CN101164689A - Nanocrystalline porous TiO2 film and preparation method thereof - Google Patents
Nanocrystalline porous TiO2 film and preparation method thereof Download PDFInfo
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- CN101164689A CN101164689A CNA2007100449932A CN200710044993A CN101164689A CN 101164689 A CN101164689 A CN 101164689A CN A2007100449932 A CNA2007100449932 A CN A2007100449932A CN 200710044993 A CN200710044993 A CN 200710044993A CN 101164689 A CN101164689 A CN 101164689A
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Abstract
The present invention relates to a nano crystal porous titanium dioxide film and its preparation method. Said film is a film with TiOn structure, in which n is 1.5-2.5, it is a polycrystalline crystal structure, its grain size is 10-500nm and its pore size is 10-500nm. Its preparation method includes the following steps: (1), cleaning matrix material by using ultrasonic wave, drying and placing the cleaned and dried matrix material in the lower portion of plasma reactor, introducing carrier gas inert gas; (2), introducing mixed gas of oxygen gas and titanium-containing gas carried by carrier gas, applying high-votage etectricity, regulating biasing electrode and pulse bias voltage, forming active granules containing titanium, under the action of biased polarization and acceleration forming wire-mesh structure, at the same time making the active granules containing titanium be carried onto matrix material surface and deposited; and (3), after the reaction deposition taking out matrix material, on the surface of matrix material can obtain the nano crystal porous TiO2 film.
Description
Technical field
The invention belongs to TiO
2Film and preparation method thereof field particularly relates to a kind of nanocrystalline porous TiO
2Film and preparation method thereof.
Background technology
Because nanoporous TiO
2Higher specific surface area and nanostructured have unique photocatalysis and photoelectricity conversion characteristic, more and more are subjected to the extensive concern of scientific and technological circle.But by nano-TiO
2Powder is processed and the vesicular texture of formation, has shortcomings such as easy inactivation, easily aggegation, difficult recovery, makes its application be subjected to certain restriction.
In recent years, TiO
2Film obtains extensive studies, obtains research and uses in each side such as dye sensitization novel solar film cell, photocatalysis film, colorimetric sensor films, has wide practical use.
Produce nano-TiO
2The method of film has multiple, as the thermal oxide of electron beam evaporation, radio-frequency sputtering, titanium perforated membrane, rapid thermal oxidation, chemical vapor deposition (CVD), sol-gel process (sol-gel) etc., three kinds of wherein the most frequently used is sputtering method, chemical vapour deposition technique and sol-gel processes.
The sputter coating method is to utilize direct current or high-frequency electric field to make inert gas generation ionization, produces glow discharge plasma, and the cation that ionization produces bombards target at a high speed, and atom or molecule on the target are sputtered out, and deposits to then and forms film on the substrate.Direct current reaction magnetic control method makes metal titanium targets at an amount of working gas O usually
2Middle sputter, titanium atom that sputters and O
2Reaction deposits TiO
2Film.Sputtering method prepares TiO
2Forming thin film is firm, but has the slow shortcoming of growth rate, and for this kind method, high-vacuum apparatus is absolutely necessary, and the course of reaction energy consumption is very big.
Chemical vapour deposition technique is to supply with substrate with containing one or more compounds and the elementary gas that constitute thin film composition, forms the method for nonvolatile solid-state rete or material at substrate surface generation chemical reaction.Its basic demand is the chemical reaction that substrate surface must have out-phase.The characteristics of this method are the film deposition rate height, and substrate shape and size are not limit, and the composition of film and crystal formation are easy to by accurately control etc. of sedimentary condition, but the film that generates is subject to the elevated temperature heat damage, influences the performance of film, and energy consumption is bigger.Depositing temperature is the principal element that influences deposition film quality, and the hear resistance of substrate is had higher requirements.
Sol-gel process is meant that metal organic or inorganic compound forms the method for oxide or other solid chemical compound through the sol-gel processing.Its process is: lipid or metal alkoxide are dissolved in solvent, evenly mix in solvent and carry out hydrolysis and polymerisation, generate stable and do not have the sol system of precipitation, adopt spin-coating method and dipping-pulling method (dip coating) system film.Relative CVD method, sol-gel process have that stoichiometric proportion is controlled easily, technological temperature is low, be convenient to advantages such as large tracts of land system film and equipment are simple, but the TiO for preparing with sol-gel process
2Film is normally amorphous, needs to realize TiO 300-800 ℃ of further annealing in process
2The commentaries on classics crystalline substance, and as a kind of wet method preparation process, easily constitute pollution to environment.
