CN101503211B - Titanium dioxide nano-pore array thin film and preparation thereof - Google Patents
Titanium dioxide nano-pore array thin film and preparation thereof Download PDFInfo
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- CN101503211B CN101503211B CN2008100206189A CN200810020618A CN101503211B CN 101503211 B CN101503211 B CN 101503211B CN 2008100206189 A CN2008100206189 A CN 2008100206189A CN 200810020618 A CN200810020618 A CN 200810020618A CN 101503211 B CN101503211 B CN 101503211B
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Abstract
The invention discloses a titanium dioxide nanometer hole array film and a preparation method thereof. A hole in the film is an ordered through hole array; the diameter of the through hole thereof is 15 to 130 nm, the hole pitch thereof is 25 to 200 nm, and the porosity thereof is 30 to 40 percent; the thickness of the film is 10 to 1000 nm; the preparation method comprises the following steps: step 1, obtaining a porous aluminum oxide template with the hole diameter of 20 to 150 nm by using the secondary oxidation process; step 2, preparing precursor solution by using absolute ethyl alcohol, glacial acetic acid, butyl titanate and water, then adding polyethylene glycol into the precursor solution after the pH value of the precursor solution is adjusted to 2 to 3 by using nitric acid, and finally obtaining precursor sol; and step 3, firstly coating the precursor sol on the porous aluminum oxide template for at least one time and thermally insulating and drying the precursor sol for at least one time, then placing the aluminum oxide template coated with the precursor sol after being annealed into strong alkaline solution to corrupt the porous aluminum oxide template, and finally preparing the titanium dioxide nanometer-hole array film. The invention can be widely applied to the fields of sensors, catalysis, photo catalysis, photonic crystal, etc.
Description
Technical field
The present invention relates to a kind of nano-pore array thin film and preparation method, especially a kind of titanium dioxide nano-pore array thin film and preparation method thereof.
Background technology
Titanium dioxide is a kind of wide band gap semiconducter, is playing the part of very important role in our life.Along with the concern of people to increasing day by day at aspects such as cleaning, the energy, senser elements, its outstanding catalysis, photocatalysis performance and the application in dye sensitization solar battery thereof have caused the more and more big attention of people.The oxide semiconductor nano thin-film that the hole array structure arranged has the focus that bigger specific surface area and excellent properties in every respect more and more become people's research because of it.Numerous performances of titanium dioxide all have directly with its specific surface area gets in touch, the specific surface area of titanium deoxid film with hole array structure is much larger than conventional film, and because its periodic hole array structure makes it at aspects such as transmitter, catalysis, photochemical catalysis and photonic crystals the potential application prospect be arranged.At present, people have done some trials and effort in order to obtain titanium dioxide hole array film, as a kind of " manufacture method of poriferous titanium dioxide " that discloses among the disclosed Chinese invention patent ublic specification of application CN1559671A on January 5th, 2005.It is intended to provide a kind of effect that utilizes chemical ingredients in the tio_2 suspension, and the method that titanium dioxide is loaded on the porous particles is securely made porous titanium dioxide thin-film; Wherein, manufacture method is for choosing nano titanium oxide, poly-alkylsiloxane, polyacrylic ester and water earlier, carry out thorough mixing and make tio_2 suspension, again with porous particles, be immersed in the above-mentioned tio_2 suspension as in porous silica gel, porousness phosphatic rock, porous ceramics or the porous alumina one or more, fully flood, or tio_2 suspension is sprayed on the porous particle surface, the porous particle oven dry after will handling at last.But, no matter be manufacture method, or its finished product, all exist weak point, at first, do not manufacture orderly hole array titanium deoxid film, particularly can not produce large-area orderly hole array titanium deoxid film; Secondly, bore dia in the porous titanium dioxide thin-film of making and pitch of holes all are at random, by the decision of template porous particles, and can not control effectively artificially.Though also there is the anonizing of use to prepare aluminum oxide porous template, fill with collosol and gel, remove template after the thermal treatment and obtain TiO 2 porous array, as what in " method that the prepares one-dimension oriented nanometer titanium dioxide tubular crystal thin film " literary composition among on May 10th, the 2006 disclosed Chinese invention patent ublic specification of application CN1769548A, mention, yet, the one, the technical scheme that really makes orderly hole array titanium deoxid film is all unexposed, particularly relates to the bore dia of TiO 2 porous array film, the thickness of porosity and film and the formulation of processing parameter thereof and controlling effectively etc. all needs people to go to explore again; The 2nd, its method is disclosed can not to make orderly hole array titanium deoxid film by it only for the preparation nanometer titanium dioxide tubular crystal thin film, and have also that technology raw material numerous and diverse, that use is many, the defective during energy charge.
