CN109455758A - A kind of titanium dioxide nanorod array film and preparation method thereof - Google Patents
A kind of titanium dioxide nanorod array film and preparation method thereof Download PDFInfo
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- CN109455758A CN109455758A CN201811425713.7A CN201811425713A CN109455758A CN 109455758 A CN109455758 A CN 109455758A CN 201811425713 A CN201811425713 A CN 201811425713A CN 109455758 A CN109455758 A CN 109455758A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
Abstract
The present invention relates to a kind of titanium dioxide nanorod array films and preparation method thereof, belong to oxide semiconductor material technical field.The preparation method of titanium dioxide nanorod array film of the invention, which specifically includes that for titanium dioxide membrane material to be put into precursor solution, carries out hydro-thermal reaction, and 30~60min is then kept the temperature at 450~550 DEG C, is finally placed in TiCl4In aqueous solution in 80~100 DEG C of 30~60min of processing to get.Technology maturation used in the present invention is easy to operate, and technology stability is good, and quality of forming film is high, advantage of lower cost, has good popularization and application basis.
Description
Technical field
The present invention relates to a kind of titanium dioxide nanorod array films and preparation method thereof, belong to oxide semiconductor material
Technical field.
Background technique
Nanometer titanic oxide material is a kind of widely applied photoanode thin film material, and the difference of morphosis can be to light
The photoelectric properties of anode generate different influences.Due to the unordered accumulation of nano-crystalline granule, light induced electron is during transmission
It needs repeatedly by the interface between nano-crystalline granule, so that the transmission range of light induced electron extends.Furthermore nano-crystalline granule
The presence of defect state, surface state also increases the recombination probability of electronics, to reduce the collection efficiency of light induced electron.It is one-dimensional
The presence of titanium dioxide nanorod array film solves the above problem, and one-dimensional titanium dioxide nano-stick array thin film can be reduced
The band edge of crystal, surface state and defect state in film, while can also effectively enhance scattering process of the light anode to light, it is photoproduction
Electronics provides direct transmission path, improves the transmission range of electronics, reduces the recombination probability of electronics, increases electron lifetime, mentions
High charge collection efficiency then improves the photoelectric properties of light anode.
Currently, the method for preparing one-dimensional titanium dioxide nano material mainly has solvent-thermal method, anodizing and template
Deng.Wherein solvent-thermal method is to prepare one of most common method of one-dimensional titanium dioxide nanometer stick array, and solvent-thermal method on the one hand can
With growth of one-dimensional titanium dioxide nano-rod direct in substrate, the cumbersome operating process of other methods is eliminated；On the other hand, two
The presence of titanium oxide compacted zone plays the role of seed layer, reduces the lattice mismatch rate between titanium dioxide and substrate, from
And it is easier to obtain the nano-stick array thin film of high orientation.In addition, solvent-thermal method is at low cost, reaction condition is easily achieved and controls
System, synthesis technology is simple, is suitble to large-scale production.
In the prior art, the Chinese invention patent application that application publication number is CN106145692A discloses a kind of using leaching
The method that stain czochralski method prepares titanium dioxide seed layer in conductive substrates, but the titanium dioxide seed layer of this method preparation exists
The problems such as in uneven thickness, thin film void is more, not fine and close and insecure in conjunction with substrate enough.Application publication number is
It is thin that the Chinese invention patent application of CN101886249A discloses a kind of titanium dioxide prepared by acid soak magnetron sputtering
The method of film prepares porous titanium dioxide thin-film, though this method is simple and easy, the porous titanium dioxide thin-film of preparation exists
Uniformity is poor, and surface orientation is chaotic, and is difficult to ensure the problems such as film thickness after acid liquid corrosion is uniform.Application publication number is
The Chinese invention patent application of CN108677156A discloses a kind of preparation method of titanium dioxide nanorod array film, the party
Method the following steps are included: carrying out chemical cleaning to baseplate material after cleaned with radio frequency plasma, then splashed using magnetic control
Technology sputtering sedimentation preparation titanium film is penetrated, to obtain the final product, this method is although environmental-friendly by heat preservation 1h at last 600 DEG C, preparation process letter
It is single, it can be difficult to guaranteeing the orientation problem of titanium dioxide crystal.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of preparation method of titanium dioxide nanorod array film.The party
Titanium dioxide crystal favorable orientation, thickness made from method are uniform, and film is firmly combined with substrate.
The present invention also provides a kind of titanium dioxide nanorod array films.The titanium dioxide nanorod array film has height
The degree of orientation, good compactness.
