CN112271238A - Metal oxide micro-nano structure, preparation method and application thereof - Google Patents
Metal oxide micro-nano structure, preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- 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
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- 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 belongs to the technical field of micro-nano material synthesis and device preparation, and particularly relates to a metal oxide micro-nano structure, and a preparation method and application thereof. According to the invention, a metal oxide precursor sol-gel and an alcohol organic modifier are mixed and coated on the surface of a substrate, a femtosecond laser is adopted to directly write a precursor sol-gel film, the metal oxide precursor is reacted to generate a metal oxide by using heat generated at the focus of the femtosecond laser, and a metal oxide micro-nano structure is formed on the surface of the substrate; due to the fact that the alcohol organic modifier is added into the sol-gel, experiments prove that the appearance of the obtained metal oxide micro-nano structure can be obviously improved, the nano particles are continuous and uniform, and the on-off ratio of the ultraviolet micro-nano photoelectric detector prepared in the preferred embodiment is improved by 64 times compared with the on-off ratio of the ultraviolet micro-nano photoelectric detector without the alcohol organic modifier.
Description
Technical Field
The invention belongs to the technical field of micro-nano material synthesis and assembly and device preparation, and particularly relates to a metal oxide micro-nano structure, and a preparation method and application thereof.
Background
In recent years, with the development of basic subjects such as physics, chemistry and the like and the development of semiconductor microelectronic technology, human beings have unprecedented breakthrough in the exploration of the micro-nano scale world, and the micro-nano photoelectric detector has huge application in the aspects of military communication, missile early warning, disaster weather forecast and biomedical detection. Among active materials of the photodetector, metal oxides are preferred materials for the photodetector with excellent performance and low cost. However, the current metal oxide-based photodetectors are still lack of flexible processing means and simple and convenient preparation procedures.
The traditional preparation process of the metal oxide nano material generally comprises chemical vapor deposition, hydrothermal synthesis and molecular beam epitaxy. These methods usually require growth under vacuum environment and high temperature conditions, and any pattern cannot be flexibly prepared, the obtained metal oxide product is often a thin film, if a metal oxide product line with a size in the micro-nano order is desired and a required pattern can be flexibly generated, multiple steps such as mask plate and photolithography are required, which is tedious and easy to introduce impurities.
In order to flexibly manufacture the metal oxide on the substrate, the synthesis of the metal oxide can be directly induced by utilizing the thermal action of ultrafast laser, and when the metal oxide material is synthesized by utilizing a laser technology, the connectivity of nanoparticles of a product is often poor, the appearance is discontinuous, so that the performance of the metal oxide micro-nano photoelectric detector prepared based on the method is low.
Sukjoon et al decompose zinc acetate with laser to form a zinc oxide seed layer, and then generate a patterned zinc oxide nanowire on a substrate by using a hydrothermal synthesis method. Junyeob et al use the heat generated by the laser to induce the precursor to form a zinc oxide nanowire at a specific location on the substrate. Fujii et al, on an ITO substrate, the assembly of zinc oxide nanoparticles was achieved by a microbubble method. These methods can realize patterned synthesis of metal oxides, but because of the heat action, metal must be evaporated on a substrate or heat must be accumulated by using a specific substrate, which makes the subsequent fabrication of micro-nano devices extremely difficult.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a laser direct writing preparation method capable of improving the appearance of a metal oxide laser direct writing micro-nano structure and further improving the application performance of the metal oxide micro-nano structure, and aims to solve the technical problems that the metal oxide micro-nano photoelectric detector based on the appearance is low in performance due to poor nanoparticle connectivity and discontinuous appearance of a laser direct writing metal oxide micro-nano structure product in the prior art.
In order to achieve the aim, the invention provides a preparation method of a metal oxide micro-nano structure, which comprises the following steps:
(1) preparing a metal oxide precursor sol-gel by adopting a sol-gel method;
(2) adding an alcohol organic modifier into the metal oxide precursor sol-gel obtained in the step (1), and uniformly mixing to obtain a modified precursor sol-gel;
(3) coating the modified precursor sol-gel obtained in the step (2) on a substrate to obtain a metal oxide precursor sol-gel film;
(4) and (3) directly writing the precursor sol-gel film by using femtosecond laser, reacting the metal oxide precursor by using heat generated at the focus of the femtosecond laser to generate metal oxide, and simultaneously forming a metal oxide micro-nano structure on the surface of the substrate.
Preferably, in the step (1), the metal oxide precursor, the solvent and the stabilizer are mixed, and the sol-gel of the metal oxide precursor is prepared by a sol-gel method.