Summary of the invention
The technical problem to be solved in the present invention is the limitation that overcomes above-mentioned various technical schemes, provides hole on a kind of film to be the titanium dioxide nano-pore array thin film of ordered arrangement.
Another technical problem that the present invention will solve is for providing a kind of method simple possible, rapidly and efficiently, controllable product shape, has the preparation method of practical value and environment amenable titanium dioxide nano-pore array thin film.
For solving technical problem of the present invention, the technical scheme that is adopted is: titanium dioxide nano-pore array thin film comprises titanium dioxide, particularly described titanium dioxide is the porous membrane shape, hole in the described porous membrane is the ordered through hole array, the bore dia of described ordered through hole array is that 15～130nm, pitch of holes are that 25～200nm, porosity are 30～40%, and the thickness of described film is 10～1000nm.
For solving another technical problem of the present invention, another technical scheme that is adopted is: the preparation method of titanium dioxide nano-pore array thin film comprises secondary oxidation method and sol-gel method, particularly it is finished according to the following steps: the first step, the aluminium flake of purity 〉=99.9% in vacuum tightness≤10
-3After Pa, temperature are 400～600 ℃ of 4～7h that anneal down, earlier it simultaneously being placed concentration is that the acid solution of 0.1～0.4M is as anode, in volts DS is that 25～165V, temperature are 0～5 ℃ of following anodic oxidation 5～7h, again it in being the mixed solution of chromic acid of 50～70 ℃ the phosphoric acid of 4～8wt% and 1～2wt%, temperature is soaked 8～12h, then, it is carried out the anodic oxidation second time 18～24h once more by the one side of anodic oxidation under same processing condition, obtain the porous alumina formwork that bore dia is 20～150nm; Second step, earlier with dehydrated alcohol, Glacial acetic acid and concentration are the tetrabutyl titanate of 0.5～0.7M, according to volume ratio is 0.8～1.2: 0.1～0.5: stirring after 0.3～0.7 mixing obtains mixed liquor A, be mix after to stir obtain mixed liquid B at 5～9: 0.6～1 dehydrated alcohol and water according to volume ratio again, then, earlier mixed liquid B is added and obtain precursor solution in the mixed liquor A, wherein, dehydrated alcohol and the volume ratio between the dehydrated alcohol in the mixed liquor A in the mixed liquid B are 5～9: 14～18, regulate pH value to 2～3 of precursor solution again with nitric acid, then, in precursor solution, add polyoxyethylene glycol earlier, wherein, the add-on of polyoxyethylene glycol is to add 18～22g in every liter of precursor solution, again it is stirred 6h at least, and ageing 12h at least, precursor sol obtained; The 3rd step, earlier precursor sol is coated on the porous alumina formwork, the porous alumina formwork that will be coated with precursor sol again places temperature to be 100～140 ℃ and is incubated 10～20min down, above-mentioned each process of the duplicate step of laying equal stress at least once, then, be 450～550 ℃ of annealing 3～5h down with it in temperature earlier, be placed on again and erode porous alumina formwork in the strong base solution, make titanium dioxide nano-pore array thin film.
As the preparation method's of titanium dioxide nano-pore array thin film further improvement, described acid solution is oxalic acid solution or phosphoric acid solution or sulphuric acid soln; Described water is deionized water or distilled water; The molecular weight of described polyoxyethylene glycol is 2000 or 4000 or 6000 or 10000 or 20000; Describedly be applied to spin coating or spraying; Described being spin-coated as will place the precursor sol on the porous alumina formwork to get rid of film with the speed rotation of 500～1000 commentaries on classics/s; Described temperature rise rate when being warming up to 100～140 ℃ is 100～140 ℃/s; The described repetition is coated on precursor sol on the porous alumina formwork, and is 2～4 times to its process that is incubated; Described strong base solution is sodium hydroxide solution or potassium hydroxide solution or lithium hydroxide solution.
