CN102199003B - Porous membrane with two-dimensional ordered arrangement, and preparation method thereof - Google Patents
Porous membrane with two-dimensional ordered arrangement, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a porous membrane with a two-dimensional ordered arrangement, and a preparation method thereof. The porous membrane comprises a oxide with large spherical apertures and small spherical apertures, wherein a large spherical aperture size is in a range of 250nm to 5000nm and a small spherical aperture size is in a range of 50nm to 250nm, and a ratio of the large spherical aperture size to the small spherical aperture size is (5 to20) to 1. A thickness of the membrane is in a range of 250nm to 25000nm. In each layer of the membrane, the large spherical apertures are arranged according to an ordered hexagonal structure, and the small spherical apertures are arranged among the large spherical apertures and are communicated with the large apertures. The steps of the preparation method comprises immersing a two-dimensional ordered colloidal crystal template into a semiconductor oxide precursor solution with a concentration of from 0.05M to 0.2M, collecting two-dimensional ordered colloidal crystals by a substrate with a needed shape when the two-dimensional ordered colloidal crystals are separated from a previous substrate and float in the semiconductor oxide precursor solution, heating the substrate covered with the two-dimensional ordered colloidal crystal dipped with the semiconductor oxide precursor solution at a temperature of from 80 DEG C to 120 DEG C for 1 to 4 hours, repeating the above steps at least one time or not repeating the above steps, and annealing the resulting products at a temperature of from 300 DEG C to 4000 DEG C for 1 to 4 hours to obtain the porous membrane with a two-dimensional ordered arrangement. The porous membrane can be widely applied to the multiple fields of phonon diffraction grids, optical filters, interferometers, and chemical and biological sensors.
Description
Technical field
The present invention relates to a kind of porous membrane and preparation method, especially a kind of porous membrane with two-dimensional ordered and preparation method thereof.
Background technology
The orderly hole of micro-nano structure film is because its numerous new good characteristics, can be widely used in the fields such as phonon diffraction grid, optical filter, selective light resorber, interferometer, reflection coating, photocell, chemistry and biosensor, in addition, this class film also has important application prospect at aspects such as microelectronics, magnetics, catalysis and nanophotonics.Up to now, the orderly hole of the micro-nano structure film that people consist of for the hole that obtains two kinds of different diameters, done unremitting effort, such as a kind of " multi-layer classification nanostructure ordered hole thin film type gas-sensitive sensor and preparation method thereof " of the applicant of disclosing among the disclosed Chinese invention patent application Publication Specification CN 101435795A on May 20th, 2009.It is intended to provide, and a kind of universality is good, highly sensitive, fast response time, thin film type gas-sensitive sensor simple for production and its preparation method.Gas sensor comprises substrate, electrode and covers thereon air-sensitive film, wherein film by two-layer above, be Hexagonal array closely and the spherical poroid conductor oxidate that is interconnected consists of, the aperture of spherical pore is 100～5000nm, the hole size of same layer is identical, and the pore size ratio between different layers is 1.5～10: 1; The preparation method is, colloid monolayer crystal template immersion concentration with different sphere diameters is in the conductor oxidate precursor solution of 0.05～0.2M first, after the colloid monolayer crystal disengaging substrate of different sphere diameters swims in the surface of precursor solution, one of pick up in the colloid monolayer crystal with the substrate gradation with electrode of desired shape, and heating 1～4h under placing 80～120 ℃, be placed on again 350～550 ℃ of lower annealing 1～4h, make the multi-layer classification nanostructure ordered hole thin film type gas-sensitive sensor.But, this thin film type gas-sensitive sensor and preparation method thereof all exists the shortcoming part, at first, though the film of gas sensor is made of the spherical pore of two kinds of different diameters, the spherical pore of right its different diameter but is distributed in the different levels, limit the field of its application and reduced its characteristic, make it can not be used for the spherical pore of different diameter at the same layer film, and the real requirement of minor diameter spherical pore between this layer major diameter spherical pore restricted again between two kinds of different diameter spherical pores the performance because of the orderly pore membrane characteristic of the due micro-nano structure of contact; Secondly, the preparation method can not make and contain two kinds of different diameter spherical pores on the same layer film, and the film of minor diameter spherical pore between this layer major diameter spherical pore.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of spherical pore of different diameter on the same layer film for overcoming shortcoming part of the prior art, and the porous membrane with two-dimensional ordered of minor diameter spherical pore between this layer major diameter spherical pore.
