CN101659519A - Method for preparing modified titanium dioxide doped thin film - Google Patents
Method for preparing modified titanium dioxide doped thin film Download PDFInfo
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- CN101659519A CN101659519A CN200910307696A CN200910307696A CN101659519A CN 101659519 A CN101659519 A CN 101659519A CN 200910307696 A CN200910307696 A CN 200910307696A CN 200910307696 A CN200910307696 A CN 200910307696A CN 101659519 A CN101659519 A CN 101659519A
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- titanium dioxide
- pei
- thin film
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- silica glass
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a method for preparing a modified titanium dioxide doped thin film. The invention solves such problems of existing titanium dioxide thin films as difficult doping modification, poor doping effect and poor binding force between the thin film obtained by the existing layer-by-layer self-assembly technique and a substrate. The method comprises the following steps: preparing an early modified titanium dioxide doped thin film by the layer-by-layer self-assembly technique, and then obtaining the modified titanium dioxide doped thin film by heat treatment. The method has advantages of stable and reliable process, simple equipment, easy operation and realizable doping modification. The titanium dioxide thin film obtained by the method has good doping modification effect, band gap of the titanium dioxide thin film decreases to 2.8eV, and the thin film is bound tightly to the substrate by alkylation treatment. The modified titanium dioxide doped thin film can be appliedto photocatalytic water decomposition for hydrogen production.
Description
Technical field
The present invention relates to a kind of preparation method of modifying titanium dioxide film.
Background technology
The titanium dioxide band gap is higher, only to ultraviolet light response, makes titanium dioxide be restricted in the practice of photocatalysis field.Simultaneously, the powder catalyzer separates, reclaims difficulty after reaction, cause secondary pollution problems easily, makes people propose new demands such as modification, curing to titanium dioxide optical catalyst.
At present the method for modifying of titanium deoxid film mainly contains sensitization, doping etc., owing to sensitizing cost height, be difficult for obtaining the uniform sensitization rete of thickness on broad area device, therefore mixing in practice becomes titania modified main means.The preparation method of traditional titanium deoxid film has chemical oxidization method and electrochemical oxidation process, and these two kinds of methods exist the shortcoming of film doping modification difficulty, doping weak effect.Existing doping vario-property means adopt high temperature or high companding infiltration method mostly, and are to the doping weak effect of titanium deoxid film, undesirable.
Layer connects a layer self-assembling method, as a synthetic technology of functional materials from bottom to top that grew up in recent years, construct various functional materialss at material surfaces such as various base materials such as silica glass, ITO conductive glass, monocrystalline silicon pieces from molecular level and obtained very ten-strike, become the focus in investigation of materials field.But, all the time, layer connects layer self-assembling technique and only obtained utilization on off-color material, major cause is that layer connects layer self-assembling technique and is used to construct the composite functional material identical with the component solution composition always, as in rete, introducing titanium dioxide, need synthesis of titanium dioxide powder in advance, dispose component solution again and remove to construct composite functional material.And the reactive force of rete that obtains and base material is electrostatic attraction, a little less than the bonding force, in use comes off easily.
Summary of the invention
The objective of the invention is in order to solve existing titanium deoxid film doping vario-property difficulty, doping weak effect, reach existing layer and connect layer self-assembling technique gained film and the weak problem of substrate caking power, the invention provides a kind of preparation method of modified titanium dioxide doped thin film.
