CN112279290B - Copper oxide micron sphere-nanowire micro-nano hierarchical structure and preparation method thereof - Google Patents
Copper oxide micron sphere-nanowire micro-nano hierarchical structure and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of photoelectricity and sensing, and particularly relates to a copper oxide micro-sphere-nanowire micro-nano hierarchical structure and a preparation method thereof. The preparation method comprises the steps of utilizing an ordered micropore array mask to sequentially superpose and deposit an ordered silver-copper-silver film array on a substrate, carrying out high-temperature infiltration and recession to obtain a silver-copper alloy microsphere array, carrying out high-temperature vacuum silver volatilization to obtain a copper microsphere array, and carrying out thermal oxidation on copper microspheres to obtain a copper oxide microsphere-nanowire micro-nano hierarchical structure. The preparation method can realize controllable preparation of the copper oxide micron ball-nanowire with quasi-continuous adjustable diameter and distance by controlling the thickness of the copper film, the size of the micron hole and preparation process parameters, the prepared copper oxide micron ball-nanowire micro-nano hierarchical structure has uniform size, uniform distribution on the substrate and strong adhesion with the substrate, solves the problem that the nanowire is easy to peel in application occasions of sensing, photoelectricity, energy storage and conversion, hydrophobic structure and the like, and is convenient to popularize and use.
Description
Technical Field
The invention belongs to the technical field of photoelectricity and sensing, and particularly relates to a copper oxide micro-sphere-nanowire micro-nano hierarchical structure and a preparation method thereof.
Background
The copper oxide has stable thermal and chemical properties, a band gap of about 1.4eV, and higher light absorption coefficients in ultraviolet-visible-near infrared bands, and is an important sunlight and thermal absorption layer, photovoltaic material, photoelectrocatalysis material and optical detection material; as an important p-type semiconductor, copper oxide is also widely used in a hole transport layer of devices such as solar cells and light emitting diodes; the copper oxide has excellent catalytic performance and has irreplaceable important application in the fields of catalysis, degerming and biochemical sensing; in addition, the copper oxide is abundant in earth reserves, environment-friendly and also an important structural function (such as hydrophilic and hydrophobic) material.
The development of the copper oxide nano material preparation technology provides a great driving force for the application of the copper oxide nano material. Among copper oxide nanostructures with various morphologies, copper oxide microspheres-nanowires with micro-nano hierarchical structures have high specific area and high surface activity, and have important applications in the fields of energy storage, catalysis, sensing, electroluminescent display and the like [ Progress in Materials Science 60(2014) 208-.
The thermal oxidation method is a simple and efficient method for growing the copper oxide nanowire, takes a copper film/powder/wire/foil as a raw material, and can generate the copper oxide nanowire on the surface of copper by oxidation at the temperature of 350-. Copper film (including graphical copper film, such as [ a copper oxide nanowire array localized growth method, CN 100402432C ]) is evaporated on a clean planar substrate, or copper micron powder is coated on the substrate, so that a copper oxide nanowire or copper oxide microsphere-nanowire hierarchical structure can be obtained on a planar insulating or conductive substrate, and the application of copper oxide in the fields of energy, catalysis, photoelectricity, sensing, display devices, hydrophobic surfaces and the like is promoted. Meanwhile, the development of the related field also puts higher requirements on the structural parameters, the uniformity, the orderliness, the adhesion with the substrate and the like of the copper oxide micro-nano hierarchical structure, the controllability and the convenience of the preparation and the large-scale preparation cost.
