CN101225510A - Plasma preparation method of super-hydrophobic and super-hydrophilic titanium oxide film - Google Patents
Plasma preparation method of super-hydrophobic and super-hydrophilic titanium oxide film Download PDFInfo
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- CN101225510A CN101225510A CNA2008100325879A CN200810032587A CN101225510A CN 101225510 A CN101225510 A CN 101225510A CN A2008100325879 A CNA2008100325879 A CN A2008100325879A CN 200810032587 A CN200810032587 A CN 200810032587A CN 101225510 A CN101225510 A CN 101225510A
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Abstract
The invention relates to a preparation method of super-hydrophobic and super-hydrophilic titanium dioxide film plasma, comprising: (1) a radio frequency plasma generator of 12-14 MHz generates plasma glow, and the plasma power is adjusted between 40W and 180W; (2) deposition by the monomer of four isopropyl-titanium acid resin, and loading by oxygen; (3) getting the super-hydrophilic titanium dioxide films from the substrates under the electrode, and getting the super-hydrophobic titanium dioxide films from the substrates far away from the electrode; (4) the super-hydrophobic titanium dioxide films after annealing in the atmospheric pressure and 500 DEG C for 1 to 2 hours, can obtain the super-hydrophilic titanium dioxide films. The preparation method of super-hydrophobic and super-hydrophilic titanium dioxide film plasma has the advantages that the titanium dioxide films can obtain both the super-hydrophobic and super-hydrophilic films only in a deposition, the process is easy to control, and provides the possibility of industrial application.
Description
Technical field
The invention belongs to the plasma body preparation field, particularly relate to the plasma preparation method of super-hydrophobicity and Superhydrophilic titanium deoxid film.
Background technology
The plasma chemical vapor deposition technique principle is to utilize low-temperature plasma (nonequilibrium plasma) to make energy source, substrate places the reaction chamber of glow discharge under the subatmospheric, utilize glow discharge to produce a large amount of charged particle and neutral particle, feed an amount of monomeric reactant gases that is loaded with then, gas forms solid film through series of chemical and plasma reaction at substrate surface.It has comprised the general technology of chemical vapour deposition, and the strengthening effect of glow discharge is arranged again.Because interparticle collision produces violent ionization of gas, and reactant gases is activated.The cathode sputtering effect takes place simultaneously, and the active high surface of cleaning is provided for deposit film.Thereby whole deposition process is with only to have heat activated process to have significantly different.The effect of this two aspect improving the coating bonding force, reduces depositing temperature, and the fast reaction speed aspects has all been created favourable condition.
Along with the develop rapidly of social progress and science and technology, more and more higher to the requirement of the functionalization of material surface, recently, the hydrophobic angle surpasses the surfaces of 150 degree, i.e. the research of ultraphobic water surface has caused people's very big interest.Ultraphobic water surface all has broad application prospect in a lot of fields such as automatically cleaning material, communication, gene transmission, microfluid and harmless liquid transmission.Since titanium dioxide came out, functions such as its unique colour effect, photocatalysis and ultraviolet screener made it just be favored once emerging, and are with a wide range of applications at aspects such as wastewater treatment, sensitive materials and historical relic's protection, sterilization, environmental protection.How to construct a kind of functional membrane that ultraphobic water-based has the titanium dioxide advantage again that promptly has, i.e. super-hydrophobicity titanium deoxid film becomes the people's in two fields the common objective of research.In general, the preparation super hydrophobic surface must satisfy two conditions: the one, and the surface of material has very low solid surface energy; The 2nd, on the surface of low surface energy material, be built with certain roughness the micron with nanophase bonded hierarchical structure.The method that current people make super dewatering titanium oxide mainly contains: ion implantation, ion completion method, anonizing, etching method, sol-gel method and photochemical method etc.
Summary of the invention
The plasma preparation method that the purpose of this invention is to provide a kind of super-hydrophobicity and Superhydrophilic titanium deoxid film, this method adopt the auxiliary plasma body down of bias voltage to strengthen the thin film of titanium oxide that sedimentary method prepares Superhydrophilic and super-hydrophobicity.The present invention can obtain Superhydrophilic and super-hydrophobicity titanium deoxid film simultaneously by single step reaction, and the super-hydrophobicity film is converted into the Superhydrophilic thin film of titanium oxide by anneal.