Preferably, the metal oxide is tin dioxide, zinc oxide or titanium dioxide; the precursor of the metal oxide is chloride, acetate or alkoxide corresponding to the metal oxide;
the solvent is one or more of ethylene glycol monomethyl ether, ethanol, dimethyl sulfoxide and dimethylformamide.
Preferably, the stabilizer is selected from the group consisting of monoethanolamine, diethanolamine and citric acid.
Preferably, step (1) is specifically: mixing a precursor of the metal oxide with a solvent, heating and stirring to promote the reaction of the precursor of the metal oxide with the solvent to form sol, cooling to room temperature, and aging to obtain the sol gel of the precursor of the metal oxide.
Preferably, the concentration of the metal cation corresponding to the metal oxide precursor in the sol-gel of step (1) is 0.5-1 mol/L.
Preferably, the concentration of the stabilizer in the sol-gel in the step (1) is 0.5-1 mol/L.
Preferably, the alcohol organic modifier in the step (2) is glycerol and/or polyethylene glycol;
preferably, the volume ratio of the alcohol organic modifier to the modified precursor sol-gel is (1-30): 100.
preferably, the volume ratio of the alcohol organic modifier to the modified precursor sol-gel is (3-20): 100.
preferably, the volume ratio of the alcohol organic modifier to the modified precursor sol-gel is (6.7-15): 100.
preferably, the femtosecond laser wavelength in the step (4) is 780-800nm, the pulse frequency is 80-100KHz, and the laser power is 40-120 mW.
According to another aspect of the invention, the metal oxide micro-nano structure prepared by the preparation method is provided.
According to another aspect of the invention, the application of the metal oxide micro-nano structure is provided, and the metal oxide micro-nano structure is used for preparing a micro-nano ultraviolet photoelectric detector.
Preferably, a photoresist is coated on the surface of the metal oxide micro-nano structure in a spinning mode, a metal electrode pattern is formed on the surface of the photoresist according to a metal electrode mask pattern, a metal electrode is deposited according to the pattern, the photoresist is cleaned and removed, and the micro-nano ultraviolet photoelectric detector is obtained.
According to another aspect of the invention, the invention provides a micro-nano ultraviolet photodetector, which comprises the metal oxide micro-nano structure and a metal electrode positioned on the surface of the micro-nano structure.
Preferably, the metal oxide is zinc oxide.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
(1) according to the invention, a metal oxide precursor sol-gel and an alcohol organic modifier are mixed and coated on the surface of a substrate, a femtosecond laser is adopted to directly write a precursor sol-gel film, the metal oxide precursor is reacted to generate a metal oxide by using heat generated at the focus of the femtosecond laser, and a metal oxide micro-nano structure is formed on the surface of the substrate; meanwhile, the organic modifier is added into the sol-gel, and experiments prove that the organic modifier can obviously improve the shape of the obtained metal oxide micro-nano structure, so that nano particles are continuous and uniform, and compared with the ultraviolet micro-nano photoelectric detector switch prepared in the preferred embodiment, the ultraviolet micro-nano photoelectric detector switch is improved by 64 times.
(2) The laser direct writing method provided by the invention can directly obtain metal oxide nano-particles with uniform and continuous appearance on the substrate in one step under the conditions of room temperature and atmospheric pressure by using a laser induction method.
(3) According to the invention, the organic modifier is added into the precursor solution, so that the appearance of the metal oxide generated by laser induction can be obviously improved, the continuity of the product is increased, the mobility of carriers in the material can be further improved, and the response of the manufactured photoelectric detector is obviously improved.
(4) The characteristic dimension of the metal oxide nano particle product line obtained by the preparation method can reach 650nm, the thickness is 50-150nm, and the preparation method has great potential in the application aspect of micro-nano photoelectric detectors.
Drawings
FIG. 1 is a schematic flow chart of a process for preparing a metal oxide micro-nano photoelectric detector by laser induction according to the invention;
FIG. 2 is a scanning electron micrograph of different patterns prepared by a method of improving a laser-induced metal oxide process using an organic modifier according to example 3 of the present invention, with a scale bar of 50 μm;
FIG. 3 is a scanning electron microscope image of metal oxides formed by laser-induced direct writing after different amounts of organic modifiers are added to the precursor according to the present invention; wherein the content a corresponds to no glycerol; the content b corresponds to 3% of the addition amount of glycerol; the content c corresponds to 6.7% of the addition amount of glycerol; the content d corresponds to 15% of the glycerol addition amount; scale bar 1 micron.
