CN111029419B - Full-transparent flexible ultraviolet light response switch and preparation method thereof - Google Patents

Full-transparent flexible ultraviolet light response switch and preparation method thereof Download PDF

Info

Publication number
CN111029419B
CN111029419B CN201911364558.7A CN201911364558A CN111029419B CN 111029419 B CN111029419 B CN 111029419B CN 201911364558 A CN201911364558 A CN 201911364558A CN 111029419 B CN111029419 B CN 111029419B
Authority
CN
China
Prior art keywords
gallium
titanium
nano
direct writing
solution
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
CN201911364558.7A
Other languages
Chinese (zh)
Other versions
CN111029419A (en
Inventor
胡三元
吴志能
张军
廖添
彭果戈
夏振宇
任奕菲
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.)
Dongguan HEC Tech R&D Co Ltd
Original Assignee
Dongguan HEC Tech R&D Co Ltd
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 Dongguan HEC Tech R&D Co Ltd filed Critical Dongguan HEC Tech R&D Co Ltd
Priority to CN201911364558.7A priority Critical patent/CN111029419B/en
Publication of CN111029419A publication Critical patent/CN111029419A/en
Application granted granted Critical
Publication of CN111029419B publication Critical patent/CN111029419B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • 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
    • H01L31/0352—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • H01L31/035209—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
    • 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
    • H01L31/09—Devices sensitive to infrared, visible or ultraviolet radiation
    • 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
    • H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
    • H01L31/1852—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising a growth substrate not being an AIIIBV compound
    • 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
    • H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
    • H01L31/1856—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising nitride compounds, e.g. GaN
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Luminescent Compositions (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a fully transparent flexible ultraviolet response switch and a preparation method thereof. The fully transparent flexible ultraviolet light response switch comprises: the surface of the flexible substrate is divided into a first fiber mesh area, a second fiber mesh area and a channel, and the channel is positioned between the first fiber mesh area and the second fiber mesh area; a titanium-containing nanoweb formed on the surface of the flexible substrate and located within the first and second web regions; a plurality of gallium-containing nanofibers formed on the surface of the flexible substrate and attached to the web of titanium-containing nanofibers; the gallium-containing nano-fibers are perpendicular to the channel, and the plurality of gallium-containing nano-fibers are parallel to each other. The fully transparent flexible ultraviolet response switch can meet the requirements of wearable equipment on light weight, flexibility, transparency and the like.

