CN102167278A - Zinc oxide micro/nano composite structure array film and preparation method thereof - Google Patents
Zinc oxide micro/nano composite structure array film and preparation method thereof Download PDFInfo
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- CN102167278A CN102167278A CN2010101165944A CN201010116594A CN102167278A CN 102167278 A CN102167278 A CN 102167278A CN 2010101165944 A CN2010101165944 A CN 2010101165944A CN 201010116594 A CN201010116594 A CN 201010116594A CN 102167278 A CN102167278 A CN 102167278A
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Abstract
The invention discloses a zinc oxide micro/nano composite structure array film and a preparation method thereof. In the film, an ordered hexagonal single-layer sphere array is arranged on a substrate; each sphere consists of a dielectric sphere, and a gold film and a zinc oxide nano-stick/cone coated in sequence on the outer surface of the dielectric sphere; the outer diameter of the dielectric sphere is 1-30 mum; the thickness of the gold film is 5-50 mum; the stick/cone axis of the zinc oxide nano-stick/cone is vertical to a sphere center; the length of the stick/cone is 200-800 nanometers; the diameter of the stick/cone is 80-160 nanometers; and the taper of the cone is 3-30 degrees. The method comprises the following steps of: performing ion sputtering and gold film deposition on the substrate with a single-layer crystal template at the pressure of 5-10 Pa to obtain a gold film sphere array; putting the gold film sphere array in zinc oxide electrolyte with the temperature of 60-80 DEG C; and performing electrolytic deposition at the deposition current density of between -0.3 mA/cm<2> and -2.0 mA/cm<2> by adopting a three-electrode method for 30 minutes to 4 hours to obtain the zinc oxide micro/nano composite structure array film. The film can be widely applied to the fields of photoelectronic devices, surface microfluids, sensors and the like.
Description
Technical field
The present invention relates to a kind of little/nano compound structure array film and preparation method, especially a kind of zinc oxide is little/nano compound structure array film and preparation method thereof.
Background technology
Little/nano compound structure the array film that has micrometer structure array and nano structural material advantage simultaneously, because of its uniform surface, active high, Stability Analysis of Structures, coupling effect is strong, be worth and have important use, can be widely used in high activity, high stability and repeatable device.For example: polystyrene micron ball/composite structure of carbon nano tube array film has adjustable moistened surface behavior, can realize the surface super hydrophobic characteristic under given conditions, have more excellent adjustable wettability than a simple carbon nano-tube film or an orderly micron ball array.Again for example: noble metal is little/and the nano compound structure array combines the high activity feature of nanostructured and the high stability characteristics of ordered micro structure, have bigger advantage as the surface-enhanced Raman scattering activity substrate time.Nano zinc oxide material has abundant physics and chemical property, and it all has important use and is worth in fields such as opto-electronic device, surperficial microfluid, sensors.Thus, people are little in order to obtain/and the nano compound structure array done some trials and effort, as a kind of " two dimension, three-dimensional order nano structure metal materials and the preparation method that are made of hollow metal sphere " who discloses among the disclosed Chinese invention patent ublic specification of application CN 1487108A on April 7th, 2004.It is intended to provide a kind of two and three dimensions ordered nano-structure metal material and preparation method who is made up of the medium ball or the hollow metal spherical shell of metal parcel; Wherein, the sequential 2 D nano structure metal materials is to form two-dimensional array by six sides arrangement by the medium ball of metal parcel or hollow metal sphere on substrate, medium ball wherein is a colloidal spheres, metal can be gold or silver etc., the preparation method is template with the colloidal crystal, adopt first wicking sensitization, again the technology of chemical plating metal.But, no matter be the sequential 2 D nano structure metal materials, or its preparation method, all exist weak point, at first, though what constitute the sequential 2 D nano structure metal materials is had bigger size difference and is belonged to composite construction between the two by the medium spheroid of the medium ball of metal parcel and the bed thickness of the metal that its outer wrapping, yet it still belongs to nanoscale together and is not little/nano compound structure array, equally, the hollow metal sphere that constitutes the sequential 2 D nano structure metal materials is a nano-scale, only be again monoshell layer structure, rather than ectonexine has heteroid composite construction, thereby it is with the same by the medium ball of metal parcel, and having limited it can obtainable superior function and unique purposes; Secondly, no matter be the medium ball of metal parcel, or hollow metal sphere, its layer on surface of metal as shell is all too smooth, make its extremely difficulty higher specific surface area is arranged, especially metal level can't have the physics and the chemical property of zinc oxide film; Once more, the preparation method can not obtain ectonexine have different little/zinc oxide array thin film of nano compound structure.
