig. 2 shows 1 to 6 for comparative example 1, example 5, example 4, comparative example 2, comparative example 3 and comparative example 4 in this order, and the results of the test using a spectrophotometer are shown in b of fig. 2. The concentration-dependent absorption spectra of the antimony nanoplates prepared in example 4 and example 5 were tested and the results are shown in fig. 4.
FIGS. 2a, b show photographs of antimony dispersed in different solvents and their absorbance values at 1000nm, for convenience of description, antimony dispersed in diluted P ([ VPIm)]PF6) And P ([ VPim)]TFSI) was named Sb/P ([ VPIm)]PF6) And Sb/P ([ VPIm)]TFSI)。
Dispersions of antimony are grey, with darker grey representing higher concentrations. The absorbance of antimony dispersed in DMF was 0.039, but P ([ VPIm ] was added to DMF]PF6)，P([VPIm]TFSI) assisted ultrasonic dispersion increased absorbance to 0.65 and 0.53, with the highest absorbance of 0.65 being more than twice the absorbance (0.30) achieved with 2-butanol ultrasonically dispersed antimony, which was 0.21 and 0.06 in IPA water (4:1) and IPA, respectively. Therefore, the effect of dispersing by using the high polymer ionic liquid in the embodiment of the invention is very ideal, and the yield of the antimony nanosheet can be obviously improved.
In the prior art, the absorbance corresponding to the dispersion without ball milling process by adopting DMF, 2-butanol, IPA: water (4:1) and IPA is less than the absorbance corresponding to the prior art. This is due to the inevitable omission of a large number of antimony chunks by manual grinding, and the low rpm ball milling pretreatment process, which results in the reduction of these chunks, greatly improves the utilization of the raw materials for the subsequent sonication.
To obtain the concentration of antimony nanoplates, the molecular extinction coefficient of the PIL modified Sb nanoplates was measured, as in fig. 4. Sb/P ([ VPIm) at a wavelength measured at 700nm]PF6) And Sb/P ([ VPIm)]TFSI) of 3.41Lg respectively-1cm-1And 4.59Lg-1cm-1。Sb/P([VPIm]PF6) In all samplesThe darkest grey colour is exhibited, with concentrations up to 0.20mg mL-1, corresponding to a yield of 20%, to the best of our knowledge, of the liquid phase exfoliation of these antimony nanoplates.
Therefore, the yield of the final antimony nanosheet is remarkably improved by matching the low-rotation-speed ball milling with the high polymer ionic liquid to achieve a good dispersing effect.
Test example 3
Sb/P ([ VPIm ] in test example 5)]PF6) And raman mapping results for bulk Sb are shown in figure 5. FIG. 5 shows bulk Sb crystals and Sb/P ([ VPIm)]PF6) Raman spectrum (excited by laser at 633 nm). By using the main scattering peak from the silicon substrate at 520cm-1The raman calibration standard is fixed. At about 110cm-1And 149cm-1The two peaks at (a) are due to Eg and Alg vibrational modes of the Sb crystal, respectively. In contrast, Sb/P ([ VPIm)]PF6) The two raman peaks of (a) show a blue shift. These changes are due to either shrinkage of the lattice constant or long range coulombic interlayer interactions as the number of layers is reduced. Observed Sb/P ([ VPIm)]PF6) The blue shift of (a) is very consistent with previous reports on few-layer antimony nanoplates, indicating that large blocks of Sb are successfully converted into thin Sb nanoplates under high polymer ionic liquid assisted exfoliation conditions.
The bulk Sb crystals, the ball-milled Sb powders and Sb/P ([ VPIm ] in example 5 were tested]PF6) The X-ray diffraction (XRD) pattern of (a) in fig. 6; bulk antimony and Sb/P ([ VPIm ] testing in example 5]PF6), as shown in fig. 6 b. Bulk Sb crystals, Sb/P ([ VPIm "), of example 4 were tested]TFSI), XPS spectra of antimony sonicated in water, see a, b and c in figure 7, respectively.