Description

Full-transparent flexible ultraviolet light response switch and preparation method thereof
Technical Field
The invention relates to the field of photoelectric devices, in particular to a fully-transparent flexible ultraviolet response switch and a preparation method thereof.
Background
The rapid development of artificial intelligence places higher demands on wearable devices, including being lightweight, flexible, and transparent, etc. The traditional ultraviolet light response switch device is integrated by a plurality of parts, so that the traditional ultraviolet light response switch device is large in size and inconvenient to carry; the integrated circuit and the components are poor in flexibility and non-transparent, so that when the wearable device is applied to wearable equipment, the rigid equipment is abraded due to long-term movement of limb joints, and the stability of the device is damaged. In addition, when the non-transparent photoelectric device is used as wearable skin, the visual appearance is poor, so that the wearable device cannot be popularized continuously. On the other hand, the traditional photoresponse optical switch device is complex in forming process and multiple in parts, and the complex process inevitably causes a long production period and high production cost.
Thus, existing uv-responsive switches remain to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to provide a fully transparent flexible ultraviolet light responsive switch and a method for manufacturing the same. The fully transparent flexible ultraviolet response switch can meet the requirements of wearable equipment on light weight, flexibility, transparency and the like.
In one aspect of the invention, a fully transparent flexible ultraviolet light responsive switch is provided. According to an embodiment of the present invention, the fully transparent flexible ultraviolet light responsive switch comprises: the surface of the flexible substrate is divided into a first fiber mesh area, a second fiber mesh area and a channel, and the channel is positioned between the first fiber mesh area and the second fiber mesh area; a titanium-containing nanoweb formed on the surface of the flexible substrate and located within the first and second web regions; a plurality of gallium-containing nanofibers formed on the surface of the flexible substrate and attached to the web of titanium-containing nanofibers; the gallium-containing nano-fibers are perpendicular to the channel, and the plurality of gallium-containing nano-fibers are parallel to each other.
According to the fully transparent flexible ultraviolet response switch provided by the embodiment of the invention, the traditional sputtered gold film electrode is replaced by the nano conductive fiber, so that the fully transparent design of the device is realized, the light transmittance in a visible light range exceeds 90%, and the good light transmittance is shown. Meanwhile, the device has good flexibility and can still normally work after being bent; in addition, the device has a planar structure, and is smaller in size and lighter in weight compared with a traditional optical switch device. In the fully transparent flexible ultraviolet response switch, the titanium-containing nanofiber net is formed by regularly arranging titanium-containing nanofibers, has excellent conductivity, can replace gold-plated electrodes in the traditional optical switch device, and realizes the transparentization of the surface electrodes of the device. The gallium-containing nano-fiber has an ultraviolet response effect, and when the gallium-containing nano-fiber is irradiated by ultraviolet light, photogenerated carriers in the gallium-containing nano-fiber are increased, and the current of the gallium-containing nano-fiber is increased under a certain bias. The high current can be passed through by matching with a high-pass current circuit, and an output signal is generated, namely the output signal corresponds to the state of 'on' or '1'; when no ultraviolet light is irradiated, the current in the gallium-containing nano fiber is reduced, the gallium-containing nano fiber cannot pass through a circuit, and no output signal exists, namely, the gallium-containing nano fiber corresponds to the state of off or 0, so that the ultraviolet light switch function of the device can be realized.
In addition, the fully transparent flexible ultraviolet light response switch according to the above embodiment of the present invention may further have the following additional technical features:
according to some embodiments of the invention, the titanium-containing nanoweb is formed of TiN.
According to some embodiments of the invention, the gallium-containing nanofibers are formed of GaN.
According to some embodiments of the invention, the diameter of the titanium-containing nanofibers in the titanium-containing nanofiber web and the diameter of the gallium-containing nanofibers are each independently 0.5 to 2 μm, such as 0.5 μm, 1 μm, 1.5 μm, 2 μm, and the like. Thus, the diameter of the nanofibers is much smaller than the size (about 20 μm) that can be recognized by the human eye. By controlling the diameter of the titanium-containing nanofibers and the diameter of the gallium-containing nanofibers in the titanium-containing nanofiber web to be within the above ranges, the light transmittance of the device can be further improved.
According to some embodiments of the invention, the width of the channel is 150 to 250 μm, such as 150 μm, 175 μm, 200 μm, 225 μm, 250 μm, and the like. Here, the width of the channel refers to the width of the channel in the longitudinal direction.
In another aspect of the present invention, the present invention provides a method of manufacturing the fully transparent flexible uv-responsive switch of the above embodiment. According to an embodiment of the invention, the method comprises: (1) mixing a titanium source, a high-molecular polymer and a solvent to obtain a titanium source precursor solution; mixing a gallium source, a high-molecular polymer and a solvent to obtain a gallium source precursor solution; (2) forming a titanium-containing precursor nano-fiber net in a first fiber net area and a second fiber net area on the surface of the flexible substrate by using the titanium source precursor liquid through a near-field direct writing process; forming gallium-containing precursor nano-fibers vertical to the flexible substrate channel on the surface of the flexible substrate by using the gallium source precursor liquid through a near-field direct writing process; (3) and (3) sequentially carrying out oxidation treatment and nitridation treatment on the product obtained in the step (2) to obtain the fully transparent flexible ultraviolet response switch.
According to the method for preparing the fully transparent flexible ultraviolet response switch, the precursor nanofiber is formed on the surface of the flexible substrate by using the titanium source precursor liquid and the gallium source precursor liquid through a near-field direct writing process, and the position of the nanofiber can be accurately regulated and controlled. And then, further combining oxidation treatment and nitridation treatment, and forming in situ on the surface of the flexible substrate to obtain the titanium-containing nanofiber web and a plurality of gallium-containing nanofibers, so that the forming process and the production cost of the optical switch device can be greatly simplified, and the prepared fully-transparent flexible ultraviolet response switch can meet the requirements of wearable equipment on light weight, flexibility, transparency and the like. Specifically, in the method, after the nano-fibers with the preset patterns or the arrangement shapes are formed on the surface of the flexible substrate through the near-field direct writing process, the titanium source can be converted into TiO through oxidation treatment2Converting the gallium source to Ga2O3And nitriding the TiO2Conversion to TiN, Ga2O3And converting into GaN, thereby completing the preparation of the device.
In addition, the method for manufacturing the fully transparent flexible ultraviolet light response switch according to the above embodiment of the present invention may further have the following additional technical features:
according to some embodiments of the invention, the titanium source comprises at least one selected from titanium tetrachloride, titanium sulfate, titanyl difluorosulfate, titanium isopropoxide, tetrabutyl titanate. The titanium source has good solubility and can form stable titanium-containing sol-gel precursor liquid.