Summary of the invention
The technical problem to be solved in the present invention is for overcoming weak point of the prior art, the outer surface that the micron ball that orderly six sides of a kind of individual layer arrange is provided be the zinc oxide of nano zine oxide little/the nano compound structure array film.
Another technical problem that the present invention will solve for provide a kind of zinc oxide little/preparation method of nano compound structure array film.
For solving technical problem of the present invention, the technical scheme that is adopted is: and zinc oxide is little/and the nano compound structure array film comprises the individual layer ball array that orderly six sides that are equipped with on the substrate arrange, particularly,
Ball in the described ball array is made of golden film and the zinc oxide nano rod/awl that medium ball and outer surface thereof are covered with successively, and wherein, the overall diameter of medium ball is that the thickness of 1～30 μ m, golden film is that the thickness of 5～50nm, zinc oxide nano rod/awl is 200～800nm;
The centre of sphere of the rod of described zinc oxide nano rod/awl/axis of cone line and described ball is perpendicular, and its rod/awl length is that 200～800nm, rod/awl diameter are that the tapering of 80～160nm, awl is 3～30 degree.
As zinc oxide little/the further improvement of nano compound structure array film, described medium ball is the polystyrene colloid ball, or silica spheres, or hollow ball.
For solving another technical problem of the present invention, another technical scheme that is adopted is: and zinc oxide is little/and the preparation method of nano compound structure array film comprises the single layer crystal template placed on the substrate, and the preparation of zinc oxide electrolyte, particularly completing steps is as follows:
Earlier the substrate that has the single layer crystal template on it being placed pressure is ion sputtering deposition gold film under 5～10Pa, obtain golden film ball array, be zinc oxide electrolyte under 60～80 ℃ with placing temperature with the substrate of golden film ball array on it again, with it as working electrode, in depositing current density be-0.3～-2.0mA/cm
2Under adopt three-electrode method electro-deposition 30min～4h, make zinc oxide little/the nano compound structure array film.
As zinc oxide little/preparation method's of nano compound structure array film further improvement, during described three-electrode method electro-deposition is graphite electrode to electrode, reference electrode is a saturated calomel electrode; Described single layer crystal template is made of the polystyrene colloid ball, or is made of silica spheres; Described substrate is a sheet metal, or monocrystalline silicon, or glass, or electro-conductive glass, or conductive rubber; Described zinc oxide electrolyte is that concentration is the zinc nitrate solution of 0.03～0.07M, or concentration is zinc nitrate/ammoniacal liquor aqueous phase solution of 0.03～0.07M; Described zinc nitrate/ammoniacal liquor aqueous phase solution becomes limpid for being that 65～75 ℃, concentration are the saturated ammoniacal liquor of dropping in the zinc nitrate solution of 0.03～0.07M to stirring temperature down until zinc nitrate solution; Described with zinc oxide little/the nano compound structure array film places dichloromethane solvent to remove the polystyrene colloid ball, obtains hollow little/nano compound structure array film; Described with zinc oxide little/the nano compound structure array film places the hydrofluoric acid solvent to remove silica spheres, obtains hollow little/nano compound structure array film.