Beneficial effect with respect to prior art is, one, use field emission scanning electron microscope, x-ray diffractometer and power spectrum tester and specific surface and analysis of porosity instrument to carry out the sign of form, structure, composition and porosity respectively to the film that makes, can spectrogram and nitrogen adsorption-the desorption graphic representation as can be known from the stereoscan photograph that obtains, X-ray diffraction spectrogram and scanning, be covered with the ordered through hole array on the film, the bore dia of this ordered through hole array is that 15～130nm, pitch of holes are that 25～200nm, porosity are 30～40%.The thickness of film is 10～1000nm.Film is made of anatase phase titanium dioxide; Its two, use porous alumina formwork to be substrate in the method, both because of its orderly vesicular structure provides precondition for complex obtains the hole array film, again for making large-area bore dia and all controlled hole array film of pitch of holes is laid a good foundation.The employing tetrabutyl titanate is that precursor, dehydrated alcohol are solvent, and polyoxyethylene glycol is a structure directing agent, make with low cost, simple to operate effectively, and the colloidal sol that obtains is uniform and stable.Coated technique only needs to carry out under air atmosphere, normal temperature, and simple and easy to do, the technology operability is good, can prepare large-area film, and is easy to peel off and translate substrate.In a word, preparation method's science, reasonable, effective and pollution-free; Its technical process is few, the processing parameter variable range is wide, and suitability is strong, good reproducibility, weak point consuming time repeats to film, thermal treatment is easily gone fast, and sintering temperature is low, and power consumption is few, be fit to the preparation of the orderly hole of high-quality titanium dioxide array film, have that required equipment is few, technology is simple, production cost is low, is suitable for the advantage of large-scale industrial production.Simultaneously, present method has portable preferably, can be used for the preparation of other oxide holes array film.
As the further embodiment of beneficial effect, the one, acid solution is preferably oxalic acid solution or phosphoric acid solution or sulphuric acid soln, not only makes the source of raw material than horn of plenty, also makes the easier enforcement of preparation technology and flexibly; The 2nd, the molecular weight of polyoxyethylene glycol is preferably 2000 or 4000 or 6000 or 10000 or 20000, can make by selection the polyoxyethylene glycol chain length, change the size of orderly hole array aggregate, thereby realize accurate control the orderly hole of titanium dioxide array hole diameter; The 3rd, apply and be preferably spin coating or spraying, spin coating wherein is preferably placing the precursor sol on the porous alumina formwork to get rid of film with the speed rotation of 500～1000 commentaries on classics/s, makes that the thickness of rete is not only suitable but also even; The 4th, the temperature rise rate when being warming up to 100～140 ℃ is preferably 100～140 ℃/s, and decapacitation is guaranteed outside the quality of rete, and is also quick; The 5th, repeat precursor sol is coated on the porous alumina formwork, and the process that it is incubated is preferably 2～4 times, can realize the universality of film in less multiplicity; The 6th, strong base solution is preferably sodium hydroxide solution or potassium hydroxide solution or lithium hydroxide solution, and decapacitation is guaranteed to erode outside the alumina formwork, also has flexibly characteristics easily.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 be take the photograph after using the Sirion200FEG type field emission scanning electron microscope (SEM) of U.S. FEI Co. that it is observed to the porous alumina formwork that makes and film the SEM photo, wherein, Fig. 1 a and Fig. 1 b are the SEM photo of porous alumina formwork, Fig. 1 c and Fig. 1 d are the SEM photo of the titanium dioxide hole array film on porous alumina formwork, and Fig. 1 e and Fig. 1 f are the SEM photo of the titanium dioxide hole array film after porous alumina formwork is removed;
Fig. 2 uses Japanese X-ray diffraction of science (XRD) instrument (RigakuD/Max-rA, λ=1.54051 to the film that makes
) XRD spectra that obtains after the test, wherein, ordinate zou is a relative intensity, and X-coordinate is a diffraction angle, and by the position of each diffraction peak in the XRD figure and relative intensity as can be known, this film is made of titanium dioxide;
Fig. 3 uses the incidental power spectrum of Sirion 200FEG type field emission scanning electron microscope (EDS) tester of U.S. FEI Co. that it is carried out the chosen point scanning resulting EDS in back figure as a result to the film that makes, by the composition among the figure as a result as can be known, film is made of anatase phase titanium dioxide.