FIG. 4 is a diagram showing a metal oxide photodetector produced in example 1 of the present invention;
FIG. 5 is the response of a metal oxide photodetector made in accordance with example 4 of the present invention under 365nm UV illumination;
FIG. 6 is a graph of the response of a metal oxide photodetector made with different levels of organic modifier under 365nm UV illumination in accordance with the present invention; content a is the response of the metal oxide photodetector under 365nm ultraviolet lamp irradiation when no modifier is added, content b is the response of the metal oxide photodetector under 365nm ultraviolet lamp irradiation when 3% of organic modifier is added, content c is the response of the metal oxide photodetector under 365nm ultraviolet lamp irradiation when 6.7% of organic modifier is added, content d is the response of the metal oxide photodetector under 365nm ultraviolet lamp irradiation when 10% of organic modifier is added, content e is the response of the metal oxide photodetector under 365nm ultraviolet lamp irradiation when 15% of organic modifier is added, and content f is the response of the metal oxide photodetector under 365nm ultraviolet lamp irradiation when 20% of organic modifier is added.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention aims to provide a method for synthesizing a metal oxide nano material and improving the appearance of the metal oxide nano material. The method provided by the invention is a method for improving the appearance of the metal oxide induced by ultrafast laser direct writing by using the organic modifier, the organic modifier with specific content is mixed in the precursor solution of the ultrafast laser direct writing, the synthesis of the metal oxide nano material and the material assembly in any selected area can be directly completed in one step in the process of the ultrafast laser direct writing, and the metal oxide nano material with the improved appearance has obvious improvement on the performance of the micro-nano photoelectric detector.
The invention provides a preparation method of a metal oxide micro-nano structure, which comprises the following steps:
(1) mixing a metal oxide precursor with a solvent, and preparing a metal oxide precursor sol-gel by adopting a sol-gel method;
(2) adding an alcohol organic modifier into the metal oxide precursor sol-gel obtained in the step (1), and uniformly mixing to obtain a modified precursor sol-gel;
(3) coating the modified precursor sol-gel obtained in the step (2) on a substrate to obtain a metal oxide precursor sol-gel film;
(4) and (3) directly writing the precursor sol-gel film by using femtosecond laser, reacting the metal oxide precursor by using heat generated at the focus of the femtosecond laser to generate metal oxide, and simultaneously forming a metal oxide micro-nano structure on the surface of the substrate.
According to the invention, the alcohol organic modifier is added into the metal oxide precursor sol-gel, so that the assembly morphology of the nano particles in the metal oxide micro-nano structure obtained by laser direct writing can be obviously improved, and the nano particles are continuous and uniform.
In some embodiments, in step (1), the metal oxide precursor, the solvent and the stabilizer are mixed, and the sol-gel of the metal oxide precursor is prepared by a sol-gel method. For some metal oxides, the addition of a stabilizer stabilizes the pH of the solution, allowing for more complete hydrolysis of the sol gel. For example, oxygen atoms and nitrogen atoms in ethanolamine can form bonds with zinc ions, and the zinc ions can be used as a stabilizer to keep the solution clear.
In some embodiments, the stabilizer is selected from monoethanolamine, diethanolamine, citric acid.
In some embodiments, the metal oxide is tin dioxide, zinc oxide, or titanium dioxide; the precursor of the metal oxide is chloride, acetate or alkoxide corresponding to the metal oxide; the solvent is one or more of ethylene glycol monomethyl ether, ethanol, dimethyl sulfoxide and dimethylformamide.
In some embodiments, step (1) is specifically: mixing a precursor of the metal oxide with a solvent, heating and stirring to promote the reaction of the precursor of the metal oxide with the solvent to form sol, cooling to room temperature, and aging to obtain the sol gel of the precursor of the metal oxide.
In some embodiments, the concentration of the metal cation corresponding to the metal oxide precursor in the sol-gel of step (1) is 0.5 to 1 mol/L. The concentration of the stabilizer in the sol-gel in the step (1) is 0.5-1 mol/L. In a preferred embodiment, the ratio of the concentration of the stabilizer to the concentration of the metal cation is 1: 1.
in some embodiments, the alcoholic organic modifier of step (2) is glycerol and/or polyethylene glycol; the volume ratio of the alcohol organic modifier to the modified precursor sol-gel is (1-30): 100, preferably (3-20): 100, more preferably (6.7 to 15): 100.
in some embodiments, step (2) adopts a magnetic stirring method to uniformly mix the metal oxide precursor sol-gel and the alcohol organic modifier.