The preparation method of a kind of modified titanium dioxide doped thin film of the present invention realizes by following steps:
Step 1, modified titanium dioxide doped early stage film preparation:
A, deoiling is carried out in the silica glass substrate handle, clean up with deionized water then, more protonated pre-treatment is carried out in the silica glass substrate;
B, will to place mass concentration through the silica glass substrate after step a handles be 5%～15% 3-TSL 8330 (SiRN), soaks 20～40min, cleans with ethanol then, again at 70 ℃～80 ℃ down dry 1～1.5h;
C, will to put into mass concentration through the silica glass substrate that step b handled be that 5% two (2 hydroxy propanoic acid) two hydroxides, two ammoniums close titanium (TALH) solution, soak 10～30min, take out the back washed with de-ionized water, place the polymine (PEI) of 2mmol/L to soak 10～30min after the seasoning again, take out, use washed with de-ionized water, seasoning forms the TALH/PEI thin layer in the silica glass substrate;
D, repetitive operation c step x-1 time form in the silica glass substrate [TALH/PEI]
xThin layer, x=2～5;
E, the silica glass substrate that 1. will be covered with thin layer through the surface that above-mentioned steps obtains place the compound that contains doped element (compound of representing to contain doped element with the M) solution of 2mmol/L to soak 10～30min, take out the back washed with de-ionized water, place the polymine (PEI) of 2mmol/L after the seasoning again, after soaking 10～30min, take out, use washed with de-ionized water, seasoning forms in the silica glass substrate [TALH/PEI]
x/ [M/PEI] thin layer, the compound solution that contains doped element is polyoxometallic acid salts solution or metal complexes;
2. will in the silica glass substrate, form [TALH/PEI] through the 1. surface that obtains of step 1. step n-1 time of silica glass repetitive operation e that is covered with thin layer of e
x/ [M/PEI]
nThin layer, n=1～6;
C～d step is operated in f, the silica glass substrate that will be covered with thin layer through the surface that above-mentioned steps obtains, and forms in the silica glass substrate [TALH/PEI]
x/ [M/PEI]
n/ [TALH/PEI]
xThin layer;
G, will be covered with [TALH/PEI] through the surface that above-mentioned steps obtains
x/ [M/PEI]
n/ [TALH/PEI]
xThe above-mentioned c of silica glass substrate repetitive operation of thin layer～f step m-1 time forms in the silica glass substrate { [TALH/PEI]
x/ [M/PEI]
n/ [TALH/PEI]
x}
m, m=2～4;
H, will be covered with { [TALH/PEI] through the surface that above-mentioned steps obtains
x/ [M/PEI]
n/ [TALH/PEI]
x}
mIt is that 5% two (2 hydroxy propanoic acid) two hydroxides, two ammoniums close titanium (TALH) solution that mass percent is put in the silica glass substrate of thin layer, soak 10～30min, taking out the back uses washed with de-ionized water, seasoning to obtain modifying titanium dioxide film in early stage: { [TALH/PEI]
x/ [M/PEI]
n/ [TALH/PEI]
x}
m/ TALH, x=2～5, n=1～6, m=2～4;
The preparation of step 2, modified titanium dioxide doped thin film: will under air atmosphere, 400 ℃～1200 ℃ conditions, calcine 1.5～5h by the modifying titanium dioxide film in early stage that step 1 obtains, and cool to room temperature with the furnace and obtain modified titanium dioxide doped thin film.
The present invention utilizes layer to connect a layer self-assembling method, by the cationic electrostatic attraction effect of polymine (PEI), realize TALH and contain the self-assembly of compound on molecular level that is doped element, and TALH is converted into target compound titanium dioxide by calcining thermal treatment, simultaneously the Elements Diffusion that is doped is finished effective doping vario-property to the titanium dioxide to titanium dioxide.The present invention broken layer and connect the drawback that layer rete composition of self-assembling method preparation is subjected to the solution component restriction, widened the utilization scope that layer connects layer self-assembling technique, realizes the conversion of membranous layer ingredient by postorder thermal treatment, obtains containing the film of target compound.
The present invention carries out alkylation pre-treatment in early stage by the b step of step 1 to the silica glass substrate, introduce the silane chain, utilize the calcining heat treatment process of step 2 to form the Si-O-Ti key then, make film close, solved that existing self-assembled film combines by electrostatic attraction with base material and problem a little less than the bonding force by chemical bond and quartz glass substrate bear building-up.
Preparation method of the present invention with the preparation of titanium deoxid film with the doping vario-property of titanium deoxid film is finished synchronously, technology is simple, reliable and stable, realizes that doping vario-property is simply easy, and the equipment that adopts is simple, easy to operate, be easy to grasp, and safe preparation process.And the present invention can prepare large area film, helps industrial production.