Beneficial effect with respect to prior art is, one uses ESEM, transmission electron microscope and X-ray diffractometer to characterize respectively to the product that makes, and by its result as can be known, product is the individual layer ball array that places orderly six sides on the substrate to arrange.Golden film that ball in the ball array is covered with successively by medium ball and outer surface thereof and zinc oxide nano rod or zinc-oxide nano awl constitute; Wherein, medium ball is polystyrene colloid ball or silica spheres or hollow ball, and the overall diameter of medium ball is 1～30 μ m, and the thickness of golden film is 5～50nm, and the thickness of zinc oxide nano rod or zinc-oxide nano awl is 200～800nm.The rod of zinc oxide nano rod or zinc-oxide nano awl or the centre of sphere of axis of cone line and ball are perpendicular, and the diameter that its length excellent or awl is 200～800nm, rod or awl is that the tapering of 80～160nm, awl is 3～30 degree; Its two, this little/the nano compound structure array film both had the characteristics of nano zinc oxide material, and was good active as high-ratio surface, the high stability of micro array structure is arranged again, thereby makes it have high using value; They are three years old, product removes the geometric shape because of its imitative lotus leaf surface, be expected to be used for outside super hydrophobic surface and the related device, more can be used as the support substrate, further be applied to the field that other needs little/nano compound structure array, such as, hydatogenesis or sputtering sedimentation gold film or silverskin on product, this structure will have nanometer roughness and micro structure array characteristic simultaneously, will be a kind of very desirable surface-enhanced Raman scattering activity substrate; Its four, materials are few in the preparation process, and are pollution-free, belong to green synthesis techniques, and the production efficiency height, are suitable for large-scale industrial production; They are five years old, the preparation method has controllability and universality, by selection to the medium sphere diameter, can control the cycle of array, the current density by to electrolyte prescription, electro-deposition the time and the control of sedimentation time can obtain the configuration of surface and the relative dimensions of different structure, simultaneously, also the preparation method can be applied to the synthetic of other little/nano compound structure array film.
As the further embodiment of beneficial effect, the one, medium ball is preferably the polystyrene colloid ball, or silica spheres, or hollow ball, and that product has been obtained is little/combination property that the nano compound structure array is had; The 2nd, during the three-electrode method electro-deposition electrode is preferably graphite electrode, reference electrode is preferably saturated calomel electrode, all is beneficial to the enforcement of electro-deposition; The 3rd, the single layer crystal template preferably is made of polystyrene colloid ball or silica spheres, not only is convenient to the making of single layer crystal template, also is easy to medium ball is processed into hollow state; The 4th, substrate is preferably sheet metal, or monocrystalline silicon, or glass, or electro-conductive glass, or conductive rubber, except that substrate is had the leeway of bigger selection, also makes the easier enforcement of preparation technology and flexible; The 5th, zinc oxide electrolyte is that preferred concentration is the zinc nitrate solution of 0.03～0.07M, or preferred concentration is zinc nitrate/ammoniacal liquor aqueous phase solution of 0.03～0.07M, both guaranteed that zinc oxide can be assembled into the outer surface of golden film ball array equably, made again that the zinc oxide pattern that generates was controlled nano bar-shape or nanometer taper.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 is that the product that makes when using zinc nitrate solution as zinc oxide electrolyte uses one of result that ESEM (SEM) characterizes.Can find out that by this SEM photo the serve as reasons club of its excellent orientation of its axis centre of sphere of product is erected on the ball of the individual layer ball array that orderly six sides arrange and constitutes.
Fig. 2 is that the product that makes when using zinc nitrate/ammoniacal liquor aqueous phase solution as zinc oxide electrolyte uses one of result that ESEM characterizes.Can find out that by this SEM photo serve as reasons taper thing that its axis of cone line points to the centre of sphere of product is erected on the ball of individual layer ball array of orderly six sides arrangement and constitutes.
The specific embodiment
At first make or buy from market with conventional method:
The monodispersed diameter of commercialization is polystyrene colloid ball and the silica spheres of 1～30 μ m, and is made into corresponding single layer crystal template;
Sheet metal, monocrystalline silicon, glass, electro-conductive glass and conductive rubber as substrate;
Concentration as zinc oxide electrolyte is the zinc nitrate solution of 0.03～0.07M and zinc nitrate/ammoniacal liquor aqueous phase solution that concentration is 0.03～0.07M, wherein, zinc nitrate/ammoniacal liquor aqueous phase solution becomes limpid for being that 65～75 ℃, concentration are the saturated ammoniacal liquor of dropping in the zinc nitrate solution of 0.03～0.07M to stirring temperature down until zinc nitrate solution.
