CN109836050A - A kind of tandem type TiN/TiO2Laminated film and its preparation method and application - Google Patents
A kind of tandem type TiN/TiO2Laminated film and its preparation method and application Download PDFInfo
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- CN109836050A CN109836050A CN201910276549.6A CN201910276549A CN109836050A CN 109836050 A CN109836050 A CN 109836050A CN 201910276549 A CN201910276549 A CN 201910276549A CN 109836050 A CN109836050 A CN 109836050A
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Abstract
The invention discloses a kind of tandem type TiN/TiO2The preparation method of laminated film, comprising: disperse TiN nano-powder and dispersing aid in deionized water, adjust pH > 6, obtain TiN plated film precursor sol after ultrasound；Clean substrate is heated to not less than 100 DEG C, obtained TiN plated film precursor sol is sprayed by substrate surface after the heating using ultrasonic atomizatio method, obtains TiAlN thin film after cooling；Obtained TiAlN thin film is made annealing treatment, tandem type TiN/TiO is obtained2Laminated film.The invention also discloses a kind of tandem type TiN/TiO that above-mentioned preparation method is prepared2Laminated film and its application in glass coating.The tandem type TiN/TiO2The hydrophily and photocatalysis performance of laminated film are controllable, increasing be plated on glass after can Effective Regulation by the performance of glass plating.
Description
Technical field
The present invention relates to laminated film fields, and in particular to a kind of tandem type TiN/TiO2Laminated film and preparation method thereof
And application.
Background technique
China is energy consumption big country, and wherein building energy consumption accounts for nearly the 40% of whole society's total energy consumption, and presents year by year
The trend of rising.Building energy consumption from be in the narrow sense the day of building it is common can, including heating, air-conditioning, illumination etc..Glass is to build
Build the main lighting material of object, it has also become the indispensable material of modern architecture.But 95% or more of China's construction area
Using common glass, this kind of glass has good translucency, but the heat of sunlight can not be stopped to building
Heat is spread to outside in interior radiation and building, cannot reach energy-efficient purpose.Increase one layer of electric conductivity of plating in glass surface
Can good functional film, can either keep the translucency of glass, but can efficient trap heat transmitting, reduce glass
Radiance makes ordinary plate glass have special performance, so as to meet a variety of demands such as energy-saving and environmental protection, decoration.
The forbidden bandwidth of titanium nitride (TiN) is 3.35~3.45eV, and titanium nitride thin membrane material both has covalent compound
The features such as high-melting-point, high rigidity, good thermal stability and corrosion resistance, but also with good thermal conductivity specific to metal and
Electrical conductance, the protective coating of cutting tool, golden decorating film, large scale integrated circuit in terms of obtain it is wide
General application, be it is a kind of have excellent performance, with development potential with the material of wide application prospect.
TiAlN thin film can be applied to glass coating because having excellent hydrophilicity.When having steam on TiN coated glass,
Steam will be spread apart on entire glass surface to be come, without congealing into droplet.Therefore, being lauched in situations such as rain drop erosion will not
Droplet is agglomerated into glass surface, is convenient for glass cleaning, realizes the self-cleaning function of glass.However, when pollutants such as organic matters
When being attached on TiN coated glass, since TiAlN thin film does not have the ability of decomposing pollutant, it is covered on so will lead to pollutant
TiAlN thin film surface makes TiN coated glass lose self-cleaning ability.
In addition, the common preparation method of TiAlN thin film has chemical vapor deposition, sol-gal process, magnetron sputtering method etc., preparation
Obtained TiAlN thin film can be realized the high transmitance of visible light wave range and the higher reflectivity of infrared band, while TiAlN thin film
Resistivity effectively can be regulated and controled and be reduced.It but is mostly the acyl of titanium using presoma used in chemical method preparation TiAlN thin film
Hydrolysis and oxidation easily occur in air and moisture for amine complex, and reaction is required in the preparation and heat treatment process of film
Ambient oxygen content is low, means suitable NH3Atmosphere or N2Atmosphere, experiment condition is harsh and there are certain risk, be not suitable for it is low at
This large-scale production.
