CN1704150A - Shape controllable ordered expanded film material and preparation method thereof - Google Patents
Shape controllable ordered expanded film material and preparation method thereof Download PDFInfo
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- CN1704150A CN1704150A CN 200410044978 CN200410044978A CN1704150A CN 1704150 A CN1704150 A CN 1704150A CN 200410044978 CN200410044978 CN 200410044978 CN 200410044978 A CN200410044978 A CN 200410044978A CN 1704150 A CN1704150 A CN 1704150A
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Abstract
The invention discloses a shape-controlled rule through-hole film material and it's preparing method. It comprises underlay, especially underlay with thin film formed by single-layer inorganic sphere through-hole with the diameter at 50-1000nm, the pore wall thickness at 20-100nm and thin film thickness at 50-1000nm. It comprises the following steps: attaching colloid ball to the surface of underlay to form single-layer colloid crystal mode, especially infiltrating inorganic salt solution with density at 0.002-0.8 mole into the part between colloid balls and between colloid ball and underlay, then heating the mode at the temperature 70-90 deg. about 0.5-2.5 hours and annealing it at the temperature 350-450 deg. about 5-8 hours, at last putting it into water and putting it into ultrasonic about 0.5-1 hours.
Description
Technical field the present invention relates to a kind of thin-film material and method for making, especially controlled ordered porous thin-film material and the preparation method of form.
Background technology ordered porous thin-film material has a lot of excellent characteristic, and using value is all arranged in a lot of fields.For example can be used as catalyst, gas sensing device, photon and opto-electronic device, heat insulator, cell culture chamber and barrier film etc.; Also all has good application prospects in fields such as information storage, Recognition of Biomolecular, microelectronics and nano photoelectric.These structure and forms of using for the hole of thin-film material all have higher requirement.At present, people often use etching method in order to obtain the ordered porous thin-film material, as photoengraving, electron beam lithography, AFM etching, soft etching etc.But these methods all exist weak point, at first, fail to make the film of nanometer or micron-sized individual layer inorganic matter spherical pore formation, particularly fail to make the film of nanometer or micron-sized individual layer di-iron trioxide or metallic zinc or cerium oxide spherical pore formation; Secondly, to the requirement height of equipment, the structure and the form of operate loaded down with trivial details and hole are all wayward during preparation, make its production cost too high be difficult to obtain large-area thin-film material and realize industrial large-scale production.Though the defective that adopts the colloidal crystal template method to avoid etching method is also arranged,, colloidal spheres forms the spin-coating method or the vertical czochralski method of template as being invested substrate surface, but also one is to fail to obtain the film that nanometer or micron-sized individual layer inorganic matter spherical pore constitute, the 2nd, can not regulate effectively the structure and the form in the hole that obtained.
The summary of the invention the technical problem to be solved in the present invention is the limitation that overcomes above-mentioned various schemes, and a kind of practicality is provided, and prepares easy form controlled ordered porous thin-film material and preparation method.
The controlled ordered porous thin-film material of form comprises substrate, be covered with the film that individual layer inorganic matter spherical pore constitutes on the particularly said substrate, the diameter of said spherical pore is that 50～1000nm, pore wall thickness are 20～100nm, and the thickness of said film is 50～1000nm.
As the further improvement of the controlled ordered porous thin-film material of form, described inorganic matter is di-iron trioxide or metallic zinc or cerium oxide; Described spherical pore is six sides arrangement closely, and is interconnected between the hole; In the hole wall between described compact arranged three spherical pores leg-of-mutton aperture is arranged; Described substrate is glass or monocrystalline silicon piece or pottery or mica or quartz.
The controlled ordered porous thin-film preparation methods of form comprises colloidal spheres is invested substrate surface and forms colloidal crystal template, particularly earlier be that the diameter that 0.002～0.8 mole inorganic salt solution infiltrates on the substrate is between the polystyrene colloid ball of 50～1000nm with concentration, and between colloidal spheres and the substrate, the template that will be impregnated with inorganic salt solution again heated 0.5～2.5 hour down in 70～90 ℃, afterwards, place 350～450 ℃ to anneal 5～8 hours down template, at last, template under water is placed ultrasonic wave 0.5～1 hour, make the controlled ordered porous thin-film material of form.