To study the crystal structures of bulk Sb, Sb powder and antimony nanoplates after ball milling, we performed XRD tests, and the results are shown in fig. 6 a. Notably, the ball-milled Sb powder gave nearly the same XRD pattern as the antimonene, with the (003) plane (corresponding peak at 23.78) of the antimony nanoplatelets being negligible compared to the bulk Sb crystals, indicating that we successfully obtained Sb nanoplatelets. FIG. 6b is Sb/P ([ VPIm ]]PF6) was analyzed by X-ray photoelectron spectroscopy (XPS). The results of the fitting analysis showed that Sb/P ([ VPIm)]PF6) Sb 3d (5/2 and 3/2) peaks of (C)Can be decomposed into five peaks. For bulk Sb, there is a significant proportion of oxide; these may be formed during storage and pre-treatment prior to XPS analysis. In contrast to the XPS spectrum of bulk Sb shown in FIG. 7a, Sb/P ([ VPIm ]]PF6) With lower Sb0Oxides (Sb) in higher and higher contents2O3And Sb2O5) And (4) content. This is mainly because the obtained antimony nanosheets had few layers and a large specific surface area, which also indicates successful exfoliation of the antimony nanosheets.
Test example 4
Sb/P ([ VPIm ] in test example 5)]PF6) Transmission Electron Microscope (TEM) image, high resolution TEM (hrtem) image (inset: corresponding selected area electron diffraction pattern), AFM images. The results are shown in FIG. 8, where a denotes Sb/P ([ VPIm ]]PF6) Transmission Electron Microscope (TEM) images of (a); b represents Sb/P ([ VPIm ]]PF6) A high resolution TEM image of (a); c and d represent Sb/P ([ VPIm)]PF6) AFM imaging of (1). (inset: corresponding height profile).
AFM images of Sb/P ([ VPIm ] PF6) in example 5 were tested and the results are shown in FIG. 9 (inset: corresponding height profile).
To study Sb/P ([ VPIm)]PF6) We tested Transmission Electron Microscopy (TEM), High Resolution Transmission Electron Microscopy (HRTEM) and Selected Area Electron Diffraction (SAED) of the samples. FIG. 8a is Sb/P ([ VPIm)]PF6) The obtained trans-naphthalene was confirmed to have a good crystal structure with a lateral size of more than 1 μm by TEM image of (a). FIG. 8b is Sb/P ([ VPIm ]]PF6) HRTEM image of (inset is corresponding SAED pattern). The resulting d-spacing of (100) was measured to be 0.23nm, consistent with the results previously reported. Sb/P ([ VPIm ] can be deduced]PF6) With a diamond-shaped structure (rim [001 ]]The tape axis is observed as the beta phase) rather than the orthorhombic structure (alpha phase). Atomic Force Microscopy (AFM) was also used to determine the thickness of the obtained antimony nanoplatelets. FIGS. 8c, d and 9 show Sb/P ([ VPIm ]]PF6) AFM imaging of (1). To ensure removal of all excess PIL, the samples were washed three times with DMF prior to AFM measurements. Notably, the lateral dimensions of the resulting antimony nanoplates are again demonstrated to be micro from fig. 8c, dRice grade. Contour analysis showed Sb/P ([ VPIm)]PF6) The thickness of the nanoplatelets varies between 2.2 and 5.1nm, corresponding to about 6 to 14 layers, assuming a thickness of about 0.37nm for the monolayer Sb. In conclusion, we succeeded in obtaining antimony nanoplates with few layers, with good crystal structure and lateral dimensions on the micrometer scale.
Test example 5
FIG. 10a is a schematic diagram of a photodetector prepared in example 8, and FIG. 10b is Sb/P ([ VPIm ]]PF6) /CdS, pure CdS and Sb/P ([ VPIm)]PF6) Raman spectroscopy of devices of thin films. In FIG. 11, a is Sb/P ([ VPIm)]PF6) the/CdS, b is a pure CdS film device, and c is an SEM image of the cross section of the device.