Embodiment
At first make or buy dehydrated alcohol, Glacial acetic acid, tetrabutyl titanate, oxalic acid solution, phosphoric acid solution, sulphuric acid soln, deionized water, distilled water, sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution and polyoxyethylene glycol from market with ordinary method, wherein, the molecular weight of polyoxyethylene glycol is 2000,4000,6000,10000 and 20000.Then,
Embodiment 1: finish preparation according to the following steps successively: the first step is purity that 99.9% aluminium flake is 10 in vacuum tightness
-3After Pa, temperature are 400 ℃ of 7h that anneal down, earlier it simultaneously being placed concentration is that the acid solution of 0.1M is as anode, in volts DS is that 25V, temperature are 0 ℃ of following anodic oxidation 7h, again it is soaked 12h in temperature is the mixed solution of chromic acid of 50 ℃ the phosphoric acid of 4wt% and 2wt%; Wherein, acid solution is an oxalic acid solution.Then, it is carried out anodic oxidation second time 24h once more by the one side of anodic oxidation under same processing condition, obtaining being similar to the bore dia shown in Fig. 1 a and Fig. 1 b is the porous alumina formwork of 20nm.Second step, be the tetrabutyl titanate of 0.5M with dehydrated alcohol, Glacial acetic acid and concentration earlier, according to volume ratio is to stir after mixing at 0.8: 0.5: 0.3 to obtain mixed liquor A, be to stir after mixing at 5: 0.6 to obtain mixed liquid B with dehydrated alcohol and water according to volume ratio again, wherein, water is deionized water.Then, obtain precursor solution first mixed liquid B is added in the mixed liquor A, and wherein, dehydrated alcohol and the volume ratio between the dehydrated alcohol in the mixed liquor A in the mixed liquid B are 5: 18; Regulate the pH value to 2 of precursor solution again with nitric acid.Then, add polyoxyethylene glycol earlier in precursor solution, wherein, the add-on of polyoxyethylene glycol is to add 18g in every liter of precursor solution, and the molecular weight of polyoxyethylene glycol is 20000; Again it is stirred 6h, and ageing 16h at least, precursor sol obtained.The 3rd step was coated on precursor sol on the porous alumina formwork earlier, wherein, was applied to spin coating, was spin-coated as to place the precursor sol on the porous alumina formwork to get rid of film with the speed rotation of 500 commentaries on classics/s; The porous alumina formwork that will be coated with precursor sol again places temperature to be 100 ℃ and is incubated 20min down, and wherein, the temperature rise rate when being warming up to 100 ℃ is 140 ℃/s; Above-mentioned each process of the duplicate step of laying equal stress at least once promptly repeats precursor sol is coated on the porous alumina formwork, and is 2 times to its process that is incubated.Then, be 450 ℃ of annealing 5h down with it in temperature earlier, obtain to be similar to the titanium dioxide hole array film on porous alumina formwork shown in Fig. 1 c and Fig. 1 d; Be placed on and erode porous alumina formwork in the strong base solution, wherein, strong base solution is a sodium hydroxide solution; Make and be similar to shown in Fig. 1 e and Fig. 1 f, and the titanium dioxide nano-pore array thin film shown in the curve among Fig. 2 and Fig. 3.