The plasma preparation method of super-hydrophobicity of the present invention and Superhydrophilic titanium deoxid film comprises step:
(1) glass substrate is used acetone, ethanol and deionized water ultrasonic cleaning 20～40 minutes respectively, put into the different positions of reactor after in nitrogen, drying up;
(2) reactor is extracted into 10～30Pa in advance by mechanical pump, the open plasma power supply begins the aura generating and pulsed bias power supply adds the bias voltage field, with the frequency is the radio-frequency (RF) plasma generator generation plasma body aura of 12-14MHZ, and the adjusting plasma power changes between 40W-180W;
(3) be that monomer kept 60～80 ℃ of constant temperature depositions 10～30 minutes with tetra isopropyl metatitanic acid fat in water-bath, and be loaded into inside reactor by oxygen;
(4) on the substrate of reactor, obtain the super-hydrophobicity titanium deoxid film, on the substrate below the pulsed bias electrode, obtain the Superhydrophilic titanium deoxid film away from glow discharge electrode and pulsed bias electrode;
(5) the super-hydrophobicity titanium deoxid film is converted into the Superhydrophilic titanium deoxid film after 500 ℃ of normal pressures were annealed 1～2 hour down.
Described super-hydrophobicity titanium deoxid film has micro-nano layer rank coarse structure, and super-hydrophilic thin film has the micron order flat structures.
Beneficial effect of the present invention:
(1) titanium deoxid film of the present invention has superpower hydrophobicity, and UV-light is had absorption preferably, and long-term placement can keep super-hydrophobicity;
(2) super-hydrophilic thin film has stronger hydrophilic effect and strong degree;
(3) the super-hydrophobicity film still is converted into super-hydrophilic thin film through 500 ℃ of not changes of structure of annealing rear film down;
(4) this method prepares titanium deoxid film and has a step deposition and obtain super-hydrophobic simultaneously and easy advantage super-hydrophilic thin film, and process is controlled easily, for industrial applications provides possibility.
Description of drawings
Fig. 1 is the sem photograph of super-hydrophobicity titanium deoxid film different multiplying, Fig. 1-(a) be * 1000 times, Fig. 1-(b) be * 20000 times;
Fig. 2 is the sem photograph of Superhydrophilic titanium deoxid film different multiplying, Fig. 2-(a) be * 1000 times, Fig. 2-(b) be * 10000 times;
Fig. 3 is the infrared spectrogram of super-hydrophobicity titanium deoxid film;
Fig. 4 is the contact angle figure of super-hydrophobicity titanium deoxid film and water;
Fig. 5 is the contact angle figure of Superhydrophilic titanium deoxid film and water;
Fig. 6 is the ultraviolet-visible spectrogram of super-hydrophobicity titanium deoxid film;
Fig. 7 is the sem photograph of titanium deoxid film after the annealing, Fig. 7-(a) be * 1000 times, Fig. 7-(b) be * 10000 times;
Fig. 8 is XRD (X-ray diffraction) spectrogram of the titanium deoxid film after the annealing;
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.
To pass through acetone, ethanol and deionized water ultrasonic cleaning 20 minutes successively, and the glass substrate that dries up is put into plasma reactor in argon gas.Reactor is evacuated down to 10～30pa, the open plasma power supply produces glow discharge, opening the pulse power then and produce the bias voltage field, be that the radio-frequency (RF) plasma generator of 13.56MHZ produces the plasma body aura with the frequency, and the adjusting plasma power changes between 40W-180W.With oxygen the tetra isopropyl metatitanic acid fat in 60 ℃ of waters bath with thermostatic control is loaded into plasma reactor deposition 10 minutes, can on glass substrate, obtain the super-hydrophobicity titanium deoxid film, on the glass substrate below the pulsed bias electrode, obtain the Superhydrophilic titanium deoxid film away from plasma electrode and pulsed bias electrode.
The SEM of super-hydrophobicity titanium dioxide can see the micro-nano surface topography that combines as shown in Figure 1, is made up of countless nanostructures above the micron-sized little mastoid process, and this meets the requirement of the surfaceness of super-hydrophobicity film.Fig. 2 is the SEM picture of super-hydrophilic thin film, can see at the auxiliary film down of pulsed bias and being made up of countless smooth small shredss, but all fragments all in one plane, seems more smooth, and this film demonstrates Superhydrophilic.
Can find the structure that the surface of film is made up of organic and inorganic mixing, and the low surface energy of organic composition one of necessary condition of super-hydrophobicity film just to the chemical structure analysis of super-hydrophobicity film surface with infrared spectra.Can be seen that by Fig. 3 along with power increases, organic group increases, and (a) is 40w, (b) is 100w, (c) is 150w, the surface of film mainly is some hydrocarbon group absorption peaks, at 400～600cm
-1Between be because the sorption of titanium oxide.
Embodiment 3
Characterize by the wettability of contact angle measurement to film, the contact angle that can measure at the surface water of super-hydrophobicity film is 160 ± 2 °, and the water contact angle on super-hydrophilic thin film surface is 6 °.Present method obtains super-hydrophobicity film and super-hydrophilic thin film as shown in Figure 4 and Figure 5 simultaneously in same reactor.