To achieve the above object, the technical scheme adopted by the invention is that:
A kind of preparation method of titanium dioxide nanorod array film, comprising the following steps:
(1) titanium dioxide membrane material is put into precursor solution, it is described in 120~150 DEG C of hydro-thermal reaction 10~15h
Precursor solution includes titanium salt and acid, and the titanium salt is one of butyl titanate, isopropyl titanate, titanium tetrachloride, the forerunner
The solvent of liquid solution is at least one of water, dehydrated alcohol；
(2) the titanium dioxide membrane material after step (1) reaction is kept the temperature into 30~60min at 450~550 DEG C；
(3) the titanium dioxide membrane material after step (2) heat preservation is placed in TiCl430 are handled in 80~100 DEG C in aqueous solution
~60min to get.
Titanium dioxide nanorod array film quality of forming film made from above-mentioned preparation method is high, fine and close and flawless, and leads
Electric substrate of glass is firmly combined, and facilitates the preparation of later period component.
The titanium dioxide membrane material includes substrate and the titanium dioxide layer that is attached in substrate.Adhere to dioxy in substrate
Change titanium layer, it is the important component of titanium dioxide nanorod array film that entirety, which is used as titanium dioxide membrane material, reduces by two
Lattice mismatch rate between TiOx nano stick crystal and base material, is conducive to the epitaxial growth of titanium dioxide nano-rod crystal
And be allowed to be firmly combined with substrate, to improve the degree of orientation of titanic oxide nanorod array, and then enhance nano titania
The uniformity and consistency of rod array film.
The substrate is any one of electro-conductive glass, common soda lime glass, quartz glass, silicon wafer.Above-mentioned substance conduct
Substrate high mechanical strength, anti-corrosive properties are strong, are suitable as substrate.
The acid is HCl, on the one hand, hydrochloric acid can alleviate the hydrolysis rate of titanium salt；Cl in another aspect hydrochloric acid?It can be with
Selectivity is adsorbed on TiO2The side of nanometer rods crystal guarantees TiO to inhibit the crystalline growth of side2Nanometer rods crystal
Crystallographic orientation growth.
The titanium dioxide membrane material is made by the method included the following steps: titanium layer is formed in substrate surface sputtered titanium,
Then TiCl is placed into 400~600 DEG C of 30~120min of sintering in having oxygen atmosphere4It is handled in aqueous solution in 80~100 DEG C
30~60min.Titanium dioxide film stability of material obtained is good under this condition, and titanium dioxide layer is firmly combined with substrate, is helped
In the preparation of later period component.
Described to be sputtered to magnetically controlled DC sputtering, the power of sputtering is 90~150W, and sputtering time is 10~30min.This is splashed
The condition of penetrating can make titanium dioxide layer stronger in conjunction with substrate, and array film is more evenly.
The precursor solution is prepared to obtain by the ratio that the sum of acid and volume of solvent are 60:1 with titanium salt by volume.
Titanium salt concentration is lower when lower than this concentration proportioning, effectively cannot generate TiO by forming core2Crystal；And titanium salt when being higher than this concentration proportioning
Excessive concentration, so that TiO2Crystal structure growth is rapid, TiO2Easily stick together fusion between nanometer rods, to destroy TiO2
Nanometer stick array structure.The TiO that the proportion is prepared2The diffracted intensity of (002) crystal face of nano-stick array thin film is stronger, can
Effectively to enhance TiO2The orientation of crystal is grown.
TiCl described in step (3)4The concentration of aqueous solution is 0.05mol/L.The TiCl of this concentration4Aqueous solution can be effective
Eliminate TiO2The surface state and defect state of nanometer rods crystal.
A kind of titanium dioxide nanorod array film, is made by method comprising the following steps:
(1) titanium dioxide membrane material is put into precursor solution, it is described in 120~150 DEG C of hydro-thermal reaction 10~15h
Precursor solution includes titanium salt and acid, and the titanium salt is one of butyl titanate, isopropyl titanate, titanium tetrachloride, the forerunner
The solvent of liquid solution is at least one of water, dehydrated alcohol；
(2) the titanium dioxide membrane material after step (1) reaction is kept the temperature into 30~60min at 450~550 DEG C；
(3) the titanium dioxide membrane material after step (2) heat preservation is placed in TiCl430 are handled in 80~100 DEG C in aqueous solution
~60min to get.