TiO2There is photocatalytic and hydrophily under light illumination, when solar irradiation is mapped to TiO2When film surface, TiO2It absorbs
Photon energy, valence-band electrons transit to conduction band, react with the oxygen molecule in air, generate Superoxide anion free radical (O2-)；Valence
The hole that band leaves generates hydroxyl radical free radical (OH), O with water molecule reaction2-The decomposition reaction of organic matter is participated in OH
In to have photocatalytic；Photohole is by lattice TiO2Oxygen capture, form Lacking oxygen, electronics is by Ti4+It is reduced into Ti3+,
Titanium water of coordination molecule discharges proton as charge compensation, and generates great amount of hydroxy group, forms chemisorption water layer, to have super close
Aqueous, the properties such as the nontoxic, cheap of titanium deoxid film, visible transparent, chemical property stabilization, are most popular light in addition
One of catalysis material.Research shows that N doping can reduce forbidden bandwidth, widen its photoresponse to visible light wave from ultraviolet light
Section promotes it in visible and infrared band photocatalytic activity.
In conclusion needing the method for finding a kind of mild, the suitable large-scale production TiAlN thin film of preparation condition, make simultaneously
TiAlN thin film has pollutant selfdecomposition ability, to develop the glass with clean of completely new Coating Materials.
Summary of the invention
For shortcoming existing for this field, the present invention provides a kind of tandem type TiN/TiO2The preparation of laminated film
Method, at low cost, preparation condition is mild, is suitble to large-scale production, is original with TiN nano-powder under normal pressure, low temperature environment
Material prepares TiAlN thin film using ultrasonic atomizatio method, the TiN/TiO with cascaded structure is obtained in conjunction with air anneal2Laminated film,
And change TiN/TiO by changing annealing temperature2The hydrophilicity of laminated film.
A kind of tandem type TiN/TiO2The preparation method of laminated film, comprising:
(1) it disperses TiN nano-powder and dispersing aid in deionized water, adjusts pH > 6, obtain TiN plated film after ultrasound
Precursor sol；
(2) clean substrate is heated to not less than 100 DEG C, obtained TiN is plated by film precursor using ultrasonic atomizatio method
The substrate surface of aerosol jet after the heating obtains TiAlN thin film after cooling；
(3) obtained TiAlN thin film is made annealing treatment, obtains tandem type TiN/TiO2Laminated film.
The present invention is using TiN nano-powder as raw material, using the characteristic of ultrasonic wave added atomization solid phase nano particle, by nanometer
The features such as particle surface energy is high, large specific surface area, realizes normal pressure, cryogenic conditions depositing TiN nano structure membrane, in air atmosphere
Annealing obtains the TiN/TiO with different degree of oxidation under different temperatures2Laminated film, realize laminated film object phase and
Hydrophilic regulation.
In step (1), the mass percent that the dispersing aid being scattered in deionized water accounts for TiN nano-powder is not more than
5%.Excessive dispersing aid will reduce the compactness of TiAlN thin film, more organic matter be remained in coating process, and to nano-powder
Dispersion do not contribute significantly.
Preferably, the primary particle size of the TiN nano-powder is less than 50nm.The excessive increase of partial size disperses difficulty, dispersion
The excessive film that will lead to open structure of particle size in liquid, influences the hydrophily of film.
Preferably, the TiN nano-powder is scattered in deionized water with dispersing aid again after ball milling.
Preferably, dispersing aid is added when the TiN nano-powder ball milling, the dispersing aid that when ball milling adds accounts for TiN
The mass percent of nano-powder is not more than 5%.Excessive dispersing aid will reduce the compactness of TiAlN thin film, in coating process
Remain more organic matter.
Preferably, the Ball-milling Time is not less than 5h.
By the way of preparatory ball milling, dispersing aid modification and ultrasonic disperse, to prepare the lesser TiN of average grain diameter
Nanometer water dispersion sol.
Preferably, the dispersing aid is in glycol methyl ether acetate, propylene glycol methyl ether acetate and Tween 80
At least one.
In step (1), hydrochloric acid can be used or sodium hydroxide adjusts pH.
In step (2), the substrate can be sheet glass, silicon wafer or quartz plate.
Preferably, clean substrate is heated to not less than 150 DEG C.
Ultrasonic atomizatio method of the present invention uses ultrasonic atomizatio assisted vapor deposition.