According to some embodiments of the invention, the gallium source comprises at least one selected from the group consisting of gallium sulfate, gallium nitrate, gallium chloride. The gallium source has good solubility and can form stable sol-gel precursor liquid containing gallium.
According to some embodiments of the invention, the high molecular polymer comprises at least one selected from polyvinylpyrrolidone, polyacrylonitrile, polypyrrole, polyvinyl alcohol, and polyvinylidene fluoride.
According to some embodiments of the invention, the solvent comprises at least one selected from the group consisting of ethanol, ethylene glycol, N-butanol, acetic acid, N-dimethylformamide, water.
The solvent may be selected according to the nature of the titanium source or the gallium source.
In some embodiments, when the titanium source is tetrabutyl titanate, the solvent is a mixture of ethanol and acetic acid, and the acetic acid can inhibit hydrolysis of the tetrabutyl titanate.
According to some embodiments of the invention, in the preparation of the gallium source precursor, the solvent is a mixture of ethanol, ethylene glycol, N-butanol, acetic acid or N, N-dimethylformamide and water.
In some embodiments, in the preparation of the gallium source precursor, the solvent is a mixed solution of ethanol and water.
The water is deionized water.
According to some embodiments of the invention, the titanium source, the high molecular polymer and the solvent are mixed according to a mass ratio of (15-30): 10-20): 50-80. Specifically, the mass fraction of the titanium source may be 15, 20, 25, 30, etc., the mass fraction of the high molecular polymer may be 10, 15, 20, etc., and the mass fraction of the solvent may be 50, 55, 60, 65, 70, 75, 80, etc.
According to some embodiments of the invention, the gallium source, the high molecular polymer and the solvent are mixed according to a mass ratio of (15-30): (10-20): 50-80). Specifically, the gallium source may be 15, 20, 25, 30, etc. in parts by mass, the high molecular polymer may be 10, 15, 20, etc. in parts by mass, and the solvent may be 50, 55, 60, 65, 70, 75, 80, etc. in parts by mass.
According to some embodiments of the invention, the process parameters of the near-field direct write process comprise: the direct writing distance is 0.5-3 mm, and the direct writing voltage is 0.5-3 kV. Specifically, the direct writing distance may be 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, or the like, and the direct writing voltage may be 0.5kV, 1kV, 1.5kV, 2kV, 2.5kV, 3kV, or the like. Therefore, the method can be further beneficial to the precise regulation and control of the micro distribution structure of the nano fiber by the near-field direct writing process.
In some embodiments, the process parameters of the near-field direct write process include: the direct writing distance is 0.5-1.5 mm, and the direct writing voltage is 1.0-2.0 kV.
According to some embodiments of the invention, the process parameters of the near-field direct write process include: the solution extrusion rate is 1-5 mL/h, the needle point inner diameter is 0.06-0.6 mm, and the collector moving speed is 5-200 mm/s. Specifically, the solution extrusion rate may be 1mL/h, 2mL/h, 3mL/h, 4mL/h, 5mL/h, etc., the inner diameter of the needle tip may be 0.06mm, 0.12mm, 0.24mm, 0.36mm, 0.48mm, 0.6mm, etc., and the collector moving speed may be 5mm/s, 20mm/s, 60mm/s, 100mm/s, 150mm/s, 200mm/s, etc. Therefore, the method can be further beneficial to the precise regulation and control of the micro distribution structure of the nano fiber by the near-field direct writing process. The inventor finds in research that if the solvent extrusion rate adopted by the near-field direct writing process is too fast or the inner diameter of the needle tip is too large, the diameter of the subsequently prepared nano-fiber is too large, and the light transmittance of the device is affected.
In some embodiments, the process parameters of the near-field direct write process include: the solution extrusion rate is 1-5 mL/h, the needle point inner diameter is 0.06-0.15 mm, and the collector moving speed is 50-150 mm/s.
According to some embodiments of the invention, the oxidation treatment is performed at 400 to 700 ℃ for 2 to 4 hours. Specifically, the treatment temperature may be 400 ℃, 500 ℃, 600 ℃, 700 ℃ and the like, and the treatment time may be 2 hours, 3 hours, 4 hours and the like. Thereby, the titanium source in the nanofiber can be efficiently convertedConversion to TiO2Converting a gallium source to Ga2O3。
According to some embodiments of the invention, the temperature rise rate used in the oxidation treatment is 5 to 10 ℃/min, for example: 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min.
According to some embodiments of the invention, the nitriding is performed at 600 to 1200 ℃ for 2 to 4 hours. Specifically, the treatment temperature may be 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃ and the like, and the treatment time may be 2h, 3h, 4h and the like. Thus, TiO in the nanofiber can be effectively reduced2Conversion into TiN, Ga2O3Converted to GaN.
In some embodiments, the temperature of the nitriding treatment is 800 to 1000 ℃.
According to some embodiments of the present invention, the temperature increase rate used in the nitridation process is 5-10 ℃/min, for example: 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min.
According to some embodiments of the invention, the nitrogen source used in the nitriding process comprises at least one selected from nitrogen gas and ammonia gas.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic diagram of a near-field direct-write apparatus employed in an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a fully transparent flexible ultraviolet light response switch in an embodiment of the present invention, where a is a schematic structural diagram of a precursor nanofiber arranged by a near-field direct writing method; b is a field emission scanning electron microscope picture of the TiN-GaN fully transparent optical switch device after heat treatment;
FIG. 3 is an elemental spectrum analysis plot of TiN nanofibers and GaN nanofibers in a fully transparent flexible UV-responsive switch in an embodiment of the present invention;
FIG. 4 is a current-time curve for a fully transparent flexible UV-responsive switch under different light source conditions in an embodiment of the present invention;
fig. 5 is an illustration of the flexibility of a fully transparent flexible ultraviolet light responsive switch in an embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present invention, unless otherwise expressly stated or limited, the terms "connected," "secured," and the like are to be construed broadly and can include, for example, fixed connections, removable connections, or integral connections; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1:
the preparation process of the TiN-GaN fully transparent flexible optical switch device comprises the following steps:
first, a sol-gel precursor solution is prepared. Dissolving 3g of tetrabutyl titanate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of acetic acid, and stirring until the tetrabutyl titanate and the polyvinylpyrrolidone are fully dissolved for later use, wherein the mark is a solution a. Dissolving 3g of gallium nitrate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of deionized water, and stirring until the gallium nitrate and the polyvinylpyrrolidone are sufficiently dissolved, wherein the solution is marked as solution b.
Then, the solution a is transferred to a near-field direct writing device shown in fig. 1, and the near-field direct writing parameters are set as follows: the direct writing distance is 1.2mm, the direct writing voltage is 1.0kV, the solution extrusion rate is 3mL/h, the needle point inner diameter is 0.08mm, the collector moving speed is 100mm/s, and the mica sheet is used as a flexible substrate to carry out near-field direct writing, so that the titanium-containing precursor nano-fiber web with the regular grid structure and the channel width of 200 mu m shown in the schematic diagram 2(a) can be obtained, and then the near-field direct writing solution b can be used for parallelly arranging gallium-containing precursor nano-fibers in the direction vertical to the channel. (in FIG. 1, 11 is a power supply, 12 is a precursor liquid, 13 is a collector, and 14 is a biaxial slide).