The prior art methods obviously do not fully satisfy the above requirements. The method for coating copper powder on a substrate and then carrying out thermal oxidation comprises the following steps: firstly, the dispersion density, the spacing and other parameters of copper particles are difficult to control in conventional metal powder coating, too sparse powder can cause the copper oxide microsphere-nanowire grown by thermal oxidation to be incapable of forming electrical contact, too thick powder can inevitably cause copper powder stacking, the thermal oxidation growth starts from the upper surface layer (rich in oxygen) of the copper powder, the copper powder far away from the bottom of the surface layer is not oxidized sufficiently, the nanowire is short, and the nanowire parameters are not uniform. The field emission display [ Journal of Vacuum Science & Technology B28 (2010)558-561 ] and the structural hydrophobic material [ Solid State Sciences 10(2008)1568e1576 ] require manipulation of the nanowire geometry and spacing; next, the particle size of the copper oxide nanowire prepared by thermal oxidation is closely related to the particle size of the initial copper powder [ Nanoscale 3(2011)4972 ], the copper powder particle is smaller than 1 μm, the copper powder can be oxidized into copper oxide quickly and lose the driving force of nanowire growth (the driving force is from the stress between the surface oxide and the lower copper and the concentration gradient between the surface and the internal oxygen ions when the copper is oxidized), the particle size of the copper powder is increased, and the length of the oxidized nanowire is increased [ Nanoscale 3(2011)4972 ]. Therefore, the structural parameters of the copper oxide microsphere-nanowire are closely related to the particle size of the used copper microsphere and the size uniformity of the copper microsphere, and the existing metal copper powder is difficult to realize the accurate control of the size and uniformity of the copper microsphere; and secondly, copper powder, especially a thicker region, coated on the substrate is subjected to thermal oxidation, and the copper oxide micro-sphere-nanowire is agglomerated into a large block, so that the copper oxide micro-sphere-nanowire is poor in adhesion with the substrate, is easy to fall off to cause stripping of devices, and blocks practical application of the copper oxide micro-sphere-nanowire micro-nano hierarchical structure.
Although a copper film with controllable area and position can be obtained by using a metal mask or photoetching or electron beam etching process (CN 100402432C), the metal film can be soaked and shrunk into particles in principle by heating to high temperature in an inert atmosphere, the melting point of copper per se is higher (1085 ℃), the copper film is difficult to soak and soak at the temperature of below 1000 ℃, copper microspheres with controllable size, position and distance are difficult to obtain, and the controllable preparation of the copper oxide microsphere-nanowire array on a substrate can be realized. Therefore, the application requirements in the fields of energy storage, catalysis, photo-thermal power generation and the like cannot be met.
Disclosure of Invention
In order to solve the technical problems, the invention provides a copper oxide microsphere-nanowire micro-nano hierarchical structure and a preparation method thereof, the method can realize the accurate control of the size, the position and the distance of the copper microsphere, can obtain a copper microsphere array with uniform size, can overcome the difficult problem of poor adhesion of the copper oxide nanowire and a (conductive) substrate, can obtain an ordered copper oxide microsphere-nanowire micro-nano hierarchical structure through thermal oxidation growth, and can regulate and control the geometric and structural parameters of the microsphere and the nanowire. The method is simple and efficient, is easy to carry out amplification production (by using a large-size mask or photoetching), and provides a new implementation scheme for the foundation and application research of developing high-performance photoelectric, sensing and catalytic devices and structural hydrophobic materials in the future.
The invention aims to overcome the defects in the prior art and provides a copper oxide microsphere-nanowire micro-nano hierarchical structure, which comprises a substrate and a copper oxide microsphere-nanowire array attached to the substrate, wherein the copper oxide microsphere-nanowire array is formed by orderly arranging a plurality of copper oxide microspheres-nanowires with uniform sizes at intervals, the copper oxide microsphere-nanowires comprise hemispherical copper oxide microspheres and copper oxide nanowires in divergent distribution on the outer surfaces of the copper oxide microspheres, the plane of each copper oxide microsphere is connected with the substrate, the diameter of each copper oxide microsphere is 5-20 micrometers, the number of the copper oxide nanowires on each copper oxide microsphere is 3500, and the diameter of each copper oxide nanowire is 20-1000nm and the length of each copper oxide nanowire is 0.5-100 micrometers.
The copper oxide microsphere-nanowire micro-nano hierarchical structure is further improved:
preferably, the spacing between adjacent copper oxide micro-spheres is 12-100 μm.
In order to overcome the defects in the prior art, the invention provides a preparation method of a copper oxide microsphere-nanowire micro-nano hierarchical structure, which comprises the following steps:
s1, orderly-arranged micropores with the size of 5-45 mu m and the interval of 12-100 mu m are prepared on a substrate with a clean surface, and a silver film, a copper film and a silver film are sequentially superposed and deposited in the micropores to prepare an ordered silver-copper-silver film array;
s2, heating the silver-copper-silver film deposited in the step S1 in a high-purity inert atmosphere to 800-950 ℃ for infiltration, and obtaining a silver-copper alloy microsphere array;
s3, heating the silver-copper alloy microsphere array obtained in the step S2 in a vacuum tube furnace until silver is completely volatilized from the silver-copper alloy microsphere, wherein the temperature of the vacuum tube furnace is 750 plus of 950 ℃, and the vacuum degree of a cavity is 0.001-10Pa, so as to obtain a copper microsphere array;
s4, heating the copper micro-sphere array prepared in the step S3 to the temperature of 300 ℃ and 700 ℃ in the air or oxygen atmosphere, preserving the heat for 0.5-30 hours, oxidizing the surface of the copper micro-sphere and growing a copper oxide nanowire to prepare the copper oxide micro-sphere-nanowire micro-nano hierarchical structure.