The present invention connects a layer self-assembling method with existing layer and compares, it is synthetic in advance to have cancelled titanium dioxide powder, directly construct modified titanium dioxide doped photocatalyst material, existing layer is connect layer self-assembling technique improve and make its functional materials of constructing have the advantageous property of structured material, good practical value is arranged.
The doping of the modified titanium dioxide doped thin film that the present invention prepares is effective, and the band gap of modified titanium dioxide doped thin film is reduced to 2.8eV, can realize photocatalytic hydrogen production by water decomposition.And the modified titanium dioxide doped thin film that obtains is vesicular, and specific surface area is big.
The present invention can pass through the control to the film number of plies, thereby realizes the control to titanium dioxide and doped element content.Solution and quartz glass substrate can reuse in preparation process simultaneously, have reduced production cost.
Description of drawings
Fig. 1 is the modified titanium dioxide doped thin film that embodiment 17, embodiment 18 and embodiment 19 obtain, reach the not ultraviolet-visible absorption spectroscopy graphic representation of modified titanium dioxide doped thin film, a is the ultraviolet-visible absorption spectroscopy curve of not modified titanium dioxide doped thin film, b is the ultraviolet-visible absorption spectroscopy curve of embodiment 17, c is the ultraviolet-visible absorption spectroscopy curve of embodiment 18, and d is the ultraviolet-visible absorption spectroscopy curve of embodiment 19; Fig. 2 is Fourier's deflection infrared spectrogram of the modified titanium dioxide doped thin film that obtains of embodiment 17; Fig. 3 is the surface topography map of the scanning electronic microscope (SEM) of the modified titanium dioxide doped thin film that obtains of embodiment 18; Fig. 4 is the energy spectrogram (EDS) of the modified titanium dioxide doped thin film of embodiment 18; Fig. 5 is the modified titanium dioxide doped thin film that embodiment 18 and embodiment 19 obtain, and the x X-ray photoelectron spectroscopy X curve (XPS) of the 2p of Ti figure in the modified titanium dioxide doped thin film not, wherein, curve a is the XPS curve of not modified titanium dioxide doped thin film, red curve wherein is the matched curve of black curve, curve b is the XPS curve of the modified titanium dioxide doped thin film that obtains of embodiment 18, and curve c is the XPS curve of the modified titanium dioxide doped thin film that obtains of embodiment 19; Fig. 6 is the modified titanium dioxide doped thin film that embodiment 18 and embodiment 19 obtain, and the x X-ray photoelectron spectroscopy X graphic representation of the 1s of O in the modified titanium dioxide doped thin film not, wherein, curve a is the XPS curve of not modified titanium dioxide doped thin film, red curve wherein is the matched curve of black curve, curve b is the XPS curve of the modified titanium dioxide doped thin film that obtains of embodiment 18, and curve c is the XPS curve of the modified titanium dioxide doped thin film that obtains of embodiment 19; Fig. 7 is the surface topography map of the scanning electronic microscope (SEM) of the modified titanium dioxide doped thin film that obtains of embodiment 19.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of present embodiment modified titanium dioxide doped thin film, realize by following steps:
The preparation of step 1, modifying titanium dioxide film in early stage:
A, deoiling is carried out in the silica glass substrate handle, clean up with deionized water then protonated pre-treatment is carried out in the silica glass substrate;
B, will to place mass concentration through the silica glass substrate after step a handles be 5%～15% 3-TSL 8330 (SiRN) solution, soaks 20～40min, cleans with ethanol then, again at 70 ℃～80 ℃ down dry 1～1.5h;
C, will to place mass concentration through the silica glass substrate that step b handled be that 5% two (2 hydroxy propanoic acid) two hydroxides, two ammoniums close titanium (TALH) solution, soak 10～30min, take out the back washed with de-ionized water, place the polymine (PEI) of 2mmol/L after the seasoning again, after soaking 10～30min, take out, use washed with de-ionized water, seasoning forms the TALH/PEI thin layer in the silica glass substrate;