As the further improvement of the controlled ordered porous thin-film preparation methods of form, described inorganic salt solution is iron nitrate solution or zinc acetate solution or cerous nitrate solution; Described iron nitrate solution or zinc acetate solution or cerous nitrate solution are added dropwise to the edge of colloidal crystal template, and colloidal crystal is floated; Step-length during described template annealing to 350～450 ℃ is 3～7 ℃/minute; Described hyperacoustic power is 80～420 watts.
Beneficial effect with respect to prior art is, one, after using field emission scanning electron microscope and x-ray diffractometer to observe and test respectively to the thin-film material that makes, from the stereoscan photograph that obtains and X-ray diffracting spectrum as can be known, the orderly spherical pore of individual layer that six sides are compact arranged by being for film, be interconnected between the hole, hole on framework (wall) is fine and close constitutes, it is covered in the surface of substrate, its aperture and film thickness are nanometer or micron order, hole wall is by inorganic matter, and promptly di-iron trioxide or metallic zinc or cerium oxide constitute; Its two, adopt inorganic salt solution, i.e. iron nitrate solution or zinc acetate solution or cerous nitrate solution, by the colloidal crystal template method, on different substrates,, just can synthesize the large tracts of land (cm of different bore dias as long as choose the polystyrene colloid ball of different-diameter and be made into colloidal crystal template
2Level) the orderly inorganic matter spherical pore of individual layer film, i.e. di-iron trioxide or metallic zinc or cerium oxide spherical pore film; They are three years old, concentration by changing inorganic salt solution and it is heating and curing below the glass point temperature of polystyrene colloid ball, just can be very neatly according to the hole wall of required acquisition different structure and form, its reason is in the process that is heating and curing, evaporation along with inorganic salt solution moisture, the polystyrene colloid ball also will deform, between ball and the ball and ball contact with point between the substrate and also can gradually become the face contact, this is directly connected to the form in final hole, and the difference of inorganic salt solution concentration, solution reaches capacity the needed time of state with regard to difference, the deformation extent of nature polystyrene colloid ball is also different, thereby the structure in the final hole that obtains is also just different with form, as under the inorganic salt solution of higher concentration, can obtain the composite holes array of spherical pore-triangular apertures, also promptly also has leg-of-mutton aperture in the hole wall between compact arranged three spherical pores, along with the reduction of inorganic salt solution concentration, triangular apertures fades away and the opening shape of only remaining spherical pore and spherical pore is also changed to regular hexagon by circle; Its four, drip iron nitrate solution or zinc acetate solution or cerous nitrate solution in the edge of colloidal crystal template, and colloidal crystal floated, can be easier to control the opening shape of spherical pore; They are five years old, under the melting temperature that is higher than the polystyrene colloid ball template after solidifying is being carried out heating anneal, burnt the polystyrene colloid ball and promoted material to become needed material mutually, the template after the annealing has been carried out ultrasonic cleaning again obtained stable pore structure; Its six, have good universality, the kind of hole wall material can spread all over the inorganic matter that metal, oxide and semiconductor are formed; Its seven, equipment used in the preparation process is few, inexpensive, technology is simple, cost is low, and is pollution-free, is suitable for suitability for industrialized production.
Description of drawings is described in further detail optimal way of the present invention below in conjunction with accompanying drawing.