Preferably, obtained TiN plated film precursor sol is sprayed by substrate surface after the heating using ultrasonic atomizatio method
When, nozzle between substrate at a distance from be 1~2cm.TiN sol solutions after atomization are dropped on hot substrate, and liquid phase, dispersing aid exist
It volatilizees under heating condition, TiN nanoparticle aggregate forms film.Nozzle distance is excessively high, the liquid phase and dispersing aid of colloidal sol drop
It has completed to volatilize before falling in hot substrate, nano particle, which is fallen in, will form powder in substrate, can not form film；Nozzle away from
From too low, spraying plated film area is too small, plated film low efficiency.It is highly preferred that nozzle between substrate at a distance from be 1.5cm, this condition
Under film-formation result it is best.
Preferably, the supersonic frequency of the ultrasonic atomizatio method is 100kHz~2MHz.
In step (3), it is preferable that the annealing is air atmosphere, and annealing temperature is 350~500 DEG C, and the time is not
Greater than 1h.Liquid phase and dispersing aid in colloidal sol can not quickly be vapored away by crossing low temperature；Temperature is excessively high then more than the receiving of glass
Ability, and oxidation rate is too fast, increases control difficulty.It is highly preferred that the temperature of the annealing is 400~450 DEG C, when
Between be not more than 0.5h, the TiO under this annealing conditions2For anatase and rutile mixing crystal form, there is optimal photocatalysis performance.
The present invention also provides the tandem type TiN/TiO described in one kind2The string that the preparation method of laminated film is prepared
Connection type TiN/TiO2Laminated film.
The tandem type TiN/TiO2TiO in laminated film2For anatase (anatase) crystal form or anatase and gold
Red stone (Rutile) mixes crystal form, makes tandem type TiN/TiO2Laminated film has efficient photocatalysis performance, under light illumination may be used
The pollutants such as the organic matter on degradable film surface.
Moreover, the tandem type TiN/TiO2TiO in laminated film2It makes annealing treatment to be formed by TiN, is doped with portion
Divide nitrogen, has widened photoresponse wavelength band, promoted photocatalytic activity.
In addition, the tandem type TiN/TiO2Laminated film also has excellent hydrophilicity.
The present invention also provides the tandem type TiN/TiO described in one kind2Application of the laminated film in glass coating.
By the tandem type TiN/TiO2Laminated film increasing is plated on surface of ordinary glass and obtains glass with clean, it is described from
Clean glass not only can efficiently trap heat transmit, and reduce the radiance of glass, and can prevent condensation vapor, it is difficult to reduce cleaning
Degree can also realize self-cleaning function using the pollutant of photocatalytic degradation glass surface attachment.
Compared with prior art, the present invention major advantage includes:
(1) TiAlN thin film presoma uses nanometer TiN powder for raw material, avoids influence of the raw material impurity to film performance.
(2) ultrasonic atomizatio method is used, can be atomized presoma becomes the lesser drop of partial size, can rationally control drop
Size achieve the purpose that control reaction rate, deposition obtain dense uniform TiAlN thin film.
(3) TiN/TiO can be prepared by making annealing treatment under air atmosphere to film2Laminated film, at heat
The regulation of reason temperature can be realized the graded oxidation of film, and change TiN and TiO in laminated film2The ratio of object phase, and then adjust
Control the hydrophily and photocatalysis performance of laminated film.
Detailed description of the invention
The TiN/TiO that Fig. 1 obtains for air anneal under TiAlN thin film in embodiment and different temperatures2The XRD of laminated film
Figure；
Fig. 2 is the TiN/TiO that air anneal obtains under TiAlN thin film (a), different temperatures in embodiment2Laminated film and
The water contact angle measurement result figure of substrate (f), wherein (b) 350 DEG C, (c) 400 DEG C, (d) 450 DEG C, (e) 500 DEG C；
Fig. 3 is the TiN/TiO that TiAlN thin film (a) and vacuum annealing obtain in embodiment2The water contact angle of laminated film measures
Result figure；
Fig. 4 is the schematic diagram of ultrasonic atomizatio assisted vapor deposition of the invention, wherein 1- carrier gas；2- ultrasonic atomizatio TiN liquid
Drop；3- nozzle；4- substrate of glass；5- heating platform.
Specific embodiment
With reference to the accompanying drawing and specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate
The present invention rather than limit the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to
Normal condition, or according to the normal condition proposed by manufacturer.
(1) after being cleaned by ultrasonic substrate of glass 30min respectively with surfactant, ethyl alcohol, water, 80 DEG C of vacuum drying.
(2) dispersing aid Tween 80 (C12H10CINO3) mixed with mass percent 3% with TiN powder, ball milling for 24 hours, takes out
For use.