D, repetitive operation step cx-1 time form in the silica glass substrate [TALH/PEI]
xThin layer, x=2～5;
E, the silica glass substrate that 1. will be covered with thin layer through the surface that above-mentioned steps obtains place the compound that contains doped element (compound of representing to contain doped element with the M) solution of 2mmol/L to soak 10～30min, take out the back washed with de-ionized water, place the polymine (PEI) of 2mmol/L to soak 10～30min after the seasoning again, take out, use washed with de-ionized water, seasoning forms in the silica glass substrate [TALH/PEI]
x/ [M/PEI] thin layer, the compound solution that contains doped element is polyoxometallic acid salts solution or metal complexes;
2. 1. step n-1 time of repetitive operation e forms in the silica glass substrate [TALH/PEI]
x/ [M/PEI]
nThin layer, n=1～6;
C～d step is operated in f, the silica glass substrate that will be covered with thin layer through the surface that above-mentioned steps obtains, and forms in the silica glass substrate [TALH/PEI]
x/ [M/PEI]
n/ [TALH/PEI]
xThin layer;
G, will be covered with [TALH/PEI] through the surface that above-mentioned steps obtains
x/ [M/PEI]
n/ [TALH/PEI]
xThe above-mentioned c of silica glass substrate repetitive operation of thin layer～f step m-1 time forms in the silica glass substrate { [TALH/PEI]
x/ [M/PEI]
n/ [TALH/PEI]
x}
m, m=2～4;
H, will be covered with { [TALH/PEI] through the surface that above-mentioned steps obtains
x/ [M/PEI]
n/ [TALH/PEI]
x}
mThe silica glass substrate to put into mass percent be that 5% two (2 hydroxy propanoic acid) two hydroxides, two ammoniums close titanium (TALH) solution and soak 10～30min, take out the back and use washed with de-ionized water, seasoning to obtain modifying titanium dioxide film in earlier stage:
{[TALH/PEI]
x/[M/PEI]
n/[TALH/PEI]
x}
m/TALH，x＝2～5，n＝1～6，m＝2～4；
The preparation of step 2, modifying titanium dioxide film: will under air atmosphere, 400 ℃～1200 ℃ conditions, calcine 1.5～5h by the modifying titanium dioxide film in early stage that step 1 obtains, and cool to room temperature with the furnace and obtain modified titanium dioxide doped thin film.
The preparation method of present embodiment with the preparation of titanium deoxid film with the doping vario-property of titanium deoxid film is finished synchronously, technology is simple, and is reliable and stable, realize that doping vario-property is simply easy, the equipment of employing is simple, and is easy to operate, be easy to grasp, and safe preparation process.
The modified titanium dioxide doped thin film that present embodiment prepares combines by chemical bond with substrate, and to connect film and substrate that layer self-assembling method obtain strong with electrostatic force bonded bonding force with existing layer.
Embodiment two: present embodiment and embodiment one are different is that silica glass substrate in a step of step 1 can also replace with substrate of ITO conductive glass or monocrystalline silicon piece substrate.Other step and parameter are identical with embodiment one.
Embodiment three: present embodiment is different with embodiment one or two is that deoiling is handled and is specially in a step of step 1: be hybridly prepared into Piranha (Piranha) solution with the vitriol oil and 30% (weight) superoxol, it is 70 ℃ Piranha solution that substrate is placed temperature, soak 20min, wherein the volume ratio of the vitriol oil and superoxol is 7: 3.Other step and parameter are identical with embodiment one or two.
Embodiment four: present embodiment and embodiment one, two or three are different is that protonated pre-treatment is in a step of step 1: it is 70 ℃ ammoniacal liquor (NH that substrate is placed temperature
32O), 30% (weight) hydrogen peroxide (H
2O
2) in the mixing solutions of solution and deionized water, soak 20min, take out the back washed with de-ionized water, acquisition has the substrate of water-wetted surface, NH
32The volume ratio of O and deionized water is 1: 5,30% (weight) hydrogen peroxide (H
2O
2) volume ratio of solution and deionized water is 1: 5.Other step and parameter are identical with embodiment one, two or three.
Embodiment five: present embodiment and embodiment one to four are different be in the b step of step 1 the silica glass substrate to place mass concentration be 8%～12% 3-TSL 8330 (SiRN) solution.Other step and parameter are identical with embodiment one to four.