Embodiment 2: finish preparation according to the following steps successively: the first step is purity that 99.9% aluminium flake is 10 in vacuum tightness
-3After Pa, temperature are 450 ℃ of 6h that anneal down, earlier it simultaneously being placed concentration is that the acid solution of 0.2M is as anode, in volts DS is that 60V, temperature are 2 ℃ of following anodic oxidation 6h, again it is soaked 11h in temperature is the mixed solution of chromic acid of 55 ℃ the phosphoric acid of 5wt% and 1.8wt%; Wherein, acid solution is an oxalic acid solution.Then, it is carried out anodic oxidation second time 23h once more by the one side of anodic oxidation under same processing condition, obtaining being similar to the bore dia shown in Fig. 1 a and Fig. 1 b is the porous alumina formwork of 50nm.Second step, be the tetrabutyl titanate of 0.55M with dehydrated alcohol, Glacial acetic acid and concentration earlier, according to volume ratio is to stir after mixing at 0.9: 0.4: 0.4 to obtain mixed liquor A, be to stir after mixing at 6: 0.7 to obtain mixed liquid B with dehydrated alcohol and water according to volume ratio again, wherein, water is deionized water.Then, obtain precursor solution first mixed liquid B is added in the mixed liquor A, and wherein, dehydrated alcohol and the volume ratio between the dehydrated alcohol in the mixed liquor A in the mixed liquid B are 6: 17; Regulate the pH value to 2 of precursor solution again with nitric acid.Then, add polyoxyethylene glycol earlier in precursor solution, wherein, the add-on of polyoxyethylene glycol is to add 19g in every liter of precursor solution, and the molecular weight of polyoxyethylene glycol is 20000; Again it is stirred 7h, and ageing 15h at least, precursor sol obtained.The 3rd step was coated on precursor sol on the porous alumina formwork earlier, wherein, was applied to spin coating, was spin-coated as to place the precursor sol on the porous alumina formwork to get rid of film with the speed rotation of 600 commentaries on classics/s; The porous alumina formwork that will be coated with precursor sol again places temperature to be 110 ℃ and is incubated 18min down, and wherein, the temperature rise rate when being warming up to 110 ℃ is 130 ℃/s; Above-mentioned each process of the duplicate step of laying equal stress at least once promptly repeats precursor sol is coated on the porous alumina formwork, and is 3 times to its process that is incubated.Then, be 480 ℃ of annealing 5h down with it in temperature earlier, obtain to be similar to the titanium dioxide hole array film on porous alumina formwork shown in Fig. 1 c and Fig. 1 d; Be placed on and erode porous alumina formwork in the strong base solution, wherein, strong base solution is a sodium hydroxide solution; Make and be similar to shown in Fig. 1 e and Fig. 1 f, and the titanium dioxide nano-pore array thin film shown in the curve among Fig. 2 and Fig. 3.
Embodiment 3: finish preparation according to the following steps successively: the first step is purity that 99.99% aluminium flake is 10 in vacuum tightness
-4After Pa, temperature are 500 ℃ of 6h that anneal down, earlier it simultaneously being placed concentration is that the acid solution of 0.3M is as anode, in volts DS is that 95V, temperature are 3 ℃ of following anodic oxidation 6h, again it is soaked 10h in temperature is the mixed solution of chromic acid of 60 ℃ the phosphoric acid of 6wt% and 1.5wt%; Wherein, acid solution is an oxalic acid solution.Then, it is carried out anodic oxidation second time 21h once more by the one side of anodic oxidation under same processing condition, the bore dia that obtains shown in Fig. 1 a and Fig. 1 b is the porous alumina formwork of 80nm.Second step, be the tetrabutyl titanate of 0.6M with dehydrated alcohol, Glacial acetic acid and concentration earlier, according to volume ratio is to stir after mixing at 1: 0.3: 0.5 to obtain mixed liquor A, be to stir after mixing at 7: 0.8 to obtain mixed liquid B with dehydrated alcohol and water according to volume ratio again, wherein, water is deionized water.Then, obtain precursor solution first mixed liquid B is added in the mixed liquor A, and wherein, dehydrated alcohol and the volume ratio between the dehydrated alcohol in the mixed liquor A in the mixed liquid B are 7: 16; Regulate the pH value to 2.5 of precursor solution again with nitric acid.Then, add polyoxyethylene glycol earlier in precursor solution, wherein, the add-on of polyoxyethylene glycol is to add 20g in every liter of precursor solution, and the molecular weight of polyoxyethylene glycol is 20000; Again it is stirred 8h, and ageing 14h at least, precursor sol obtained.The 3rd step was coated on precursor sol on the porous alumina formwork earlier, wherein, was applied to spin coating, was spin-coated as to place the precursor sol on the porous alumina formwork to get rid of film with the speed rotation of 800 commentaries on classics/s; The porous alumina formwork that will be coated with precursor sol again places temperature to be 120 ℃ and is incubated 15min down, and wherein, the temperature rise rate when being warming up to 120 ℃ is 120 ℃/s; Above-mentioned each process of the duplicate step of laying equal stress at least once promptly repeats precursor sol is coated on the porous alumina formwork, and is 3 times to its process that is incubated.Then, be 500 ℃ of annealing 4h down with it in temperature earlier, obtain the titanium dioxide hole array film on porous alumina formwork shown in Fig. 1 c and Fig. 1 d; Be placed on and erode porous alumina formwork in the strong base solution, wherein, strong base solution is a sodium hydroxide solution; Make shown in Fig. 1 e and Fig. 1 f, and the titanium dioxide nano-pore array thin film shown in the curve among Fig. 2 and Fig. 3.