(3) dispersing aid Tween 80 is with the TiN powder common distribution after mass percent 3% and ball milling in deionized water
In, configuration concentration 0.2molL-1TiN aqueous liquid dispersion, and with titration sodium hydroxide, make the pH=10 of aqueous liquid dispersion,
It is ultrasonically treated dispersion liquid 30min, obtains the TiN aqueous dispersion colloidal sol that average grain diameter is 172nm, as painting film precursor.
(4) substrate of glass after cleaning is heated to 150 DEG C, with the temperature of temperature-measuring gun measurement substrate, temperature change control
Within the scope of ± 5 DEG C.
(5) the aqueous presoma of scattered TiN is poured into the charging gear of ultrasonic atomizer, adjusts nozzle and glass base
The distance at bottom is 1.5cm, opens ultrasonic atomizer, as shown in Figure 4.Being passed through carrier gas 1 makes TiN presoma be mixed into ultrasonic atomizatio
After TiN drop 2,4 surface of substrate of glass on heating platform 5 is injected in by nozzle 3.
(6) after depositing 5min, heating platform is closed, naturally cools to the substrate of glass for being deposited with TiN with heating platform
Room temperature removes the sample for being coated with TiAlN thin film later.
(7) above-mentioned sample is packed into porcelain boat, is put into cabinet-type electric furnace, is set separately 350 DEG C, 400 DEG C, 450 DEG C and 500
DEG C heat treatment temperature, under air atmosphere, heat treatment time 30min cools to room temperature with the furnace, after obtaining air anneal
TiN/TiO2Laminated film.
(8) TiAlN thin film sample described in step (6) is packed into porcelain boat, electron tubes type electric furnace is put into, using mechanical pumping
Gas, background pressure about 20Pa are heated to 700 DEG C, keep the temperature 4 hours, cool to room temperature with the furnace, the TiN/ after obtaining vacuum annealing
TiO2Laminated film.
The TiN/TiO that air anneal obtains under different temperatures in the present embodiment2Laminated film XRD diagram is as shown in Figure 1.350
The TiN/TiO that DEG C air anneal obtains2TiO in laminated film2Ratio is very low, and is unformed shape.400 DEG C of air anneals
Obtained TiN/TiO2The TiO of laminated film2For anatase crystal.450 DEG C, the obtained TiN/TiO of 500 DEG C of air anneals2It is compound
The TiO of film2It is coexisted for anatase crystal and rutile crystal type.It can be seen that TiN/TiO can be realized by adjusting annealing temperature2
The crystal phase of laminated film regulates and controls, to obtain the TiN/TiO of different hydrophilic and photocatalysis performance2Laminated film.
Water contact angle test equipment is the video optics contact angle measurement (OCA 20) of Dataphysics company, Germany.
The water contact angle measurement result of air anneal laminated film is as shown in Figure 2.The water contact angle of substrate of glass is
42.6 °, and the water contact angle of the TiAlN thin film without annealing is 0 °.After TiAlN thin film at different temperatures air anneal
Water contact angle variation is as follows: water contact angle is 8.5 ° after 300 DEG C of annealing, and water contact angle is 12.9 ° after 400 DEG C of annealing, and 450 DEG C are moved back
Water contact angle is 13.8 ° after fire, and water contact angle is 14.0 ° after 500 DEG C of annealing.It can be seen that can be with by adjusting annealing temperature
The hydrophily of Effective Regulation laminated film.
The water contact angle measurement result of vacuum annealing laminated film is as shown in Figure 3.The water of TiAlN thin film without annealing
Contact angle is 0 °, the TiN/TiO that vacuum annealing obtains2The water contact angle of laminated film is 153 °.It can be seen that vacuum annealing meeting
The TiN/TiO caused2Laminated film is changed into strong-hydrophobicity from strongly hydrophilic.Annealing atmosphere is to TiN/TiO2Laminated film
Hydrophilicity have great influence.
In addition, it should also be understood that, those skilled in the art can be to this hair after having read foregoing description content of the invention
Bright to make various changes or modifications, these equivalent forms also fall within the scope of the appended claims of the present application.