Embodiment six: present embodiment and embodiment one to five are different is to soak 30min in the b step of step 1, cleans with ethanol then, again at 75 ℃ of dry 1h down.Other step and parameter are identical with embodiment one to five.
Embodiment seven: present embodiment and embodiment one to six are different is to place TALH solution to soak 20min in the c step of step 1, places PEI to soak 20min.Other step and parameter are identical with embodiment one to six.
Embodiment eight: present embodiment and embodiment one to seven are different is x=3 in the d step of step 1.Other step and parameter are identical with embodiment one to seven.
Embodiment nine: present embodiment and embodiment one to seven are different is x=4 in the d step of step 1.Other step and parameter are identical with embodiment one to seven.
Embodiment ten: present embodiment and embodiment one to nine are different is that 1. the e of step 1 places the compound solution that contains doped element of 2mmol/L to soak 20min in the step, places PEI to soak 20min.Other step and parameter are identical with embodiment one to nine.
Embodiment 11: present embodiment and embodiment one to ten are different is that the compound solution that 1. e of step 1 contains doped element in the step is polyoxometallic acid salts solution or metal complexes, and wherein, the polyoxometallic acid salts solution is selected from Na
16P
4W
30Mn
4(H
2O)
2O
112Solution (Mn
4Wo
30Solution), K
6P
2Mo
18O
62Solution or H
3PMo
12O
32Solution, metal complex solution are 1, and 10-phenanthroline ruthenium solution, tetrachloro close silver-colored solution, hexahydroxy-closes copper solutions or Sodium dodecylbenzene sulfonate solution.Other step and parameter are identical with embodiment one to ten.
Decide according to the kind of required doped element in the actually operating when choosing the compound that contains doped element in the present embodiment, the kind that is fit to the compound solution that contains doped element of present embodiment is not limit the above compound solution of lifting.
The compound that contains doped element of present embodiment is the commercially available prod.
Embodiment 12: present embodiment and embodiment one to 11 are different is 2. n=3～7 in the step of e of step 1.Other step and parameter are identical with embodiment one to 11.
Embodiment 13: present embodiment and embodiment one to 11 are different is the 2. n=5 in the step of e of step 1.Other step and parameter are identical with embodiment one to 11.
Embodiment 14: present embodiment and embodiment one to 13 are different is m=3 in the g step of step 1.Other step and parameter are identical with embodiment one to 13.
Embodiment 15: what present embodiment and embodiment one to 14 were different is that the temperature rise rate with 3～6 ℃/min is warming up to 400 ℃～1200 ℃ in the step 2.Other step and parameter are identical with embodiment one to 14.
Embodiment 16: what present embodiment and embodiment one to 15 were different is to calcine 2h under 450 ℃～800 ℃ conditions in the step 2.Other step and parameter are identical with embodiment one to 15.
Embodiment 17: present embodiment and embodiment one are different be in the b step of step 1 the silica glass substrate to place mass concentration be that 10% 3 TSL 8330 (SiRN) solution soaks 30min, clean with ethanol then, drier 1h under 75 ℃; To place mass concentration be that 5% TALH solution soaks 20min in the silica glass substrate in the c step of step 1, places the polymine (PEI) of 2mmol/L to soak 20min; X=3 in the d step of step 1; In the e step of step 1 1., will be covered with [TALH/PEI] through the surface that above-mentioned steps obtains
3The silica glass substrate of layer places the Mn of 2mmol/L
4W
30Soak 20min in the solution, place the polymine (PEI) of 2mmol/L to soak 20min again, in the e step 2. in n=1 (be inoperation step e 2.); M=2 in the g step of step 1; Soak 20min in the h step of step 1, obtain modifying titanium dioxide film in early stage: { [TALH/PEI]
3/ [Mn
4W
30/ PEI]/[TALH/PEI]
3}
2/ TALH; Under air atmosphere, 500 ℃ of conditions, calcine 2h in the step 2.Other step and parameter are identical with embodiment one.