Finally, placing the precursor nanofiber in an air furnace for calcination and oxidation, wherein the temperature is 500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2 h; and then transferring the nano-fiber to an ammonia gas atmosphere for calcination and nitridation at the temperature of 1000 ℃, at the heating rate of 5 ℃/min and at the heat preservation time of 2h to obtain the nano-fiber arrangement SEM image shown in the figure 2 (b). After calcination, the diameter of the nanofiber is about 0.5-2 μm, the nanofiber cannot be identified by naked eyes, and the device is in a transparent state. The nano-fiber grid structure and the parallel arrangement structure still keep complete, and the nano-fibers are in a highly regular arrangement state and show good light transmission. (in FIG. 2, 21 is a titanium-containing precursor nanofiber, 22 is a gallium-containing precursor nanofiber, 23 is a TiN nanofiber, and 24 is a GaN nanofiber),
To further characterize the main components of the heat treated fibers, two types of nanofibers were characterized using energy spectroscopy. As shown in fig. 3, it was revealed that the main components of the web of the nanofibers having a lattice-like structure were Ti and N elements, and the main components of the nanofibers aligned in parallel in the channel were Ga and N elements. This indicates that the oxide nanofibers after air calcination were nitrided, resulting in TiN and GaN.
Because the TiN nano-fiber net has excellent conductivity, and the diameter of the nano-fiber is far smaller than the size (20 mu m) which can be identified by naked eyes, the regular nano-fiber net structure prepared by the near-field direct writing process ensures the good light transmittance of the device. Therefore, the TiN nanometer fiber net shows the visible light transmittance higher than 90% (the commercial transparent electrode generally requires the visible light transmittance to be higher than 85%), and the TiN nanometer fiber net plays a role of a symmetrical transparent electrode in a fully transparent optical switch device and replaces a traditional non-transparent metal coating electrode. GaN has a good photoresponse characteristic, and its conductivity increases due to an increase in carrier concentration upon irradiation with ultraviolet light. The device may have an optical switching effect, as a result of an integrated analysis. To this end, the fully transparent photovoltaic device was tested for current-time curves under different light source conditions, as shown in fig. 4. As can be seen from the graph, when a bias voltage of 0.5V was applied across the transparent electrode and irradiated with ultraviolet light having a wavelength of 365nm, the test current increased from about 20nA to 10000nA, showing an extremely high ultraviolet response sensitivity, and the relaxation time was extremely short, so that the current curve with time was close to a square wave shape. With the help of the high-pass current field effect tube, when the ultraviolet light is turned on, the high current has an output signal through the field effect tube, namely the state is '1' or 'on'; when the ultraviolet light is turned off, no output signal is generated when the low current passes through the field effect tube, namely, the state is '0' or 'off'. Therefore, the device has excellent ultraviolet light switching performance.
In addition to excellent ultraviolet light switching performance, the substrate is a mica sheet with good flexibility and light transmission during the forming process, and the prepared nanofiber web cannot be identified by naked eyes, so that the light transmission is higher than 90%. The photoelectric device can still recover and normally work even if the photoelectric device is bent by 180 degrees (see figure 5).
Comprehensive analysis shows that the near-field direct writing technology is adopted as the optical switch forming process for the first time, so that one-step in-situ forming of the optical switch device is realized, and the forming process and the production cost of the optical switch device are greatly simplified; the conductive electrode in the device adopts the transparent conductive nano fiber net to replace the traditional sputtered gold film electrode, so that the full-transparent design of the device is realized; the device with the transparent, flexible and planar film structure is adopted to replace the traditional non-transparent and rigid multi-component integrated optical switch device, and the requirements of light weight, flexibility and transparency required by wearable equipment are met.
Example 2:
the preparation process of the TiN-GaN fully transparent flexible optical switch device comprises the following steps:
first, a sol-gel precursor solution is prepared. Dissolving 3g of tetrabutyl titanate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of acetic acid, and stirring until the tetrabutyl titanate and the polyvinylpyrrolidone are fully dissolved for later use, wherein the mark is a solution a. Dissolving 3g of gallium nitrate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of deionized water, and stirring until the gallium nitrate and the polyvinylpyrrolidone are sufficiently dissolved, wherein the solution is marked as solution b.
Then, the solution a is transferred to a near-field direct writing device shown in fig. 1, and the near-field direct writing parameters are set as follows: the direct writing distance is 1.2mm, the direct writing voltage is 1.5kV, the solution extrusion rate is 3mL/h, the needle point inner diameter is 0.08mm, the collector moving speed is 100mm/s, and the mica sheet is used as a flexible substrate to carry out near-field direct writing, so that the titanium-containing precursor nano-fiber net with the regular grid structure and the channel width of 200 micrometers can be obtained. And then the near-field direct-writing solution b can arrange the gallium-containing precursor nanofibers in parallel in the direction vertical to the channel.
Finally, placing the precursor nanofiber in an air furnace for calcination and oxidation, wherein the temperature is 500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2 h; and then transferring the nano-fiber array to an ammonia atmosphere for calcination and nitridation, wherein the temperature is 1000 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2h, so that the nano-fiber array can be obtained. After calcination, the diameter of the nanofiber is about 0.5-2 μm, the nanofiber cannot be identified by naked eyes, and the device is in a transparent state. The nano-fiber grid structure and the parallel arrangement structure still keep complete, and the nano-fibers are in a highly regular arrangement state and show good light transmission.
Example 3
The preparation process of the TiN-GaN fully transparent flexible optical switch device comprises the following steps: first, a sol-gel precursor solution is prepared. Dissolving 3g of tetrabutyl titanate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of acetic acid, and stirring until the tetrabutyl titanate and the polyvinylpyrrolidone are fully dissolved for later use, wherein the mark is a solution a. Dissolving 3g of gallium nitrate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of deionized water, and stirring until the gallium nitrate and the polyvinylpyrrolidone are sufficiently dissolved, wherein the solution is marked as solution b. Then, the solution a is transferred to a near-field direct writing device shown in fig. 1, and the near-field direct writing parameters are set as follows: the direct writing distance is 1.0mm, the direct writing voltage is 1.5kV, the solution extrusion rate is 3mL/h, the needle point inner diameter is 0.08mm, the collector moving speed is 100mm/s, and the mica sheet is used as a flexible substrate to carry out near-field direct writing, so that the titanium-containing precursor nano-fiber net with the regular grid structure and the channel width of 200 micrometers can be obtained. And then the near-field direct-writing solution b can arrange the gallium-containing precursor nanofibers in parallel in the direction vertical to the channel.
Finally, placing the precursor nanofiber in an air furnace for calcination and oxidation, wherein the temperature is 500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2 h; and then transferring the nano-fiber array to an ammonia atmosphere for calcination and nitridation, wherein the temperature is 1000 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2h, so that the nano-fiber array can be obtained. After calcination, the diameter of the nanofiber is about 0.5-2 μm, the nanofiber cannot be identified by naked eyes, and the device is in a transparent state. The nano-fiber grid structure and the parallel arrangement structure still keep complete, and the nano-fibers are in a highly regular arrangement state and show good light transmission.