The preparation method of the ordered copper oxide micron sphere-nanowire micro-nano hierarchical structure is further improved as follows:
preferably, in step S1, the substrate is an insulating substrate or an insulating substrate plated with indium tin oxide or an insulating substrate of a fluorine-doped tin oxide conductive film, and the insulating substrate is made of any one of quartz glass, aluminum oxide, a silicon-silicon oxide composite material, and a silicon-silicon nitride composite material.
Preferably, the thin film is deposited in step S1 by any one of magnetron sputtering, dc sputtering, thermal evaporation, electron beam evaporation, and pulsed laser deposition.
Preferably, the step S1 of preparing the ordered silver-copper-silver thin film array on the substrate includes the following specific steps: the method comprises the following steps of clinging a stainless steel or copper or molybdenum metal mask to the surface of a substrate, wherein the metal mask is 10-100 mu m in thickness and is provided with orderly-arranged micron holes penetrating through the metal mask, putting the substrate pasted with the mask into a vacuum chamber, sequentially superposing and depositing a silver film, a copper film and a silver film, and then removing the metal mask on the substrate to obtain an orderly silver-copper-silver film array on the substrate.
Preferably, the step S1 of preparing the ordered silver-copper-silver thin film array on the substrate specifically comprises the following steps: spin-coating a photoresist film on a substrate to a thickness of 10-20 μm, baking and curing, using photoetching and laser direct writing to describe a micron hole array which is orderly arranged, developing to obtain the micron hole array penetrating through the photoresist film on the photoresist film, putting the developed substrate into a vacuum chamber, sequentially superposing and depositing a silver film, a copper film and a silver film, putting the substrate into a stripping solution, removing the residual photoresist film and a metal film deposited above the photoresist film, and preparing an ordered silver-copper-silver film array deposited on the substrate;
or spin-coating an electron beam adhesive film with the thickness of 10-20 μm on the substrate, baking and curing, using an electron beam for exposure, engraving the orderly-arranged micropore array, developing to obtain the micropore array penetrating through the electron beam adhesive film on the electron beam adhesive film, putting the developed substrate into a vacuum chamber, sequentially superposing and depositing a silver film, a copper film and a silver film, putting the substrate into stripping liquid, and removing the residual electron beam adhesive and the metal film above the electron beam adhesive film to obtain the ordered silver-copper-silver film array deposited on the substrate.
Preferably, the shape of the micropores in step S1 is any one of a square, a regular hexagon, and a circular hole.
Preferably, in step S1, the thickness of the copper thin film is 10-3000nm, the thickness of the silver thin film is 20-4000nm, the thickness of the copper thin film is 1-41% of the total thickness of the silver-copper-silver thin film, and the total thickness of the silver-copper-silver thin film is greater than 3% of the micrometer aperture size.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention considers that pure copper has high melting point (1085 ℃) and is difficult to be degraded and infiltrated, and proposes that silver is used as a sacrificial layer, because the eutectic temperature of copper-silver alloy (the weight ratio is 28.1:71.9) is 779 ℃, the copper-silver alloy is favorably guided to be degraded and infiltrated near the melting point and is contracted into silver-copper alloy microspheres (which are not overlapped and have random intervals) on a planar substrate; and then removing silver from the copper-silver alloy by vacuum evaporation by using the vapor pressure of the silver which is obviously higher than that of the copper to obtain a copper microsphere, and generating the copper oxide nanowire on the surface of the copper microsphere by thermal oxidation. The invention further provides a method for controlling the arrangement mode (including the distance) of the infiltrated copper microspheres on the substrate by utilizing the ordered holes of the metal mask/photoresist mask, thereby realizing the regulation and control of the distance between the copper oxide microspheres and the nano-wire micro-nano hierarchical structure;
(2) the diameter of the copper microsphere can be determined by the size of the hole of the metal/photoresist mask and the thickness of the evaporated copper film, the size and the uniformity of the infiltrated copper microsphere can be controlled by virtue of the ordered holes with uniform size contained in the metal/photoresist mask, and the copper oxide microsphere-nanowire micro-nano hierarchical structure with uniform nanowire size can be obtained when the copper oxide microsphere-nanowire micro-nano hierarchical structure grows under the same thermal oxidation (temperature, oxygen concentration and time) parameters.