Embodiment 4: finish preparation according to the following steps successively: the first step is purity that 99.9% aluminium flake is 10 in vacuum tightness
-3After Pa, temperature are 550 ℃ of 5h that anneal down, earlier it simultaneously being placed concentration is that the acid solution of 0.35M is as anode, in volts DS is that 130V, temperature are 4 ℃ of following anodic oxidation 5h, again it is soaked 9h in temperature is the mixed solution of chromic acid of 65 ℃ the phosphoric acid of 7wt% and 1.3wt%; Wherein, acid solution is an oxalic acid solution.Then, it is carried out anodic oxidation second time 20h once more by the one side of anodic oxidation under same processing condition, obtaining being similar to the bore dia shown in Fig. 1 a and Fig. 1 b is the porous alumina formwork of 120nm.Second step, be the tetrabutyl titanate of 0.65M with dehydrated alcohol, Glacial acetic acid and concentration earlier, according to volume ratio is to stir after mixing at 1.1: 0.2: 0.6 to obtain mixed liquor A, be to stir after mixing at 8: 0.9 to obtain mixed liquid B with dehydrated alcohol and water according to volume ratio again, wherein, water is deionized water.Then, obtain precursor solution first mixed liquid B is added in the mixed liquor A, and wherein, dehydrated alcohol and the volume ratio between the dehydrated alcohol in the mixed liquor A in the mixed liquid B are 8: 15; Regulate the pH value to 3 of precursor solution again with nitric acid.Then, add polyoxyethylene glycol earlier in precursor solution, wherein, the add-on of polyoxyethylene glycol is to add 21g in every liter of precursor solution, and the molecular weight of polyoxyethylene glycol is 20000; Again it is stirred 9h, and ageing 13h at least, precursor sol obtained.The 3rd step was coated on precursor sol on the porous alumina formwork earlier, wherein, was applied to spin coating, was spin-coated as to place the precursor sol on the porous alumina formwork to get rid of film with the speed rotation of 900 commentaries on classics/s; The porous alumina formwork that will be coated with precursor sol again places temperature to be 130 ℃ and is incubated 13min down, and wherein, the temperature rise rate when being warming up to 130 ℃ is 110 ℃/s; Above-mentioned each process of the duplicate step of laying equal stress at least once promptly repeats precursor sol is coated on the porous alumina formwork, and is 3 times to its process that is incubated.Then, be 530 ℃ of annealing 3h down with it in temperature earlier, obtain to be similar to the titanium dioxide hole array film on porous alumina formwork shown in Fig. 1 c and Fig. 1 d; Be placed on and erode porous alumina formwork in the strong base solution, wherein, strong base solution is a sodium hydroxide solution; Make and be similar to shown in Fig. 1 e and Fig. 1 f, and the titanium dioxide nano-pore array thin film shown in the curve among Fig. 2 and Fig. 3.