Fig. 1 be to thin-film material take the photograph after with the observation of Japanese JEOL 6700 type field emission scanning electron microscopes photo, wherein, Figure 1A～E is for being that colloidal crystal template, inorganic salt solution that the polystyrene colloid ball of 1000nm is made are the pore structure of the orderly spherical pore film of individual layer of the different shape that forms of iron nitrate solution with the diameter, and what the concentration of iron nitrate solution was selected for use respectively in Figure 1A～E is: 0.8M, 0.08M, 0.06M, 0.02M, 0.002M; Fig. 1 F is for being that colloidal crystal template, inorganic salt solution that the polystyrene colloid ball of 200nm is made are the pore structure and the form of the orderly spherical pore film of individual layer that forms of iron nitrate solution with the diameter, and the concentration of iron nitrate solution is 0.8M; The upper left corner of Figure 1A, Figure 1B and Fig. 1 F is respectively this figure partial enlarged drawing of this point in the drawings, therefrom can comparatively be clear that the pore structure and the form of the orderly spherical pore film of individual layer of this point, as from the partial enlarged drawing of Figure 1A, Figure 1B and Fig. 1 F, seeing the composite holes array that spherical pore-triangular apertures is formed;
Fig. 2 is to the orderly spherical pore film of the pairing individual layer of Figure 1A～F among Fig. 1, with the X-ray diffracting spectrum (XRD) that obtains after the test of PhillipsX ' Pert type x-ray diffractometer, wherein, abscissa is the angle of diffraction, ordinate is a relative intensity, by the position of each diffraction maximum of XRD and relative intensity as can be known, the orderly spherical pore film of this individual layer is to be made of di-iron trioxide;
Fig. 3 be to thin-film material take the photograph after with the observation of Japanese JEOL 6700 type field emission scanning electron microscopes photo, by pore structure and the form that can see the orderly spherical pore film of individual layer among the figure, wherein, the figure upper right corner is this figure partial enlarged drawing of this point in the drawings, therefrom can comparatively be clear that the pore structure and the form of the orderly spherical pore film of individual layer of this point;
Fig. 4 is the X-ray diffracting spectrum (XRD) that obtains after the orderly spherical pore film of the individual layer among Fig. 3 is tested with PW 1700 type x-ray diffractometers, wherein, abscissa is the angle of diffraction, ordinate is a relative intensity, by the position of each diffraction maximum of XRD and relative intensity as can be known, the orderly spherical pore film of this individual layer is to be made of metallic zinc;
Fig. 5 be to thin-film material take the photograph after with the observation of Japanese JEOL 6700 type field emission scanning electron microscopes photo, by pore structure and the form that can see the orderly spherical pore film of individual layer among the figure, wherein, the figure upper left corner is this figure partial enlarged drawing of this point in the drawings, therefrom can comparatively be clear that the pore structure and the form of the orderly spherical pore film of individual layer of this point;
Fig. 6 is the X-ray diffracting spectrum (XRB) that obtains after the orderly spherical pore film of the individual layer among Fig. 5 is tested with Phillips X ' Pert type x-ray diffractometer, wherein, abscissa is the angle of diffraction, ordinate is a relative intensity, by the position of each diffraction maximum of XRD and relative intensity as can be known, the orderly spherical pore film of this individual layer is to be made of cerium oxide.
The specific embodiment at first makes or buys from market the polystyrene colloid ball that the monodispersed diameter of commercialization is 50～1000nm with conventional method.
Embodiment 1: is that the polystyrene colloid ball of 1000nm invests the colloidal crystal template that forms on glass with spin-coating method with diameter.Then, earlier be the edge that 0.8 mole iron nitrate solution is added drop-wise to colloidal crystal template with concentration, it is infiltrated between colloidal spheres on glass, and colloidal crystal is floated; The template that will be impregnated with iron nitrate solution again heated 0.5 hour down in 90 ℃.Afterwards, template is placed 350 ℃ of down annealing 8 hours, wherein, the step-length during template annealing to 350 ℃ is 3 ℃/minute.At last, template under water was placed ultrasonic wave 0.5 hour, hyperacoustic power is 120 watts, makes as Figure 1A and the orderly spherical pore film of di-iron trioxide individual layer shown in Figure 2.
Embodiment 2: is that the polystyrene colloid ball of 1000nm invests and forms colloidal crystal template on the monocrystalline silicon piece with vertical czochralski method with diameter.Then, earlier be the edge that 0.08 mole iron nitrate solution is added drop-wise to colloidal crystal template with concentration, it is infiltrated between colloidal spheres on monocrystalline silicon piece, and colloidal crystal is floated; The template that will be impregnated with iron nitrate solution again heated 1 hour down in 85 ℃.Afterwards, template is placed 375 ℃ of down annealing 7 hours, wherein, the step-length during template annealing to 375 ℃ is 4 ℃/minute.At last, template under water was placed ultrasonic wave 0.6 hour, hyperacoustic power is 110 watts, makes as Figure 1B and the orderly spherical pore film of di-iron trioxide individual layer shown in Figure 2.