(3) When the silver-copper-silver film is removed from the soaking, the film is contracted into micro-spheres under the action of surface tension, after the silver is removed by vacuum evaporation, the size of the copper micro-spheres is further contracted, and the contact area between the copper micro-spheres and the substrate is smaller (25-400 mu m) 2 ) And the microspheres are isolated from each other, so that the stress between metals/oxides during copper oxidation can be effectively released, the adhesion between the microspheres and the nanowire and the substrate is remarkably improved, and the problem that the nanowire is easy to peel off in application occasions such as sensing/photoelectricity/sensing, hydrophobic structure and the like is solved.
(4) The selection of the silver-copper-silver three-layer film, the thickness of the silver film and the copper film, the desizing and infiltrating temperature, the evaporating temperature and the growth temperature jointly determine whether the copper microspheres and the copper oxide nanowires can grow out, and the strategy and the selection of the corresponding parameters are very important.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of copper oxide microspheres-nanowires prepared in example 1; wherein FIGS. 1(a) - (c) are preparation flow charts, FIG. 1(d) is a top view of SEM, and FIG. 1(e) is a cross-sectional SEM.
FIG. 2 is a graph representing morphology and phase of the ordered copper oxide microspheres-nanowires prepared in example 2; wherein FIG. 2(a) is a SEM top view, FIG. 2(b) is a cross-sectional SEM view, and FIG. 2(c) is X-ray diffraction (XRD).
FIGS. 3(a) - (d) are flow charts of the preparation method of example 2 using Ag film and example 3 without using Ag film; wherein FIGS. 3(e) - (h) are SEM images of the products of each step of example 2, and FIGS. 3(i) - (k) are SEM images of the products of each step of example 3.
Fig. 4(a) - (d) are flow charts of the preparation of copper oxide microspheres-nanowires using the complete silver-copper-silver three-layer film (no metal or photoresist mask is used when depositing the metal film) in example 4, and SEM images of the products of each step in the examples of fig. 4(e) - (g).
Fig. 5(a) - (d) are SEM images of the size of the copper microsphere array controlled by controlling the size of the micropores and the thickness of the copper film, and (e) - (h) are SEM images of the copper microsphere pitch controlled by controlling the pitch size of the micropores.
FIGS. 6(a) - (c) are graphs showing the results of the ultrasonic vibration test of the copper oxide microspheres and nanowires obtained in example 1, and FIGS. 6(d) - (f) are graphs showing the test results of the ultrasonic vibration test of the copper oxide microspheres and nanowires obtained in example 4; in fig. 6, (a) and (d) are photographs of copper microspheres dispersed in a quartz substrate, the upper right drawing is a high-power optical microscope photograph, (b) and (e) are photographs of copper oxide microspheres-nanowires obtained by thermal oxidation growth, the upper right drawing is a high-power optical microscope photograph, and (c) and (f) are photographs after 10 minutes of ultrasonic vibration and a high-power optical microscope photograph.
FIG. 7 is a graph comparing the hydrophobic properties of structures; wherein FIG. 7(a) shows a modified octadecyltrichlorosilane (C) 18 H 37 Cl 3 Si) wettability picture of blank substrate after hydrophobic monolayer, fig. 7(b) is wettability picture of copper oxide microsphere-nanowire modified octadecyl trichlorosilane hydrophobic monolayer prepared in example 1, and fig. 7(c) is wettability picture of copper oxide microsphere-nanowire modified octadecyl trichlorosilane hydrophobic monolayer prepared in example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments, and all other embodiments obtained by a person of ordinary skill in the art without making creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
And (3) scattering the purchased copper powder with the particle size of 5-40 mu m on a substrate with a clean surface, heating to 450 ℃ in an oxygen atmosphere, preserving the temperature for 15 hours, oxidizing the surface of the copper microsphere and growing a copper oxide nanowire to obtain a comparison sample 1 of the copper oxide microsphere-nanowire micro-nano hierarchical structure.