Another technical problem that the present invention will solve is for providing a kind of preparation method of porous membrane with two-dimensional ordered.
For solving technical problem of the present invention, the technical scheme that adopts is: porous membrane with two-dimensional ordered is comprised of substrate and the film on it, particularly,
Described film is made of the spherical poroid oxide compound of two kinds of different diameters, and the size between described two kinds of spherical pore diameters is 5～20: 1, and wherein, the diameter of major diameter spherical pore is that the diameter of 250～5000nm, minor diameter spherical pore is 50～250nm;
Described every layer of major diameter spherical pore arranged by six side's ordered structures, and described minor diameter spherical pore and is interconnected between every layer of large and small diameter spherical pore between this layer major diameter spherical pore;
The thickness of described film is 250～25000nm, and described oxide compound is conductor oxidate.
As the further improvement of porous membrane with two-dimensional ordered, described conductor oxidate is indium trioxide, or tindioxide, or zinc oxide, or ferric oxide; Described substrate is glass, or monocrystalline silicon piece, or pottery, or mica, or quartzy, and being shaped as of substrate is plane, or convex-shaped, or concave shape, or dome shape.
For solving another technical problem of the present invention, another technical scheme that adopts is: the preparation method of porous membrane with two-dimensional ordered comprises that the colloidal spheres with two kinds of different diameters invests substrate surface formation major diameter colloidal spheres by six side's ordered structure monolayer alignment, the binary ordered colloidal crystal template of minor diameter colloidal spheres between the major diameter colloidal spheres, and particularly completing steps is as follows:
Step 1, first the binary ordered colloidal crystal template being immersed concentration is in the conductor oxidate precursor solution of 0.05～0.2M, after the binary ordered colloidal crystal breaks away from substrate and swims in the precursor solution, substrate with desired shape picks up the binary ordered colloidal crystal, and make it be covered in substrate surface, again the substrate that is covered with the binary ordered colloidal crystal that is soaked with precursor solution on it is placed 80～120 ℃ of lower heating 1～4h;
Step 2, the number of times of repeating step 1 be more than 0 time after, be placed on 300～400 ℃ of lower annealing 1～4h, make porous membrane with two-dimensional ordered.
As the preparation method's of porous membrane with two-dimensional ordered further improvement, described conductor oxidate precursor solution is indium nitrate solution, or tin tetrachloride solution, or zinc acetate solution, or iron nitrate solution; The number of times of described repeating step 1 is 1～4 time; Described temperature rise rate when being warming up to 300～400 ℃ is 3～10 ℃/min; Being shaped as of described substrate is plane, or convex-shaped, or concave shape, or dome shape, and substrate is glass, or monocrystalline silicon piece, or pottery, or mica, or quartzy; It is that 10～30: 1 ratio mixes according to volume ratio that the forming of described binary ordered colloidal crystal template is mass percent solubility first 1.5～10% major diameter polystyrene colloid ball solution and minor diameter polystyrene colloid ball solution, obtain mixed solution, spin coating is thrown away after mixed solution being dropped in the substrate again, is 24～28 ℃ seasoning afterwards through temperature; It is 4～10 μ L that described mixed solution drops to suprabasil volume, and the rotating speed when spin coating is thrown away is 300～1000r/s.
Beneficial effect with respect to prior art is, one, use respectively scanning electron microscope and X-ray diffractometer to characterize to the product that makes, by its result as can be known, the smooth surface of product, even thickness, it is the film that places the spherical poroid oxide compound by two kinds of different diameters on the substrate to consist of, wherein, the thickness of film is 250～25000nm, size between two kinds of spherical pore diameters is 5～20: 1, the diameter of major diameter spherical pore is 250～5000nm, the diameter of minor diameter spherical pore is 50～250nm, every layer of major diameter spherical pore arranged by six side's ordered structures, the minor diameter spherical pore is between this layer major diameter spherical pore, and every layer large, be interconnected between the minor diameter spherical pore.Oxide compound is conductor oxidate, and it is indium trioxide, or tindioxide, or zinc oxide, or ferric oxide.Substrate is glass, or monocrystalline silicon piece, or pottery, or mica, or quartzy, and being shaped as of substrate is plane, or convex-shaped, or concave shape, or dome shape; They are two years old, the spherical pore of two kinds of different diameters of this employing is on the same layer film, and the porous membrane with two-dimensional ordered of minor diameter spherical pore between this layer major diameter spherical pore, not only gather around the advantage of eurypyloue rapid diffusion and transmission, and also contain simultaneously foraminate high-specific surface area and highly active characteristics, the characteristic and the field that has enlarged its application of the orderly pore membrane of micro-nano structure have greatly been improved, only need the real requirement of this kind structure except having satisfied, its performance is fully played; They are three years old, the preparation method has universality, as long as choose the binary ordered colloidal crystal template of suitable aperture and aperture ratio, by changing concentration and the chemical ingredients of precursor solution, just can synthesize the large-area porous membrane with two-dimensional ordered of heterogeneity and film thickness.That is, not only can prepare the inorganic semiconductor porous membrane with two-dimensional ordered, and can prepare organic porous membrane with two-dimensional ordered, greatly improve its value in actual applications; Its four, equipment used in the preparation process is few, inexpensive, technique is simple, cost is low, and is pollution-free, is suitable for large-scale industrial production.