Example 4
The preparation process of the TiN-GaN fully transparent flexible optical switch device comprises the following steps:
first, a sol-gel precursor solution is prepared. Dissolving 3g of tetrabutyl titanate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of acetic acid, and stirring until the tetrabutyl titanate and the polyvinylpyrrolidone are fully dissolved for later use, wherein the mark is a solution a. Dissolving 3g of gallium nitrate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of deionized water, and stirring until the gallium nitrate and the polyvinylpyrrolidone are sufficiently dissolved, wherein the solution is marked as solution b.
Then, the solution a is transferred to a near-field direct writing device shown in fig. 1, and the near-field direct writing parameters are set as follows: the direct writing distance is 0.8mm, the direct writing voltage is 1.5kV, the solution extrusion rate is 3mL/h, the needle point inner diameter is 0.08mm, the collector moving speed is 100mm/s, and the mica sheet is used as a flexible substrate to carry out near-field direct writing, so that the titanium-containing precursor nano-fiber net with the regular grid structure and the channel width of 200 micrometers can be obtained. And then the near-field direct-writing solution b can arrange the gallium-containing precursor nanofibers in parallel in the direction vertical to the channel.
Finally, placing the precursor nanofiber in an air furnace for calcination and oxidation, wherein the temperature is 500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2 h; and then transferring the nano-fiber array to an ammonia atmosphere for calcination and nitridation, wherein the temperature is 1000 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2h, so that the nano-fiber array can be obtained. After calcination, the diameter of the nanofiber is about 0.5-2 μm, the nanofiber cannot be identified by naked eyes, and the device is in a transparent state. The nano-fiber grid structure and the parallel arrangement structure still keep complete, and the nano-fibers are in a highly regular arrangement state and show good light transmission.
Example 5
The preparation process of the TiN-GaN fully transparent flexible optical switch device comprises the following steps:
first, a sol-gel precursor solution is prepared. Dissolving 3g of tetrabutyl titanate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of acetic acid, and stirring until the tetrabutyl titanate and the polyvinylpyrrolidone are fully dissolved for later use, wherein the mark is a solution a. Dissolving 3g of gallium nitrate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of deionized water, and stirring until the gallium nitrate and the polyvinylpyrrolidone are sufficiently dissolved, wherein the solution is marked as solution b.
Then, the solution a is transferred to a near-field direct writing device shown in fig. 1, and the near-field direct writing parameters are set as follows: the direct writing distance is 1.2mm, the direct writing voltage is 1.5kV, the solution extrusion rate is 2mL/h, the needle point inner diameter is 0.08mm, the collector moving speed is 100mm/s, and the mica sheet is used as a flexible substrate to carry out near-field direct writing, so that the titanium-containing precursor nano-fiber net with the regular grid structure and the channel width of 200 micrometers can be obtained. And then the near-field direct-writing solution b can arrange the gallium-containing precursor nanofibers in parallel in the direction vertical to the channel.
Finally, placing the precursor nanofiber in an air furnace for calcination and oxidation, wherein the temperature is 500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2 h; and then transferring the nano-fiber array to an ammonia atmosphere for calcination and nitridation, wherein the temperature is 1000 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2h, so that the nano-fiber array can be obtained. After calcination, the diameter of the nanofiber is about 0.5-2 μm, the nanofiber cannot be identified by naked eyes, and the device is in a transparent state. The nano-fiber grid structure and the parallel arrangement structure still keep complete, and the nano-fibers are in a highly regular arrangement state and show good light transmission.
Example 6
The preparation process of the TiN-GaN fully transparent flexible optical switch device comprises the following steps:
first, a sol-gel precursor solution is prepared. Dissolving 3g of tetrabutyl titanate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of acetic acid, and stirring until the tetrabutyl titanate and the polyvinylpyrrolidone are fully dissolved for later use, wherein the mark is a solution a. Dissolving 3g of gallium nitrate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of deionized water, and stirring until the gallium nitrate and the polyvinylpyrrolidone are sufficiently dissolved, wherein the solution is marked as solution b.
Then, the solution a is transferred to a near-field direct writing device shown in fig. 1, and the near-field direct writing parameters are set as follows: the direct writing distance is 1.2mm, the direct writing voltage is 1.5kV, the solution extrusion rate is 4mL/h, the needle point inner diameter is 0.08mm, the collector moving speed is 100mm/s, and the mica sheet is used as a flexible substrate to carry out near-field direct writing, so that the titanium-containing precursor nano-fiber net with the regular grid structure and the channel width of 200 micrometers can be obtained. And then the near-field direct-writing solution b can arrange the gallium-containing precursor nanofibers in parallel in the direction vertical to the channel.
Finally, placing the precursor nanofiber in an air furnace for calcination and oxidation, wherein the temperature is 500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2 h; and then transferring the nano-fiber array to an ammonia atmosphere for calcination and nitridation, wherein the temperature is 1000 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2h, so that the nano-fiber array can be obtained. After calcination, the diameter of the nanofiber is about 0.5-2 μm, the nanofiber cannot be identified by naked eyes, and the device is in a transparent state. The nano-fiber grid structure and the parallel arrangement structure still keep complete, and the nano-fibers are in a highly regular arrangement state and show good light transmission.
Example 7
The preparation process of the TiN-GaN fully transparent flexible optical switch device comprises the following steps:
first, a sol-gel precursor solution is prepared. Dissolving 3g of tetrabutyl titanate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of acetic acid, and stirring until the tetrabutyl titanate and the polyvinylpyrrolidone are fully dissolved for later use, wherein the mark is a solution a. Dissolving 3g of gallium nitrate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of deionized water, and stirring until the gallium nitrate and the polyvinylpyrrolidone are sufficiently dissolved, wherein the solution is marked as solution b.
Then, the solution a is transferred to a near-field direct writing device shown in fig. 1, and the near-field direct writing parameters are set as follows: the direct writing distance is 1.2mm, the direct writing voltage is 1.5kV, the solution extrusion rate is 5mL/h, the needle point inner diameter is 0.08mm, the collector moving speed is 100mm/s, and the mica sheet is used as a flexible substrate to carry out near-field direct writing, so that the titanium-containing precursor nano-fiber net with the regular grid structure and the channel width of 200 micrometers can be obtained. And then the near-field direct-writing solution b can arrange the gallium-containing precursor nanofibers in parallel in the direction vertical to the channel.
Finally, placing the precursor nanofiber in an air furnace for calcination and oxidation, wherein the temperature is 500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2 h; and then transferring the nano-fiber array to an ammonia atmosphere for calcination and nitridation, wherein the temperature is 1000 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2h, so that the nano-fiber array can be obtained. After calcination, the diameter of the nanofiber is about 0.5-2 μm, the nanofiber cannot be identified by naked eyes, and the device is in a transparent state. The nano-fiber grid structure and the parallel arrangement structure still keep complete, and the nano-fibers are in a highly regular arrangement state and show good light transmission.