Claims (10)
1. a kind of tandem type TiN/TiO2The preparation method of laminated film, comprising:
(1) it disperses TiN nano-powder and dispersing aid in deionized water, adjusts pH > 6, TiN plating membrane precursor is obtained after ultrasound
Body colloidal sol；
(2) clean substrate is heated to not less than 100 DEG C, the TiN plated film precursor sol that will be obtained using ultrasonic atomizatio method
The substrate surface of injection after the heating, obtains TiAlN thin film after cooling；
(3) obtained TiAlN thin film is made annealing treatment, obtains tandem type TiN/TiO2Laminated film.
2. tandem type TiN/TiO according to claim 12The preparation method of laminated film, which is characterized in that step (1)
In, the dispersing aid being scattered in deionized water accounts for the mass percent of TiN nano-powder no more than 5%.
3. tandem type TiN/TiO according to claim 12The preparation method of laminated film, which is characterized in that the TiN
The primary particle size of nano-powder is less than 50nm.
4. tandem type TiN/TiO according to claim 1 or 32The preparation method of laminated film, which is characterized in that described
TiN nano-powder is scattered in deionized water with dispersing aid again after ball milling, and the Ball-milling Time is not less than 5h.
5. tandem type TiN/TiO according to claim 42The preparation method of laminated film, which is characterized in that the TiN
Add dispersing aid when nano-powder ball milling, the mass percent that the dispersing aid that when ball milling adds accounts for TiN nano-powder is little
In 5%.
6. tandem type TiN/TiO according to claim 12The preparation method of laminated film, which is characterized in that step (2)
In, when obtained TiN plated film precursor sol being sprayed substrate surface after the heating using ultrasonic atomizatio method, nozzle and substrate
Between distance be 1~2cm.
7. tandem type TiN/TiO according to claim 1 or 62The preparation method of laminated film, which is characterized in that described
The supersonic frequency of ultrasonic atomizatio method is 100kHz~2MHz.
8. tandem type TiN/TiO according to claim 12The preparation method of laminated film, which is characterized in that described moves back
Fire processing is air atmosphere, and annealing temperature is 350~500 DEG C, and the time is not more than 1h.
9. tandem type TiN/TiO described in a kind of any claim according to claim 1~82The preparation method system of laminated film
Standby obtained tandem type TiN/TiO2Laminated film.
10. a kind of tandem type TiN/TiO according to claim 92Application of the laminated film in glass coating.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111437857A (en) * | 2019-12-30 | 2020-07-24 | 浙江大学 | Novel photocatalytic film based on titanium nitride and titanium oxide and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1670252A (en) * | 2005-03-09 | 2005-09-21 | 南开大学 | Device and method for preparing nanometer oxide nesa by ultrasound rapid deposition method |
| JP2007063059A (en) * | 2005-08-30 | 2007-03-15 | Tohoku Univ | Film depositing method of partially nitrided titanium oxide thin film |
| CN101157021A (en) * | 2007-11-01 | 2008-04-09 | 复旦大学 | A preparation method of visible light active nitrogen doping nanometer titania film |
| CN102534531A (en) * | 2012-01-10 | 2012-07-04 | 清华大学 | Preparation method of titanium dioxide/titanium nitride composite film with adjustable band gaps |
| CN107698171A (en) * | 2017-08-31 | 2018-02-16 | 浙江大学 | A kind of preparation method of TiN coated glasses |
-
2019
- 2019-04-08 CN CN201910276549.6A patent/CN109836050B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1670252A (en) * | 2005-03-09 | 2005-09-21 | 南开大学 | Device and method for preparing nanometer oxide nesa by ultrasound rapid deposition method |
| JP2007063059A (en) * | 2005-08-30 | 2007-03-15 | Tohoku Univ | Film depositing method of partially nitrided titanium oxide thin film |
| CN101157021A (en) * | 2007-11-01 | 2008-04-09 | 复旦大学 | A preparation method of visible light active nitrogen doping nanometer titania film |
| CN102534531A (en) * | 2012-01-10 | 2012-07-04 | 清华大学 | Preparation method of titanium dioxide/titanium nitride composite film with adjustable band gaps |
| CN107698171A (en) * | 2017-08-31 | 2018-02-16 | 浙江大学 | A kind of preparation method of TiN coated glasses |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111437857A (en) * | 2019-12-30 | 2020-07-24 | 浙江大学 | Novel photocatalytic film based on titanium nitride and titanium oxide and preparation method thereof |
| CN111437857B (en) * | 2019-12-30 | 2021-06-29 | 浙江大学 | Photocatalytic film based on titanium nitride and titanium oxide and preparation method thereof |
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