In some embodiments, the substrate in step (3) is a glass slide, the glass slide is ultrasonically cleaned in an ultrasonic cleaning machine sequentially by using acetone, isopropanol and deionized water before use, and after the clean glass slide is dried, the surface of the glass slide is subjected to surface modification by using a plasma cleaning machine, so that the uniform film formation of the precursor sol-gel is more facilitated. In some embodiments, the slide size is 20 x 0.17mm, the ultrasonic cleaning time is 10-20 minutes, and the plasma cleaning treatment time is 5-7 minutes.
In some embodiments, the modified precursor sol-gel is spin-coated on the substrate in step (3), and the spin-coating parameters are spin-coating at 500-. Firstly, the solution is uniformly spread on the substrate by spin coating at low speed, and then the solution is formed into a film on the substrate by spin coating at high speed.
In some embodiments, the laser in step (4) is a femtosecond laser with a wavelength of 780-800nm, a pulse frequency of 80-100KHz, and a laser power of 40-120 mW. In some embodiments, 40, 60, 100 times oil lens is used for focusing, and the moving speed of the displacement table controlled by computer software is 10-100 μm/s.
The invention also provides a metal oxide micro-nano structure prepared by the preparation method and application of the metal oxide micro-nano structure, and the metal oxide micro-nano structure can be used for preparing a micro-nano ultraviolet photodetector.
In some embodiments, a photoresist is coated on the surface of the metal oxide micro-nano structure in a spinning mode, a metal electrode pattern is formed on the surface of the photoresist according to a metal electrode mask pattern, a metal electrode is deposited according to the pattern, the photoresist is cleaned and removed, and the micro-nano ultraviolet photoelectric detector is obtained.
In some embodiments, two layers of photoresist are spin-coated on the surface of the metal oxide micro-nano structure, namely a bottom layer photoresist and a top layer photoresist, wherein the bottom layer photoresist is LOL2000, and the top layer photoresist is AZ 5214. The dissolution rate of the bottom layer photoresist in the developing solution is greater than that of the top layer photoresist, but the bottom layer photoresist has no photosensitivity and cannot be subjected to ultraviolet photoetching exposure. Thus, when the ultraviolet photoetching is carried out, the top layer photoresist is exposed to ultraviolet light to form a predesigned pattern, and a developing solution can remove a part of the bottom layer photoresist after washing the exposed area of the top layer photoresist in the developing step. Therefore, when the metal electrode is plated and the subsequent stripping is carried out, the bottom photoresist can fall off more quickly due to the high dissolution rate, and the metal oxide micro-nano structure adhered to the substrate cannot fall off when falling off.
The invention also provides a micro-nano ultraviolet photoelectric detector which comprises the metal oxide micro-nano structure and a metal electrode positioned on the surface of the micro-nano structure. In a preferred embodiment, the metal oxide is zinc oxide.
In some embodiments, the metal electrode is a noble metal nanolayer having two layers, the first layer is metal chromium or titanium, the second layer is gold or other conductive electrode material, and the electron beam evaporation thickness of the first layer and the electron beam evaporation thickness of the second layer are 10-20nm and 80-100nm respectively. Because a single layer of gold electrode is easy to fall off or is damaged in the subsequent steps after being evaporated on the substrate, the first layer of chromium or titanium is evaporated to increase the adhesion between the metal electrode and the substrate.
According to the invention, the shape of the metal oxide micro-nano structure prepared by ultrafast laser is improved by using an organic modifier in the process of preparing the metal oxide micro-nano structure, and the metal oxide micro-nano structure is further used for preparing a photoelectric detector. The method is characterized in that a specific organic matter is added when a precursor solution is prepared, so that the metal oxide nanoparticles prepared by laser induction are uniform and controllable in appearance, and a formed photoelectric detector has higher current switching ratio and response speed than those of the photoelectric detector without an organic modifier.
The following are examples:
comparative example 1
A zinc oxide ultraviolet photoelectric detector is synthesized by laser induction when no glycerin modifier is added.
The method of the invention is that a sol-gel precursor solution containing zinc ions and a stabilizing agent is utilized, the precursor solution is uniformly coated on a glass slide substrate in a spinning way, metal cations are oxidized by utilizing the thermal action of laser on the precursor solution, and the formed product is deposited on the substrate. And evaporating electrodes on the zinc oxide sample by using an ultraviolet photoetching and electron beam evaporation mode to form the zinc oxide-based ultraviolet photoelectric detector.