Summary of the invention
The purpose of this invention is to provide a kind of nanocrystalline porous TiO
2Film and preparation method, this nanocrystalline porous TiO
2Film is the porous network shape structure that is evenly distributed at substrate surface, the preparation method adopts dry process, pollute little, advantage with sputtering method and the direct film former of chemical vapour deposition technique, can avoid the pollution of sol-gel process, simultaneously, not need vacuum equipment environment, low, the consuming time weak point of energy consumption, equipment is simple, cost is low, thereby is rich in the prospect of large-scale industrial application.
Nanocrystalline porous TiO of the present invention
2Film is the film of TiOn structure, and wherein n is 1.5-2.5, polycrystalline crystal structure, crystal particle scale 10-500nm, aperture 10-5000nm.
Nanocrystalline porous TiO of the present invention
2The preparation method of film comprises the following steps:
(1) the matrix material ultrasonic cleaning is clean, oven dry places the plasma reactor bottom, feeds the carrier gas inert gas;
(2) mist of aerating oxygen and the titaniferous gas brought into by carrier gas, apply high-tension electricity, regulate bias electrode and pulsed bias, form the active particle of titaniferous, and under the polarization of bias voltage and acceleration, form the rail network structure while and brought to be blown to substrate material surface and deposit by carrier gas;
(3) behind the reactive deposition, take out matrix material, on substrate material surface, can get nanocrystalline porous TiO
2Film.
Described matrix material is glass, quartz, corundum, silicon chip, polyester film or stainless steel, polytetrafluoroethylene (PTFE), filter paper, nonwoven;
Described reactor is made up of coaxial high-field electrode and earth electrode, between the 1-2 layer thickness is arranged is the medium interlayer of 1-30mm, dielectric layer is quartz, corundum, glass or mica, cover cooling liquid sleeve pipe in the high-field electrode;
Distance between described reactor and the matrix material is 0.1-30mm;
Described feeding inert gas is meant and feeds nitrogen, argon, neon or helium 5-10 minute;
Described titaniferous gas comprises TiCl
4, titanium tetraisopropylate (TTIP) gas;
Described mist is meant monomer: oxygen: the volume ratio of inert gas is 1: 1-50: 0-500, flow are 0.1-8SLM;
Described high-tension electricity frequency is 10-100KHz, and voltage is 5000-30000V, and discharge power is 200-2000W;
Described adjusting bias electrode and pulsed bias are meant that the distance of regulating between bias electrode and reactor is 0.3-50mm, add on the bias electrode-pulsed bias of 2000---500;
Described reactive deposition is 5 seconds-20 minutes.
Beneficial effect of the present invention:
(1) positive and negative, the pulsation that this nanocrystalline porous TiO2 film crystal particle scale and aperture can be by plasma discharge and bias voltages is tens nanometer to 500 nanometer than regulating, aperture 10-5000nm, and the crystalline state internal resistance is little;
(2) this method is cracked into active group by the normal temperature and pressure dielectric barrier discharge with the reaction mixture gas body of titaniferous and the molecule of inert gas carrier gas, just can directly synthesize the nanocrystalline TiO that contains porous network shape structure on base material in tens of seconds time
2Deposited film;
(3) device of the present invention and preparation method's cost low, pollute little, simple equipments, generated time is short, quick and convenient, be adapted to various medium substrate, can be applied to DSSC, help electronics by outwards shifting fast in the film, increase electricity conversion, also can be applied to other light-catalysed filter membrane, sensor etc.
Description of drawings
Fig. 1 is an atmospheric dielectric barrier discharge plasma reactor schematic diagram;
Fig. 2 is ESEM (SEM) picture of gained result among the embodiment 1;
Fig. 3 is the SEM picture of gained result among the embodiment 2;
Fig. 4 is the petrographic microscope picture of gained result among the embodiment 3.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Adopt plasma reactor shown in Figure 1.Under the normal temperature and pressure, the coaxial quartz glass tube that adopts two bed thickness 2mm is a block media, aluminium foil electrode, thickness of electrode 0.2mm, electrode spacing 8mm, power 1000W.Bias voltage is 300v, and pulsation is than 0.18.
Common slide ultrasonic cleaning is clean, place 0.5mm place under the reactor, now fed pure Ar (1SLM) 5 minutes, and fed O2 then and the mist of the monomer brought into by Ar, mixing ratio is TiCl4: O2: Ar=1: 5: 100, flow 1SLM, discharge and take out sample after 3 minutes, sem observation is the crystal structure of loose structure, crystal particle scale is 100-500nm, aperture 20-5000nm.ESEM as shown in Figure 2.