The microsphere-nanowire prepared by the method is scanned by an electron microscope (SEM), and an image is shown in FIG. 1, wherein FIG. 1(a) is a top view and FIG. 1(b) is a cross-sectional view. As can be seen from fig. 1, the copper oxide microspheres-nanowires prepared by the method are unevenly distributed on the substrate, some copper oxide microspheres-nanowires are stacked together, and the copper oxide microspheres-nanowires on the surface are not in contact with the substrate, so that the copper oxide microspheres-nanowires are poor in adhesion and easy to fall off; the thermal oxidation starts from the upper surface layer of the copper powder, the copper powder far away from the surface layer is not oxidized enough, the nano wire is shorter, and the size and the property of the micro ball-nano wire are not uniform; the copper powder has different particle sizes, so that the copper oxide microspheres in the prepared copper oxide microsphere-nanowire have different sizes and the nanowire has larger difference in length and thickness.
Example 2
S1, clinging a metal molybdenum mask to the surface of the substrate with a clean surface, placing the substrate with the mask in a vacuum cavity, sequentially superposing and depositing a 1000nm silver film, a 1200nm copper film and a 1000nm silver film on the metal mask with the micron holes, and removing the metal mask to obtain the ordered silver-copper-silver film array deposited on the substrate, wherein the metal mask is provided with the orderly-arranged square micron hole arrays with the aperture diameter of 10.5 microns and the center-to-center distance of 16.5 microns.
S2, heating the silver-copper-silver film deposited in the step S1 in a high-purity argon inert atmosphere to 850 ℃ for deglutition and infiltration to obtain a silver-copper alloy microsphere array;
s3, placing the silver-copper alloy microsphere array obtained in the step S2 in a vacuum tube furnace, keeping the vacuum tube furnace at 850 ℃ and the vacuum degree of a cavity at 0.01Pa for 1 hour until silver is completely volatilized from the microspheres, and obtaining a copper microsphere array;
s4, heating the copper micro-sphere array prepared in the step S3 to 425 ℃ in an oxygen atmosphere, preserving heat for 30 hours, oxidizing the surface of the copper micro-sphere and growing a copper oxide nanowire to obtain the copper oxide micro-sphere-nanowire micro-nano hierarchical structure.
The copper oxide micro-sphere-nano wire prepared by the method is subjected to electron microscope (SEM) scanning and X-ray diffraction, and the result is shown in fig. 2, wherein fig. 2(a) is an SEM top view, fig. 2(b) is a 45-degree cross-sectional view (b), and fig. 2(c) is X-ray diffraction (XRD).
As can be seen from fig. 2, the copper oxide microspheres-nanowires prepared by the preparation method of the present invention are orderly and uniformly distributed on the substrate and have uniform size, the nanowires on the copper oxide microspheres are uniformly arranged, and the number, length and thickness of the nanowires on each copper oxide microsphere are uniform; as can be seen from X-ray diffraction, the thermal oxidation time is 0.5 hours, the thermal oxidation product is a composite phase of cuprous oxide and cupric oxide, unoxidized copper can be detected, the thermal oxidation time is prolonged to 5 hours, diffraction peaks of the cuprous oxide and the copper disappear, and the product is pure cupric oxide.
Example 3
S1, clinging a metal molybdenum mask to the surface of the substrate with a clean surface, wherein the mask is provided with ordered square micron holes with the aperture of 10.5 and the distance of 16.5 mu m, putting the substrate pasted with the mask into a vacuum chamber, depositing a 1200nm copper film, and removing the metal mask to obtain an ordered copper film array;
s2, heating the copper film deposited in the step S1 in a high-purity argon inert atmosphere to 850 ℃ for infiltration, and obtaining a copper film array with partial infiltration;
s3, heating the partially degummed copper film array prepared in the step S2 to 450 ℃ in an oxygen atmosphere, and preserving heat for 20 hours to enable only short nanowires to grow on the surface.