As shown in fig. 1, the method for synthesizing metal oxide by using laser induction comprises the following steps:
(1) forming a precursor solution: first, 0.54g of zinc acetate dihydrate powder was added to 5mL of ethylene glycol monomethyl ether solvent together with 0.155mL of monoethanolamine solution, and the mixture was stirred in a water bath heating environment at 60 ℃ for two hours to be sufficiently dissolved, thereby obtaining a sol-gel precursor solution. The obtained solution is packaged for standby.
(2) Preparation of laser direct writing sample: the clean slide substrate used was 20 x 0.17mm size glass. Firstly, a clean glass slide is sequentially ultrasonically cleaned for 15 minutes in an ultrasonic cleaning machine by using acetone, isopropanol and deionized water, and after the clean glass slide is dried, the surface of the glass slide is modified by treating for 5 minutes by using a plasma cleaning machine, so that the glass slide has hydrophilicity and is more beneficial to forming a film on the glass slide by using a precursor solution. Spin-coating the precursor solution obtained in the step (1) on a glass sheet by using a spin coater with the model of easy coater4, wherein the spin-coating parameters are 500rpm and 5 s; 3000rpm, 25 s.
(3) Laser induction: firstly, placing a glass slide coated with a precursor solution on a sample table of a laser direct writing system; then, the action of laser and solute in the precursor is controlled by a computer program, the metal oxide nano particles are directly synthesized and deposited on the substrate by the laser through the photothermal action, the used objective lens is a 60-time oil lens, the action direction of the laser penetrates through the substrate and acts on the inside of the precursor solution, and the laser power is 120 mW. And finally, soaking and cleaning the substrate for 30 minutes by using ethylene glycol monomethyl ether solution to remove solutes which are not processed by laser, thereby obtaining the zinc oxide nano-particles on the substrate.
(4) Manufacturing a micro-nano ultraviolet detector: after the laser direct-writing zinc oxide sample is obtained through the steps (1), (2) and (3), spin-coating photoresist LOL2000 on the zinc oxide sample, wherein the spin-coating parameters are 500rpm and 5 s; 3000rpm, 25s, placing the photoresist on a heating plate at 130 ℃ for prebaking for 10 minutes, and spin-coating the photoresist AZ5214 on the photoresist, wherein the spin-coating parameter is 500rpm and 5 s; 3000rpm, 25s, the photoresist was placed on a hot plate at 110 ℃ and pre-baked for 60 s. Exposing an electrode pattern designed in computer software to a specific position of a sample by using a maskless photoetching machine, cleaning an ultraviolet exposed area by using a cleaning solution to obtain a photoresist layer with the electrode pattern, and manufacturing a metal electrode on the photoresist layer by using an electron beam evaporation method, wherein the metal electrode is made of chromium and gold, and the thicknesses of the metal electrode are respectively 20nm and 100 nm. And (3) after the sample coated with the electrode is subjected to postbaking for 5 minutes at 90 ℃, and then the photoresist of the unexposed area is cleaned by utilizing N-methylpyrrolidone solution, so that the zinc oxide micro-nano ultraviolet photoelectric detector is obtained.
(5) Detection of ultraviolet light signals: and (3) detecting the sensing performance of the micro-nano ultraviolet detector at normal temperature and normal pressure. The test instruments used were a probe station and a semiconductor parametric analyzer. In a dark environment without ultraviolet irradiation, when a voltage across the device was applied to 10V, the device current was 210 nA. Under the irradiation of 365nm ultraviolet light, the photocurrent of the device is 1.5 muA, and the optical on-off ratio is about 7.
Example 1
The glycerol modifier is utilized to improve the appearance of the product, and the zinc oxide ultraviolet photoelectric detector is synthesized by laser induction.
The proper amount of glycerol modifier is added into the precursor solution, so that the appearance of the laser-induced zinc oxide nanoparticle product can be obviously improved, the sample connectivity is increased, and the performance of the manufactured ultraviolet photoelectric detector is obviously improved. As shown in fig. 1, the specific steps are as follows:
(1) forming a precursor solution: first, 0.54g of zinc acetate dihydrate powder was added to 5mL of ethylene glycol monomethyl ether solvent together with 0.155mL of monoethanolamine solution, and the mixture was stirred in a water bath heating environment at 60 ℃ for two hours to be sufficiently dissolved, thereby obtaining a sol-gel precursor solution.
(2) Modification of sol-gel precursor solution: adding 3% glycerol modifier (volume ratio of glycerol to sol gel is 3:100) into the sol gel precursor solution, and stirring to obtain modified precursor solution.