Further embodiment as beneficial effect, the one, conductor oxidate is preferably indium trioxide or tindioxide or zinc oxide or ferric oxide, substrate is preferably glass or monocrystalline silicon piece or pottery or mica or quartz, the shape of substrate is preferably plane or convex-shaped or concave shape or dome shape, not only so that raw-material source, has also been satisfied various use occasions than horn of plenty to the requirement of product component and shape; The 2nd, the conductor oxidate precursor solution is preferably indium nitrate solution or tin tetrachloride solution or zinc acetate solution or iron nitrate solution, except the shaping that is beneficial to conductor oxidate, also makes the easier enforcement of preparation technology and flexible; The 3rd, the number of times of repeating step 1 is preferably 1～4 time, has guaranteed that the thickness of product can satisfy actual application demand, is again stay-in-grade; The 4th, the temperature rise rate when being warming up to 300～400 ℃ is preferably 3～10 ℃/min, has guaranteed the quality of product and the stability of quality; The 5th, the formation of binary ordered colloidal crystal template is preferably and first mass percent solubility is 1.5～10% major diameter polystyrene colloid ball solution and minor diameter polystyrene colloid ball solution is that 10～30: 1 ratio mixes according to volume ratio, obtain mixed solution, spin coating is thrown away after mixed solution being dropped in the substrate again, be 24～28 ℃ seasoning afterwards through temperature, guaranteed that the binary ordered colloidal crystal template that obtains is that to place the suprabasil thickness that is made of the polystyrene colloid ball of two kinds of different diameters be the colloidal crystal of 250～5000nm, size between two kinds of colloidal spheres diameters is 5～20: 1, wherein, the spherical diameter of major diameter colloidal spheres is 250～5000nm, the spherical diameter of minor diameter colloidal spheres is 50～250nm, and the diameter between no matter large or small diameter colloidal spheres is poor and how blending ratio changes, all by six side's ordered structure monolayer alignment, the minor diameter colloidal spheres is all between the major diameter colloidal spheres for major diameter colloidal spheres in the colloidal crystal; The 6th, mixed solution drops to suprabasil volume and is preferably 4～10 μ L, is beneficial to the formation of template, and the rotating speed when spin coating is thrown away is preferably 300～1000r/s, is convenient to mixed solution is thrown away equably.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 is one of result who respectively the binary ordered colloidal crystal template that obtains and the product use scanning electron microscope (SEM) that makes is characterized.Wherein, Figure 1A is for being that the polystyrene colloid ball of 1000nm and 200nm invests major diameter colloidal spheres that plane forms by the SEM photo of six side's ordered structure monolayer alignment, the binary ordered colloidal crystal template of minor diameter colloidal spheres between the major diameter colloidal spheres with diameter, and the upper left corner of photo is its SEM photo that has amplified; Figure 1B is take the binary ordered colloidal crystal template shown in Figure 1A as template, tin tetrachloride solution is the conductor oxidate precursor solution, plane ceramic plate is the 1000nm major diameter spherical pore periodic arrangement that substrate makes, and 200nm minor diameter spherical pore is centered around the product between its ball crack---the SEM photo of porous membrane with two-dimensional ordered.
Fig. 2 be to take diameter as 2000nm and the binary ordered colloidal crystal template made of the polystyrene colloid ball of 200nm be template, indium nitrate solution is precursor solution, the result that the product that plane quartz makes for substrate uses scanning electron microscope to characterize.