Embodiment 5: finish preparation according to the following steps successively: the first step is purity that 99.9% aluminium flake is 10 in vacuum tightness
-3After Pa, temperature are 600 ℃ of 4h that anneal down, earlier it simultaneously being placed concentration is that the acid solution of 0.4M is as anode, in volts DS is that 165V, temperature are 5 ℃ of following anodic oxidation 5h, again it is soaked 8h in temperature is the mixed solution of chromic acid of 70 ℃ the phosphoric acid of 8wt% and 1wt%; Wherein, acid solution is an oxalic acid solution.Then, it is carried out anodic oxidation second time 18h once more by the one side of anodic oxidation under same processing condition, obtaining being similar to the bore dia shown in Fig. 1 a and Fig. 1 b is the porous alumina formwork of 150nm.Second step, be the tetrabutyl titanate of 0.7M with dehydrated alcohol, Glacial acetic acid and concentration earlier, according to volume ratio is to stir after mixing at 1.2: 0.1: 0.7 to obtain mixed liquor A, be to stir after mixing at 9: 1 to obtain mixed liquid B with dehydrated alcohol and water according to volume ratio again, wherein, water is deionized water.Then, obtain precursor solution first mixed liquid B is added in the mixed liquor A, and wherein, dehydrated alcohol and the volume ratio between the dehydrated alcohol in the mixed liquor A in the mixed liquid B are 9: 14; Regulate the pH value to 3 of precursor solution again with nitric acid.Then, add polyoxyethylene glycol earlier in precursor solution, wherein, the add-on of polyoxyethylene glycol is to add 22g in every liter of precursor solution, and the molecular weight of polyoxyethylene glycol is 20000; Again it is stirred 10h, and ageing 12h at least, precursor sol obtained.The 3rd step was coated on precursor sol on the porous alumina formwork earlier, wherein, was applied to spin coating, was spin-coated as to place the precursor sol on the porous alumina formwork to get rid of film with the speed rotation of 1000 commentaries on classics/s; The porous alumina formwork that will be coated with precursor sol again places temperature to be 140 ℃ and is incubated 10min down, and wherein, the temperature rise rate when being warming up to 140 ℃ is 100 ℃/s; Above-mentioned each process of the duplicate step of laying equal stress at least once promptly repeats precursor sol is coated on the porous alumina formwork, and is 4 times to its process that is incubated.Then, be 550 ℃ of annealing 3h down with it in temperature earlier, obtain to be similar to the titanium dioxide hole array film on porous alumina formwork shown in Fig. 1 c and Fig. 1 d; Be placed on and erode porous alumina formwork in the strong base solution, wherein, strong base solution is a sodium hydroxide solution; Make and be similar to shown in Fig. 1 e and Fig. 1 f, and the titanium dioxide nano-pore array thin film shown in the curve among Fig. 2 and Fig. 3.
Select phosphoric acid solution or sulphuric acid soln as acid solution more respectively for use, as the distilled water of water, as the potassium hydroxide solution or the lithium hydroxide solution of strong base solution, and to select the molecular weight of polyoxyethylene glycol for use be 2000 or 4000 or 6000 or 10000.Repeat the foregoing description 1～5, make equally as or be similar to shown in Fig. 1 e and Fig. 1 f and the titanium dioxide nano-pore array thin film shown in the curve among Fig. 2 and Fig. 3.
Obviously, those skilled in the art can carry out various changes and modification to titanium dioxide nano-pore array thin film 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 (9)
1. titanium dioxide nano-pore array thin film, comprise titanium dioxide, it is characterized in that described titanium dioxide is the porous membrane shape, hole in the described porous membrane is the ordered through hole array, the bore dia of described ordered through hole array is that 15～130nm, pitch of holes are that 25～200nm, porosity are 30～40%, and the thickness of described film is 10～1000nm.