As shown in FIG. 10a, the flexible indium tin oxide/polyethylene terephthalate (ITO/PET) substrate has a width of about 0.4cm and a length of about 2 cm. Concentrated Sb/P ([ VPIm ]]PF6) The nano-sheet is directly centrifugally cast on an ITO/PET substrate to obtain a uniform thin film, Sb/P ([ VPIm)]PF6) The film was on top of the ITO electrode with a gap ≈ 100 microns. A Sb layer of 0.05cm was exposed above the surface of the subsequent S-CBD solution.
FIG. 10b shows the successful deposition of CdS on Sb/P ([ VPIm)]PF6) On the layer. The active layer topography of the device can be seen in fig. 11. Surface SEM images (fig. 11a) show that CdS grows uniformly on antimony nanosheets, whereas CdS alone is easily aggregated (fig. 11 b). The thickness of the active layer can be obtained from a cross-sectional SEM image (FIG. 11c) with an average of about 5 μm.
Test example 6
The performance of the photodetector prepared in example 8 was tested, including photocurrent density, I-V characteristic curve, photocurrent density when bent at different curvatures, stability, and the like. The results are shown in FIG. 12, where in FIG. 12: a represents the photocurrent density; b represents an I-V characteristic curve; c represents the photocurrent density at different curvature bends; d represents the stability test. In fig. 13, a represents the photocurrent density at different potentials; b represents an I-V characteristic curve; c represents the stability test. FIG. 14A shows an I-V characteristic curve; b represents the stability test.
Analysis of FIGS. 12-14: FIG. 12a showsSb/P ([ VPIm ] under different biases]PF6) Photocurrent response of a/CdS flexible photodetector device, wherein the power intensity of the light source is maintained at about 20mW cm-2. The photocurrent density increased with increasing bias voltage, about 20nA cm at 0V bias-2Increased to 160nA cm at 3V-2. At 1V bias, the switching ratio of the flexible photodetector is 26.8. As shown in fig. 12 b. Sb/P ([ VPIm ] at a bias potential of 3V]PF6) Responsivity of/CdS flexible photoelectric detector is 10 mu AW-1. For comparison, microns also measure pure CdS and pure Sb/P ([ VPIm)]PF6) The performance of the flexible photodetector is shown in fig. 13 and 14. In fig. 13a, the current of a pure CdS based flexible photodetector suddenly rises and falls when light suddenly appears and disappears. Because of its non-central symmetry as a thermoelectric material, CdS will generate transient potentials at both extremes from induced thermoelectric polarization charges (thermal charges) when suddenly heated or cooled by light irradiation. However, in the Sb/P based ([ VPIm ]]PF6) This phenomenon is not observed in the flexible photodetector for/CdS, which also demonstrates that CdS has been successfully compared to Sb/P ([ VPIm)]PF6) And (4) compounding. When the I-V curves of the CdS-based photoelectric detector devices are compared, the switching ratio of the pure CdS-based flexible photoelectric detector device under the bias voltage of 1V is 9.4, and is only one third of that of a composite film device. In addition, based on Sb/P ([ VPIm)]PF6) The switch of the flexible photodetector device of (1) is relatively small, which shows that CdS mainly plays a role in light absorption in the hybrid device.
An important feature of the flexible photodetector is flexibility, so we tested the stability of the Sb/P ([ VPIm ] PF6)/CdS flexible photodetector in various bending states, as shown in fig. 12 c. The inset photo shows the corresponding degree of bending of the flexible photodetector. The high-concentration antimony nanosheet with a proper band gap has excellent mechanical flexibility; the high polymer ionic liquid wrapping layer of the antimony nanosheet provides good material to contact with the electrode; and the Sb nanosheets provide a flat substrate for the proper distribution of CdS quantum dots. The photodetector is hardly affected by the external bending stress.