Fig. 3 is the result who uses X-ray diffraction (XRD) instrument to characterize to Figure 1B and product shown in Figure 2 respectively.Wherein, Fig. 3 A is the XRD spectra of product shown in Figure 1B, and Fig. 3 B is the XRD spectra of product shown in Figure 2; By the position of each diffraction peak in these two XRD spectra and relative intensity as can be known, product is made of tindioxide shown in the corresponding Figure 1B of Fig. 3 A, and the corresponding product shown in Figure 2 of Fig. 3 B is made of indium trioxide.
Embodiment
At first buy from market or make with ordinary method:
Mass percent solubility is 1.5～10% major diameter polystyrene colloid ball solution and minor diameter polystyrene colloid ball solution; Wherein, the colloidal spheres diameter of major diameter polystyrene colloid ball solution is that the colloidal spheres diameter of 250～5000nm, minor diameter polystyrene colloid ball solution is 50～250nm.On this basis, first mass percent solubility being 1.5～10% major diameter polystyrene colloid ball solution and minor diameter polystyrene colloid ball solution is that 10～30: 1 ratio mixes according to volume ratio, obtain mixed solution, spin coating is thrown away after mixed solution being dropped in the substrate again, wherein, it is 4～10 μ L that mixed solution drops to suprabasil volume, rotating speed when spin coating is thrown away is 300～1000r/s, be 24～28 ℃ seasoning afterwards through temperature, obtain as or be similar to the colloidal spheres with two kinds of different diameters shown in Figure 1A and invest substrate surface formation 250～5000nm major diameter colloidal spheres by six side's ordered structure monolayer alignment, the binary ordered colloidal crystal template of 50～250nm minor diameter colloidal spheres between 250～5000nm major diameter colloidal spheres.
Indium nitrate solution, tin tetrachloride solution, zinc acetate solution and iron nitrate solution as the conductor oxidate precursor solution.
As glass, monocrystalline silicon piece, pottery, mica and the quartz of substrate, wherein, being shaped as of substrate is plane, or convex-shaped, or concave shape, or dome shape.
Then,
Embodiment 1
The concrete steps of preparation are:
Step 1, the binary ordered colloidal crystal template immersion concentration that first the colloidal spheres diameter on it is respectively 1000nm and 200nm is in the conductor oxidate precursor solution of 0.05M, after the binary ordered colloidal crystal breaks away from substrate and swims in the precursor solution, substrate with desired shape picks up the binary ordered colloidal crystal, and makes it be covered in substrate surface; Wherein, the conductor oxidate precursor solution is tin tetrachloride solution, and substrate is plane pottery.Again the substrate that is covered with the binary ordered colloidal crystal that is soaked with precursor solution on it is placed 80 ℃ of lower heating 4h.
Step 2 after the number of times of repeating step 1 is 0 time, is placed on 300 ℃ of lower annealing 4h; Temperature rise rate when wherein, being warming up to 300 ℃ is 3 ℃/min.Make as shown in Figure 1B, and the porous membrane with two-dimensional ordered shown in the curve among Fig. 3 A.
Embodiment 2
The concrete steps of preparation are:
Step 1, the binary ordered colloidal crystal template immersion concentration that first the colloidal spheres diameter on it is respectively 2000nm and 200nm is in the conductor oxidate precursor solution of 0.08M, after the binary ordered colloidal crystal breaks away from substrate and swims in the precursor solution, substrate with desired shape picks up the binary ordered colloidal crystal, and makes it be covered in substrate surface; Wherein, the conductor oxidate precursor solution is indium nitrate solution, and substrate is plane quartz.Again the substrate that is covered with the binary ordered colloidal crystal that is soaked with precursor solution on it is placed 90 ℃ of lower heating 3h.
Step 2 after the number of times of repeating step 1 is 1 time, is placed on 330 ℃ of lower annealing 3h; Temperature rise rate when wherein, being warming up to 330 ℃ is 5 ℃/min.Make as shown in Figure 2, and the porous membrane with two-dimensional ordered shown in the curve among Fig. 3 B.