Example 8
The preparation process of the TiN-GaN fully transparent flexible optical switch device comprises the following steps:
first, a sol-gel precursor solution is prepared. Dissolving 3g of tetrabutyl titanate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of acetic acid, and stirring until the tetrabutyl titanate and the polyvinylpyrrolidone are fully dissolved for later use, wherein the mark is a solution a. Dissolving 3g of gallium nitrate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of deionized water, and stirring until the gallium nitrate and the polyvinylpyrrolidone are sufficiently dissolved, wherein the solution is marked as solution b.
Then, the solution a is transferred to a near-field direct writing device shown in fig. 1, and the near-field direct writing parameters are set as follows: the direct writing distance is 1.2mm, the direct writing voltage is 1.5kV, the solution extrusion rate is 2mL/h, the needle point inner diameter is 0.08mm, the collector moving speed is 100mm/s, and the mica sheet is used as a flexible substrate to carry out near-field direct writing, so that the titanium-containing precursor nano-fiber net with the regular grid structure and the channel width of 200 micrometers can be obtained. And then the near-field direct-writing solution b can arrange the gallium-containing precursor nanofibers in parallel in the direction vertical to the channel.
Finally, placing the precursor nanofiber in an air furnace for calcination and oxidation, wherein the temperature is 500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2 h; and then transferring the nano-fiber array to an ammonia atmosphere for calcination and nitridation, wherein the temperature is 900 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2h, so that the nano-fiber array can be obtained. After calcination, the diameter of the nanofiber is about 0.5-2 μm, the nanofiber cannot be identified by naked eyes, and the device is in a transparent state. The nano-fiber grid structure and the parallel arrangement structure still keep complete, and the nano-fibers are in a highly regular arrangement state and show good light transmission.
Example 9
The preparation process of the TiN-GaN fully transparent flexible optical switch device comprises the following steps:
first, a sol-gel precursor solution is prepared. 1.5g of tetrabutyl titanate and 1.0g of polyvinylpyrrolidone are dissolved in a mixed solvent of 5g of ethanol and 2.5g of acetic acid, and stirred until the solutions are sufficiently dissolved for standby, and the solution is marked as solution a. Gallium nitrate 1.5g and polyvinylpyrrolidone 1.0g were dissolved in a mixed solvent of ethanol 5g and deionized water 2.5g, and the solution was labeled as solution b by stirring until they were sufficiently dissolved.
Then, the solution a is transferred to a near-field direct writing device shown in fig. 1, and the near-field direct writing parameters are set as follows: the direct writing distance is 1.2mm, the direct writing voltage is 1.5kV, the solution extrusion rate is 2mL/h, the needle point inner diameter is 0.08mm, the collector moving speed is 100mm/s, and the mica sheet is used as a flexible substrate to carry out near-field direct writing, so that the titanium-containing precursor nano-fiber net with the regular grid structure and the channel width of 200 micrometers can be obtained. And then the near-field direct-writing solution b can arrange the gallium-containing precursor nanofibers in parallel in the direction vertical to the channel.
Finally, placing the precursor nanofiber in an air furnace for calcination and oxidation, wherein the temperature is 500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2 h; and then transferring the nano-fiber array to an ammonia atmosphere for calcination and nitridation, wherein the temperature is 800 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2h, so that the nano-fiber array can be obtained. After calcination, the diameter of the nanofiber is about 0.5-2 μm, the nanofiber cannot be identified by naked eyes, and the device is in a transparent state. The nano-fiber grid structure and the parallel arrangement structure still keep complete, and the nano-fibers are in a highly regular arrangement state and show good light transmission.
Comparative example 1
For comparison, the preparation process of the TiN-GaN flexible optical switch device is as follows:
first, a sol-gel precursor solution is prepared. Dissolving 3g of tetrabutyl titanate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of acetic acid, and stirring until the tetrabutyl titanate and the polyvinylpyrrolidone are fully dissolved for later use, wherein the mark is a solution a. Dissolving 3g of gallium nitrate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of deionized water, and stirring until the gallium nitrate and the polyvinylpyrrolidone are sufficiently dissolved, wherein the solution is marked as solution b.
Then, the solution a is transferred to a near-field direct writing device shown in fig. 1, and the near-field direct writing parameters are set as follows: the direct writing distance is 1.2mm, the direct writing voltage is 1.5kV, the solution extrusion rate is 6mL/h, the needle point inner diameter is 0.08mm, the collector moving speed is 100mm/s, and the mica sheet is used as a flexible substrate to carry out near-field direct writing, so that the titanium-containing precursor fiber net with the regular grid structure and the channel width of 200 micrometers can be obtained. The near-field direct-write solution b can then align the gallium-containing precursor fibers in parallel in a direction perpendicular to the channel.
Finally, placing the precursor fiber in an air furnace to calcine the sample, wherein the temperature is 500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2 h; and then transferring the fiber array to an ammonia atmosphere for calcination and nitridation, wherein the temperature is 1000 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2h, so that the fiber array can be obtained. After calcination, the fibers had a diameter of about 40 μm and were visually recognizable as a web and parallel aligned fibers on the surface of the device. The fiber grid structure and the parallel arrangement structure still keep complete, and the nano fibers are in a highly regular arrangement state, but the light transmittance is lower than 85%.
Comparative example 2
For comparison, the preparation process of the TiN-GaN flexible optical switch device is as follows:
first, a sol-gel precursor solution is prepared. Dissolving 3g of tetrabutyl titanate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of acetic acid, and stirring until the tetrabutyl titanate and the polyvinylpyrrolidone are fully dissolved for later use, wherein the mark is a solution a. Dissolving 3g of gallium nitrate and 2g of polyvinylpyrrolidone into a mixed solvent of 4g of ethanol and 1g of deionized water, and stirring until the gallium nitrate and the polyvinylpyrrolidone are sufficiently dissolved, wherein the solution is marked as solution b.
Then, the solution a is transferred to a near-field direct writing device shown in fig. 1, and the near-field direct writing parameters are set as follows: the direct writing distance is 1.2mm, the direct writing voltage is 1.5kV, the solution extrusion rate is 5mL/h, the needle point inner diameter is 0.84mm, the collector moving speed is 100mm/s, and the mica sheet is used as a flexible substrate to carry out near-field direct writing, so that the titanium-containing precursor fiber net with the regular grid structure and the channel width of 200 micrometers can be obtained. The near-field direct-write solution b can then align the gallium-containing precursor fibers in parallel in a direction perpendicular to the channel.
Finally, placing the precursor fiber in an air furnace to calcine the sample, wherein the temperature is 500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2 h; and then transferring the fiber array to an ammonia atmosphere for calcination and nitridation, wherein the temperature is 1000 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2h, so that the fiber array can be obtained. After calcination, the fibers had a diameter of about 60 μm and were visually recognizable as a web and parallel aligned fibers on the surface of the device. The fiber grid structure and the parallel arrangement structure still keep complete, and the nano fibers are in a highly regular arrangement state, but the light transmittance is lower than 85%.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (19)