Present embodiment is carried out the ultraviolet-visible absorption spectroscopy test with the modified titanium dioxide doped thin film that obtains, and test result is shown in b curve among Fig. 1.As a comparison, present embodiment dispenses e step in the step 1, obtains [TALH/PEI]
12/ TALH obtains the not titanium deoxid film of doping vario-property by step 2 again, and the titanium deoxid film of the not doping vario-property that will obtain carries out ultraviolet-visible absorption spectroscopy test, and test result is shown in a curve among Fig. 1.Contrasted as can be known by a among Fig. 1 and b curve, effective doping has been carried out in the UV, visible light ABSORPTION EDGE red shift of modified titanium dioxide doped thin film.
Present embodiment is carried out Fourier's deflection examination of infrared spectrum with the modified titanium dioxide doped thin film that obtains, and test result as shown in Figure 2.As shown in Figure 2,860cm
-1And 920cm
-1Be respectively the stretching vibration of Ti-O-Ti and Ti-O, 950cm
-1Neighbouring is the Ti-O-Si stretching vibration peak, 1070cm
-1Neighbouring is the Si-O-Si stretching vibration peak, 700cm
-1Neighbouring is the W-O-W stretching vibration peak.The major ingredient that modified titanium dioxide doped thin film is described is hexangle type Tungsten oxide 99.999 (h-WO
3) and the TiO that is doped
2, and film combines the bonding force enhancing with substrate dependence Ti-O-Si.
Embodiment 18: present embodiment and embodiment 17 are different be step 1 the e step 2. in repetitive operation e 1. step 1 time, i.e. n=2.Other step and parameter are identical with embodiment 17.
Titanium dioxide is Detitanium-ore-type in the modified titanium dioxide doped thin film that present embodiment obtains, the Mn after the doping
4W
30In tungsten (W) with the tungstic oxide (WO of hexangle type
3) the form existence, make the long-pending increase of microcosmic surface of modified titanium dioxide doped thin film, as shown in Figure 3.
Present embodiment is carried out constituent content test (EDS) in the film with the modified titanium dioxide doped thin film that obtains, test result as shown in Figure 4, as seen from Figure 4, include Ti, W, Mn and four kinds of elements of O in the modified titanium dioxide doped thin film, the doping that present embodiment is described is successful.
Present embodiment is carried out the ultraviolet-visible absorption spectroscopy test with the modified titanium dioxide doped thin film that obtains, and test result is shown in c curve among Fig. 1.Analyze as can be known, the UV, visible light ABSORPTION EDGE red shift of the modified titanium dioxide doped thin film of present embodiment is more than the red shift position of embodiment 17, has also carried out effective doping.
Present embodiment is carried out x-ray photoelectron power spectrum (XPS) test with the modified titanium dioxide doped thin film that obtains, and Ti2p that test obtains and the XPS curve of O 1s are respectively shown in b curve among b curve and Fig. 6 among Fig. 5.As a comparison, present embodiment adopts embodiment 17 described methods to obtain the not titanium deoxid film of doping vario-property, and it is carried out x-ray photoelectron power spectrum (XPS) test, Ti2p that test obtains and the XPS curve of O 1s are respectively shown in a curve among a curve and Fig. 6 among Fig. 5.More as can be known, displacement has taken place in the bound energy of the 2p of Ti in the modified titanium dioxide doped thin film, illustrates that titanium dioxide is effectively mixed by a curve among Fig. 5 and b curve ratio.More as can be known, displacement has also taken place in the bound energy of the 1s of O in the modified titanium dioxide doped thin film, also illustrates that titanium dioxide is effectively mixed by a curve among Fig. 6 and b curve ratio.
Present embodiment is carried out the contact angle test with the modified titanium dioxide doped thin film that obtains, test result shows that the contact angle of modified titanium dioxide doped thin film is 66.99 °, as a comparison, present embodiment adopts embodiment 17 described methods to obtain the not titanium deoxid film of doping vario-property, and it is carried out contact angle test, test result shows that the contact angle of the titanium deoxid film of doping vario-property is not 83.86 °, and as seen, the wetting ability of the titanium deoxid film behind the doping vario-property strengthens.