Embodiment 3
The concrete steps of preparation are:
Step 1, the binary ordered colloidal crystal template immersion concentration that first the colloidal spheres diameter on it is respectively 1000nm and 200nm is in the conductor oxidate precursor solution of 0.1M, after the binary ordered colloidal crystal breaks away from substrate and swims in the precursor solution, substrate with desired shape picks up the binary ordered colloidal crystal, and makes it be covered in substrate surface; Wherein, the conductor oxidate precursor solution is tin tetrachloride solution, and substrate is plane pottery.Again the substrate that is covered with the binary ordered colloidal crystal that is soaked with precursor solution on it is placed 100 ℃ of lower heating 2h.
Step 2 after the number of times of repeating step 1 is 2 times, is placed on 350 ℃ of lower annealing 2h; Temperature rise rate when wherein, being warming up to 350 ℃ is 7 ℃/min.Make as shown in Figure 1B, and the porous membrane with two-dimensional ordered shown in the curve among Fig. 3 A.
Embodiment 4
The concrete steps of preparation are:
Step 1, the binary ordered colloidal crystal template immersion concentration that first the colloidal spheres diameter on it is respectively 2000nm and 200nm is in the conductor oxidate precursor solution of 0.015M, after the binary ordered colloidal crystal breaks away from substrate and swims in the precursor solution, substrate with desired shape picks up the binary ordered colloidal crystal, and makes it be covered in substrate surface; Wherein, the conductor oxidate precursor solution is indium nitrate solution, and substrate is plane quartz.Again the substrate that is covered with the binary ordered colloidal crystal that is soaked with precursor solution on it is placed 110 ℃ of lower heating 1.5h.
Step 2 after the number of times of repeating step 1 is 3 times, is placed on 380 ℃ of lower annealing 1.5h; Temperature rise rate when wherein, being warming up to 380 ℃ is 8.5 ℃/min.Make as shown in Figure 2, and the porous membrane with two-dimensional ordered shown in the curve among Fig. 3 B.
Embodiment 5
The concrete steps of preparation are:
Step 1, the binary ordered colloidal crystal template immersion concentration that first the colloidal spheres diameter on it is respectively 1000nm and 200nm is in the conductor oxidate precursor solution of 0.2M, after the binary ordered colloidal crystal breaks away from substrate and swims in the precursor solution, substrate with desired shape picks up the binary ordered colloidal crystal, and makes it be covered in substrate surface; Wherein, the conductor oxidate precursor solution is tin tetrachloride solution, and substrate is plane pottery.Again the substrate that is covered with the binary ordered colloidal crystal that is soaked with precursor solution on it is placed 120 ℃ of lower heating 1h.
Step 2 after the number of times of repeating step 1 is 4 times, is placed on 400 ℃ of lower annealing 1h; Temperature rise rate when wherein, being warming up to 400 ℃ is 10 ℃/min.Make as shown in Figure 1B, and the porous membrane with two-dimensional ordered shown in the curve among Fig. 3 A.
Select respectively again the colloidal spheres diameter on it to be respectively the binary ordered colloidal crystal template that the arbitrary diameter among 250～5000nm and the 50～250nm forms, and select indium nitrate solution or tin tetrachloride solution or zinc acetate solution or iron nitrate solution as the conductor oxidate precursor solution, glass or monocrystalline silicon piece or pottery or mica or quartz as substrate, wherein, substrate be shaped as plane or convex-shaped or concave shape or dome shape, repeat above-described embodiment 1～5, made equally as or be similar to Figure 1B or shown in Figure 2, and as or be similar to the porous membrane with two-dimensional ordered shown in the curve among Fig. 3 A or Fig. 3 B.
Obviously, those skilled in the art can carry out various changes and modification to porous membrane with two-dimensional ordered of the present invention and preparation method thereof and 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)
1. a porous membrane with two-dimensional ordered is comprised of substrate and the film on it, it is characterized in that:
Described film is made of the spherical poroid oxide compound of two kinds of different diameters, and the size between described two kinds of spherical pore diameters is 5～20: 1, and wherein, the diameter of major diameter spherical pore is that the diameter of 250～5000nm, minor diameter spherical pore is 50～250nm;
Described every layer of major diameter spherical pore arranged by six side's ordered structures, and described minor diameter spherical pore and is interconnected between every layer of large and small diameter spherical pore between this layer major diameter spherical pore;
The thickness of described film is 250～25000nm, and described oxide compound is conductor oxidate.
2. porous membrane with two-dimensional ordered according to claim 1 is characterized in that conductor oxidate is indium trioxide, or tindioxide, or zinc oxide, or ferric oxide.
