CN100564591C - A kind of self-cleaning oxidate film and preparation method and application thereof - Google Patents
A kind of self-cleaning oxidate film and preparation method and application thereof Download PDFInfo
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- CN100564591C CN100564591C CNB2007100216275A CN200710021627A CN100564591C CN 100564591 C CN100564591 C CN 100564591C CN B2007100216275 A CNB2007100216275 A CN B2007100216275A CN 200710021627 A CN200710021627 A CN 200710021627A CN 100564591 C CN100564591 C CN 100564591C
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- 238000004140 cleaning Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 87
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 24
- 238000000137 annealing Methods 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000919 ceramic Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 4
- 239000004566 building material Substances 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000007858 starting material Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910002367 SrTiO Inorganic materials 0.000 abstract description 65
- 238000000034 method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract 2
- 239000010408 film Substances 0.000 description 120
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- 229910010413 TiO 2 Inorganic materials 0.000 description 19
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 14
- 229960000907 methylthioninium chloride Drugs 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000004887 air purification Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000003978 X-ray ultraviolet photoelectron spectroscopy Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A kind of self-cleaning oxidate film is by the adulterated SrTiO of different valence state metal ion X
3, use formula X:SrTiO
3Expression, wherein X is Cr
3+, Zn
2+, Al
3+, Ga
3+, Ge
3+, In
3+, W
6+, Ta
5+, Nb
5+Or V
5+In a kind of; Its doping content is 0.01-10mol%; Its method for making is by the organic salt of the doping content weighing raw materials X of X or nitrate, (CH
3COO)
2Sr.0.5H
2O and Ti (OC
2H
5)
4, above-mentioned raw materials is added to respectively in the methyl alcohol, add acetic acid then respectively, heated and stirred is ended to transparent, will contain Sr then
2+, Ti
4+Mix with three kinds of methanol solutions of X, be stirred to transparent, regulate concentration with methyl alcohol, regulate pH with acetic acid or ammoniacal liquor, with whirl coating equipment above-mentioned mixing solutions is deposited on the substrate, places tube furnace annealing to obtain the first layer film, through repeatedly depositing until thick 10 nanometers-1 micron of reaching of film, place tube furnace to anneal film again, make the complete crystallization of film.Coating and indoor local air that this film can be applicable to building material surface, minute surface, metal and ceramic ware surface purify.
Description
One. technical field
The invention belongs to ceramic and function ceramics thin-film material field, be specifically related to be applied to a kind of sull and the preparation method and application thereof of environmental purification with self-cleaning function.
Two. background technology
TiO in recent years
2The photic wetting ability transformation on monocrystalline and polycrystal film surface and the character of decomposition environmentally hazardous substance are by people's broad research [document 1:R.Wang, K.Hashimoto, A.Fujishima, M.Chikuni, E.Kojima, A.Kitamura, M.Shimohigoshi, T.Watanabe, Nature 388,431 (1997); Document 2:R.Wang, N.Sakai, A.Fujishima, T.Watanabe, K.Hashimoto, J.Phys.Chem.B 103,2188 (1999)].TiO
2These character of film have obtained to use widely, as the automatic cleaning coating of building surface, and the antifogging coating of vehicle backing rear-view mirror, the sterilization coating of material of construction and indoor local air purification etc.TiO
2The wetting ability of monocrystalline and film surface is that water drops in the (see figure 1) that its lip-deep contact angle characterizes, and is when water contact angle is in its surface spent less than 5, super hydrophilic when material surface is called as.Under uviolizing, TiO
2(detesting the state of water relatively) was reduced near 0 degree (super hydrophily) about the contact angle of water was spent from 70 on film or the single-crystal surface.At this moment water and TiO
2Film or single-crystal surface soak into fully.The viewpoint of main flow is thought [A.Fujishima, T.Watanabe, K.Hashimoto, J.Phys.Chem.B 103,2188 (1999) for document 2:R.Wang, N.Sakai], TiO
2The photic Superhydrophilic of monocrystalline and film surface changes can be owing to TiO under uviolizing
2The surface forms surface imperfection.These surface imperfection have caused water molecules at TiO
2The absorption of dissociating on surface, and cause OH
-Groups density increases.These OH
-Group is at TiO
2The evidence that the surface exists is used x-ray photoelectron power spectrum (XPS) and fourier transform infrared spectrometry to observe [document 2:R.Wang, N.Sakai, A.Fujishima by people, T.Watanabe, K.Hashimoto, J.Phys.Chem.B 103,2188 (1999), document 3:R.D.Sun, A.Nakajima, T.Watanabe, K.Hashimoto, J.Phys.Chem.B 105,1984 (2001)].Another kind of viewpoint is thought clean TiO