Embodiment 4
The super-hydrophobicity titanium deoxid film demonstrates the ultraviolet radiation absorption characteristic, can see the increase along with power, absorbs to move to short wavelength's direction, (a) be 40W, (b) being 100W, (c) is 150W, can prove that the super-hydrophobicity film has good ultraviolet absorption characteristic.As shown in Figure 6.
The super-hydrophobicity film through behind 500 ℃ of annealing 1h, will be converted into super-hydrophilic thin film, and the surface topography of film does not change in air atmosphere.The surface topography of film meets the micro-nano requirement that combines of super-hydrophilic thin film, as shown in Figure 7.
Embodiment 6
Under power 40W and the generating of 100W aura, film is unformed state.Film after as a child of annealing detects through XRD that to find that titanium deoxid film has been converted into by unformed state anatase structured in the air atmosphere, and the crystalline structure of the film before and after the annealing as shown in Figure 8.
Claims (3)
1. the plasma preparation method of super-hydrophobicity and Superhydrophilic titanium deoxid film comprises step:
(1) be the radio-frequency (RF) plasma generator generation plasma body aura of 12-14MHZ with the frequency, and the adjusting plasma power change between 40W-180W;
(2) be monomer deposition with tetra isopropyl metatitanic acid fat, and be written into by oxygen;
(3) obtain the Superhydrophilic titanium deoxid film on the substrate of electrode below, on substrate, obtain the super-hydrophobicity titanium deoxid film away from electrode;
(4) the super-hydrophobicity titanium deoxid film gets the Superhydrophilic titanium deoxid film after 500 ℃ of normal pressures were annealed 1～2 hour down.
2. the plasma preparation method of super-hydrophobicity according to claim 1 and Superhydrophilic titanium deoxid film is characterized in that: deposition is 60～80 ℃ of constant temperature water bath depositions 10～30 minutes in the described step (2).
3. the plasma preparation method of super-hydrophobicity according to claim 1 and Superhydrophilic titanium deoxid film, it is characterized in that: described super-hydrophobicity titanium deoxid film has micro-nano layer rank coarse structure, and super-hydrophilic thin film has the micron order flat structures.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010001A (en) * | 2010-11-17 | 2011-04-13 | 东华大学 | Preparation method of titanium dioxide cubic cone crystal |
| CN102345134A (en) * | 2011-09-13 | 2012-02-08 | 蔺增 | Preparation method for wettability controllable porous structure of titanium and titanium alloy surface |
| CN105084306A (en) * | 2015-07-30 | 2015-11-25 | 西北大学 | Controllable preparation method of large-area laminated micro-nano composite structure |
| CN107966865A (en) * | 2017-12-18 | 2018-04-27 | 深圳市华星光电半导体显示技术有限公司 | Production method, array base palte and the display panel of array base palte |
| CN110144569A (en) * | 2019-07-03 | 2019-08-20 | 东莞市和域战士纳米科技有限公司 | The preparation method of long-acting hydrophilic film |
| CN110606736A (en) * | 2019-08-23 | 2019-12-24 | 广东工业大学 | Solvent-free synthesized ceramic microsphere and preparation method and application thereof |
| CN114656863A (en) * | 2022-03-16 | 2022-06-24 | 浙江工业大学 | Super-hydrophilic polycaprolactone film and preparation method thereof |
-
2008
- 2008-01-11 CN CNA2008100325879A patent/CN101225510A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010001A (en) * | 2010-11-17 | 2011-04-13 | 东华大学 | Preparation method of titanium dioxide cubic cone crystal |
| CN102345134A (en) * | 2011-09-13 | 2012-02-08 | 蔺增 | Preparation method for wettability controllable porous structure of titanium and titanium alloy surface |
| CN105084306A (en) * | 2015-07-30 | 2015-11-25 | 西北大学 | Controllable preparation method of large-area laminated micro-nano composite structure |
| CN107966865A (en) * | 2017-12-18 | 2018-04-27 | 深圳市华星光电半导体显示技术有限公司 | Production method, array base palte and the display panel of array base palte |
| CN110144569A (en) * | 2019-07-03 | 2019-08-20 | 东莞市和域战士纳米科技有限公司 | The preparation method of long-acting hydrophilic film |
| CN110606736A (en) * | 2019-08-23 | 2019-12-24 | 广东工业大学 | Solvent-free synthesized ceramic microsphere and preparation method and application thereof |
| CN114656863A (en) * | 2022-03-16 | 2022-06-24 | 浙江工业大学 | Super-hydrophilic polycaprolactone film and preparation method thereof |
| CN114656863B (en) * | 2022-03-16 | 2023-04-07 | 浙江工业大学 | Super-hydrophilic polycaprolactone film and preparation method thereof |
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