Embodiment 3: is that the polystyrene colloid ball of 1000nm invests pottery and goes up and form colloidal crystal template with drop-coating with diameter.Then, earlier be the edge that 0.06 mole iron nitrate solution is added drop-wise to colloidal crystal template with concentration, it is infiltrated between colloidal spheres on pottery, and colloidal crystal is floated; The template that will be impregnated with iron nitrate solution again heated 1.5 hours down in 80 ℃.Afterwards, template is placed 400 ℃ of down annealing 6.5 hours, wherein, the step-length during template annealing to 400 ℃ is 5 ℃/minute.At last, template under water was placed ultrasonic wave 0.8 hour, hyperacoustic power is 100 watts, makes as Fig. 1 C and the orderly spherical pore film of di-iron trioxide individual layer shown in Figure 2.
Embodiment 4: is that the polystyrene colloid ball of 1000nm invests and forms colloidal crystal template on the mica with spin-coating method with diameter.Then, earlier be the edge that 0.02 mole iron nitrate solution is added drop-wise to colloidal crystal template with concentration, it is infiltrated between colloidal spheres on mica, and colloidal crystal is floated; The template that will be impregnated with iron nitrate solution again heated 2 hours down in 75 ℃.Afterwards, template is placed 425 ℃ of down annealing 6 hours, wherein, the step-length during template annealing to 425 ℃ is 6 ℃/minute.At last, template under water was placed ultrasonic wave 0.9 hour, hyperacoustic power is 90 watts, makes as Fig. 1 D and the orderly spherical pore film of di-iron trioxide individual layer shown in Figure 2.
Embodiment 5: is that the polystyrene colloid ball of 1000nm invests quartzy going up and forms colloidal crystal template with vertical czochralski method with diameter.Then, earlier be the edge that 0.002 mole iron nitrate solution is added drop-wise to colloidal crystal template with concentration, it is infiltrated between colloidal spheres on quartz, and colloidal crystal is floated; The template that will be impregnated with iron nitrate solution again heated 2.5 hours down in 70 ℃.Afterwards, template is placed 450 ℃ of down annealing 5 hours, wherein, the step-length during template annealing to 450 ℃ is 7 ℃/minute.At last, template under water was placed ultrasonic wave 1 hour, hyperacoustic power is 80 watts, makes as Fig. 1 E and the orderly spherical pore film of di-iron trioxide individual layer shown in Figure 2.
Embodiment 6: is that the polystyrene colloid ball of 200nm invests the colloidal crystal template that forms on glass with drop-coating with diameter.Then, earlier be the edge that 0.8 mole iron nitrate solution is added drop-wise to colloidal crystal template with concentration, it is infiltrated between colloidal spheres on glass, and colloidal crystal is floated; The template that will be impregnated with iron nitrate solution again heated 0.5 hour down in 90 ℃.Afterwards, template is placed 350 ℃ of down annealing 8 hours, wherein, the step-length during template annealing to 350 ℃ is 3 ℃/minute.At last, template under water was placed ultrasonic wave 0.5 hour, hyperacoustic power is 120 watts, makes as Fig. 1 F and the orderly spherical pore film of di-iron trioxide individual layer shown in Figure 2.
Embodiment 7: is that the polystyrene colloid ball of 50nm invests the colloidal crystal template that forms on glass with spin-coating method with diameter.Then, earlier be the edge that 0.8 mole zinc acetate solution is added drop-wise to colloidal crystal template with concentration, it is infiltrated between colloidal spheres on glass, and colloidal crystal is floated; The template that will be impregnated with zinc acetate solution again heated 0.5 hour down in 90 ℃.Afterwards, template is placed 350 ℃ of down annealing 8 hours, wherein, the step-length during template annealing to 350 ℃ is 3 ℃/minute.At last, template under water was placed ultrasonic wave 0.5 hour, hyperacoustic power is 120 watts, makes the orderly spherical pore film of the metallic zinc individual layer that is similar to as shown in Figure 3 and Figure 4, and wherein, the aperture of spherical pore is 50nm, and the thickness of film is 25nm.