2The surface was Superhydrophilic originally, owing to be exposed in the air TiO
2The surface is polluted by airborne organic molecule, and under uviolizing, these organic molecules are again because TiO
2The photocatalysis property that has and being decomposed.TiO like this
2It is super hydrophilic that the surface becomes again.TiO
2The automatically cleaning character of film comprises the implication of following two aspects: on the one hand, under irradiation of sunlight, the organic molecule that is adsorbed on film surface is because TiO
2The photocatalysis property of film is broken down into CO
2And H
2O.On the other hand, because the infiltration character fully of water and film surface under the uviolizing, rainwater is to there being cleanup action attached to the dust of film surface etc.Utilize TiO
2Film carries out indoor local air purification and depends on TiO
2The following photocatalysis property of film, promptly under uviolizing, TiO
2Film can decompose airborne organism, thereby reaches the purpose that purifies air.Because TiO
2The optical band gap of film can only absorb ultraviolet ray more than the 3.O electron-volt, and the content of ultraviolet ray in the sunlight power spectrum is between 4-5%, and visible light content is about 45%.TiO in addition
2Film is an isolator, and its specific conductivity is very low.These feature limits TiO
2Film application in some aspects.In addition because TiO
2The mechanism that the photic Superhydrophilic in surface changes does not also have final conclusion, and this has also hindered the invention of other novel self-cleaning oxidate film.
Three. summary of the invention
1. goal of the invention
The object of the present invention is to provide the preparation method and the application thereof of a kind of self-cleaning oxidate film and film.
2. technical scheme
A kind of self-cleaning oxidate film, main points are included in sull SrTiO
3Process of growth in other metal ion that mixes, cause SrTiO
3The middle defective that produces.Utilize SrTiO
3In defective make film surface possess the ability that photic Superhydrophilic changes.In original oxide compound, do not comprise adulterated metal ion, and adulterated ionic valence condition is different with the ionic valence condition in original oxide compound.This film is by the adulterated SrTiO of different valence state metal ion X
3, use formula X:SrTiO
3Expression, wherein X is Cr
3+, Zn
2+, Al
3+, Ga
3+, Ge
3+, In
3+, W
6+, Ta
5+, Nb
5+Or V
5+In a kind of; Its doping content is 0.01-10mol%; The thickness of this sull is 10 nanometers-1 micron.
A kind of preparation method of self-cleaning oxidate film, its preparation process is as follows:
(1) comes organic salt or the nitrate of weighing X by the doping content n mol% of metal ion X, (CH
3COO)
2Sr.0.5H
2O and Ti (OC
2H
5)
4, the molar ratio of its metal ion is: Sr: Ti: X=1: 1: 0.01n, and wherein X is Zn, Al or Nb, n=1;
(2) with the organic salt of starting material X or nitrate and (CH
3COO)
2Sr.0.5H
2O is added in the methyl alcohol respectively, and then to add volume ratio respectively in above-mentioned methanol solution be the acetic acid of 1%-8%, more above-mentioned solution is heated to 60-100 ℃, heats while stirring, till the complete clear of solution; With starting material Ti (OC
2H
5)
4Be added in the methyl alcohol, adding volume ratio again in mixing solutions is the acetic acid of 1%-8%, stirs while adding, till the complete clear of solution;
(3) with above-mentioned metal ion Sr
2+, Ti
4+Mix with three kinds of methanol solutions of X, and stir, till the complete clear of mixing solutions;
(4) utilize methyl alcohol that the volumetric molar concentration of above-mentioned mixing solutions is adjusted to the 0.05-0.7 mol;
(5) utilize acetic acid or ammoniacal liquor that the pH value of above-mentioned mixing solutions is adjusted to 0-7;
(6) utilize whirl coating equipment that above-mentioned mixing solutions is deposited on the substrate, then film is placed the tube furnace that is connected with the oxygen that flows to anneal, annealing temperature is the 80-150 degree, and annealing time is 5-30 minute, obtains the first layer film;
(7) repeating step (6) is through deposition repeatedly, until reaching film thickness 10 nanometers-1 micron;
(8) above-mentioned repeatedly post-depositional film is placed the tube furnace that is connected with the oxygen that flows anneal, temperature rise rate is 1-20 ℃/minute, and annealing temperature is 450-750 ℃, and annealing time is 0.5-4 hour, makes the complete crystallization of film.Fig. 2 shows Nb:SrTiO
3The X-ray diffractogram of film.Each doping ratio Nb:SrTiO among the figure
3The X-ray diffraction peak of film can mark by its structure, and all crystallizations well of all films are described.Fig. 3 shows the Nb:SrTiO that arrives with scanning electron microscopic observation
3The surface topography of film, therefrom film surface is very even as can be seen;
The doping content n mol% of metal ion X described in the above-mentioned steps (1) represents that the mole number of metal ion X is SrTiO
3The 0.01n of mole number doubly.