(3) Preparation of laser direct writing sample: the clean slide substrate used was 20 x 0.17mm size glass. Firstly, a clean glass slide is sequentially ultrasonically cleaned for 15 minutes in an ultrasonic cleaning machine by using acetone, isopropanol and deionized water, and after the clean glass slide is dried, the surface of the glass slide is modified by treating for 5 minutes by using a plasma cleaning machine, so that the glass slide has hydrophilicity and is more beneficial to forming a film on the glass slide by using a precursor solution. Spin-coating the modified precursor solution obtained in the step (2) on a glass sheet by using a spin coater with the model of easy coater4, wherein the spin-coating parameters are 500rpm and 5 s; 3000rpm, 25 s.
(4) Laser induction: firstly, placing a glass slide coated with a modified precursor solution on a sample table of a laser direct writing system; then, the action of laser and solute in the precursor is controlled by a computer program, the metal oxide nano particles are directly synthesized and deposited on the substrate by the laser through the photothermal action, the used objective lens is a 60-time oil lens, the action direction of the laser penetrates through the substrate and acts on the inside of the precursor solution, and the laser power is 120 mW. And finally, soaking and cleaning the substrate for 30 minutes by using ethylene glycol monomethyl ether solution to remove solutes which are not processed by laser, thereby obtaining the zinc oxide nano-particles on the substrate.
(5) Manufacturing a micro-nano ultraviolet detector: after the laser direct-writing zinc oxide sample is obtained through the steps (1), (2), (3) and (4), spin-coating photoresist LOL2000 on the zinc oxide sample, wherein the spin-coating parameter is 500rpm and is 5 s; 3000rpm, 25s, placing the photoresist on a heating plate at 130 ℃ for prebaking for 10 minutes, and spin-coating the photoresist AZ5214 on the photoresist, wherein the spin-coating parameter is 500rpm and 5 s; 3000rpm, 25s, the photoresist was placed on a hot plate at 110 ℃ and pre-baked for 60 s. Exposing an electrode pattern designed in computer software to a specific position of a sample by using a maskless photoetching machine, cleaning an ultraviolet exposed area by using a cleaning solution to obtain a photoresist layer with the electrode pattern, and manufacturing a metal electrode on the photoresist layer by using an electron beam evaporation method, wherein the metal electrode is made of chromium and gold, and the thicknesses of the metal electrode are respectively 20nm and 100 nm. And (3) after the sample coated with the electrode is subjected to postbaking for 5 minutes at 90 ℃, and then the photoresist of the unexposed area is cleaned by utilizing N-methylpyrrolidone solution, so that the zinc oxide micro-nano ultraviolet photoelectric detector is obtained.
(6) Detection of ultraviolet light signals: and detecting the sensing performance of the micro-nano ultraviolet detector manufactured after the appearance and the connectivity of the sample are improved at normal temperature and normal pressure. When the voltage across the device is 10V in a dark environment without ultraviolet irradiation, the current of the device is 50nA when the ultraviolet detector manufactured by adding 3% of glycerol modifier is added. Under the irradiation of 365nm ultraviolet light, the photocurrent of the device is 1.8 muA, the on-off ratio is 40, and the performance is obviously improved compared with a sample without glycerol modifier.
Example 2
The glycerol modifier is utilized to improve the appearance of the product, and the zinc oxide ultraviolet photoelectric detector is synthesized by laser induction.
Steps (1), (2), (3), (4) and (5) were performed in the same manner as in example 1 except that the step (2) was performed by adding a glycerol modifier in an amount of 6.7% by volume to the obtained sol-gel solution and sufficiently stirring the mixture uniformly for use.
(6) Detection of ultraviolet light signals: and detecting the sensing performance of the micro-nano ultraviolet detector manufactured after the appearance and the connectivity of the sample are improved at normal temperature and normal pressure. When the voltage across the device is increased to 10V under the dark environment without ultraviolet irradiation, the current of the ultraviolet detector manufactured by adding 6.7% of glycerol modifier is 3 nA. Under the irradiation of 365nm ultraviolet light, the photocurrent of the device is 420nA, the on-off ratio is about 150, and the performance is remarkably improved compared with a sample without the glycerol modifier and a sample with 3% of the glycerol modifier.
Example 3
The glycerol modifier is utilized to improve the appearance of the product, and the zinc oxide ultraviolet photoelectric detector is synthesized by laser induction.