Above-mentioned titanium dioxide nanorod array film has high-orientation and high-crystallinity, reduces the defect of crystal, material
Material photoelectric properties effectively improve.
Detailed description of the invention
Fig. 1 is the titanium dioxide nanorod array film in the embodiment 1 of titanium dioxide nanorod array film of the present invention
X ray diffracting spectrum；
Fig. 2 is the X ray diffracting spectrum of the titanium dioxide nanorod array film in comparative example 2 of the present invention；
Fig. 3 is the titanium dioxide nanorod array film in the embodiment 1 of titanium dioxide nanorod array film of the present invention
The scanning electron microscope (SEM) photograph of longitudinal section；
Fig. 4 is the scanning electron microscope (SEM) photograph of the titanium dioxide nanorod array film longitudinal section in comparative example 2 of the present invention；
Fig. 5 is the titanium dioxide nanorod array film in the embodiment 1 of titanium dioxide nanorod array film of the present invention
The scanning electron microscope (SEM) photograph on surface；
Fig. 6 is the scanning electron microscope (SEM) photograph on the titanium dioxide nanorod array film surface in comparative example 2 of the present invention；
Fig. 7 is the titanium dioxide nano-rod in the embodiment 1 and comparative example 2 of titanium dioxide nanorod array film of the present invention
The fluorogram of array film.
Specific embodiment
Specific embodiments of the present invention will be further explained with reference to the accompanying drawing.
Substrate of the invention can also be that ITO electro-conductive glass, AZO are conductive other than the FTO electro-conductive glass in embodiment
Glass.
In following example sputtering be magnetically controlled DC sputtering, the parameter of sputtering technology specifically: target-substrate distance be 60~
80mm, sputtering pressure are 0.5~1.0Pa, background vacuum is lower than 10-4Pa。
Below in the embodiment of the preparation method of titanium dioxide nanorod array film, titanium dioxide membrane material in step (6)
Material and interior substrate be at 45 °~75 ° of angles, titanic oxide material and interior substrate it is at 45 °~75 ° of angles can have stomata to avoid film
Or defect.
The concentration range of concentrated hydrochloric acid used is 36.5~38% in following example.
Titanium salt of the invention, which does not limit to, can also be other titanium sources or Titanium alkoxides with the titanium salt in embodiment.
The embodiment 1 of the preparation method of titanium dioxide nanorod array film
The preparation method of titanium dioxide nanorod array film of the invention, comprising the following steps:
(1) using the FTO electro-conductive glass of 15 × 15 × 2.2mm as substrate, with detergent, acetone, isopropanol and deionization
Water ultrasonic cleaning is clean, is dried for standby；Taking purity is the titanium target of 99.99wt%, and the size of titanium target is 50 × 4mm of Φ.
(2) titanium target and FTO electro-conductive glass are put into magnetron sputtering chamber, reach 10 to background vacuum-4When Pa, room temperature
Under be passed through 99.99% argon gas, target-substrate distance is adjusted to 60mm, under 1.0Pa pressure, control argon flow be 30sccm, sputtering
Power is 100W, sputters 10min, and the FTO electro-conductive glass for being deposited with metallic titanium membrane is made.
(3) electro-conductive glass for being deposited with metallic titanium membrane is put into dehydrated alcohol and is cleaned by ultrasonic 20min, room temperature is dried；
It is subsequently placed in ceramic crucible, places into high tempering furnace 400 DEG C of oxidation 120min under the mixed atmosphere of air and oxygen,
Cooled to room temperature obtains sample after oxidation.
(4) sample is put into dehydrated alcohol and is cleaned by ultrasonic 5min, room temperature places into the TiCl of 0.05M after drying4It is water-soluble
80 DEG C of processing 30min in liquid；Then it is cleaned with deionized water and dries to obtain titanium dioxide dense layer film, i.e. titanium dioxide membrane material
Material.
(5) taking 15mL concentration is that 36.5% concentrated hydrochloric acid, 15mL deionized water and 0.5mL butyl titanate is configured to presoma
It is as clear as crystal to solution that 2h is stirred at room temperature in solution.
(6) titanium dioxide film material is put into polytetrafluoroethyllining lining down, is placed with liner angle at 45 °, it will
Precursor solution is poured into liner and is closed；Liner is put into stainless steel cauldron again and is closed.
(7) reaction kettle is put into thermostatic drying chamber, reacts 15h in 120 DEG C of incubation water heatings.