Embodiment 8: is that the polystyrene colloid ball of 350nm invests and forms colloidal crystal template on the monocrystalline silicon piece with vertical czochralski method with diameter.Then, earlier be the edge that 0.002 mole zinc acetate solution is added drop-wise to colloidal crystal template with concentration, it is infiltrated between colloidal spheres on monocrystalline silicon piece, and colloidal crystal is floated; The template that will be impregnated with zinc acetate solution again heated 1 hour down in 85 ℃.Afterwards, template is placed 375 ℃ of down annealing 7 hours, wherein, the step-length during template annealing to 375 ℃ is 4 ℃/minute.At last, template under water was placed ultrasonic wave 0.6 hour, hyperacoustic power is 110 watts, makes the orderly spherical pore film of the metallic zinc individual layer that is similar to as shown in Figure 3 and Figure 4, and wherein, the aperture of spherical pore is 350nm, and the thickness of film is 150nm.
Embodiment 9: is that the polystyrene colloid ball of 550nm invests pottery and goes up and form colloidal crystal template with drop-coating with diameter.Then, earlier be the edge that 0.05 mole zinc acetate solution is added drop-wise to colloidal crystal template with concentration, it is infiltrated between colloidal spheres on pottery, and colloidal crystal is floated; The template that will be impregnated with zinc acetate solution again heated 1.5 hours down in 80 ℃.Afterwards, template is placed 400 ℃ of down annealing 6.5 hours, wherein, the step-length during template annealing to 400 ℃ is 5 ℃/minute.At last, template under water was placed ultrasonic wave 0.8 hour, hyperacoustic power is 100 watts, makes the orderly spherical pore film of the metallic zinc individual layer that is similar to as shown in Figure 3 and Figure 4, and wherein, the aperture of spherical pore is 550nm, and the thickness of film is 280nm.
Embodiment 10: is that the polystyrene colloid ball of 750nm invests and forms colloidal crystal template on the mica with spin-coating method with diameter.Then, earlier be the edge that 0.01 mole zinc acetate solution is added drop-wise to colloidal crystal template with concentration, it is infiltrated between colloidal spheres on mica, and colloidal crystal is floated; The template that will be impregnated with zinc acetate solution again heated 2 hours down in 75 ℃.Afterwards, template is placed 425 ℃ of down annealing 6 hours, wherein, the step-length during template annealing to 425 ℃ is 6 ℃/minute.At last, template under water was placed ultrasonic wave 0.9 hour, hyperacoustic power is 90 watts, makes the orderly spherical pore film of the metallic zinc individual layer that is similar to as shown in Figure 3 and Figure 4, and wherein, the aperture of spherical pore is 750nm, and the thickness of film is 350nm.
Embodiment 11: is that the polystyrene colloid ball of 1000nm invests quartzy going up and forms colloidal crystal template with vertical czochralski method with diameter.Then, earlier be the edge that 0.1 mole zinc acetate solution is added drop-wise to colloidal crystal template with concentration, it is infiltrated between colloidal spheres on quartz, and colloidal crystal is floated; The template that will be impregnated with zinc acetate solution again heated 2.5 hours down in 70 ℃.Afterwards, template is placed 450 ℃ of down annealing 5 hours, wherein, the step-length during template annealing to 450 ℃ is 7 ℃/minute.At last, template under water was placed ultrasonic wave 1 hour, hyperacoustic power is 80 watts, makes the orderly spherical pore film of metallic zinc individual layer as shown in Figure 3 and Figure 4.