For practical applications, long-term stability is a key parameter for determining the lifetime of a flexible photodetector. Thus, Sb/P ([ VPIm ] was tested]PF6) Stability of the/CdS flexible photodetector, as shown in FIG. 12 d. The photocurrent density decreased only by less than 10% after 15 days of exposure to the ambient environment. Moreover, the photocurrent density remained almost unchanged for experimental times exceeding 160 s. However, a large drop (over 80%) in photocurrent density occurred compared to the performance of the pure CdS based flexible photodetector (fig. 13 c). In a single test, the photocurrent intensity of the pure CdS-based flexible photoelectric detector is reduced by nearly 40%, which indicates that the stability of the pure CdS-based flexible photoelectric detector is poor. Thus, Sb/P ([ VPIm)]PF6) And the recombination of the CdS quantum dots remarkably improves the photocurrent density and the stability of the device.
Test example 7
The inventors tested Sb/P ([ VPIm ]]PF6) The working mechanism of the flexible photodetector of/CdS is speculated, and the result is shown in FIG. 15. Based on the above experimental results in combination with the analysis of the antimony and cadmium sulfide energy bands, FIG. 15 shows a graph based on Sb/P ([ VPIm)]PF6) The working mechanism of the flexible photoelectric detector of/CdS is schematic. Under visible light illumination with energy matching the band gap of the active layer, the main energy absorbed is CdS quantum dots. We speculate that Sb/P ([ VPIm)]PF6) Can be used as a hole transport layer, so that holes left from the valence band of CdS under light excitation can effectively move to Sb/P ([ VPIm)]PF6) The surface of the layer. Thereby inhibiting the photo-corrosion of CdS and enhancing Sb/P ([ VPIm)]PF6) Stability of the CdS layer. Further, Sb/P ([ VPIm ] is formed by this hole transport process]PF6) The layer mainly transports holes, while the CdS layer mainly transports electrons, thereby improving the photocurrent response of the device.
In conclusion, the stripping method for the antimony nanosheets provided by the invention adopts the two high polymer ionic liquids provided by the invention to dilute and then serve as the liquid-phase stripping liquid, and the antimony nanosheets subjected to ultrasonic treatment have high yield and good market application prospects. The nanosheet prepared by the method for stripping antimony nanosheet is Sb/P ([ VPIm)]PF6) Nanosheets or Sb/P ([ VPIm)]TFSI) nanosheets, which can be applied to the preparation of photodetectors.
The embodiment of the invention providesThe preparation method of the photodetector comprises the steps of preparing Sb/P ([ VPIm ] by the stripping method of the antimony nanosheets]PF6) Nanosheets or Sb/P ([ VPIm)]TFSI) nano-sheet, and then compounding the nano-sheet and cadmium sulfide quantum dots to form the photodetector, which is a flexible photodetector. The flexible photodetector provided by the embodiment of the invention is prepared by the preparation method of the photodetector, and is prepared by Sb/P ([ VPIm)]PF6) and CdS quantum dots remarkably improve the photocurrent density and stability of the device.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention 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 given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (12)

1. A method for stripping antimony nanosheets is characterized by comprising the following steps:
mixing antimony powder with liquid-phase stripping liquid, and performing ultrasonic treatment for 2-4 h;
the liquid-phase stripping solution is a mixture of a diluent and a high polymer ionic liquid, the diluent is an oily solvent, and the high polymer ionic liquid is poly (1-vinyl-3-propylimidazole hexafluorophosphate) and/or poly (1-vinyl-3-propylimidazole bistrifluoromethanesulfonylimide); the diluent is at least one selected from N-methyl pyrrolidone, dichloromethane, ethyl acetate, petroleum ether and N, N-dimethylformamide; the antimony powder is prepared by grinding antimony crystals for 5-15min and then ball-milling for 2-4 h;
the dosage of the antimony powder is that 0.5-2mg of the antimony powder is added into each milliliter of the liquid-phase stripping solution, the concentration of the poly-1-vinyl-3-propylimidazole hexafluorophosphate in the diluent is 12-14mg/mL, and the concentration of the poly-1-vinyl-3-propylimidazole bistrifluoromethanesulfonimide in the diluent is 7-8 mg/mL.
2. The method of stripping antimony nanosheets as recited in claim 1, wherein the diluent is N, N-dimethylformamide.
3. The method for stripping antimony nanosheets as claimed in claim 1, wherein the amount of antimony powder used is 0.7-1.2mg per ml of the liquid-phase stripping solution.