(8) after reaction, be cooled to room temperature to reaction kettle, take out titanium dioxide membrane material, with dehydrated alcohol and go from
Sub- water rinses repeatedly, and then room temperature is dried.
(9) the titanium dioxide membrane material after drying is put into ceramic crucible, 450 DEG C of heat preservations in high temperature sintering furnace
60min takes out after cooled to room temperature.
(10) titanium dioxide after step (9) heat preservation is placed in the TiCl of 0.05M480 DEG C of processing 30min in aqueous solution, most
It is cleaned and is dried up to titanium dioxide nanorod array film with deionized water afterwards.
The embodiment 2 of the preparation method of titanium dioxide nanorod array film
The preparation method of titanium dioxide nanorod array film of the invention, comprising the following steps:
(1) using the FTO electro-conductive glass of 15 × 15 × 2.2mm as substrate, with detergent, acetone, isopropanol and deionization
Water ultrasonic cleaning is clean, is dried for standby；Taking purity is the titanium target of 99.99wt%, and the size of titanium target is 50 × 4mm of Φ.
(2) titanium target and FTO electro-conductive glass are put into magnetron sputtering chamber, reach 10 to background vacuum-4When Pa, room temperature
Under be passed through 99.99% argon gas, target-substrate distance is adjusted to 70mm, under 1.0Pa pressure, control argon flow be 30sccm, sputtering
Power is 125W, sputters 10min, and the FTO electro-conductive glass for being deposited with metallic titanium membrane is made.
(3) electro-conductive glass for being deposited with metallic titanium membrane is put into dehydrated alcohol and is cleaned by ultrasonic 20min, room temperature is dried；
It is subsequently placed in ceramic crucible, places into high tempering furnace 500 DEG C of oxidation 60min under the mixed atmosphere of air and oxygen,
Cooled to room temperature obtains sample after oxidation.
(4) sample is put into dehydrated alcohol and is cleaned by ultrasonic 5min, room temperature places into the TiCl of 0.05M after drying4It is water-soluble
80 DEG C of processing 40min in liquid；Then it is cleaned with deionized water and dries to obtain titanium dioxide dense layer film, i.e. titanium dioxide membrane material
Material.
(5) it takes 15mL concentrated hydrochloric acid, 15mL deionized water and 0.5mL butyl titanate to be configured to precursor solution, is stirred at room temperature
2h is as clear as crystal to solution.
(6) titanium dioxide film material is put into polytetrafluoroethyllining lining down, is placed with liner at 60 ° of angles, it will
Precursor solution is poured into liner and is closed；Liner is put into stainless steel cauldron again and is closed.
(7) reaction kettle is put into thermostatic drying chamber, in 130 DEG C of hydro-thermal reaction 13h.
(8) after reaction, be cooled to room temperature to reaction kettle, take out titanium dioxide membrane material, with dehydrated alcohol and go from
Sub- water rinses repeatedly, and then room temperature is dried.
(9) the titanium dioxide membrane material after drying is put into ceramic crucible, 500 DEG C of heat preservations in high temperature sintering furnace
45min takes out after cooled to room temperature.
(10) titanium dioxide after step (9) heat preservation is placed in the TiCl of 0.05M480 DEG C of processing 40min in aqueous solution, most
It is cleaned and is dried up to titanium dioxide nanorod array film with deionized water afterwards.
The embodiment 3 of the preparation method of titanium dioxide nanorod array film
The preparation method of titanium dioxide nanorod array film of the invention, comprising the following steps:
(1) using the FTO electro-conductive glass of 15 × 15 × 2.2mm as substrate, with detergent, acetone, isopropanol and deionization
Water ultrasonic cleaning is clean, is dried for standby；Taking purity is the titanium target of 99.99wt%, and the size of titanium target is 50 × 4mm of Φ.
(2) titanium target and FTO electro-conductive glass are put into magnetron sputtering chamber, reach 10 to background vacuum-4When Pa, room temperature
Under be passed through 99.99% argon gas, target-substrate distance is from being adjusted to 80mm, and under 1.0Pa pressure, control argon flow is 30sccm, splashes
Penetrating power is 140W, sputters 20min, and the FTO electro-conductive glass for being deposited with metallic titanium membrane is made.
(3) electro-conductive glass for being deposited with metallic titanium membrane is put into dehydrated alcohol and is cleaned by ultrasonic 20min, room temperature is dried；
It is subsequently placed in ceramic crucible, places into high tempering furnace 600 DEG C of oxidation 30min under the mixed atmosphere of air and oxygen,
Cooled to room temperature obtains sample after oxidation.