Then,
Embodiment 1
The concrete steps of preparation are:
Earlier with have on it by bulb diameter be the substrate of the single layer crystal template that constitutes of the polystyrene colloid ball (or silica spheres) of 2 μ m to place pressure be under the 5Pa, ion sputtering deposition thickness is one deck gold film of 5nm, obtains golden film ball array; Wherein, substrate is a glass.Be zinc oxide electrolyte under 60 ℃ with placing temperature with the substrate of golden film ball array on it again, with it as working electrode, in depositing current density be-0.3mA/cm
2Under adopt three-electrode method electro-deposition 4h; Wherein, during the three-electrode method electro-deposition is graphite electrode to electrode, and reference electrode is a saturated calomel electrode, and zinc oxide electrolyte is that concentration is the zinc nitrate solution of 0.03M.Make be similar to medium ball shown in Figure 1 be polystyrene colloid ball, polystyrene colloid outer surface of ball be covered with successively the zinc oxide of golden film and zinc oxide nano rod little/the nano compound structure array film.
If the zinc oxide electrolyte that uses is the zinc nitrate/ammoniacal liquor aqueous phase solution of concentration as 0.03M, then make be similar to medium ball shown in Figure 2 be polystyrene colloid ball, polystyrene colloid outer surface of ball be covered with successively the zinc oxide that golden film and zinc-oxide nano bore little/the nano compound structure array film.
If desire obtains hollow little/nano compound structure array film, then only need again above-mentioned product to be placed dichloromethane solvent to remove polystyrene colloid ball (or placing the hydrofluoric acid solvent to remove silica spheres), obtain being similar to medium ball shown in Figure 1 and be hollow ball, hollow ball outer surface be covered with successively the zinc oxide of golden film and zinc oxide nano rod little/the nano compound structure array film, or obtain being similar to medium ball shown in Figure 2 be hollow ball, hollow ball outer surface be covered with successively the zinc oxide of golden film and zinc-oxide nano awl little/the nano compound structure array film.
Embodiment 2
The concrete steps of preparation are:
Earlier with have on it by bulb diameter be the substrate of the single layer crystal template that constitutes of the polystyrene colloid ball (or silica spheres) of 2 μ m to place pressure be under the 6.5Pa, ion sputtering deposition thickness is one deck gold film of 15nm, obtains golden film ball array; Wherein, substrate is a glass.Be zinc oxide electrolyte under 65 ℃ with placing temperature with the substrate of golden film ball array on it again, with it as working electrode, in depositing current density be-0.6mA/cm
2Under adopt three-electrode method electro-deposition 2.5h; Wherein, during the three-electrode method electro-deposition is graphite electrode to electrode, and reference electrode is a saturated calomel electrode, and zinc oxide electrolyte is that concentration is the zinc nitrate solution of 0.04M.Make be similar to medium ball shown in Figure 1 be polystyrene colloid ball, polystyrene colloid outer surface of ball be covered with successively the zinc oxide of golden film and zinc oxide nano rod little/the nano compound structure array film.
If the zinc oxide electrolyte that uses is the zinc nitrate/ammoniacal liquor aqueous phase solution of concentration as 0.04M, then make be similar to medium ball shown in Figure 2 be polystyrene colloid ball, polystyrene colloid outer surface of ball be covered with successively the zinc oxide that golden film and zinc-oxide nano bore little/the nano compound structure array film.
If desire obtains hollow little/nano compound structure array film, then only need again above-mentioned product to be placed dichloromethane solvent to remove polystyrene colloid ball (or placing the hydrofluoric acid solvent to remove silica spheres), obtain being similar to medium ball shown in Figure 1 and be hollow ball, hollow ball outer surface be covered with successively the zinc oxide of golden film and zinc oxide nano rod little/the nano compound structure array film, or obtain being similar to medium ball shown in Figure 2 be hollow ball, hollow ball outer surface be covered with successively the zinc oxide of golden film and zinc-oxide nano awl little/the nano compound structure array film.
Embodiment 3
The concrete steps of preparation are:
Earlier with have on it by bulb diameter be the substrate of the single layer crystal template that constitutes of the polystyrene colloid ball (or silica spheres) of 2 μ m to place pressure be under the 8Pa, ion sputtering deposition thickness is one deck gold film of 25nm, obtains golden film ball array; Wherein, substrate is a glass.Be zinc oxide electrolyte under 70 ℃ with placing temperature with the substrate of golden film ball array on it again, with it as working electrode, in depositing current density be-1mA/cm
2Under adopt three-electrode method electro-deposition 1h; Wherein, during the three-electrode method electro-deposition is graphite electrode to electrode, and reference electrode is a saturated calomel electrode, and zinc oxide electrolyte is that concentration is the zinc nitrate solution of 0.05M.Make as shown in Figure 1 medium ball and be polystyrene colloid ball, polystyrene colloid outer surface of ball be covered with successively the zinc oxide of golden film and zinc oxide nano rod little/the nano compound structure array film.