The steps (1), (2), (3), (4) and (5) are the same as the example 1, except that the step (2) is to add 10 volume percent of glycerol modifier into the obtained sol-gel solution, and fully stir the mixture evenly for standby.
(6) Detection of ultraviolet light signals: and detecting the sensing performance of the micro-nano ultraviolet detector manufactured after the appearance and the connectivity of the sample are improved at normal temperature and normal pressure. When the voltage across the device is 10V, the current of the device is 2.5nA under the dark environment without ultraviolet irradiation. Under the irradiation of 365nm ultraviolet light, the photocurrent of the device is 622nA, the on-off ratio is about 250, and the performance is obviously improved compared with a sample without the glycerol modifier and a sample with 3% and 6.7% of the glycerol modifier.
Example 4
The glycerol modifier is utilized to improve the appearance of the product, and the zinc oxide ultraviolet photoelectric detector is synthesized by laser induction.
Steps (1), (2), (3), (4) and (5) are the same as example 1 except that step (2) is performed by adding a 15 vol% glycerin modifier to the obtained sol-gel solution and stirring the mixture sufficiently and uniformly for use.
(6) Detection of ultraviolet light signals: and detecting the sensing performance of the micro-nano ultraviolet detector manufactured after the appearance and the connectivity of the sample are improved at normal temperature and normal pressure. When the voltage across the device is increased to 10V under the dark environment without ultraviolet irradiation, the current of the device is 2nA by adding 15% of glycerol modifier. Under the irradiation of 365nm ultraviolet light, the photocurrent of the device is 1.27 muA, the on-off ratio is about 450, and the performance is remarkably improved compared with a sample without glycerol modifier and a sample with 3%, 6.7% and 10% of glycerol modifier.
Example 5
The glycerol modifier is utilized to improve the appearance of the product, and the zinc oxide ultraviolet photoelectric detector is synthesized by laser induction.
Steps (1), (2), (3), (4) and (5) are the same as example 1 except that step (2) is performed by adding 20 vol% of glycerin modifier to the obtained sol-gel solution and stirring the mixture sufficiently and uniformly for use.
(6) Detection of ultraviolet light signals: and detecting the sensing performance of the micro-nano ultraviolet detector manufactured after the appearance and the connectivity of the sample are improved at normal temperature and normal pressure. When the voltage across the device is increased to 10V, the current of the device is 2.5nA under the dark environment without ultraviolet irradiation by using an ultraviolet detector made by adding 20% of glycerol modifier. Under the irradiation of 365nm ultraviolet light, the photocurrent of the device is 290nA, the on-off ratio is about 100, and the performance is obviously improved compared with a sample without the glycerol modifier and a sample with 3% of the glycerol modifier, but is reduced compared with samples with 6.7%, 10% and 15% of the glycerol modifier.
FIG. 2 is a scanning electron microscope image of an ultraviolet detector prepared by the method for improving the laser-induced metal oxide process by using the organic modifier in example 3 of the present invention. FIG. 3 is a scanning electron microscope image of metal oxides formed by laser-induced direct writing after different amounts of organic modifiers are added to the precursor according to the present invention; wherein content a corresponds to the amount of glycerol added without addition (comparative example 1); content b was 3% of glycerin (example 1); content c corresponds to 6.7% of glycerol addition (example 2); content d corresponds to 15% of glycerol addition (example 3); it can be seen that the metallic zinc oxide nanoparticles obtained by laser direct writing are not continuously accumulated when no organic modifier is added; then, as the volume fraction of the added glycerin is gradually increased, the corresponding nano zinc oxide particles are uniform and continuous in appearance and are gradually compact.
FIG. 4 is a diagram showing a metal oxide photodetector produced in example 1 of the present invention; the active substance of the ultraviolet photoelectric detector is zinc oxide directly written by laser, and the interdigital metal electrode is a chromium/gold electrode prepared by electron beam evaporation.
FIG. 5 is the response of a metal oxide photodetector made in accordance with example 4 of the present invention under 365nm UV illumination; the ultraviolet micro-nano photoelectric detector manufactured by the method has obvious photoelectric response under the irradiation of ultraviolet light.