The flow charts of the preparation methods of example 2 and example 3 are shown in fig. 3(a) to (d). The products of the preparation steps S1-S4 of example 2 were characterized by Scanning Electron Microscope (SEM), respectively, and the scanning results are shown in fig. 3(e) - (h), wherein the copper oxide microspheres-nanowires are orderly and uniformly distributed on the substrate and have uniform size, the nanowires on the copper oxide microspheres are uniformly arranged, and the number, length and thickness of the nanowires on each copper oxide microsphere are uniform; referring to the SEM images of the products of preparation steps S1, S2, and S3 of example 3 as shown in fig. 3(i) - (k), it is understood from fig. 3(i) - (k) that when a silver sacrificial layer is not used, the copper film (i) having the same size and thickness slightly shrinks at the four corners under the same dewetting condition, and most of the area remains as a thin film (j), and the nanowire obtained using this copper film as a source under the same thermal oxidation growth condition is very short (k).
Example 4
S1, sequentially superposing and depositing a 380nm silver film, a 480nm copper film and a 380nm silver film on a substrate with a clean surface to obtain a silver-copper-silver film;
s2, heating the silver-copper-silver film deposited in the step S1 in a high-purity argon inert atmosphere to 900 ℃ for deglutition and infiltration to obtain a silver-copper alloy microsphere array;
s3, placing the silver-copper alloy microsphere array obtained in the step S2 in a vacuum tube furnace, keeping the temperature of the vacuum tube furnace at 750 ℃ and the vacuum degree of a cavity at 0.001Pa for 30 hours until silver is completely volatilized from the microspheres, and obtaining a copper microsphere array;
s4, heating the copper micro-sphere array prepared in the step S3 to 450 ℃ in the air or oxygen atmosphere, preserving the temperature for 15 hours, oxidizing the surface of the copper micro-sphere and growing a copper oxide nanowire to obtain the copper oxide micro-sphere-nanowire micro-nano hierarchical structure.
The flow of the above-mentioned production method is shown in FIGS. 4(a) to (d). Wherein, a Scanning Electron Microscope (SEM) picture of the silver-copper alloy microsphere array obtained in step S2 is shown in fig. 4(e), an SEM picture of the copper microsphere array obtained in step S3 is shown in fig. 4(f), and a copper oxide microsphere-nanowire micro-nano hierarchical structure sample 1 obtained in step S4 is shown in fig. 4 (g); as can be seen from fig. 4(e), after the silver-copper-silver thin film prepared without the mask is subjected to dewetting, the obtained silver-copper alloy microsphere array is dispersed in a single layer (particles are not stacked and connected with particles), the alloy particles are randomly distributed and are not uniform in spacing, and the size difference between the silver-copper alloy microspheres is large, so that the prepared copper microsphere array and the copper oxide microsphere-nanowire single layer are randomly distributed, the number, length and thickness of nanowires on the copper oxide microsphere-nanowire are not uniform, and nanowires on adjacent copper oxide microsphere-nanowires are in a bridging state and are in a separation state.
Example 5
S1, clinging a metal molybdenum mask to the surface of the substrate with a clean surface, placing the metal mask with an ordered square micron hole array with the aperture of 10.5 microns and the center distance of 16.5 microns into a vacuum chamber, depositing a 400nm silver film, a 10nm copper film and a 400nm silver film on the metal mask with the micron holes in sequence, and removing the metal mask to obtain an ordered silver-copper-silver film array 1;
clinging a metal molybdenum mask to the surface of the substrate, placing the substrate pasted with the mask into a vacuum chamber, sequentially depositing a 1000nm silver film, a 1200nm copper film and a 1000nm silver film on the metal mask with the micron holes, and removing the metal mask to obtain an ordered silver-copper-silver film array 2, wherein the metal mask is provided with an ordered square micron hole array with the aperture of 10.5 microns and the center distance of 16.5 microns;
clinging a metal molybdenum mask to the surface of the substrate, placing the substrate pasted with the mask into a vacuum chamber, sequentially depositing a 400nm silver film, a 500nm copper film and a 400nm silver film on the metal mask with the micropores, and uncovering the metal mask to obtain an ordered silver-copper-silver film array 3, wherein the metal mask is provided with an ordered square micropore array with the aperture of 37 micrometers and the center distance of 62 micrometers;
clinging a metal molybdenum mask to the surface of the substrate, placing the substrate pasted with the mask into a vacuum cavity, sequentially depositing a 1200nm silver film, a 1500nm copper film and a 1200nm silver film on the metal mask with the micron holes, and removing the metal mask to obtain an ordered silver-copper-silver film array 4, wherein the metal mask is provided with an ordered square micron hole array with the aperture of 37 microns and the center distance of 62 microns;
s2, respectively heating the 4 parts of copper films deposited in the step S1 in a high-purity argon inert atmosphere to 850 ℃ for dewetting, and obtaining a silver-copper alloy microsphere array;
s3, respectively placing the 4 parts of silver-copper alloy microsphere arrays obtained in the step S2 in a vacuum tube furnace, keeping the vacuum tube furnace at 900 ℃ and the vacuum degree of a cavity at 0.1Pa for 5 hours until silver is completely volatilized from the microspheres, and obtaining copper microsphere arrays;
as shown in fig. 5(a) - (d), the Scanning Electron Microscope (SEM) for 4 parts of copper microsphere arrays prepared by the above method is shown in fig. 5, and it can be known from fig. 5 that the ordered copper microsphere arrays can be obtained by the ordered micropore arrays in the metal mask in combination with the deposition of the silver-copper-silver film. By changing the size of the metal mask hole and the thickness of the copper film, the quasi-continuous adjustment of the diameter of the ordered copper micron sphere array from 1.5 to 20 mu m can be realized; similarly, by changing the center-to-center distance of the metal mask ordered micron holes, the quasi-continuous adjustment of the ordered copper micron ball array distance from 12.5 to 62 μm can be realized.