Embodiment 2
Adopt plasma reactor shown in Figure 1.Under the normal temperature and pressure, the coaxial alumina ceramic tube that adopts 1 bed thickness 3mm is a block media, aluminium foil electrode, thickness of electrode 0.2mm, electrode spacing 10mm, power 2000W.Bias voltage-600V.The silicon chip ultrasonic cleaning is clean, place 5mm place under the reactor, now fed pure Ar (1SLM) 5 minutes, and fed O2 then and the mist of the TEOS monomer brought into by Ar, mixing ratio is TEOS: O2: Ar=1: 50: 300, flow 5SLM, discharge and take out sample after 10 minutes, sem observation is the crystal structure of loose structure, crystal particle scale is 20-200nm, aperture 20-3000nm.ESEM as shown in Figure 3.
Embodiment 3
Adopt plasma reactor shown in Figure 1.Under the normal temperature and pressure, the coaxial quartz glass tube that adopts two bed thickness 2mm is a block media, aluminium foil electrode, thickness of electrode 0.2mm, electrode spacing 5mm, power 500W.Bias voltage-200V.
The quartz plate ultrasonic cleaning is clean, place 1mm place under the reactor, now fed pure He (1SLM) 5 minutes, the mist of the TiCl4 monomer that feeds O2 then and bring into by He, mixing ratio is TiCl4: O2: Ar=1: 10: 500, flow 0.5SLM discharged and takes out sample after 15 minutes, polarized light microscope observing demonstrates shinny crystal grain structure under the polarisation.Petrographic microscope as shown in Figure 4.
Claims (10)
1. nanocrystalline porous TiO2 film, it is characterized in that: this film is the film of TiOn structure, wherein n is 1.5-2.5, polycrystalline crystal structure, crystal particle scale 10-500nm, aperture 10-5000nm.
2. the preparation method of nanocrystalline porous TiO2 film comprises the following steps:
(1) the matrix material ultrasonic cleaning is clean, oven dry places the plasma reactor bottom, feeds the carrier gas inert gas;
(2) mist of aerating oxygen and the titaniferous gas brought into by carrier gas, apply high-tension electricity, regulate bias electrode and pulsed bias, form the active particle of titaniferous, and under the polarization of bias voltage and acceleration, form rail network structure and brought to substrate material surface simultaneously and deposit;
(3) reactive deposition takes out matrix material after 5 seconds-20 minutes, can get nanocrystalline porous TiO2 film on substrate material surface.
3. preparation method according to claim 2 is characterized in that: described matrix material is glass, quartz, corundum, silicon chip, polyester film or stainless steel, polytetrafluoroethylene (PTFE), filter paper, nonwoven.
4. preparation method according to claim 2, it is characterized in that: described reactor is made up of coaxial high-field electrode and earth electrode, between the 1-2 layer thickness is arranged is the medium interlayer of 1-30mm, dielectric layer is quartz, corundum, glass or mica, cover cooling liquid sleeve pipe in the high-field electrode.
5. preparation method according to claim 2 is characterized in that: the distance between described reactor and the matrix material is 0.1-30mm.
6. preparation method according to claim 2 is characterized in that: described feeding inert gas is meant and feeds nitrogen, argon, neon or helium 5-10 minute.
7. preparation method according to claim 2 is characterized in that: described titaniferous gas comprises TiCl
4, titanium tetraisopropylate (TTIP) gas.
8. preparation method according to claim 2 is characterized in that: described mist is meant monomer: oxygen: the volume ratio of inert gas is 1: 1-50: 0-500, flow are 0.1-8SLM.
9. preparation method according to claim 2 is characterized in that: described high-tension electricity frequency is 10-100KHz, and voltage is 5000-30000V, and discharge power is 200-2000W.