The rotating speed of whirl coating equipment is 2500-5500 rev/min in the above-mentioned steps (6), and described substrate material is simple glass, silica glass, oxide monocrystal sheet such as SrTiO
3, MgO, LaAlO
3And NdGaO
3, a kind of in silicon single crystal flake, tinsel or the ceramic plate.
Above-mentioned self-cleaning film is at buildings or list of building materials finishing coat, mirror antifogging coating, metal or pottery top coat and in the application of aspects such as indoor local air purification
The performance test methods of self-cleaning oxidate film:
To self-cleaning performance sull X:SrTiO
3Performance test comprise that photic Superhydrophilic changes performance test and decomposing organic matter performance test, specific as follows:
Photic Superhydrophilic changes performance test:
(1) utilizes film X:SrTiO
3Water droplet characterizes with the contact angle of the film surface variation relation with irradiation time under uviolizing on the surface;
(2) water is deionized water;
(3) measure water at sull X:SrTiO
3On the surface equipment of contact angle be a kind of contact angle measurement (DropMaster 100 system, Kyowa Interface Science Co., LTD., Japan);
(4) ultraviolet light source is common blackout pipe (black light bulb), and power is 0.36W/cm
2
(5) test under solar simulator (AM1.5G) irradiation water and film X:SrTiO
3Surface contact angle is with the variation relation of irradiation time.
The decomposing organic matter performance test:
(1) test self-cleaning film X:SrTiO
3The ability of under uviolizing, decomposing MB (Methylene Blue);
(2) with the MB solution soaking film X:SrTiO of 0.1 mol
3, the film that soaked is dried in baking oven, and removes MB on the substrate back (the not one side of deposit film);
(3) utilize the transmissivity of ultraviolet-visible-near infrared spectrometer MEASUREMENTS OF THIN, judge that according to the variation of film film transmissivity under uviolizing it decomposes the ability of MB;
(4) ultraviolet light source is common blackout pipe (black light bulb), and power is 0.36W/cm
2
3. beneficial effect
(1) at SrTiO
3Behind the middle doping different valence state metal ion X, SrTiO
3The ability that the photic wetting ability of film changes significantly strengthens.Fig. 4 represents Nb doping SrTiO
3The contact angle of water is penetrated the variation relation of the time of photograph on the film surface with ultraviolet ray.At pure SrTiO
3On the film surface, the contact angle of water is 26 degree during without ultraviolet irradiation, and after 440 minutes, contact angle is 10 degree through uviolizing; At the adulterated SrTiO of 1.0mol%Nb
3On the film surface, the contact angle of water is 25.8 degree during without ultraviolet irradiation, and after 95 minutes, contact angle is 0.8 degree (super hydrophilic) through uviolizing; At the adulterated SrTiO of 5.0mol%Nb
3On the film surface, the contact angle of water is 24.8 degree during without ultraviolet irradiation, and after 106 minutes, contact angle is 0.9 degree (super hydrophilic) through uviolizing.This effect is expected to obtain following application: a.X:SrTiO
3Film is as the top coat of buildings and material of construction, under the uviolizing in sunlight, and rainwater and X:SrTiO
3Film surface soaks into fully, and rainwater has cleanup action to building surface; B.X:SrTiO
3Film is as the antifogging coating of minute surface, under the uviolizing in sunlight, and water and X:SrTiO
3Film surface soaks into fully, can avoid producing the globule on minute surface, thereby play antifog effect;
(2) under solar simulator (AM1.5G) irradiation, the adulterated SrTiO of different valence state metal ion X
3Film surface also has the ability that Superhydrophilic changes.Fig. 5 shows the adulterated SrTiO of 1.0mol%Nb
3The contact angle of water is with the variation relation of solar simulator (AM1.5G) irradiation time on the film surface.Without irradiation the time, water contact angle from the teeth outwards is 27.2 degree, and after shining 356 minutes, water contact angle from the teeth outwards is 2.5 degree (super hydrophilic).This means the uviolizing X:SrTiO in the sunlight
3Film is enough to make X:SrTiO
3Photic Superhydrophilic takes place film surface changes.