Example 6
The copper oxide microspheres-nanowires prepared in example 1 and example 4 were subjected to ultrasonic vibration experiments, and the whole and part of the copper microspheres, copper oxide microspheres-nanowires dispersed on the substrate, and copper oxide microspheres-nanowires after ultrasonic vibration for 10 minutes were photographed by a high power optical microscope, as shown in fig. 6. As can be seen from the pictures, the copper powder coated in example 1 is locally stacked, the adhesion between the copper oxide microsphere-nanowire generated after thermal oxidation and the substrate is not strong, and the local peeling phenomenon (c) is found after ultrasonic vibration. In example 4, the copper microspheres obtained by infiltrating and removing the silver-copper-silver film are dispersed in a single layer, and the adhesion between the copper oxide microsphere-nanowire hierarchical structure and the substrate after thermal oxidation is relatively tight (f).
Example 7
The copper oxide microsphere-nanowire hierarchical structures obtained in the examples 1 and 4 are respectively used as carriers, and octadecyltrichlorosilane (C) is modified on the carriers 18 H 37 Cl 3 Si) hydrophobic monolayer, and then performing a contact angle test together with a blank planar substrate modified with a hydrophobic monolayer of octadecyltrichlorosilane, the result is shown in fig. 7, where fig. 7(a) is a blank planar substrate and the contact angle is 73 °; FIG. 7(b) shows the copper oxide microsphere-nanowire hierarchical structure prepared in example 1, with a contact angle of 104 °; fig. 7(c) is the copper oxide microsphere-nanowire hierarchical structure prepared in example 4, with a contact angle of 127 °; it can be known that, in example 4, the hydrophobicity of the copper oxide micro-sphere-nanowire micro-nano hierarchical structure obtained by infiltrating and removing the silver-copper-silver film is obviously superior to that of the copper oxide micro-sphere-nanowire micro-nano hierarchical structure obtained in example 1 and the blank planar substrate.
It should be understood by those skilled in the art that the foregoing is only illustrative of several embodiments of the invention, and not of all embodiments. It should be noted that many variations and modifications are possible to those skilled in the art, and all variations and modifications that do not depart from the gist of the invention are intended to be within the scope of the invention as defined in the appended claims.