Embodiment 19: present embodiment and embodiment 17 are different be step 1 the e step 2. in repetitive operation e 1. step 3 time, i.e. n=4.Other step and parameter are identical with embodiment 17.
Titanium dioxide is Detitanium-ore-type in the modified titanium dioxide doped thin film that present embodiment obtains, the SEM surface topography map of modified titanium dioxide doped thin film as shown in Figure 7, as seen from Figure 7, the modified titanium dioxide doped thin film porous, microcosmic surface is long-pending big.
Present embodiment is carried out the ultraviolet-visible absorption spectroscopy test with the modified titanium dioxide doped thin film that obtains, and test result is shown in d curve among Fig. 1.By all tracing analysiss among Fig. 1 as can be known, along with increasing of tungsten and manganese doping, the UV, visible light ABSORPTION EDGE red shift wavelength of modified titanium dioxide doped thin film is many more.Band gap calculation result shows, along with the increase of step e repetitive operation frequency n value, (curve a) is reduced to 2.8eV (curve d among Fig. 1) to the titanium deoxid film band gap gradually among Fig. 1 by 3.4eV.Illustrate and carried out effective doping vario-property.
Present embodiment is carried out x-ray photoelectron power spectrum (XPS) test with the modified titanium dioxide doped thin film that obtains, and Ti2p that test obtains and the XPS curve of O 1s are respectively shown in c curve among c curve and Fig. 6 among Fig. 5.More as can be known, displacement has taken place in the bound energy of the 2p of Ti in the modified titanium dioxide doped thin film, illustrates that titanium dioxide is effectively mixed by a curve among Fig. 5 and c curve ratio.More as can be known, displacement has also taken place in the bound energy of the 1s of O in the modified titanium dioxide doped thin film, also illustrates that titanium dioxide is effectively mixed by a curve among Fig. 6 and c curve ratio.
Present embodiment is carried out the contact angle test with the modified titanium dioxide doped thin film that obtains, and test result shows that the contact angle of modified titanium dioxide doped thin film is 58.60 °, and the wetting ability of the titanium deoxid film behind the doping vario-property strengthens.
Embodiment 20: what present embodiment and embodiment 17,18 or 19 were different is to calcine 2h in the step 2 under air atmosphere, 800 ℃ of conditions.Other step and parameter are identical with embodiment 17,18 or 19.
Titanium dioxide is rutile-type in the modified titanium dioxide doped thin film that present embodiment obtains.
Claims (10)
1. the preparation method of a modified titanium dioxide doped thin film is characterized in that this method realizes by following steps:
Step 1, modified titanium dioxide doped early stage film preparation:
A, deoiling is carried out in the silica glass substrate handle, clean up with deionized water then, more protonated pre-treatment is carried out in the silica glass substrate;
B, will to place mass concentration through the silica glass substrate after step a handles be 5%～15% 3 TSL 8330 solution, soaks 20～40min, cleans with ethanol then, again at 70 ℃～80 ℃ down dry 1～1.5h;
C, will to place mass concentration through the silica glass substrate that step b handled be that 5% two (2 hydroxy propanoic acid) two hydroxides, two ammoniums close titanium solution, soak 10～30min, take out the back washed with de-ionized water, place the polymine of 2mmol/L to soak 10～30min after the seasoning again, take out, use washed with de-ionized water, seasoning forms the TALH/PEI thin layer in the silica glass substrate;
D, repetitive operation c step x-1 time form [TALH/PEI] x thin layer, x=2～5 in the silica glass substrate;
E, the silica glass substrate that 1. will be covered with thin layer through the surface that above-mentioned steps obtains places the compound solution that contains doped element of 2mmol/L to soak 10～30min, take out the back washed with de-ionized water, place the polymine of 2mmol/L after the seasoning again, after soaking 10～30min, take out, use washed with de-ionized water, seasoning, in the silica glass substrate, form [TALH/PEI] x/[M/PEI] thin layer, wherein, M represents to contain the compound of doped element, and the compound solution that contains doped element is polyoxometallic acid salts solution or metal complex solution;