10. preparation method according to claim 2 is characterized in that: described adjusting bias electrode and pulsed bias are meant that the distance of regulating between bias electrode and reactor is 0.3-50mm, add on the bias electrode-pulsed bias of 2000---500.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905902A (en) * | 2010-08-16 | 2010-12-08 | 邓隽 | Meshed nano titanium dioxide and preparation method thereof |
| CN102010001A (en) * | 2010-11-17 | 2011-04-13 | 东华大学 | Preparation method of titanium dioxide cubic cone crystal |
| CN102503518A (en) * | 2011-11-16 | 2012-06-20 | 黑龙江大学 | Preparation method of porous crystalline TiO2 foamed ceramic |
| CN102522569A (en) * | 2011-12-21 | 2012-06-27 | 东方电气集团东方汽轮机有限公司 | Method for modifying carbon porous material |
| CN102539407A (en) * | 2010-12-07 | 2012-07-04 | 索尼公司 | Method for evaluation of oxide semiconductor electrode, apparatus for evaluation of oxide semiconductor electrode, and apparatus for production of oxide semiconductor electrode |
| CN103030304A (en) * | 2013-01-09 | 2013-04-10 | 华北电力大学 | Preparation method of titanium dioxide nano porous film material |
| CN103194731A (en) * | 2013-04-12 | 2013-07-10 | 中国科学院山西煤炭化学研究所 | Method for preparing nitrogen-doped titanium dioxide porous membrane |
| CN103308242A (en) * | 2013-05-13 | 2013-09-18 | 上海天沐自动化仪表有限公司 | Thin-film pressure sensor adopting titanium oxynitride as strain material and manufacturing method thereof |
| CN104073774A (en) * | 2014-03-28 | 2014-10-01 | 能源X控股有限公司 | Device for preparing nano thin film in porous structure and application of device |
| CN105755452A (en) * | 2016-04-18 | 2016-07-13 | 北京大学 | Device for spraying TiO2 nano coating on inner wall of pipe cavity |
| CN107497413A (en) * | 2017-07-27 | 2017-12-22 | 东华大学 | A kind of preparation method of black titanium dioxide coating |
| CN109750276A (en) * | 2019-01-28 | 2019-05-14 | 中国科学院电工研究所 | Based on inert gas/oxygen plasma membrane deposition method and device |
| CN112213005A (en) * | 2020-10-13 | 2021-01-12 | 新余学院 | Titanium dioxide/carbon dot composite film pressure sensor and preparation method thereof |
| CN113372109A (en) * | 2021-05-18 | 2021-09-10 | 景德镇陶瓷大学 | Preparation method of large-area defect-free nano-scale thickness compact ceramic film and ceramic film prepared by same |
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2007
- 2007-08-17 CN CNA2007100449932A patent/CN101164689A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905902A (en) * | 2010-08-16 | 2010-12-08 | 邓隽 | Meshed nano titanium dioxide and preparation method thereof |
| CN102010001A (en) * | 2010-11-17 | 2011-04-13 | 东华大学 | Preparation method of titanium dioxide cubic cone crystal |
| CN102539407A (en) * | 2010-12-07 | 2012-07-04 | 索尼公司 | Method for evaluation of oxide semiconductor electrode, apparatus for evaluation of oxide semiconductor electrode, and apparatus for production of oxide semiconductor electrode |
| CN102503518A (en) * | 2011-11-16 | 2012-06-20 | 黑龙江大学 | Preparation method of porous crystalline TiO2 foamed ceramic |
| CN102522569A (en) * | 2011-12-21 | 2012-06-27 | 东方电气集团东方汽轮机有限公司 | Method for modifying carbon porous material |
| CN103030304A (en) * | 2013-01-09 | 2013-04-10 | 华北电力大学 | Preparation method of titanium dioxide nano porous film material |
| CN103194731A (en) * | 2013-04-12 | 2013-07-10 | 中国科学院山西煤炭化学研究所 | Method for preparing nitrogen-doped titanium dioxide porous membrane |
| CN103308242B (en) * | 2013-05-13 | 2015-04-29 | 上海天沐自动化仪表有限公司 | Thin-film pressure sensor adopting titanium oxynitride as strain material and manufacturing method thereof |
| CN103308242A (en) * | 2013-05-13 | 2013-09-18 | 上海天沐自动化仪表有限公司 | Thin-film pressure sensor adopting titanium oxynitride as strain material and manufacturing method thereof |
| CN104073774A (en) * | 2014-03-28 | 2014-10-01 | 能源X控股有限公司 | Device for preparing nano thin film in porous structure and application of device |
| CN105755452A (en) * | 2016-04-18 | 2016-07-13 | 北京大学 | Device for spraying TiO2 nano coating on inner wall of pipe cavity |
| CN107497413A (en) * | 2017-07-27 | 2017-12-22 | 东华大学 | A kind of preparation method of black titanium dioxide coating |
| CN109750276A (en) * | 2019-01-28 | 2019-05-14 | 中国科学院电工研究所 | Based on inert gas/oxygen plasma membrane deposition method and device |
| CN112213005A (en) * | 2020-10-13 | 2021-01-12 | 新余学院 | Titanium dioxide/carbon dot composite film pressure sensor and preparation method thereof |
| CN112213005B (en) * | 2020-10-13 | 2022-04-29 | 新余学院 | Titanium dioxide/carbon dot composite film pressure sensor and preparation method thereof |
| CN113372109A (en) * | 2021-05-18 | 2021-09-10 | 景德镇陶瓷大学 | Preparation method of large-area defect-free nano-scale thickness compact ceramic film and ceramic film prepared by same |
| CN113372109B (en) * | 2021-05-18 | 2022-12-13 | 景德镇陶瓷大学 | Preparation method of large-area defect-free nano-scale thickness compact ceramic film and ceramic film prepared by same |
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Open date: 20080423 |