(3) the adulterated SrTiO of X that will be after uviolizing
3After film was placed in the dark environment, the contact angle of water can increase gradually on the film surface.Fig. 6 shows the adulterated SrTiO of 1.0mol%Nb after uviolizing
3The contact angle of water is with the film variation relation of storage period in the dark on the film surface.When not being placed in the dark, the contact angle of water is 0.8 degree on the film surface, is placed in the dark after 17.5 hours, and the contact angle of film surface is 11.3 degree;
(4) the adulterated SrTiO of X
3Photic Superhydrophilic on the film surface change with water molecules chemistry from the teeth outwards dissociate adsorb relevant.To the adulterated SrTiO of the Nb after uviolizing
3Film surface carries out x-ray photoelectron power spectrum (XPS) to be measured, and has found and the water molecules relevant OH of absorption that dissociates
-The signal of group.Fig. 7 shows the adulterated SrTiO of 1.0mol%Nb
3X ray ultraviolet photoelectron spectroscopy (XPS) figure of film surface.After uviolizing, sharply strengthen with water molecules relevant " shoulder " type signal of absorption that dissociates near 534 electron-volts in the drawings, illustrate that after uviolizing, water molecules is at SrTiO
3The film surface absorption of dissociating is placed on sample the high vacuum (1 * 10 of XPS instrument
-8Mbar) in the sample chamber (dark surrounds), certain interval of time is the xps energy spectrum of measure sample again, can find the increase of the time in the dark surrounds that is placed on along with sample, in the x-ray photoelectron power spectrum (XPS) of sample surfaces with the water molecules relevant OH of absorption that dissociates
-The strength of signal of group dies down gradually, and the result of this and Fig. 6 is on all four.The adulterated SrTiO of Nb
3The contact angle of film surface water increases, and means the wetting ability variation on surface, dissociates with water molecules on the surface and adsorbs relevant OH
-The density of group reduces.This effect is expected to obtain following application: by at SrTiO
3The metal ion X of middle doping different valence state can be at SrTiO
3Produce defective in the film, cause under uviolizing water molecules at SrTiO
3The film surface absorption of dissociating, thus preparation has the film X:SrTiO of self-cleaning performance
3
(5) the adulterated SrTiO of X under uviolizing
3Film has the ability of decomposing organic matter.Fig. 8 is presented under the uviolizing, the adulterated SrTiO of 5.0mol%Nb that has MB (methylene Blue) to cover
3The optical transmittance of film (substrate is quartzy) and the variation relation of ultraviolet irradiation time.Vibration among the figure is owing to air, [document 5:J.Yin, Z.C.Wu, Z.L.Wang, Y.Y.Zhu, Z.G.Liu, J.Phys.D:Appl.Phys.31,3185 (1998)] that the light refractive index difference between MB and film and the quartz substrate causes.The height of " paddy " of near the transmittance curve among the figure 610 nanometers constantly rises with the increase of ultraviolet irradiation time, means the adulterated SrTiO of 5.0mol%Nb
3The amount of the MB that covers on the film surface reduces gradually.After 4 hours, most of MB of film surface is decomposed through uviolizing.This effect is expected to obtain following application: a.X:SrTiO
3Film under the uviolizing in sunlight, is adsorbed on X:SrTiO as the top coat of buildings and material of construction
3The airborne organic molecule that comes from of film surface can be because X:SrTiO
3The photocatalysis property of film is broken down into carbonic acid gas and water, thereby plays automatic cleaning action.
Four, description of drawings
Fig. 1. water and TiO
2During the film surface contact, the contact angle definition synoptic diagram of water and film surface, tangent line are that the profile of these lines and water droplet is tangent from the lines that the place is done that contact of water droplet with film surface, and contact angle is film surface and tangent line angulation.