3. porous membrane with two-dimensional ordered according to claim 1 is characterized in that substrate is glass, or monocrystalline silicon piece, or pottery, or mica, or quartzy, and being shaped as of substrate is plane, or convex-shaped, or concave shape, or dome shape.
4. the preparation method of the described porous membrane with two-dimensional ordered of claim 1, comprise that the colloidal spheres with two kinds of different diameters invests substrate surface formation major diameter colloidal spheres by six side's ordered structure monolayer alignment, the binary ordered colloidal crystal template of minor diameter colloidal spheres between the major diameter colloidal spheres, is characterized in that completing steps is as follows:
Step 1, first the binary ordered colloidal crystal template being immersed concentration is in the conductor oxidate precursor solution of 0.05～0.2M, after the binary ordered colloidal crystal breaks away from substrate and swims in the precursor solution, substrate with desired shape picks up the binary ordered colloidal crystal, and make it be covered in substrate surface, again the substrate that is covered with the binary ordered colloidal crystal that is soaked with precursor solution on it is placed 80～120 ℃ of lower heating 1～4h;
Step 2, the number of times of repeating step 1 be more than 0 time after, be placed on 300～400 ℃ of lower annealing 1～4h, make porous membrane with two-dimensional ordered.
5. the preparation method of porous membrane with two-dimensional ordered according to claim 4 is characterized in that the conductor oxidate precursor solution is indium nitrate solution, or tin tetrachloride solution, or zinc acetate solution, or iron nitrate solution.
6. the preparation method of porous membrane with two-dimensional ordered according to claim 4, the number of times that it is characterized in that repeating step 1 is 1～4 time.
7. the preparation method of porous membrane with two-dimensional ordered according to claim 4, the temperature rise rate when it is characterized in that being warming up to 300～400 ℃ is 3～10 ℃/min.
8. the preparation method of porous membrane with two-dimensional ordered according to claim 4 is characterized in that being shaped as of substrate is plane, or convex-shaped, or concave shape, or dome shape, and substrate is glass, or monocrystalline silicon piece, or pottery, or mica, or quartzy.
9. the preparation method of porous membrane with two-dimensional ordered according to claim 4, it is characterized in that it is that 10～30: 1 ratio mixes according to volume ratio that forming of binary ordered colloidal crystal template is mass percent solubility first 1.5～10% major diameter polystyrene colloid ball solution and minor diameter polystyrene colloid ball solution, obtain mixed solution, spin coating is thrown away after mixed solution being dropped in the substrate again, is 24～28 ℃ seasoning afterwards through temperature.
10. the preparation method of porous membrane with two-dimensional ordered according to claim 9 is characterized in that it is 4～10 μ L that mixed solution is dropped to suprabasil volume, and the rotating speed when spin coating is thrown away is 300～1000r/s.
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| CN103288359B (en) * | 2013-04-03 | 2018-03-30 | 中国科学院合肥物质科学研究院 | The oxygen plasma irradiating preparation process of the structurally ordered porous array of oxide micro-nano rice |
| CN103739007B (en) * | 2013-12-30 | 2016-01-20 | 扬州大学 | The porous SnO 2 nanostructure that template synthesis size is controlled |
| CN105016296A (en) * | 2015-06-11 | 2015-11-04 | 吉林大学 | Three-dimensionally ordered macro-porous structured thin film and electric sensor for detecting diabetes and lung cancer markers |
| TWI610804B (en) * | 2016-05-23 | 2018-01-11 | 國立成功大學 | Energy-saving Glass and Method of Manufacturing the Same |
| CN106082363B (en) * | 2016-05-26 | 2017-09-19 | 中国科学院合肥物质科学研究院 | Iron-doped Nickel Oxide composite hollow ball array films and preparation method thereof |
| CN108963080B (en) * | 2018-07-07 | 2020-05-26 | 河南大学 | Preparation method of porous organic semiconductor film |
| CN112340787B (en) * | 2020-11-09 | 2023-01-24 | 东北大学秦皇岛分校 | Single-phase spinel type high-entropy oxide, preparation method and application |
| CN115072765B (en) * | 2022-06-22 | 2023-06-23 | 通化师范学院 | Method for preparing hexagonal prism-shaped zinc oxide |
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| US5858462A (en) * | 1995-08-14 | 1999-01-12 | Central Glass Company, Limited | Porous metal-oxide thin film and method of forming same on glass substrate |
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