(4) sample is put into dehydrated alcohol and is cleaned by ultrasonic 5min, room temperature places into the TiCl of 0.05M after drying4It is water-soluble
100 DEG C of processing 60min in liquid；Then it is cleaned with deionized water and dries to obtain titanium dioxide dense layer film, i.e. titanium dioxide membrane material
Material.
(5) it takes 15mL concentrated hydrochloric acid, 15mL deionized water and 0.5mL butyl titanate to be configured to precursor solution, is stirred at room temperature
2h is as clear as crystal to solution.
(6) titanium dioxide film material is put into polytetrafluoroethyllining lining down, is placed with liner at 75 ° of angles, it will
Precursor solution is poured into liner and is closed；Liner is put into stainless steel cauldron again and is closed.
(7) reaction kettle is put into thermostatic drying chamber, in 150 DEG C of hydro-thermal reaction 10h.
(8) after reaction, be cooled to room temperature to reaction kettle, take out titanium dioxide membrane material, with dehydrated alcohol and go from
Sub- water rinses repeatedly, and then room temperature is dried.
(9) the titanium dioxide membrane material after drying is put into ceramic crucible, 550 DEG C of heat preservations in high temperature sintering furnace
30min takes out after cooled to room temperature.
(10) titanium dioxide after step (9) heat preservation is placed in the TiCl of 0.05M4100 DEG C of processing 45min in aqueous solution,
It is finally cleaned and is dried up to titanium dioxide nanorod array film with deionized water.
The embodiment 1 of titanium dioxide nanorod array film
The titanium dioxide nanorod array film of the present embodiment is the preparation method by titanium dioxide nanorod array film
Embodiment 1 in preparation method made from.
The embodiment 2 of titanium dioxide nanorod array film
The titanium dioxide nanorod array film of the present embodiment is the preparation method by titanium dioxide nanorod array film
Embodiment 2 in preparation method made from.
The embodiment 3 of titanium dioxide nanorod array film
The titanium dioxide nanorod array film of the present embodiment is the preparation method by titanium dioxide nanorod array film
Embodiment 3 in preparation method made from.
Comparative example 1
The preparation method of the titanium dioxide nanorod array film of this comparative example, comprising the following steps:
(1) using the FTO electro-conductive glass of 15 × 15 × 2.2mm as substrate, with detergent, acetone, isopropanol and deionization
Water ultrasonic cleaning is clean, is dried for standby.
(2) it takes 15mL concentrated hydrochloric acid, 15mL deionized water and 0.5mL butyl titanate to be configured to precursor solution, is stirred at room temperature
2h is as clear as crystal to solution.
(3) electro-conductive glass after drying in step (1) is put into liner down, precursor solution is poured into liner
And it closes；Liner is put into stainless steel cauldron again and is closed.
(4) reaction kettle is put into thermostatic drying chamber, reacts 15h in 150 DEG C of incubation water heatings.
(5) after reaction, be cooled to room temperature to reaction kettle, take out titanium dioxide membrane material, with dehydrated alcohol and go from
Sub- water rinses repeatedly, and then room temperature is dried.
(6) the titanium dioxide membrane material after drying is put into ceramic crucible, 450 DEG C of heat preservations in high temperature sintering furnace
30min takes out after cooled to room temperature.
(7) titanium dioxide after step (6) heat preservation is placed in the TiCl of 0.05M480 DEG C of processing 30min in aqueous solution, most
It is cleaned and is dried up to titanium dioxide nanorod array film with deionized water afterwards.
Comparative example 2
The titanium dioxide nanorod array film of this comparative example is by titanium dioxide nanorod array film in comparative example 1
Made from preparation method.
Test example
This test example in the embodiment 1 of titanium dioxide nanorod array film titanium dioxide nanorod array film and
For titanium dioxide nanorod array film in comparative example 2, to the SEM of the longitudinal section of titanium dioxide nanorod array film,
Surface SEM, XRD spectrum and fluorescence intensity compare, as a result as shown in Fig. 1~7.
As can be seen from Figure 1 the titanium dioxide in the embodiment 1 of titanium dioxide nanorod array film be in Rutile Type, two
TiOx nano stick crystal has good orientation, and film is grown along (002) crystal orientation preferred orientation；Figure it is seen that right
Titanium dioxide in ratio 2 is in Rutile Type, and titanium dioxide nano-rod film is equally grown along (002) crystal orientation preferred orientation, but
Intensity is weak much compared to the embodiment 1 of titanium dioxide nanorod array film, illustrates nano titania prepared by the present invention
Rod array film oriented growth is stronger.