Fig. 2 .Nb:SrTiO
3The X-ray diffractogram of film.
Fig. 3. the Nb:SrTiO that arrives with scanning electron microscopic observation
3The surface topography of film.
Fig. 4 .Nb doping SrTiO
3The contact angle of water is with the variation relation of ultraviolet irradiation time on the film surface.
The adulterated SrTiO of Fig. 5 .1.0mol%Nb
3The contact angle of water is with the variation relation of solar simulator (AM1.5G) irradiation time on the film surface.
Fig. 6. the adulterated SrTiO of the 1.0mol%Nb after uviolizing
3The contact angle of water is with the film variation relation of storage period in the dark on the film surface.
The adulterated SrTiO of Fig. 7 .1.0mol%Nb
3X ray ultraviolet photoelectron spectroscopy (XPS) figure of film surface.
Fig. 8. under uviolizing, the adulterated SrTiO of 5.0mol%Nb that has MB (methylene Blue) to cover
3The optical transmittance of film (substrate is quartzy) and the variation relation of ultraviolet irradiation time.
Five, embodiment
1. 1 kinds of self-cleaning oxidate films of embodiment is characterized in that this film is by metal ion Nb
5+Adulterated SrTiO
3, use formula Nb:SrTiO
3Expression, its doping content is 1.0mol%; The thickness of this sull is 0.4 micron.
2. 1 kinds of self-cleaning oxidate films of embodiment is characterized in that this film is by metal ion Al
3+Adulterated SrTiO
3, use formula Al:SrTiO
3Expression, its doping content is 1.0%; The thickness of this sull is 0.5 micron.
3. 1 kinds of self-cleaning oxidate films of embodiment is characterized in that this film is by configuration metal ions Zn
2+Adulterated SrTiO
3, use formula Zn:SrTiO
3Expression, its doping content is 1.0%; The thickness of this sull is 0.6 micron.
The preparation method of 4. 1 kinds of self-cleaning oxidate films of embodiment, its preparation process is as follows:
(1) the doping content 1.0mol% by Nb comes weighing Nb (OC
2H
5), (CH
3COO)
2Sr.0.5H
2O and Ti (OC
2H
5)
4, the molar ratio of its metal ion is: Sr: Ti: Nb=1: 1: 0.01;
(2) with starting material (CH
3COO)
2Sr.0.5H
2O is added in the methyl alcohol, and then to add volume ratio in above-mentioned methanol solution be 5% acetic acid, more above-mentioned solution is heated to 80 ℃, heats while stirring, till the complete clear of solution; With starting material Ti (OC
2H
5)
4Be added in the methyl alcohol, in mixing solutions, add volume ratio again and be 2% acetic acid, stir while adding, till the complete clear of solution; With material N b (OC
2H
5) be added in the methyl alcohol, stir while adding, till the complete clear of solution;
(3) with above-mentioned metal ion Sr
2+, Ti
4+And Nb
5+Three kinds of methanol solutions mix, and stir, till the complete clear of mixing solutions;
(4) utilize methyl alcohol that the volumetric molar concentration of above-mentioned mixing solutions is adjusted to 0.2 mol;
(5) utilize acetic acid that the pH value of above-mentioned mixing solutions is adjusted to 5;
(6) utilize whirl coating equipment that above-mentioned mixing solutions is deposited on the quartz substrate, whirl coating equipment rotating speed is 4500 rev/mins, then film is placed the tube furnace that is connected with the oxygen that flows to anneal, and annealing temperature is 130 ℃, annealing time is 10 minutes, obtains the first layer film;
(7) repeating step (6) is through repeatedly depositing, until reaching 0.4 micron of film thickness;
(8) above-mentioned repeatedly post-depositional film is placed the tube furnace that is connected with the oxygen that flows anneal, temperature rise rate is 1 ℃/minute, and annealing temperature is 650 ℃, and annealing time is 1 hour, makes the complete crystallization of film.