Embodiment 12: is that the polystyrene colloid ball of 50nm invests the colloidal crystal template that forms on glass with drop-coating with diameter.Then, earlier be the edge that 0.8 mole cerous nitrate solution is added drop-wise to colloidal crystal template with concentration, it is infiltrated between colloidal spheres on glass, and colloidal crystal is floated; The template that will be impregnated with cerous nitrate solution again heated 0.5 hour down in 90 ℃.Afterwards, template is placed 350 ℃ of down annealing 8 hours, wherein, the step-length during template annealing to 350 ℃ is 3 ℃/minute.At last, template under water was placed ultrasonic wave 0.5 hour, hyperacoustic power is 120 watts, makes the orderly spherical pore film of the cerium oxide individual layer that is similar to as shown in Figure 5 and Figure 6, and wherein, the aperture of spherical pore is 50nm, and the thickness of film is 25nm.
Embodiment 13: is that the polystyrene colloid ball of 350nm invests and forms colloidal crystal template on the monocrystalline silicon piece with spin-coating method with diameter.Then, earlier be the edge that 0.3 mole cerous nitrate solution is added drop-wise to colloidal crystal template with concentration, it is infiltrated between colloidal spheres on monocrystalline silicon piece, and colloidal crystal is floated; The template that will be impregnated with cerous nitrate solution again heated 1 hour down in 85 ℃.Afterwards, template is placed 375 ℃ of down annealing 7 hours, wherein, the step-length during template annealing to 375 ℃ is 4 ℃/minute.At last, template under water was placed ultrasonic wave 0.6 hour, hyperacoustic power is 110 watts, makes the orderly spherical pore film of the cerium oxide individual layer that is similar to as shown in Figure 5 and Figure 6, and wherein, the aperture of spherical pore is 350nm, and the thickness of film is 200nm.
Embodiment 14: is that the polystyrene colloid ball of 550nm invests pottery and goes up and form colloidal crystal template with vertical czochralski method with diameter.Then, earlier be the edge that 0.002 mole cerous nitrate solution is added drop-wise to colloidal crystal template with concentration, it is infiltrated between colloidal spheres on pottery, and colloidal crystal is floated; The template that will be impregnated with cerous nitrate solution again heated 1.5 hours down in 80 ℃.Afterwards, template is placed 400 ℃ of down annealing 6.5 hours, wherein, the step-length during template annealing to 400 ℃ is 5 ℃/minute.At last, template under water was placed ultrasonic wave 0.8 hour, hyperacoustic power is 100 watts, makes the orderly spherical pore film of the cerium oxide individual layer that is similar to as shown in Figure 5 and Figure 6, and wherein, the aperture of spherical pore is 550nm, and the thickness of film is 275nm.
Embodiment 15: is that the polystyrene colloid ball of 750nm invests and forms colloidal crystal template on the mica with drop-coating with diameter.Then, earlier be the edge that 0.01 mole cerous nitrate solution is added drop-wise to colloidal crystal template with concentration, it is infiltrated between colloidal spheres on mica, and colloidal crystal is floated; The template that will be impregnated with cerous nitrate solution again heated 2 hours down in 75 ℃.Afterwards, template is placed 425 ℃ of down annealing 6 hours, wherein, the step-length during template annealing to 425 ℃ is 6 ℃/minute.At last, template under water was placed ultrasonic wave 0.9 hour, hyperacoustic power is 90 watts, makes the orderly spherical pore film of the cerium oxide individual layer that is similar to as shown in Figure 5 and Figure 6, and wherein, the aperture of spherical pore is 750nm, and the thickness of film is 350nm.
Embodiment 16: is that the polystyrene colloid ball of 1000nm invests quartzy going up and forms colloidal crystal template with spin-coating method with diameter.Then, earlier be the edge that 0.05 mole cerous nitrate solution is added drop-wise to colloidal crystal template with concentration, it is infiltrated between colloidal spheres on quartz, and colloidal crystal is floated; The template that will be impregnated with cerous nitrate solution again heated 2.5 hours down in 70 ℃.Afterwards, template is placed 450 ℃ of down annealing 5 hours, wherein, the step-length during template annealing to 450 ℃ is 7 ℃/minute.At last, template under water was placed ultrasonic wave 1 hour, hyperacoustic power is 80 watts, makes the orderly spherical pore film of cerium oxide individual layer as shown in Figure 5 and Figure 6.