4. The method for stripping antimony nanosheets as recited in claim 1, wherein the rotation speed during the ball milling process is 450-550 rpm.
5. Antimony nanosheet produced by the method for exfoliation of antimony nanosheets as defined in any one of claims 1 to 4, wherein the antimony nanosheet is Sb/P ([ VPIm)]PF6) Nanosheets or Sb/P ([ VPIm)]TFSI) nanosheets.
6. A method of making a photodetector, comprising the steps of:
preparation of nanosheets to be processed according to the method for exfoliation of antimony nanosheets according to any one of claims 1 to 4, the nanosheets to be processed being Sb/P ([ VPIm)]PF6) Nanosheets or Sb/P ([ VPIm)]TFSI) nanoplatelets;
and compounding the nanosheet to be processed with the cadmium sulfide quantum dot.
7. The method for preparing the photodetector according to claim 6, wherein the process of compounding the nanosheet to be processed with the cadmium sulfide quantum dot comprises the steps of:
concentrating the nano sheet to be processed to 0.1-0.3mg/mL, and then drying the nano sheet on a substrate film to form a film to obtain a substrate material with a nano sheet layer;
and compounding cadmium sulfide quantum dots on the substrate material with the nanosheet layer by a sequential chemical bath deposition method.
8. The method for preparing the photodetector according to claim 7, wherein the substrate film is an ITO/PET substrate, the film thickness of the nanosheet to be processed is 4-6 μm, and the electrode spacing is 90-110 nm.
9. The method of claim 7, wherein the step of compositing the cadmium sulfide quantum dots on the nanosheet layer of the base material comprises: sequentially immersing the substrate material with the nanosheet layer into four different vessels, wherein the residence time of each vessel is 25-35 s; wherein the first vessel is filled with CdCl2The aqueous solution is filled with Na in a second vessel2And the water solution of S is filled in the third vessel and the fourth vessel.
10. The method of claim 9, wherein the CdCl is present in the composition2An aqueous solution and the Na2The concentration of the S aqueous solution is 0.04-0.06 mol/L.
11. The method of claim 10, wherein the dipping of the nanosheet layer of substrate material into four different vessels in sequence is repeated 8-12 times.
12. A flexible photodetector produced by the method for producing a photodetector according to any one of claims 6 to 11.
CN201811528364.1A 2018-12-13 2018-12-13 Antimony nanosheet and stripping method thereof, and flexible photodetector and preparation method thereof Active CN109648095B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811528364.1A CN109648095B (en) 2018-12-13 2018-12-13 Antimony nanosheet and stripping method thereof, and flexible photodetector and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811528364.1A CN109648095B (en) 2018-12-13 2018-12-13 Antimony nanosheet and stripping method thereof, and flexible photodetector and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109648095A CN109648095A (en) 2019-04-19
CN109648095B true CN109648095B (en) 2021-12-14

Family

ID=66114026

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811528364.1A Active CN109648095B (en) 2018-12-13 2018-12-13 Antimony nanosheet and stripping method thereof, and flexible photodetector and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109648095B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112808994A (en) * 2019-11-15 2021-05-18 南京理工大学 Preparation method of antimony nanosheet
CN111644636B (en) * 2020-06-12 2022-09-30 陕西师范大学 Method for synthesizing antimony nanosheet in controllable manner through high-temperature liquid phase
CN112008086B (en) * 2020-08-25 2022-11-29 沈阳航空航天大学 Antimonene nanosheet effectively stripped through physical modification and preparation method thereof
CN112679801A (en) * 2020-12-15 2021-04-20 中国科学院理化技术研究所 Organic silicon functionalized antimonene nanosheet and preparation method and application thereof