2. will in the silica glass substrate, form [TALH/PEI] x/[M/PEI through the 1. surface that obtains of step 1. step n-1 time of silica glass repetitive operation e that is covered with thin layer of e] the n thin layer, n=1～6;
C～d step is operated in f, the silica glass substrate that will be covered with thin layer through the surface that above-mentioned steps obtains, and forms [TALH/PEI] x/[M/PEI in the silica glass substrate] n/[TALH/PEI] the x thin layer;
G, will be covered with [TALH/PEI] x/[M/PEI through the surface that above-mentioned steps obtains] n/[TALH/PEI] the above-mentioned c of silica glass substrate repetitive operation～f step m-1 time of x thin layer, in the silica glass substrate, form [TALH/PEI] x/[M/PEI] n/[TALH/PEI] x}m, m=2～4;
H, will be covered with through the surface that above-mentioned steps obtains [TALH/PEI] x/[M/PEI] n/[TALH/PEI] to put into mass percent be that 5% two (2 hydroxy-propionic acids), two hydroxides, two ammoniums close titanium solution for the silica glass substrate of x}m, soak 10～30min, take out the back washed with de-ionized water, seasoning obtains modifying titanium dioxide film in early stage: and [TALH/PEI] x/[M/PEI] n/[TALH/PEI] x}m/TALH, x=2～5, n=1～6, m=2～4;
The preparation of step 2, modified titanium dioxide doped thin film: will under air atmosphere, 400 ℃～1200 ℃ conditions, calcine 1.5～5h by the film in modified titanium dioxide doped early stage that step 1 obtains, and cool to room temperature with the furnace and obtain modified titanium dioxide doped thin film.
2. the preparation method of a kind of modified titanium dioxide doped thin film according to claim 1 is characterized in that the silica glass substrate in a step of step 1 can also replace with substrate of ITO conductive glass or monocrystalline silicon piece substrate.
3. the preparation method of a kind of modified titanium dioxide doped thin film according to claim 1 and 2, it is characterized in that deoiling is handled in a step of step 1 is specially: be hybridly prepared into Piranha solution with the vitriol oil and 30% (weight) superoxol, it is that 70 ℃ Piranha solution soaks 20min that substrate is placed temperature, and wherein the volume ratio of the vitriol oil and superoxol is 7: 3.
4. the preparation method of a kind of modified titanium dioxide doped thin film according to claim 3, it is characterized in that protonated pre-treatment is in a step of step 1: it is 70 ℃ ammoniacal liquor, 30% (weight) superoxol and the mixing solutions of deionized water that substrate is placed temperature, soak 20min, take out the back washed with de-ionized water, acquisition has the substrate of water-wetted surface, the volume ratio of ammoniacal liquor and deionized water is 1: 5, and the volume ratio of 30% (weight) superoxol and deionized water is 1: 5.
5. according to the preparation method of claim 1,2 or 4 described a kind of modified titanium dioxide doped thin films, it is characterized in that the silica glass substrate places 8%～12% (weight) 3=TSL 8330 solution in the b step of step 1.
6. the preparation method of a kind of modified titanium dioxide doped thin film according to claim 5, the e that it is characterized in that step 1 1. in the step polyoxometallic acid salts solution be selected from Na
16P
4W
30Mn
4(H
2O)
2O
112Solution, K
6P
2Mo
18O
62Solution or H
3PMo
12O
32Solution, metal complex solution are that 1,10 phenanthroline ruthenium solution, tetrachloro close silver-colored solution, hexahydroxy-closes copper solutions or Sodium dodecylbenzene sulfonate solution.
7. according to the preparation method of claim 1,2,4 or 6 described a kind of modified titanium dioxide doped thin films, the e that it is characterized in that step 1 is n=3～7 in the step 2..
8. the preparation method of a kind of modified titanium dioxide doped thin film according to claim 7 is characterized in that m=3 in the g step of step 1.
9. according to the preparation method of claim 1,2,4,6 or 8 described a kind of modified titanium dioxide doped thin films, it is characterized in that calcining 2h under 450 ℃～800 ℃ conditions in the step 2.
10. the preparation method of a kind of modified titanium dioxide doped thin film according to claim 9 is characterized in that calcining 2h under 500 ℃ of conditions in the step 2.
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