Obviously, those skilled in the art can carry out various changes and modification to the controlled ordered porous thin-film material of form of the present invention and preparation method 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, the controlled ordered porous thin-film material of a kind of form, comprise substrate, it is characterized in that being covered with the film that individual layer inorganic matter spherical pore constitutes on the said substrate, the diameter of said spherical pore is that 50～1000nm, pore wall thickness are 20～100nm, and the thickness of said film is 50～1000nm.
2, the controlled ordered porous thin-film material of form according to claim 1 is characterized in that inorganic matter is di-iron trioxide or metallic zinc or cerium oxide.
3, the controlled ordered porous thin-film material of form according to claim 2, six sides arrange to it is characterized in that being closely by spherical pore, and are interconnected between the hole.
4, the controlled ordered porous thin-film material of form according to claim 3 is characterized in that in the hole wall between compact arranged three spherical pores leg-of-mutton aperture being arranged.
5, the controlled ordered porous thin-film material of form according to claim 1 is characterized in that substrate is glass or monocrystalline silicon piece or pottery or mica or quartz.
6, the ordered porous thin-film preparation methods that form according to claim 1 is controlled, comprise colloidal spheres is invested substrate surface and forms colloidal crystal template, it is characterized in that earlier being that the diameter that 0.002～0.8 mole inorganic salt solution infiltrates on the substrate is between the polystyrene colloid ball of 50～1000nm with concentration, and between colloidal spheres and the substrate, the template that will be impregnated with inorganic salt solution again heated 0.5～2.5 hour down in 70～90 ℃, afterwards, place 350～450 ℃ to anneal 5～8 hours down template, at last, template under water is placed ultrasonic wave 0.5～1 hour, make the controlled ordered porous thin-film material of form.
7, the controlled ordered porous thin-film preparation methods of form according to claim 6 is characterized in that inorganic salt solution is iron nitrate solution or zinc acetate solution or cerous nitrate solution.
8, the controlled ordered porous thin-film preparation methods of form according to claim 7 is characterized in that iron nitrate solution or zinc acetate solution or cerous nitrate solution are added drop-wise to the edge of colloidal crystal template colloidal crystal being floated.
9, the controlled ordered porous thin-film preparation methods of form according to claim 6, the step-length when it is characterized in that template annealing to 350～450 ℃ is 3～7 ℃/minute.
10, the controlled ordered porous thin-film preparation methods of form according to claim 6 is characterized in that hyperacoustic power is 80～120 watts.
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| CN100538291C (en) * | 2007-01-25 | 2009-09-09 | 中国科学院合肥物质科学研究院 | Transmission type wavelength meter for ordered hole array and measuring method thereof |
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| CN100538291C (en) * | 2007-01-25 | 2009-09-09 | 中国科学院合肥物质科学研究院 | Transmission type wavelength meter for ordered hole array and measuring method thereof |
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| CN103003213A (en) * | 2010-07-19 | 2013-03-27 | 旭硝子欧洲玻璃公司 | Process for producing a deposition of inorganic nanoparticles, comprising microvoids, on a support that is transparent to light |
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| CN103194740A (en) * | 2012-01-10 | 2013-07-10 | 中国科学院合肥物质科学研究院 | Preparation method of metal silver ordered porous array membrane |
| CN103194740B (en) * | 2012-01-10 | 2015-04-29 | 中国科学院合肥物质科学研究院 | Preparation method of metal silver ordered porous array membrane |
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| CN110124528A (en) * | 2014-02-28 | 2019-08-16 | 帕尔公司 | Hollow-fibre membrane with six side gaps |
| CN104959045A (en) * | 2015-06-16 | 2015-10-07 | 陕西科技大学 | Method for manufacturing polyvinylidene fluoride nano array pore membranes |
| CN104959045B (en) * | 2015-06-16 | 2017-03-29 | 陕西科技大学 | A kind of method for preparing polyvinylidene fluoride nanometer array pore membrane |
| CN106215575A (en) * | 2016-08-31 | 2016-12-14 | 芜湖恒耀汽车零部件有限公司 | Automobile tail gas filtering device ceramic membrane filter material |
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