If the zinc oxide electrolyte that uses is the zinc nitrate/ammoniacal liquor aqueous phase solution of concentration as 0.05M, then make as shown in Figure 2 medium ball and be polystyrene colloid ball, polystyrene colloid outer surface of ball be covered with successively the zinc oxide that golden film and zinc-oxide nano bore little/the nano compound structure array film.
If desire obtains hollow little/nano compound structure array film, then only need again above-mentioned product to be placed dichloromethane solvent to remove polystyrene colloid ball (or placing the hydrofluoric acid solvent to remove silica spheres), obtain as shown in Figure 1 medium ball and be hollow ball, hollow ball outer surface be covered with successively the zinc oxide of golden film and zinc oxide nano rod little/the nano compound structure array film, or obtain as shown in Figure 2 medium ball be hollow ball, hollow ball outer surface be covered with successively the zinc oxide of golden film and zinc-oxide nano awl little/the nano compound structure array film.
Embodiment 4
The concrete steps of preparation are:
Earlier with have on it by bulb diameter be the substrate of the single layer crystal template that constitutes of the polystyrene colloid ball (or silica spheres) of 2 μ m to place pressure be under the 9Pa, ion sputtering deposition thickness is one deck gold film of 33nm, obtains golden film ball array; Wherein, substrate is a glass.Be zinc oxide electrolyte under 75 ℃ with placing temperature with the substrate of golden film ball array on it again, with it as working electrode, in depositing current density be-1.5mA/cm
2Under adopt three-electrode method electro-deposition 45min; Wherein, during the three-electrode method electro-deposition is graphite electrode to electrode, and reference electrode is a saturated calomel electrode, and zinc oxide electrolyte is that concentration is the zinc nitrate solution of 0.06M.Make be similar to medium ball shown in Figure 1 be polystyrene colloid ball, polystyrene colloid outer surface of ball be covered with successively the zinc oxide of golden film and zinc oxide nano rod little/the nano compound structure array film.
If the zinc oxide electrolyte that uses is the zinc nitrate/ammoniacal liquor aqueous phase solution of concentration as 0.06M, then make be similar to medium ball shown in Figure 2 be polystyrene colloid ball, polystyrene colloid outer surface of ball be covered with successively the zinc oxide that golden film and zinc-oxide nano bore little/the nano compound structure array film.
If desire obtains hollow little/nano compound structure array film, then only need again above-mentioned product to be placed dichloromethane solvent to remove polystyrene colloid ball (or placing the hydrofluoric acid solvent to remove silica spheres), obtain being similar to medium ball shown in Figure 1 and be hollow ball, hollow ball outer surface be covered with successively the zinc oxide of golden film and zinc oxide nano rod little/the nano compound structure array film, or obtain being similar to medium ball shown in Figure 2 be hollow ball, hollow ball outer surface be covered with successively the zinc oxide of golden film and zinc-oxide nano awl little/the nano compound structure array film.
Embodiment 5
The concrete steps of preparation are:
Earlier with have on it by bulb diameter be the substrate of the single layer crystal template that constitutes of the polystyrene colloid ball (or silica spheres) of 2 μ m to place pressure be under the 10Pa, ion sputtering deposition thickness is one deck gold film of 50nm, obtains golden film ball array; Wherein, substrate is a glass.Be zinc oxide electrolyte under 80 ℃ with placing temperature with the substrate of golden film ball array on it again, with it as working electrode, in depositing current density be-2.0mA/cm
2Under adopt three-electrode method electro-deposition 30min; Wherein, during the three-electrode method electro-deposition is graphite electrode to electrode, and reference electrode is a saturated calomel electrode, and zinc oxide electrolyte is that concentration is the zinc nitrate solution of 0.07M.Make be similar to medium ball shown in Figure 1 be polystyrene colloid ball, polystyrene colloid outer surface of ball be covered with successively the zinc oxide of golden film and zinc oxide nano rod little/the nano compound structure array film.