The preparation method of 5. 1 kinds of self-cleaning oxidate films of embodiment, its preparation process is as follows:
(1) the doping content 1.0mol% by Al comes weighing Al (NO
3)
3, (CH
3COO)
2Sr.0.5H
2O and Ti (OC
2H
5)
4, the molar ratio of its metal ion is: Sr: Ti: Al=1: 1: 0.01;
(2) with starting material Al (NO
3)
3(CH
3COO)
2Sr.0.5H
2O is added in the methyl alcohol respectively, and then to add volume ratio respectively in above-mentioned methanol solution be 5% acetic acid, more above-mentioned solution is heated to 80 ℃, heats while stirring, till the complete clear of solution; With starting material Ti (OC
2H
5)
4Be added in the methyl alcohol, in mixing solutions, add volume ratio again and be 2% acetic acid, stir while adding, till the complete clear of solution;
(3) with above-mentioned metal ion Sr
2+, Ti
4+And Al
3+Three kinds of methanol solutions mix, and stir, till the complete clear of mixing solutions;
(4) utilize methyl alcohol that the volumetric molar concentration of above-mentioned mixing solutions is adjusted to 0.3 mol;
(5) utilize acetic acid that the pH value of above-mentioned mixing solutions is adjusted to 5;
(6) utilize whirl coating equipment that above-mentioned mixing solutions is deposited on the quartz substrate, whirl coating equipment rotating speed is 4500 rev/mins, then film is placed the tube furnace that is connected with the oxygen that flows to anneal, and annealing temperature is 130 ℃, annealing time is 10 minutes, obtains the first layer film;
(7) repeating step (6) is through repeatedly depositing, until reaching 0.5 micron of thickness;
(8) above-mentioned repeatedly post-depositional film is placed the tube furnace that is connected with the oxygen that flows anneal, temperature rise rate be 1 degree/minute, annealing temperature is 650 ℃, annealing time is 1 hour, makes the complete crystallization of film.
The preparation method of 6. 1 kinds of self-cleaning oxidate films of embodiment, its preparation process is as follows:
(1) the doping content 1.0mol% by Zn comes weighing (CH
3COO)
2Zn.2H
2O, (CH
3COO)
2Sr.0.5H
2O and Ti (OC
2H
5)
4, the molar ratio of its metal ion is: Sr: Ti: Zn=1: 1: 0.01;
(2) with starting material (CH
3COO)
2Zn.2H
2O and (CH
3COO)
2Sr.0.5H
2O is added in the methyl alcohol respectively, and then to add volume ratio respectively in above-mentioned methanol solution be 5% acetic acid, more above-mentioned solution is heated to 80 ℃, heats while stirring, till the complete clear of solution; With starting material Ti (OC
2H
5)
4Be added in the methyl alcohol, in mixing solutions, add volume ratio again and be 2% acetic acid, stir while adding, till the complete clear of solution;
(3) with above-mentioned metal ion Sr
2+, Ti
4+And Zn
2+Three kinds of methanol solutions mix, and stir, till the complete clear of mixing solutions;
(4) utilize methyl alcohol that the volumetric molar concentration of above-mentioned mixing solutions is adjusted to 0.4 mol;
(5) utilize ammoniacal liquor that the pH value of above-mentioned mixing solutions is adjusted to 6;
(6) utilize whirl coating equipment that above-mentioned mixing solutions is deposited on the silicon single crystal flake substrate, whirl coating equipment rotating speed is 4500 rev/mins, then film is placed the tube furnace that is connected with the oxygen that flows to anneal, and annealing temperature is 130 ℃, annealing time is 10 minutes, obtains the first layer film;
(7) repeating step (6) is through repeatedly depositing, until reaching 0.6 micron of thickness;
(8) above-mentioned repeatedly post-depositional film is placed the tube furnace that is connected with the oxygen that flows anneal, temperature rise rate is 1 ℃/minute, and annealing temperature is 650 ℃, and annealing time is 1 hour, makes the complete crystallization of film.
The application of 7. 1 kinds of self-cleaning oxidate films of embodiment, specific as follows:
(1) without the simulated solar rayed time, water is at the adulterated SrTiO of 1.0mol%Nb
3Contact angle on the film surface is 27.2 ℃, and after 356 minutes, water is at the adulterated SrTiO of 1.0mol%Nb through the simulated solar rayed
3Contact angle on the film surface is 2.5 ℃ (super hydrophilic).
(2) the adulterated SrTiO of 5.0mol%Nb
3The amount of the MB that covers on the film surface reduces gradually and gradually with ultraviolet irradiation time, and after 4 hours, most of MB of film surface is decomposed and finishes through uviolizing.