1. A fully transparent flexible ultraviolet light responsive switch, comprising:
the surface of the flexible substrate is divided into a first fiber mesh area, a second fiber mesh area and a channel, and the channel is positioned between the first fiber mesh area and the second fiber mesh area;
a titanium-containing nanoweb formed on the surface of the flexible substrate and located within the first and second web regions;
a plurality of gallium-containing nanofibers formed on the surface of the flexible substrate and attached to the web of titanium-containing nanofibers; the gallium-containing nano-fibers are perpendicular to the channel, and the plurality of gallium-containing nano-fibers are parallel to each other.
2. The fully transparent flexible ultraviolet-responsive switch of claim 1, wherein the titanium-containing nanoweb is formed of TiN.
3. The fully transparent flexible ultraviolet-responsive switch of claim 1, wherein the gallium-containing nanofibers are formed of GaN.
4. The fully transparent flexible ultraviolet-responsive switch according to claim 1, wherein the diameter of the titanium-containing nanofibers in the titanium-containing nanofiber web and the diameter of the gallium-containing nanofibers are each independently 0.5 to 2 μm.
5. The all-transparent flexible ultraviolet-responsive switch according to claim 1, wherein the width of the channel is 150 to 250 μm.
6. A method for preparing the fully transparent flexible ultraviolet light response switch according to any one of claims 1 to 5, comprising:
(1) mixing a titanium source, a high-molecular polymer and a solvent to obtain a titanium source precursor solution; mixing a gallium source, a high-molecular polymer and a solvent to obtain a gallium source precursor solution;
(2) forming a titanium-containing precursor nano-fiber net in a first fiber net area and a second fiber net area on the surface of the flexible substrate by using the titanium source precursor liquid through a near-field direct writing process; forming gallium-containing precursor nano-fibers vertical to the flexible substrate channel on the surface of the flexible substrate by using the gallium source precursor liquid through a near-field direct writing process;
(3) and (3) sequentially carrying out oxidation treatment and nitridation treatment on the product obtained in the step (2) to obtain the fully transparent flexible ultraviolet response switch.
7. The method of claim 6, wherein the titanium source comprises at least one selected from the group consisting of titanium tetrachloride, titanium sulfate, titanyl difluoride, titanium isopropoxide, and tetrabutyl titanate.
8. The method of claim 6, wherein the gallium source comprises at least one selected from the group consisting of gallium sulfate, gallium nitrate, and gallium chloride.
9. The method according to claim 6, wherein the high molecular polymer comprises at least one selected from polyvinylpyrrolidone, polyacrylonitrile, polypyrrole, polyvinyl alcohol, and polyvinylidene fluoride.
10. The method according to claim 6, wherein the solvent comprises at least one selected from the group consisting of ethanol, ethylene glycol, N-butanol, acetic acid, N-dimethylformamide, and water.
11. The method of claim 6, wherein the titanium source, the high molecular polymer, and the solvent are mixed at a mass ratio of (15-30): (10-20): (50-80).
12. The method of claim 6, wherein the gallium source, the high molecular polymer, and the solvent are mixed in a mass ratio of (15-30): (10-20): (50-80).
13. The method of claim 6, wherein the process parameters of the near-field direct write process comprise: the direct writing distance is 0.5-3 mm, and the direct writing voltage is 0.5-3 kV.
14. The method of claim 6, wherein the process parameters of the near-field direct write process comprise: the solution extrusion rate is 1-5 mL/h, the needle point inner diameter is 0.06-0.6 mm, and the collector moving speed is 5-200 mm/s.
15. The method according to claim 6, wherein the oxidation treatment is carried out at 400 to 700 ℃ for 2 to 4 hours.
16. The method according to claim 6, wherein the temperature increase rate used in the oxidation treatment is 5 to 10 ℃/min.
17. The method of claim 6, wherein the nitriding is performed at 600-1200 ℃ for 2-4 hours.
18. The method according to claim 6, wherein the temperature increase rate used in the nitriding treatment is 5 to 10 ℃/min.
19. The method according to claim 6, wherein the nitrogen source used in the nitriding treatment comprises at least one selected from nitrogen gas and ammonia gas.
CN201911364558.7A 2019-12-26 2019-12-26 Full-transparent flexible ultraviolet light response switch and preparation method thereof Active CN111029419B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911364558.7A CN111029419B (en) 2019-12-26 2019-12-26 Full-transparent flexible ultraviolet light response switch and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911364558.7A CN111029419B (en) 2019-12-26 2019-12-26 Full-transparent flexible ultraviolet light response switch and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111029419A CN111029419A (en) 2020-04-17
CN111029419B true CN111029419B (en) 2021-08-31