If the zinc oxide electrolyte that uses is the zinc nitrate/ammoniacal liquor aqueous phase solution of concentration as 0.07M, then make be similar to medium ball shown in Figure 2 be polystyrene colloid ball, polystyrene colloid outer surface of ball be covered with successively the zinc oxide that golden film and zinc-oxide nano bore little/the nano compound structure array film.
If desire obtains hollow little/nano compound structure array film, then only need again above-mentioned product to be placed dichloromethane solvent to remove polystyrene colloid ball (or placing the hydrofluoric acid solvent to remove silica spheres), obtain being similar to medium ball shown in Figure 1 and be hollow ball, hollow ball outer surface be covered with successively the zinc oxide of golden film and zinc oxide nano rod little/the nano compound structure array film, or obtain being similar to medium ball shown in Figure 2 be hollow ball, hollow ball outer surface be covered with successively the zinc oxide of golden film and zinc-oxide nano awl little/the nano compound structure array film.
Selecting bulb diameter more respectively for use is that the polystyrene colloid ball or the silica spheres of the arbitrary bulb diameter among 1～30 μ m made the single layer crystal template; Selecting the concentration as zinc oxide electrolyte for use is the zinc nitrate solution of 0.03～0.07M, or concentration is zinc nitrate/ammoniacal liquor aqueous phase solution of 0.03～0.07M; Repeat the foregoing description 1～5, made equally as or be similar to medium ball illustrated in figures 1 and 2 be polystyrene colloid ball or silica spheres or hollow ball, polystyrene colloid ball or silica spheres or hollow ball outer surface be covered with successively the zinc oxide of golden film and zinc oxide nano rod or zinc-oxide nano awl little/the nano compound structure array film.
Obviously, those skilled in the art can/nano compound structure array film little to zinc oxide of the present invention and preparation method thereof carries out various changes and modification and does not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (10)
- A zinc oxide little/the nano compound structure array film, comprise the individual layer ball array that orderly six sides that are equipped with on the substrate arrange, it is characterized in that:Ball in the described ball array is made of golden film and the zinc oxide nano rod/awl that medium ball and outer surface thereof are covered with successively, and wherein, the overall diameter of medium ball is that the thickness of 1～30 μ m, golden film is that the thickness of 5～50nm, zinc oxide nano rod/awl is 200～800nm;The centre of sphere of the rod of described zinc oxide nano rod/awl/axis of cone line and described ball is perpendicular, and its rod/awl length is that 200～800nm, rod/awl diameter are that the tapering of 80～160nm, awl is 3～30 degree.
- 2. zinc oxide according to claim 1 is little/the nano compound structure array film, it is characterized in that medium ball is the polystyrene colloid ball, or silica spheres, or hollow ball.
- The described zinc oxide of claim 1 little/preparation method of nano compound structure array film, comprise the single layer crystal template is placed on the substrate, and the preparation of zinc oxide electrolyte, it is characterized in that completing steps is as follows:Earlier the substrate that has the single layer crystal template on it being placed pressure is ion sputtering deposition gold film under 5～10Pa, obtain golden film ball array, be zinc oxide electrolyte under 60～80 ℃ with placing temperature with the substrate of golden film ball array on it again, with it as working electrode, in depositing current density be-0.3～-2.0mA/cm 2Under adopt three-electrode method electro-deposition 30min～4h, make zinc oxide little/the nano compound structure array film.
- 4. zinc oxide according to claim 3 is little/preparation method of nano compound structure array film, and when it is characterized in that the three-electrode method electro-deposition is graphite electrode to electrode, reference electrode is a saturated calomel electrode.
- 5. zinc oxide according to claim 3 is little/preparation method of nano compound structure array film, and it is characterized in that the single layer crystal template is made of the polystyrene colloid ball, or constitute by silica spheres.
- 6. zinc oxide according to claim 3 is little/preparation method of nano compound structure array film, it is characterized in that substrate is a sheet metal, or monocrystalline silicon, or glass, or electro-conductive glass, or conductive rubber.