Claims (6)
1. the preparation method of a self-cleaning oxidate film, its preparation process is as follows:
(1) comes organic salt or the nitrate of weighing X by the doping content n mol% of metal ion X, (CH
3COO)
2Sr.0.5H
2O and Ti (OC
2H
5)
4, the molar ratio of its metal ion is: Sr: Ti: X=1: 1: 0.01n, and wherein X is Zn, Al or Nb, n=1;
(2) with the organic salt of starting material X or nitrate and (CH
3COO)
2Sr.0.5H
2O is added in the methyl alcohol respectively, and then to add volume ratio respectively in above-mentioned methanol solution be the acetic acid of 1%-8%, more above-mentioned solution is heated to 60-100 ℃, heats while stirring, till the complete clear of solution; With starting material Ti (OC
2H
5)
4Be added in the methyl alcohol, adding volume ratio again in mixing solutions is the acetic acid of 1%-8%, stirs while adding, till the complete clear of solution;
(3) with above-mentioned metal ion Sr
2+, Ti
4+Mix with three kinds of methanol solutions of X, and stir, till the complete clear of mixing solutions;
(4) utilize methyl alcohol that the volumetric molar concentration of above-mentioned mixing solutions is adjusted to the 0.05-0.7 mol;
(5) utilize acetic acid or ammoniacal liquor that the pH value of above-mentioned mixing solutions is adjusted to 0-7;
(6) utilize whirl coating equipment that above-mentioned mixing solutions is deposited on the substrate, then film is placed the tube furnace that is connected with the oxygen that flows to anneal, annealing temperature is 80-150 ℃, and annealing time is 5-30 minute, obtains the first layer film;
(7) repeating step (6) is through deposition repeatedly, until reaching film thickness 10 nanometers-1 micron;
(8) above-mentioned repeatedly post-depositional film is placed the tube furnace that is connected with the oxygen that flows anneal, temperature rise rate is 1-20 ℃/minute, and annealing temperature is 450-750 ℃, and annealing time is 0.5-4 hour, makes the complete crystallization of film.
2. the preparation method of self-cleaning oxidate film according to claim 2, it is characterized in that the rotating speed of whirl coating equipment is 2500-5500 rev/min in the step (6), described substrate material is a kind of in simple glass, silica glass, oxide monocrystal sheet, silicon single crystal flake, tinsel or the ceramic plate.
3. the application of self-cleaning oxidate film as claimed in claim 1 in buildings or list of building materials finishing coat.
4. the application of self-cleaning oxidate film as claimed in claim 1 in the mirror antifogging coating.
5. the application of self-cleaning oxidate film as claimed in claim 1 in the top coat of metal and pottery.
6. the application of self-cleaning oxidate film as claimed in claim 1 in indoor local air purifies.
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| CN101333107B (en) * | 2008-08-04 | 2011-05-04 | 西南交通大学 | Process for preparing niobium-doped strontium titanate film |
| RU2444396C1 (en) * | 2010-08-10 | 2012-03-10 | Федеральное государственное учреждение "Федеральный центр токсикологической и радиационной безопасности животных" (ФГУ "ФЦТРБ-ВНИВИ") | Method of cleaning water from ammonium vapours |
| CN103833352B (en) * | 2014-01-13 | 2015-10-07 | 河南科技大学 | A kind of preparation method of auto-doping strontium titanate ferroelectric membranc |
| CN111537539A (en) * | 2020-05-12 | 2020-08-14 | 西安交通大学 | Method for measuring photoelectron spectrum of polymer sublayer by plasma etching |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1276438A (en) * | 1999-06-08 | 2000-12-13 | 中国科学院物理研究所 | Antimony-doped strontium titanate film and preparation method thereof |
| CN1094916C (en) * | 2000-01-03 | 2002-11-27 | 中国科学院物理研究所 | manganese-doped strontium titanate film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1276438A (en) * | 1999-06-08 | 2000-12-13 | 中国科学院物理研究所 | Antimony-doped strontium titanate film and preparation method thereof |
| CN1094916C (en) * | 2000-01-03 | 2002-11-27 | 中国科学院物理研究所 | manganese-doped strontium titanate film and preparation method thereof |
Non-Patent Citations (2)
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| 掺铝钛酸锶薄膜及其与CrOx复合膜的制备及氧敏性能的研究. 刘丽月等.硅酸盐学报，第28卷第5期. 2000 |
| 掺铝钛酸锶薄膜及其与CrOx复合膜的制备及氧敏性能的研究. 刘丽月等.硅酸盐学报，第28卷第5期. 2000 * |
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