Claims (8)
1. A preparation method of a copper oxide micron sphere-nanowire micro-nano hierarchical structure is characterized in that, the copper oxide micro-sphere-nanowire micro-nano hierarchical structure comprises a substrate and a copper oxide micro-sphere-nanowire array attached to the substrate, the copper oxide microsphere-nanowire array is formed by orderly arranging a plurality of copper oxide microspheres-nanowires with uniform sizes at intervals, the copper oxide microsphere-nanowire comprises hemispherical copper oxide microspheres and copper oxide nanowires divergently distributed on the outer surfaces of the copper oxide microspheres, the plane of the copper oxide micro-sphere is connected with the substrate and has the diameter of 5-20 mu m, the number of the copper oxide nano-wires on a single copper oxide micro-sphere is 100-3500, the diameter of the copper oxide nano-wires is 20-1000nm, and the length of the copper oxide nano-wires is 0.5-100 mu m;
the preparation method comprises the following steps:
s1, orderly-arranged micropores with the size of 5-45 mu m and the interval of 12-100 mu m are prepared on a substrate with a clean surface, and a silver film, a copper film and a silver film are sequentially superposed and deposited in the micropores to prepare an ordered silver-copper-silver film array;
s2, heating the silver-copper-silver film deposited in the step S1 in a high-purity inert atmosphere to 800-950 ℃ for infiltration, and obtaining a silver-copper alloy microsphere array;
s3, heating the silver-copper alloy microsphere array obtained in the step S2 in a vacuum tube furnace until silver is completely volatilized from the silver-copper alloy microsphere, wherein the temperature of the vacuum tube furnace is 750-950 ℃, and the vacuum degree of a cavity is 0.001-10Pa, so as to obtain a copper microsphere array;
s4, heating the copper micro-sphere array prepared in the step S3 to the temperature of 300 ℃ and 700 ℃ in the air or oxygen atmosphere, preserving the heat for 0.5-30 hours, oxidizing the surface of the copper micro-sphere and growing a copper oxide nanowire to prepare the copper oxide micro-sphere-nanowire micro-nano hierarchical structure.
2. The preparation method of the copper oxide microsphere-nanowire micro-nano hierarchical structure according to claim 1, wherein a distance between adjacent copper oxide microspheres is 12-100 μm.
3. The method according to claim 1, wherein the substrate in step S1 is an insulating substrate or an insulating substrate plated with indium tin oxide or an insulating substrate of a fluorine-doped tin oxide conductive film, and the insulating substrate is made of any one of quartz glass, aluminum oxide, a silicon-silicon oxide composite material and a silicon-silicon nitride composite material.
4. The method for preparing the copper oxide microsphere-nanowire micro-nano hierarchical structure according to claim 1, wherein the film deposition mode in step S1 is any one of magnetron sputtering, direct current sputtering, thermal evaporation, electron beam evaporation and pulsed laser deposition.
5. The method for preparing the copper oxide microsphere-nanowire micro-nano hierarchical structure according to claim 1, wherein the step S1 is to prepare an ordered silver-copper-silver thin film array on the substrate by the specific steps of: and (2) tightly attaching a stainless steel or copper or molybdenum metal mask with the thickness of 10-100 mu m and orderly-arranged micropores penetrating through the metal mask to the surface of the substrate, putting the substrate attached with the mask into a vacuum chamber, sequentially superposing and depositing a silver film, a copper film and a silver film, and then removing the metal mask on the substrate to obtain an ordered silver-copper-silver film array on the substrate.
6. The method for preparing the copper oxide microsphere-nanowire micro-nano hierarchical structure according to claim 1, wherein the step S1 comprises the following specific steps of: spin-coating a photoresist film on a substrate with the thickness of 10-20 microns, baking and curing, then using photoetching and laser direct writing to describe a micron hole array which is orderly arranged, developing to obtain the micron hole array which penetrates through the photoresist film on the photoresist film, putting the developed substrate into a vacuum chamber, sequentially superposing and depositing a silver film, a copper film and a silver film, putting the substrate into stripping liquid, and removing the photoresist film and a metal film deposited above the photoresist film to prepare an ordered silver-copper-silver film array deposited on the substrate;
or spin-coating an electron beam adhesive film with the thickness of 10-20 μm on the substrate, baking and curing, using an electron beam for exposure, engraving the orderly-arranged micropore array, developing to obtain the micropore array penetrating through the electron beam adhesive film on the electron beam adhesive film, putting the developed substrate into a vacuum chamber, sequentially superposing and depositing a silver film, a copper film and a silver film, putting the substrate into stripping liquid, and removing the residual electron beam adhesive and the metal film above the electron beam adhesive film to obtain the ordered silver-copper-silver film array deposited on the substrate.
7. The method for preparing the copper oxide microsphere-nanowire micro-nano hierarchical structure according to claim 1, wherein the shape of the micropores in step S1 is any one of a square, a regular hexagon and a circular hole.
8. The method for preparing the copper oxide microsphere-nanowire micro-nano hierarchical structure according to claim 1, wherein in step S1, the thickness of the copper film is 10-3000nm, the thickness of the silver film is 20-4000nm, the thickness of the copper film accounts for 1-41% of the total thickness of the silver-copper-silver film, and the total thickness of the silver-copper-silver film is greater than 3% of the diameter of the micrometer pore ruler.
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