- 7. zinc oxide according to claim 3 is little/preparation method of nano compound structure array film, it is characterized in that zinc oxide electrolyte is that concentration is the zinc nitrate solution of 0.03～0.07M, or concentration is zinc nitrate/ammoniacal liquor aqueous phase solution of 0.03～0.07M.
- 8. zinc oxide according to claim 7 is little/preparation method of nano compound structure array film, it is characterized in that zinc nitrate/ammoniacal liquor aqueous phase solution for being that 65～75 ℃, concentration are the saturated ammoniacal liquor of dropping in the zinc nitrate solution of 0.03～0.07M to stirring temperature down, becomes limpid until zinc nitrate solution.
- 9. zinc oxide according to claim 5 is little/preparation method of nano compound structure array film, it is characterized in that with zinc oxide little/the nano compound structure array film places dichloromethane solvent to remove the polystyrene colloid ball, obtains hollow little/nano compound structure array film.
- 10. zinc oxide according to claim 5 is little/preparation method of nano compound structure array film, it is characterized in that with zinc oxide little/the nano compound structure array film places the hydrofluoric acid solvent to remove silica spheres, obtains hollow little/nano compound structure array film.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107101988A (en) * | 2017-03-16 | 2017-08-29 | 中国科学院合肥物质科学研究院 | A kind of high density nanometer pinpoint array of golden film covering and its application |
| CN108198670A (en) * | 2018-01-08 | 2018-06-22 | 江苏神马电力股份有限公司 | A kind of composite insulator and preparation method thereof |
| CN108459004A (en) * | 2018-01-17 | 2018-08-28 | 安徽农业大学 | A kind of preparation method of silver and gold nano grain coating zinc oxide surface enhanced Raman scattering effect substrate |
| CN110252297A (en) * | 2019-06-25 | 2019-09-20 | 中国科学院合肥物质科学研究院 | A kind of gold nano grain-zinc-oxide nano cap array and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1007750B1 (en) * | 1997-08-19 | 2004-05-26 | Titanox Developments Limited | Titanium alloy based dispersion-strengthened composites |
| CN1588650A (en) * | 2004-09-13 | 2005-03-02 | 武汉大学 | Method for preparing nano crystal thin film from nano particles |
| CN1751983A (en) * | 2005-10-20 | 2006-03-29 | 南京大学 | Non close parked metal hollow ball shell ordered network structure material and its making method |
| CN101559951A (en) * | 2009-05-15 | 2009-10-21 | 江苏大学 | Method for preparing nanoscale silica hollow microspheres |
-
2010
- 2010-02-26 CN CN2010101165944A patent/CN102167278B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1007750B1 (en) * | 1997-08-19 | 2004-05-26 | Titanox Developments Limited | Titanium alloy based dispersion-strengthened composites |
| CN1588650A (en) * | 2004-09-13 | 2005-03-02 | 武汉大学 | Method for preparing nano crystal thin film from nano particles |
| CN1751983A (en) * | 2005-10-20 | 2006-03-29 | 南京大学 | Non close parked metal hollow ball shell ordered network structure material and its making method |
| CN101559951A (en) * | 2009-05-15 | 2009-10-21 | 江苏大学 | Method for preparing nanoscale silica hollow microspheres |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107101988A (en) * | 2017-03-16 | 2017-08-29 | 中国科学院合肥物质科学研究院 | A kind of high density nanometer pinpoint array of golden film covering and its application |
| CN107101988B (en) * | 2017-03-16 | 2020-08-28 | 中国科学院合肥物质科学研究院 | Gold film covered high-density nanometer needle tip array and application thereof |
| CN108198670A (en) * | 2018-01-08 | 2018-06-22 | 江苏神马电力股份有限公司 | A kind of composite insulator and preparation method thereof |
| CN108459004A (en) * | 2018-01-17 | 2018-08-28 | 安徽农业大学 | A kind of preparation method of silver and gold nano grain coating zinc oxide surface enhanced Raman scattering effect substrate |
| CN110252297A (en) * | 2019-06-25 | 2019-09-20 | 中国科学院合肥物质科学研究院 | A kind of gold nano grain-zinc-oxide nano cap array and preparation method thereof |
| CN110252297B (en) * | 2019-06-25 | 2022-08-26 | 中国科学院合肥物质科学研究院 | Gold nanoparticle-zinc oxide nano-cap array and preparation method thereof |
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