2. the preparation method of titanium dioxide nano-pore array thin film according to claim 1 comprises secondary oxidation method and sol-gel method, it is characterized in that finishing according to the following steps:
The first step, the aluminium flake of purity 〉=99.9% in vacuum tightness≤10
-3After Pa, temperature are 400～600 ℃ of 4～7h that anneal down, earlier it simultaneously being placed concentration is that the acid solution of 0.1～0.4M is as anode, in volts DS is that 25～165V, temperature are 0～5 ℃ of following anodic oxidation 5～7h, again it in being the mixed solution of chromic acid of 50～70 ℃ the phosphoric acid of 4～8wt% and 1～2wt%, temperature is soaked 8～12h, then, it is carried out the anodic oxidation second time 18～24h once more by the one side of anodic oxidation under same processing condition, obtain the porous alumina formwork that bore dia is 20～150nm;
Second step, earlier with dehydrated alcohol, Glacial acetic acid and concentration are the tetrabutyl titanate of 0.5～0.7M, according to volume ratio is 0.8～1.2: 0.1～0.5: stirring after 0.3～0.7 mixing obtains mixed liquor A, be mix after to stir obtain mixed liquid B at 5～9: 0.6～1 dehydrated alcohol and water according to volume ratio again, then, earlier mixed liquid B is added and obtain precursor solution in the mixed liquor A, wherein, dehydrated alcohol and the volume ratio between the dehydrated alcohol in the mixed liquor A in the mixed liquid B are 5～9: 14～18, regulate pH value to 2～3 of precursor solution again with nitric acid, then, in precursor solution, add polyoxyethylene glycol earlier, wherein, the add-on of polyoxyethylene glycol is to add 18～22g in every liter of precursor solution, again it is stirred 6h at least, and ageing 12h at least, precursor sol obtained;
The 3rd step, earlier precursor sol is coated on the porous alumina formwork, the porous alumina formwork that will be coated with precursor sol again places temperature to be 100～140 ℃ and is incubated 10～20min down, above-mentioned each process of the duplicate step of laying equal stress at least once, then, be 450～550 ℃ of annealing 3～5h down with it in temperature earlier, be placed on again and erode porous alumina formwork in the strong base solution, make titanium dioxide nano-pore array thin film.
3. the preparation method of titanium dioxide nano-pore array thin film according to claim 2 is characterized in that acid solution is oxalic acid solution or phosphoric acid solution or sulphuric acid soln.
4. the preparation method of titanium dioxide nano-pore array thin film according to claim 2, the molecular weight that it is characterized in that polyoxyethylene glycol is 2000 or 4000 or 6000 or 10000 or 20000.
5. the preparation method of titanium dioxide nano-pore array thin film according to claim 2 is characterized in that being applied to spin coating or spraying.
6. the preparation method of titanium dioxide nano-pore array thin film according to claim 5 is characterized in that being spin-coated as and will place the precursor sol on the porous alumina formwork to get rid of film with the speed rotation of 500～1000 commentaries on classics/s.
7. the preparation method of titanium dioxide nano-pore array thin film according to claim 2, the temperature rise rate when it is characterized in that being warming up to 100～140 ℃ is 100～140 ℃/s.
8. the preparation method of titanium dioxide nano-pore array thin film according to claim 2 is characterized in that repeating precursor sol is coated on the porous alumina formwork, and is 2～4 times to its process that is incubated.
9. the preparation method of titanium dioxide nano-pore array thin film according to claim 2 is characterized in that strong base solution is sodium hydroxide solution or potassium hydroxide solution or lithium hydroxide solution.
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| CN102888645B (en) * | 2011-07-21 | 2014-11-26 | 中国科学院合肥物质科学研究院 | Preparation method of titanium dioxide nanopore array film |
| CN103048363B (en) * | 2011-10-12 | 2015-01-14 | 中国科学院合肥物质科学研究院 | Metallic oxide material with mesoporous-macroporous composite structure as well as preparation method and application thereof |
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| WO2019051734A1 (en) * | 2017-09-14 | 2019-03-21 | 季春柳 | Method for preparing tio2 capillary monolithic column |
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| CN110396309A (en) * | 2019-07-15 | 2019-11-01 | 中国科学院合肥物质科学研究院 | TiOx nano porous coating and preparation method thereof |
| CN113499762B (en) * | 2021-05-18 | 2022-05-10 | 浙江大学 | Simple preparation method of blue/black titanium dioxide photocatalytic material |
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