Family

ID=70214551

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911364558.7A Active CN111029419B (en) 2019-12-26 2019-12-26 Full-transparent flexible ultraviolet light response switch and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111029419B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107785443A (en) * 2016-08-26 2018-03-09 中国科学院金属研究所 Transparent flexible non-polar GaN nano wire ultraviolet detector and preparation method thereof
CN110144674A (en) * 2019-06-11 2019-08-20 东华大学 A kind of preparation method of compliant conductive ceramic fibre film
KR102033714B1 (en) * 2019-01-21 2019-10-18 리그마글라스주식회사 TRANSPARENT HEATING SUBSTRATE USING IoT AND METHOD OF MANUFACTURING THE SUBSTRATE
CN110534568A (en) * 2019-08-27 2019-12-03 西交利物浦大学 A kind of field effect transistor and preparation method thereof of flexible nano fiber oxidation zinc-tin

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107785443A (en) * 2016-08-26 2018-03-09 中国科学院金属研究所 Transparent flexible non-polar GaN nano wire ultraviolet detector and preparation method thereof
KR102033714B1 (en) * 2019-01-21 2019-10-18 리그마글라스주식회사 TRANSPARENT HEATING SUBSTRATE USING IoT AND METHOD OF MANUFACTURING THE SUBSTRATE
CN110144674A (en) * 2019-06-11 2019-08-20 东华大学 A kind of preparation method of compliant conductive ceramic fibre film
CN110534568A (en) * 2019-08-27 2019-12-03 西交利物浦大学 A kind of field effect transistor and preparation method thereof of flexible nano fiber oxidation zinc-tin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Ag/TiN异质结构纳米纤维的合成及在透明电极中的应用";胡三元等;《第十九届全国高技术陶瓷学术年会摘要集》;20161031;全文 *

Also Published As

Publication number Publication date
CN111029419A (en) 2020-04-17

Similar Documents

Publication Publication Date Title
CN110512354B (en) Preparation method of flexible barium titanate ceramic nanofiber membrane
KR100666477B1 (en) Titanium dioxide nanorod and its fabrication method
CN110144674B (en) Preparation method of flexible conductive ceramic fiber membrane
KR101172037B1 (en) Manufacturing method of titanium dioxide fiber added silver
Gokana et al. Effects of patterned electrode on near infrared light-triggered cesium tungsten bronze/poly (vinylidene) fluoride nanocomposite-based pyroelectric nanogenerator for energy harvesting
CN107938027B (en) A kind of pure tungsten nanofiber, preparation method and application
CN101239737A (en) Titanium dioxide thin film material with hierarchical structure and preparation method thereof
CN106601803A (en) Method for preparing indium oxide/aluminium oxide nanofiber filed effect transistor through UV light pretreatment
CN105800953A (en) Visible-light response carbon @ graphite phase carbon nitride film electrode and preparation method thereof
CN111705419B (en) Metal-loaded carbon nitride-doped graphene-based flexible non-woven fabric and preparation method and application thereof
CN106400202A (en) A method of preparing copper sulphide nanometer fibers
CN110624558A (en) Preparation method and application of cobaltosic oxide and tin oxide compound nanowire
CN111029419B (en) Full-transparent flexible ultraviolet light response switch and preparation method thereof
JP2011073912A (en) Method for forming nanostructure
Li et al. Recent advances in one-dimensional electrospun semiconductor nanostructures for UV photodetector applications: a review
CN104701404B (en) Ultraviolet light sensor based on nano structure of zinc oxide and preparation method thereof
CN111270348B (en) SrVO 3 Nanofiber preparation method and related products
CN108735826A (en) Fiberglass-based flexible gallium oxide nano-array solar blind ultraviolet detector of one kind and preparation method thereof
CN106381574B (en) It is a kind of to prepare Bi5O7The method of I nanofibers
CN105002597B (en) ZnO meso-porous nano fibers
CN113284960B (en) Flexible nanofiber membrane light-transmitting electrode with light conversion function and preparation method and application thereof
WO2015081665A1 (en) Zinc oxide nano structure based sensor and preparation method thereof
CN108574197A (en) A kind of regulatable Doped nanocrystal saturable absorber and preparation method thereof
CN109686497B (en) Method for preparing copper nano grid transparent electrode based on gas phase reduction of copper oxide
CN102605473A (en) Preparation method of nickel sulfide nanobelts

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