FIG. 6 is a graph of the response of a metal oxide photodetector made with different levels of the organic modifier glycerol under 365nm UV illumination in accordance with the present invention; content a is the response of the metal oxide photodetector under 365nm ultraviolet lamp irradiation when no modifier is added, content b is the response of the metal oxide photodetector under 365nm ultraviolet lamp irradiation when 3% of organic modifier is added, content c is the response of the metal oxide photodetector under 365nm ultraviolet lamp irradiation when 6.7% of organic modifier is added, content d is the response of the metal oxide photodetector under 365nm ultraviolet lamp irradiation when 10% of organic modifier is added, content e is the response of the metal oxide photodetector under 365nm ultraviolet lamp irradiation when 15% of organic modifier is added, and content f is the response of the metal oxide photodetector under 365nm ultraviolet lamp irradiation when 20% of organic modifier is added. It can be seen that the on-off ratio of the uv photodetector increased from 7 when glycerol was not added to 450 when 15% as the proportion of the glycerol modifier increased, but when the amount of the glycerol modifier reached 20%, the on-off ratio decreased to 100 because the amount of glycerol in the precursor was too large, resulting in an insufficient amount of zinc oxide product being generated at the time of laser direct writing. Therefore, when the micro-nano structure metal oxide is prepared by laser direct writing, even if a small amount of glycerol modifier is added, such as 3%, the shape of the obtained micro-nano structure of the metal oxide is remarkably improved compared with the shape of the metal oxide without the glycerol modifier, the switch of the correspondingly prepared micro-nano ultraviolet detection device is increased from 7 to 40 compared with the switch of the micro-nano ultraviolet detection device without the glycerol modifier, and the maximum on-off ratio can be increased to 450 along with the gradual increase of the glycerol modifier, so that the introduction of the glycerol modifier can be really and remarkably improve the performance of the device by improving the shape of the micro-nano structure metal oxide.
In the experiment, glycerol or polyethylene glycol modifier is added when the tin dioxide micro-nano structure and the titanium dioxide micro-nano structure are prepared by laser direct writing, the experiment shows that the prepared micro-nano structure is more continuous in appearance than the micro-nano structure without the glycerol or polyethylene glycol, and when the micro-nano structure is used for preparing the micro-nano ultraviolet detector according to the method, the on-off ratio of the ultraviolet detector is obviously improved due to the addition of the glycerol or polyethylene glycol.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a metal oxide micro-nano structure is characterized by comprising the following steps:
(1) preparing a metal oxide precursor sol-gel by adopting a sol-gel method;
(2) adding an alcohol organic modifier into the metal oxide precursor sol-gel obtained in the step (1), and uniformly mixing to obtain a modified precursor sol-gel;
(3) coating the modified precursor sol-gel obtained in the step (2) on a substrate to obtain a metal oxide precursor sol-gel film;
(4) and (3) directly writing the precursor sol-gel film by using femtosecond laser, reacting the metal oxide precursor by using heat generated at the focus of the femtosecond laser to generate metal oxide, and simultaneously forming a metal oxide micro-nano structure on the surface of the substrate.
2. The preparation method according to claim 1, wherein in the step (1), the metal oxide precursor, the solvent and the stabilizer are mixed, and the metal oxide precursor sol-gel is prepared by a sol-gel method.
3. The method of claim 2, wherein the metal oxide is tin dioxide, zinc oxide, or titanium dioxide; the precursor of the metal oxide is chloride, acetate or alkoxide corresponding to the metal oxide;
the solvent is one or more of ethylene glycol monomethyl ether, ethanol, dimethyl sulfoxide and dimethylformamide.
4. The method of claim 2, wherein the stabilizer is selected from the group consisting of monoethanolamine, diethanolamine, and citric acid.
5. The method according to claim 1, wherein the concentration of the metal cation corresponding to the metal oxide precursor in the sol-gel of step (1) is 0.5 to 1 mol/L.
6. The method according to claim 1, wherein the alcoholic organic modifier in the step (2) is glycerin and/or polyethylene glycol; the volume ratio of the alcohol organic modifier to the modified precursor sol-gel is (1-30): 100, preferably (3-20): 100, more preferably (6.7 to 15): 100.
7. the metal oxide micro-nano structure prepared by the preparation method according to any one of claims 1 to 6.
8. The application of the metal oxide micro-nano structure according to claim 7, which is used for preparing a micro-nano ultraviolet photodetector.
9. The application of claim 8, wherein a photoresist is spin-coated on the surface of the metal oxide micro-nano structure, a metal electrode pattern is formed on the surface of the photoresist according to a metal electrode mask pattern, a metal electrode is deposited according to the pattern, and the photoresist is cleaned and removed to obtain the micro-nano ultraviolet photodetector.
10. A micro-nano ultraviolet photodetector is characterized by comprising the metal oxide micro-nano structure of claim 7 and further comprising a metal electrode positioned on the surface of the micro-nano structure.
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