CN113333736B (en) * 2021-05-10 2023-07-14 武汉理工大学 Antimoney based on microwave stripping and preparation method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2597112A1 (en) * 2011-11-25 2013-05-29 The Provost, Fellows, Foundation Scholars, & the other members of Board, of the College of the Holy & Undiv. Trinity of Queen Elizabeth near Dublin Process for producing a composite product by combination of solution and melt processing
CN103130212A (en) * 2011-11-30 2013-06-05 李汶军 Preparation method of graphene
CN107416784B (en) * 2016-12-29 2020-05-26 深圳大学 Two-dimensional black phosphorus nanosheet and liquid-phase stripping preparation method thereof
CN107055496A (en) * 2017-01-12 2017-08-18 昆明理工大学 A kind of magnanimity preparation method of phosphorus alkene
CN107243642B (en) * 2017-06-20 2019-02-22 太原理工大学 The method for preparing antimony alkene using ionic liquid auxiliary
CN108550640B (en) * 2018-04-17 2020-02-28 张晗 Cadmium telluride nanocrystalline composite broadband black phosphorus photoelectric detector and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Advanced applications of ionic liquids in polymer science;Jianmei Lua 等;《Progress in Polymer Science》;20090113;第34卷(第5期);第432-448页 *

Also Published As

Publication number Publication date
CN109648095A (en) 2019-04-19

Similar Documents

Publication Publication Date Title
CN109648095B (en) Antimony nanosheet and stripping method thereof, and flexible photodetector and preparation method thereof
Li et al. Application of nanostructured TiO2 in UV photodetectors: A review
Wang et al. Broadband photodetectors based on 2D group IVA metal chalcogenides semiconductors
Baturay et al. Modification of electrical and optical properties of CuO thin films by Ni doping
Liu et al. Non-planar vertical photodetectors based on free standing two-dimensional SnS 2 nanosheets
Salim et al. Electrical conductivity inversion for Nb2O5 nanostructure thin films at different temperatures
Makableh et al. Enhancement of GaAs solar cell performance by using a ZnO sol–gel anti-reflection coating
Zhu et al. High photoresponse sensitivity of lithium-doped ZnO (LZO) thin films for weak ultraviolet signal photodetector
Li et al. High detectivity photodetectors based on perovskite nanowires with suppressed surface defects
Shafique et al. Improving the performance of V2O5/rGO hybrid nanocomposites for photodetector applications
Karyaoui et al. Physical properties of graphene oxide GO-doped ZnO thin films for optoelectronic application
Shirazi et al. Influence of doping behavior of Al on nanostructure, morphology and optoelectronic properties of Al Doped ZnO thin film grown on FTO substrate
Aal et al. Nanostructure lanthanum doped zinc oxide optical materials
Vivek et al. Fabrication of Cu/Y-MoO3/p-Si type Schottky barrier diodes by facile spray pyrolysis technique for photodetection application
Huang et al. Chemical vapor deposition growth of nonlayered γ-In2Se3 nanosheets on SiO2/Si substrates and its photodetector application
You et al. Manipulation of ferroelectric polarization and light absorption in non-noble metal/Aurivillius ferroelectric hybrid to enhance self-driven photodetection by coupling ferro-pyro-phototronic and plasmonic effect
Sheng et al. Effect of graphene-doping and vacuum-annealing on the structure and properties of In: ZnO thin films
Ismail et al. Improved growth conditions of pulsed laser-deposited PbI2 nanostructure film: towards high-photosensitivity PbI2/CNTs/Si photodetectors
Wang et al. Ultrasensitive photodetector based on 2D WS2/AgInGaS quantum dots heterojunction with interfacial charge transfer
Xu et al. An ultra-flexible silicon substrate with light-trapping structures: The application for visible-NIR photodetectors
Ali et al. Pulse laser deposition of HfO2 nanoporous-like structure, physical properties for device fabrication
Yao et al. Enhanced photoresponse of graphene oxide functionalised SnSe films
Sun et al. Enhanced performance in perovskites films by defect engineering and charge carrier transportation via pulsed laser doping of 2D MoS2
Huang et al. Solution-Processed UV Photodiodes Based on Cs2Ag0. 35Na0. 65InCl6 Perovskite Nanocrystals
Arab et al. Effect of the annealing process on the properties of ZnO thin films prepared by the sol-gel method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant