CN105540654B - A kind of multi-level TiO2The preparation method of nano-structure array material - Google Patents
A kind of multi-level TiO2The preparation method of nano-structure array material Download PDFInfo
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- CN105540654B CN105540654B CN201510917987.8A CN201510917987A CN105540654B CN 105540654 B CN105540654 B CN 105540654B CN 201510917987 A CN201510917987 A CN 201510917987A CN 105540654 B CN105540654 B CN 105540654B
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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
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention discloses a kind of multi-level TiO2The preparation method of nano-structure array material, preparation process is：TiO is prepared using soft nanometer embossing2Nano-pore array thin film；Gained film is placed in hydrothermal reaction kettle and carries out TiO under certain condition2Trunk grows；Then to TiO2Trunk is performed etching, finally in TiCl4TiO is carried out in the aqueous solution2The growth of nano particle, after rinse, drying, is produced.The present invention is prepared for TiO using soft nanometer embossing2Nano-pore array thin film, additionally provides growth TiO while specific surface area is added2The Seed Layer of nano wire trunk；TiO is carried out successively on the seed layer using wet chemistry method2Growth, etching and the growth nano particle of trunk, realize inexpensive, controllable, high duplication multi-level TiO2It is prepared by nano-structure array material；Obtained TiO2Nano-structure array material specific surface area is big, and the characteristics of take into account nano-structure array carrier transport, can significantly improve based on TiO2The performance of nano-structure array material devices.
Description
Technical field
The invention belongs to inorganic semiconductor nanometer material technical field, and in particular to a kind of multi-level TiO2Nanostructured battle array
The preparation method of row material.
Background technology
TiO2It is a kind of wide bandgap semiconductor that environment-friendly, property is stable, PhotoelectrochemicalProperties Properties are excellent, extensively should at present
For fields such as solar cell, photocatalysis and gas sensors.Nano-structure array material refers to have within the specific limits
Certain arrangement rule stablizes the material of nanostructured in order.At present, TiO2Nano-structure array material is broadly divided into one-dimensional TiO2Receive
Rice array of structures and multi-level TiO2Nano-structure array.
Integrated TiO in the devices2One-dimensional nano structure array, such as nano wire, nanotube and nano-pore, using the teaching of the invention it is possible to provide straight
Vertical electron transport passage, improves the collection efficiency of carrier；But the introducing of one-dimensional nano structure array but reduces TiO2
Specific surface area, influence device performance.
Multi-level TiO2Nano-structure array can take into account electric transmission and the aspect performance of specific surface area two, and they have showed
Go out good application prospect, for example：TiO2" nanoforest ", i.e., in TiO2Grown on nano-wire array " trunk " secondary " dendritic "
Nanostructured.Current multi-level TiO2The preparation method of nano-structure array mainly has two classes：Gas-liquid-solid (VLS) method and chemistry
Liquid phase method.VLS methods, can be with by the use of being attached to the metal nanoparticle of primary trunk side as the growing point of secondary nanostructured
Prepare racemosus nanostructured.But VLS methods need to generally be carried out at high temperature, expensive equipment and harsh synthesis condition are undoubtedly limited
Multi-level TiO2The controllable preparation of nano-structure array.Chemical liquid phase reaction is general to be carried out in the aqueous solution or organic solution, tool
Have the advantages that low temperature, it is cheap, multi-level TiO can be grown with one or multi-step2Nano-structure array.But use simple chemical liquids
Xiang Fa, it is difficult to accurately control response parameter, repeatability is poor, slightly mistake, is readily obtained the TiO of densification2Film.
The content of the invention
It is an object of the invention to provide a kind of multi-level TiO2The preparation method of nano-structure array material, is solved existing
The problem of preparation method is needed by expensive equipment, harsh synthesis condition and low preparation process controllability.
The technical solution adopted in the present invention is, a kind of multi-level TiO2The preparation method of nano-structure array material, tool
Body comprises the following steps：
Step 1, polymethyl methacrylate/dimethyl silicone polymer (PMMA/PDMS) soft template is prepared；
Step 2, TiO is prepared2Colloidal sol, TiO is prepared followed by nano impression2Seed Layer；
Step 3, Hydrothermal Growth TiO2Trunk：Ionized water and hydrochloric acid are removed respectively, and titanium is added thereto after being well mixed
After acid butyl ester, stirring 10min, mixed liquor is obtained, mixed liquor is transferred in hydrothermal reaction kettle；To step 2 gained TiO2Seed Layer
Hydro-thermal reaction is carried out, after hydro-thermal reaction terminates, reactor of being had a shower with running water takes out the deionized water rinse of hydro-thermal reaction product
3~5 times, finally dried with nitrogen, it is standby；
Step 4, chemical etching method etching TiO2Trunk：Deionized water is added into hydrothermal reaction kettle and the mixing of hydrochloric acid is molten
Step 3 resulting materials are performed etching reaction by liquid；Subsequent reactor of being had a shower with running water, takes out the material after etching processing and uses
Deionized water rinse 3~5 times, is then dried with nitrogen, standby；
Step 5, wet-chemical surface treatment growth TiO2Nano particle：By the material product after step 4 gained etching processing
It is vertical to be placed on the TiCl that molar concentration is 40~100mM4In the aqueous solution react 20~40min, water bath temperature be 60~
80℃；It is washed with deionized water 3~5 times, after then being dried with nitrogen, produces multi-level TiO2Nano-structure array material.
It is of the invention to be further characterized in that,
In step 1, the preparation process of PMMA/PDMS soft templates is：
Step 1.1：Use two-step electrochemical anodizing mass concentration for 10% H3PO4Anode is prepared in solution
Aluminum oxide AAO templates, wherein：First step voltage is 160V, and temperature is 2 DEG C, and oxidization time is 5h；Voltage is in second step
160V, temperature is 2 DEG C, and oxidization time is 1~5min；Gained AAO templates are then placed in the H that concentration is 5%3PO4In solution,
In 45 DEG C of condition UR 30min, obtain aperture and pitch of holes be respectively 300nm and 450nm AAO templates；
Step 1.2：Chlorobenzene solution by mass concentration for 10% PMMA is equably spin-coated in AAO templates, spin coating ginseng
Number is 3000rpm × 30s；Then template is placed in below 200Pa vacuum environments under the conditions of being heated to 200 DEG C, 200 DEG C and be incubated
4h, is cooled to room temperature, recovers normal pressure；
Step 1.3：Spin coating PDMS in template after step 1.2 processing, spin coating parameters are 500rpm × 10s, 90 DEG C of bars
Solidify 50min under part；PMMA/PDMS soft templates are produced after scrubbed, dry.
In step 1.3, washing, drying process are：Removed first with mass concentration for 10% NaOH solution under PMMA layers
Al2O3With Al layers, the then watery hydrochloric acid with mass concentration for 1% and deionized water rinse 3~5 times, drying at room temperature successively.
In step 2, TiO2The preparation process of colloidal sol is：Butyl titanate is dissolved in absolute ethyl alcohol, solution A is obtained；Again will
Water, absolute ethyl alcohol are mixed with nitric acid, obtain mixed solution B；It is subsequently agitated for solution A and mixed solution B is slowly dropped to solution A
In, continue to stir 24h at room temperature, produce；Wherein, the mol ratio of butyl titanate and nitric acid is 1:0.15, butyl titanate and water
Mol ratio is 1:1, the mol ratio of butyl titanate and ethanol is 1:15~30.
In step 2, TiO2The preparation process of Seed Layer is：Appropriate TiO is taken according to required film size2Colloidal sol is added drop-wise to base
On bottom, the PMMA/PDMS soft templates obtained by step 1 are then placed in TiO2Above colloidal sol, in 1~5MPa, 80~90 DEG C of conditions
5~10h of lower impressing, after pressure release, peels off PDMS layers, then is dissolved PMMA with acetonitrile, produces.
In step 3, deionized water and the volume ratio of hydrochloric acid are 1 in gained mixed liquor:1, the addition of butyl titanate is to go
The 1/60~1/30 of ion water volume.
In step 3, hydrothermal reaction process is：First by step 2 gained TiO2Seed Layer is heat-treated 30min at 500 DEG C, with
It is tiltedly placed in the Teflon liner of hydrothermal reaction kettle afterwards, angle of inclination is 68~72 °, TiO2Down, it is hydro-thermal is anti-
Answer kettle to be placed in air dry oven, in 160~200 DEG C of environment, react 50min~240min.
In step 4, the amount ratio of deionized water and hydrochloric acid is volume ratio 1 in mixed solution:0.5~2.
In step 4, etching reaction process is：It will be tiltedly placed on through step 3 resulting materials in the Teflon of hydrothermal reaction kettle
In lining, angle of inclination is 68~72 °, TiO2Down, hydrothermal reaction kettle is placed in air dry oven, in 150 DEG C of environment
React 1~5h.
The beneficial effects of the invention are as follows the present invention is prepared for TiO using soft nanometer embossing2Nano-pore array thin film,
On the one hand specific surface area is added, on the other hand again as growth TiO2The Seed Layer of nano wire trunk；Followed by wet-chemical
Method carries out TiO successively on the seed layer2Growth, etching and the growth nano particle of trunk, realize inexpensive, controllable, Gao Chong
The multi-level TiO of renaturation2The preparation of nano-structure array material；Obtained TiO2Nano-structure array material specific surface area is big, and simultaneous
The characteristics of turning round and look at nano-structure array carrier transport, can significantly improve based on TiO2The performance of nano-structure array material devices.
Brief description of the drawings
Fig. 1 is a kind of multi-level TiO of the present invention2The flow chart of the preparation method of nano-structure array material.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
A kind of multi-level TiO of the present invention2The flow chart of the preparation method of nano-structure array material is as shown in Fig. 1；
Embodiment 1
Step 1, polymethyl methacrylate/dimethyl silicone polymer (PMMA/PDMS) soft template is prepared：
Step 1.1：Use two-step electrochemical anodizing concentration for 10% H3PO4Anodic oxidation is prepared in solution
Aluminum alloy pattern plate, wherein：First step voltage is 160V, and temperature is 2 DEG C, and oxidization time is 5h；Voltage is 160V in second step, and temperature is
2 DEG C, oxidization time is 1min；Gained anodic oxidation aluminium formwork is then placed in the H that concentration is 5%3PO4In solution, in 45 DEG C of bars
Part UR 30min, obtains aperture and pitch of holes is respectively the certain AAO templates of 300nm and 450nm, hole depth；
Step 1.2：By mass concentration for 10% PMMA (350kg/mol, Alfa Aesar) chlorobenzene solution equably
It is spin-coated in AAO templates, spin coating parameters are 3000rpm × 30s；Then template is placed in below 200Pa vacuum environments and heated
4h is incubated under the conditions of to 200 DEG C, 200 DEG C, room temperature is cooled to, recovers normal pressure；
Step 1.3：Spin coating PDMS (Dowcorning Sylgard184) in template after step 1.2 processing, spin coating ginseng
Number is 500rpm × 10s, solidifies 50min under the conditions of 90 DEG C；Template is cleaned with concentration for 10% NaOH solution, PMMA is removed
Al under layer2O3With Al layers, then with quality solubility for 1% watery hydrochloric acid rinse 3 times, with deionized water successively rinse 3 times, room
Temperature is dried, and produces PMMA/PDMS soft templates.
Step 2, butyl titanate is dissolved in absolute ethyl alcohol, obtains solution A；Water, absolute ethyl alcohol are mixed with nitric acid again, obtained
Mixed solution B；It is subsequently agitated for solution A and mixed solution B is slowly dropped in solution A, continues to stir 24h at room temperature, produce；
Wherein, the mol ratio of butyl titanate and nitric acid is 1:0.15, the mol ratio of butyl titanate and water is 1:1, butyl titanate and ethanol
Mol ratio be 1:15.
Appropriate TiO is taken according to required film size2Colloidal sol is added drop-wise in substrate, then by the PMMA/PDMS obtained by step 1
Soft template is placed in TiO2Above colloidal sol, 5h is imprinted under the conditions of 5MPa, 80 DEG C, after pressure release, PDMS layer is peeled off, then use second
Nitrile dissolves PMMA, produces TiO2Seed Layer；
Step 3,15mL deionized waters and 15mL hydrochloric acid (36.5~38wt%) are taken respectively, are added thereto after being well mixed
After 0.25ml butyl titanates, stirring 10min, mixed liquor is obtained, mixed liquor is transferred in hydrothermal reaction kettle；By obtained by step 2
TiO2Seed Layer is heat-treated 30min at 500 DEG C, and TiO is grown as Seed Layer2Nano wire trunk, is then tiltedly placed on water by it
In the Teflon liner of thermal response kettle, angle of inclination is 68 °, TiO2Down, hydrothermal reaction kettle is placed in air dry oven,
In 200 DEG C of environment, after reaction 50min, reactor of being had a shower with running water takes out the deionized water rinse of hydro-thermal reaction product
3 times, finally dried with nitrogen, it is standby；
Step 4, it is 1 that deionized water is added into hydrothermal reaction kettle with hydrochloric acid volume ratio:0.5 mixed solution, will be through step
Rapid 3 resulting materials are tiltedly placed in the Teflon liner of hydrothermal reaction kettle, and angle of inclination is 68 °, TiO2Down, it is hydro-thermal is anti-
Answer kettle to be placed in air dry oven, 1h is reacted in 150 DEG C of environment；Subsequent reactor of being had a shower with running water, takes out etching processing
The deionized water rinse 3 times of material afterwards, is then dried with nitrogen, standby；
Step 5, the material product after step 4 gained etching processing is placed on the TiCl that molar concentration is 40mM vertically4
40min is reacted in the aqueous solution, water bath temperature is 60 DEG C；With deionized water rinse 3 times, after then being dried with nitrogen, produce
Multi-level TiO2Nano-structure array material.
Embodiment 2
Step 1, polymethyl methacrylate/dimethyl silicone polymer (PMMA/PDMS) soft template is prepared：
Step 1.1：Use two-step electrochemical anodizing concentration for 10% H3PO4Anodic oxidation is prepared in solution
Aluminium (AAO) template, wherein：First step voltage is 160V, and temperature is 2 DEG C, and oxidization time is 5h；Voltage is 160V in second step,
Temperature is 2 DEG C, and oxidization time is 5min；Gained AAO templates are then placed in the H that concentration is 5%3PO4In solution, in 45 DEG C of bars
Part UR 30min, obtains aperture and pitch of holes is respectively the certain AAO templates of 300nm and 450nm, hole depth；
Step 1.2：By mass concentration for 10% PMMA (350kg/mol, Alfa Aesar) chlorobenzene solution equably
It is spin-coated in AAO templates, spin coating parameters are 3000rpm × 30s；Then template is placed in below 200Pa vacuum environments and heated
4h is incubated under the conditions of to 200 DEG C, 200 DEG C, room temperature is cooled to, recovers normal pressure；
Step 1.3：Spin coating PDMS (Dowcorning Sylgard184) in template after step 1.2 processing, spin coating ginseng
Number is 500rpm × 10s, solidifies 50min under the conditions of 90 DEG C；Template is cleaned with mass concentration for 10% NaOH solution, removed
Al under PMMA layers2O3With Al layers, watery hydrochloric acid and deionized water rinse 5 times, room respectively successively that then use quality solubility is 1%
Temperature is dried, and produces PMMA/PDMS soft templates.
Step 2, butyl titanate is dissolved in absolute ethyl alcohol, obtains solution A；Water, absolute ethyl alcohol are mixed with nitric acid again, obtained
Mixed solution B；It is subsequently agitated for solution A and mixed solution B is slowly dropped in solution A, continues to stir 24h at room temperature, produce；
Wherein, the mol ratio of butyl titanate and nitric acid is 1:0.15, the mol ratio of butyl titanate and water is 1:1, butyl titanate and ethanol
Mol ratio be 1:30.
Appropriate TiO is taken according to required film size2Colloidal sol is added drop-wise in substrate, then by the PMMA/PDMS obtained by step 1
Soft template is placed in TiO2Above colloidal sol, 10h is imprinted under the conditions of 1MPa, 80 DEG C, after pressure release, PDMS layer is peeled off, then use second
Nitrile dissolves PMMA, produces TiO2Seed Layer；
Step 3,15mL deionized waters and 15mL hydrochloric acid (36.5~38wt%) are taken respectively, are added thereto after being well mixed
After 0.5ml butyl titanates, stirring 10min, mixed liquor is obtained, mixed liquor is transferred in hydrothermal reaction kettle；By step 2 gained TiO2
Seed Layer is heat-treated 30min at 500 DEG C, then it is tiltedly placed in the Teflon liner of hydrothermal reaction kettle, angle of inclination
For 72 °, TiO2Down, hydrothermal reaction kettle is placed in air dry oven, in 160 DEG C of environment, after reaction 240min, used
Running water is had a shower reactor, is taken out the deionized water rinse 5 times of hydro-thermal reaction product, is finally dried with nitrogen, standby；
Step 4, it is 1 that deionized water is added into hydrothermal reaction kettle with hydrochloric acid volume ratio:2 mixed solution, will be through step 3
Resulting materials are tiltedly placed in the Teflon liner of hydrothermal reaction kettle, and angle of inclination is 72 °, TiO2Down, by hydro-thermal reaction
Kettle is placed in air dry oven, and 5h is reacted in 150 DEG C of environment；Subsequent reactor of being had a shower with running water, takes out after etching processing
Material deionized water rinse 5 times, then dried with nitrogen, it is standby；
Step 5, the material product after step 4 gained etching processing is placed on the TiCl that molar concentration is 100mM vertically4
20min is reacted in the aqueous solution, water bath temperature is 80 DEG C；Then it is washed with deionized water 5 times, after then being dried with nitrogen, i.e.,
Obtain multi-level TiO2Nano-structure array material.
Embodiment 3
Step 1, polymethyl methacrylate/dimethyl silicone polymer (PMMA/PDMS) soft template is prepared：
Step 1.1：Use two-step electrochemical anodizing concentration for 10% H3PO4Anodic oxidation is prepared in solution
Aluminium (AAO) template, wherein：First step voltage is 160V, and temperature is 2 DEG C, and oxidization time is 5h；Voltage is 160V in second step,
Temperature is 2 DEG C, and oxidization time is 3min；Gained AAO templates are then placed in the H that concentration is 5%3PO4In solution, in 45 DEG C of bars
Part UR 30min, obtains aperture and pitch of holes is respectively the certain AAO templates of 300nm and 450nm, hole depth；
Step 1.2：By mass concentration for 10% PMMA (350kg/mol, Alfa Aesar) chlorobenzene solution equably
It is spin-coated in AAO templates, spin coating parameters are 3000rpm × 30s；Then template is placed in below 200Pa vacuum environments and heated
4h is incubated under the conditions of to 200 DEG C, 200 DEG C, room temperature is cooled to, recovers normal pressure；
Step 1.3：Spin coating PDMS (Dowcorning Sylgard184) in template after step 1.2 processing, spin coating ginseng
Number is 500rpm × 10s, solidifies 50min under the conditions of 90 DEG C；Template is cleaned with mass concentration for 10% NaOH solution, removed
Al under PMMA layers2O3With Al layers, watery hydrochloric acid and deionized water rinse 4 times, room respectively successively that then use mass concentration is 1%
Temperature is dried, and produces PMMA/PDMS soft templates.
Step 2, butyl titanate is dissolved in absolute ethyl alcohol, obtains solution A；Water, absolute ethyl alcohol are mixed with nitric acid again, obtained
Mixed solution B；It is subsequently agitated for solution A and mixed solution B is slowly dropped in solution A, continues to stir 24h at room temperature, produce；
Wherein, the mol ratio of butyl titanate and nitric acid is 1:0.15, the mol ratio of butyl titanate and water is 1:1, butyl titanate and ethanol
Mol ratio be 1:20.
Appropriate TiO is taken according to required film size2Colloidal sol is added drop-wise in substrate, then by the PMMA/PDMS obtained by step 1
Soft template is placed in TiO2Above colloidal sol, 7h is imprinted under the conditions of 3MPa, 85 DEG C, after pressure release, PDMS layer is peeled off, then use acetonitrile
By PMMA dissolvings, TiO is produced2Seed Layer；
Step 3,15mL deionized waters and 15mL hydrochloric acid (36.5~38wt%) are taken respectively, are added thereto after being well mixed
After 0.35ml butyl titanates, stirring 10min, mixed liquor is obtained, mixed liquor is transferred in hydrothermal reaction kettle；By obtained by step 2
TiO2Seed Layer is heat-treated 30min at 500 DEG C, and then it is tiltedly placed in the Teflon liner of hydrothermal reaction kettle, tilts
Angle is 70 °, TiO2Down, hydrothermal reaction kettle is placed in air dry oven, in 180 DEG C of environment, reacts 120min
Afterwards, had a shower with running water reactor, take out the deionized water rinse 4 times of hydro-thermal reaction product, finally dried with nitrogen, it is standby；
Step 4, it is 1 that deionized water is added into hydrothermal reaction kettle with hydrochloric acid volume ratio:1 mixed solution, will be through step 3
Resulting materials are tiltedly placed in the Teflon liner of hydrothermal reaction kettle, and angle of inclination is 70 °, TiO2Down, by hydro-thermal reaction
Kettle is placed in air dry oven, and 3h is reacted in 150 DEG C of environment；Subsequent reactor of being had a shower with running water, takes out after etching processing
Material deionized water rinse 4 times, then dried with nitrogen, it is standby；
Step 5, the material product after step 4 gained etching processing is placed on the TiCl that molar concentration is 70mM vertically4
30min is reacted in the aqueous solution, water bath temperature is 70 DEG C；Then it is washed with deionized water 4 times, after then being dried with nitrogen, i.e.,
Obtain multi-level TiO2Nano-structure array material.
The soft nano impression of combination and wet chemistry method of the present invention prepare multi-level TiO2The side of nano-structure array
Method has the advantages that inexpensive, controllable and repeated high, and the nanostructured of preparation has great specific surface area, and keeps perpendicular
The shape characteristic of in line row, is expected to obviously improve based on TiO2The classes of semiconductors device performance of nano-structure array, such as：The sun
Energy battery, photocatalysis hydrogen production gas, gas sensor etc..
Utilize the multi-level TiO of the gained of the embodiment of the present invention 22Dye sensitization of solar prepared by nano-structure array material
Battery (A) is shown in Table 1 with nano-wire array DSSC (B) performance comparison：
Table 1
As can be seen from Table 1, the multi-level TiO obtained by the inventive method is utilized2Dye prepared by nano-structure array material
Expect the short circuit current flow and fill factor, curve factor of sensitization solar battery compared with TiO2Nano-wire array DSSC has greatly
Amplitude is improved, and photoelectric transformation efficiency is significantly improved to 3.7% by 1.3%.
Past research is found：The TiO prepared by soft nano impression2The solar cell of nanohole array assembling is obvious
Compared with plane TiO2Thin-film solar cells efficiency high, this is attributed to the specific surface area and enhanced carrier transport ability of increase；
And wet chemistry method etching TiO2Nano-wire array can also increase the specific surface area of nano wire and improve charge collection efficiency, finally carry
The efficiency of high DSSC；TiCl4It is surface-treated TiO2The method that electrode obtains nano particle is also proved in the past
For the approach of effectively increase specific surface area.The ingenious soft nanometer embossing of combination of the present invention is made with wet chemistry method there is provided one kind
Standby multi-level TiO2The approach of nano-structure array material, while increasing TiO2Specific surface area and keep nano-structure array
The characteristics of material carrier is transported, is expected to be applied to the fields such as solar cell, photocatalysis hydrogen production gas and gas sensor.
Claims (7)
1. a kind of multi-level TiO2The preparation method of nano-structure array material, it is characterised in that specifically include following steps：
Step 1, polymethyl methacrylate/dimethyl silicone polymer (PMMA/PDMS) soft template is prepared；
Step 1.1：Anodised aluminium AAO templates are prepared using two-step electrochemical anodizing, electrolyte is mass concentration
10% H3PO4Solution, wherein：First step voltage is 160V, and temperature is 2 DEG C, and oxidization time is 5h；Voltage is in second step
160V, temperature is 2 DEG C, and oxidization time is 1~5min；Gained AAO templates are then placed in the H that mass concentration is 5%3PO4After locate
Manage in solution, in 45 DEG C of condition URs reaction 30min, obtain aperture and pitch of holes be respectively 300nm and 450nm AAO templates；
Step 1.2：Chlorobenzene solution by mass concentration for 10% PMMA is equably spin-coated in AAO templates, and spin coating parameters are
3000rpm×30s；Then template is placed in below 200Pa vacuum environments under the conditions of being heated to 200 DEG C, 200 DEG C and is incubated 4h,
Room temperature is cooled to, recovers normal pressure；
Step 1.3：Spin coating PDMS in template after step 1.2 processing, spin coating parameters are 500rpm × 10s, under the conditions of 90 DEG C
Solidify 50min；PMMA/PDMS soft templates are produced after scrubbed, dry；
Step 2, TiO is prepared2Colloidal sol, TiO is prepared followed by nano impression2Seed Layer；In step 2, TiO2The preparation of colloidal sol
Cheng Wei：Butyl titanate is dissolved in absolute ethyl alcohol, solution A is obtained；Water, absolute ethyl alcohol are mixed with nitric acid again, mixed solution is obtained
B；It is subsequently agitated for solution A and mixed solution B is slowly dropped in solution A, continues to stir 24h at room temperature, produce；Wherein, titanium
The mol ratio of acid butyl ester and nitric acid is 1:0.15, the mol ratio of butyl titanate and water is 1:1, the mol ratio of butyl titanate and ethanol
For 1:15~30；
Step 3, Hydrothermal Growth TiO2Trunk：Ionized water and hydrochloric acid are removed respectively, and metatitanic acid fourth is added thereto after being well mixed
After ester, stirring 10min, mixed liquor is obtained, mixed liquor is transferred in hydrothermal reaction kettle；To step 2 gained TiO2Seed Layer is carried out
Hydro-thermal reaction, after hydro-thermal reaction terminates, reactor of being had a shower with running water takes out the deionized water rinse 3~5 of hydro-thermal reaction product
It is secondary, finally dried with nitrogen, it is standby；
Step 4, chemical etching method etching TiO2Trunk：The mixed solution of deionized water and hydrochloric acid is added into hydrothermal reaction kettle, it is right
Step 3 resulting materials perform etching reaction；Subsequent reactor of being had a shower with running water, takes out the material deionization after etching processing
Water rinse 3~5 times, is then dried with nitrogen, standby；
Step 5, wet-chemical surface treatment growth TiO2Nano particle：Material product after step 4 gained etching processing is put vertically
Put in the TiCl that molar concentration is 40~100mM420~40min is reacted in the aqueous solution, water bath temperature is 60~80 DEG C；With
Deionization is washed 3~5 times, after then being dried with nitrogen, produces multi-level TiO2Nano-structure array material.
2. a kind of multi-level TiO according to claim 12The preparation method of nano-structure array material, it is characterised in that
In step 1.3, washing, drying process are：It is the Al under 10% PMMA layers of NaOH solution removing first with mass concentration2O3With
Al layers, the then watery hydrochloric acid with mass concentration for 1% and deionized water rinse 3~5 times, drying at room temperature successively.
3. a kind of multi-level TiO according to claim 12The preparation method of nano-structure array material, it is characterised in that
In step 2, TiO2The preparation process of Seed Layer is：Appropriate TiO is taken according to required film size2Colloidal sol is added drop-wise in substrate, then
PMMA/PDMS soft templates obtained by step 1 are placed in TiO2Above colloidal sol, 5 are imprinted under the conditions of 1~5MPa, 80~90 DEG C~
10h, after pressure release, peels off PDMS layer, then is dissolved PMMA with acetonitrile, produces.
4. a kind of multi-level TiO according to claim 12The preparation method of nano-structure array material, it is characterised in that
In step 3, deionized water and the volume ratio of hydrochloric acid are 1 in gained mixed liquor:1, the addition of butyl titanate is deionization water body
Long-pending 1/60~1/30.
5. a kind of multi-level TiO according to claim 42The preparation method of nano-structure array material, it is characterised in that
In step 3, hydrothermal reaction process is：First by step 2 gained TiO2Seed Layer is heat-treated 30min at 500 DEG C, then that its is oblique
It is placed in the Teflon liner of hydrothermal reaction kettle, angle of inclination is 68~72 °, TiO2Down, hydrothermal reaction kettle is placed in
In air dry oven, in 160~200 DEG C of environment, 50min~240min is reacted.
6. a kind of multi-level TiO according to claim 12The preparation method of nano-structure array material, it is characterised in that
In step 4, the amount ratio of deionized water and hydrochloric acid is volume ratio 1 in mixed solution:0.5~2.
7. a kind of multi-level TiO according to claim 12The preparation method of nano-structure array material, it is characterised in that
In step 4, etching reaction process is：It will tiltedly be placed in the Teflon liner of hydrothermal reaction kettle, tilt through step 3 resulting materials
Angle is 68~72 °, TiO2Down, hydrothermal reaction kettle is placed in air dry oven, 1~5h is reacted in 150 DEG C of environment.
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