From Fig. 3, Fig. 4 it is known that the titanium dioxide in the embodiment 1 of titanium dioxide nanorod array film of the present invention is received
The thickness of rice rod array film longitudinal section is about 3 μm, and the thickness of the titanium dioxide nanorod array film longitudinal section in comparative example 2
About 2 μm of degree.
It can be seen that compared with the titanium dioxide nanorod array film in comparative example 2 from Fig. 5, Fig. 6, reality of the invention
The titanium dioxide nanorod array film uniformity applied in example 1 is more preferable, and titanium dioxide nano-rod is more carefully conducive to improve compactness
And it is merged between titanium dioxide nano-rod without adhesion.
As can be seen from Figure 7, compared with comparative example 2, titanium dioxide in the embodiment 1 of titanium dioxide nanorod array film is utilized
The fluorescence intensity of titanium dioxide nanorod array film made from the preparation method of nano-stick array thin film is significant lower, illustrates it
Light induced electron coincidence rate is lower.In addition, the wavelength of fluorescence of titanium dioxide array film made from preparation method of the invention is to length
Wave direction is mobile, illustrates that it has widened the absorption region to visible light.In short, utilizing dioxy made from preparation method of the invention
The photoelectric properties for changing titanium nano-stick array thin film have obtained effective promotion.
Claims (9)
1. a kind of preparation method of titanium dioxide nanorod array film, it is characterised in that: the following steps are included:
(1) titanium dioxide membrane material is put into precursor solution, in 120~150 DEG C of 10~15h of hydro-thermal reaction, the forerunner
Liquid solution includes titanium salt and acid, and the titanium salt is one of butyl titanate, isopropyl titanate, titanium tetrachloride, and the presoma is molten
The solvent of liquid is at least one of water, dehydrated alcohol；
(2) the titanium dioxide membrane material after step (1) reaction is kept the temperature into 30~60min at 450~550 DEG C；
(3) the titanium dioxide membrane material after step (2) heat preservation is placed in TiCl4In aqueous solution in 80~100 DEG C handle 30~
60min to get.
2. the preparation method of titanium dioxide nanorod array film according to claim 1, it is characterised in that: the dioxy
Change the titanium dioxide layer that titanium film material includes substrate and is attached in substrate.
3. the preparation method of titanium dioxide nanorod array film according to claim 2, it is characterised in that: the substrate
For any one of electro-conductive glass, common soda lime glass, quartz glass, silicon wafer.
4. the preparation method of titanium dioxide nanorod array film according to claim 1, it is characterised in that: the acid is
HCl。
5. the preparation method of titanium dioxide nanorod array film according to claim 1 to 3, feature exist
In: the titanium dioxide membrane material is made by the method included the following steps: being formed titanium layer in substrate surface sputtered titanium, is then existed
Have in oxygen atmosphere in 400~600 DEG C of 30~120min of sintering, places into TiCl4In aqueous solution in 80~100 DEG C handle 30~
60min。
6. the preparation method of titanium dioxide nanorod array film according to claim 5, it is characterised in that: the sputtering
For magnetically controlled DC sputtering, the power of sputtering is 90~150W, and sputtering time is 10~30min.
7. the preparation method of titanium dioxide nanorod array film according to claim 1, it is characterised in that: the forerunner
Liquid solution is prepared to obtain by the ratio that the sum of acid and volume of solvent are 60:1 with titanium salt by volume.
8. the preparation method of titanium dioxide nanorod array film according to claim 1, it is characterised in that: step (3)
The TiCl4The concentration of aqueous solution is 0.05mol/L.
9. a kind of titanium dioxide nanorod array film, it is characterised in that: be made by method comprising the following steps:
(1) titanium dioxide membrane material is put into precursor solution, in 120~150 DEG C of 10~15h of hydro-thermal reaction, the forerunner
Liquid solution includes titanium salt and acid, and the titanium salt is one of butyl titanate, isopropyl titanate, titanium tetrachloride, and the presoma is molten
The solvent of liquid is at least one of water, dehydrated alcohol；
(2) the titanium dioxide membrane material after step (1) reaction is kept the temperature into 30~60min at 450~550 DEG C；
(3) the titanium dioxide membrane material after step (2) heat preservation is placed in TiCl4In aqueous solution in 80~100 DEG C handle 30~
60min to get.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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