CN102888598A - Preparation method of titanium dioxide based selective absorbing thin film - Google Patents
Preparation method of titanium dioxide based selective absorbing thin film Download PDFInfo
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- CN102888598A CN102888598A CN201210385538XA CN201210385538A CN102888598A CN 102888598 A CN102888598 A CN 102888598A CN 201210385538X A CN201210385538X A CN 201210385538XA CN 201210385538 A CN201210385538 A CN 201210385538A CN 102888598 A CN102888598 A CN 102888598A
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- tetrabutyl titanate
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Abstract
The invention relates to a preparation method of a titanium dioxide based selective absorbing thin film; according to the method, the thin film is plated on a substrate by using a sol-gel method, then the thin film is thermally treated under a high-volume condition in order to enable the organisms in a thin film precursor to carbonize partially or completely, as a result, a conductive network and independent carbon particles are formed in a TiO2 substrate; the obtained titanium dioxide based thin film has higher selectively spectrum absorbency (namely absorbency in a visible spectrum area) and has higher reflectivity in a middle-far infrared area. The preparation method is simple in process, does not need any expensive equipment, is low in cost, can coat the film on the substrate in any shape, and is beneficial for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of titania-based selection absorbing membrane, select the preparation method of absorbing membrane in particular for solar spectrum.
Background technology
Solar spectrum selects absorbing film to require to have higher specific absorption at 300nm～3000nm wave band, can change sun power into heat energy, has higher reflectivity at the mid and far infrared wave band again simultaneously, the calorific loss that causes to reduce self thermal radiation.Because material is the result of free carrier and Electromagnetic Field in mid and far infrared wave band radiant ratio, so radiant ratio is directly related with film conductivity.Tradition selects absorbing membrane extensively to adopt cascaded structure, namely is coated with dielectric material film in metal substrate, utilizes metal to have higher specific conductivity to obtain low-E, utilizes dielectric material film to obtain high spectral absorption.But such film cording has multi-layer film structure, complex process, and the control difficulty increases, and cost is higher.
TiO
2Be a kind of wide bandgap semiconductor, its energy gap is generally 3.0eV～3.2eV, under UV-light activity is arranged, and can produce a large amount of photoelectrons and hole, has very strong redox ability.TiO
2Have good chemical stability, mechanical property, simultaneously cheap, therefore be used widely in the function film field.While TiO
2Have and hold preferably performance, the TiO in its structure
6Octahedral structure can be adjusted structure by the mode such as vert, and is a kind of preferably body material.These characteristics make TiO
2Preparing individual layer as matrix selects absorbing membrane to become possibility.
Summary of the invention
The object of the present invention is to provide a kind of with low cost, easy and simple to handle, preparation method of being easy to the titania-based selection absorbing membrane of individual layer that the industrialization big area produces.
The preparation method of titania-based selection absorbing membrane of the present invention may further comprise the steps:
1) base-plate cleaning is clean;
2) tetrabutyl titanate and additive are mixed, additive and tetrabutyl titanate mol ratio are 0.2～1.0, obtain solution A; Described additive is methyl ethyl diketone or dimethyl formamide;
Catalyzer, water and carbon source additive are put into ethanol, mix, obtain B solution; The mol ratio of catalyzer and tetrabutyl titanate is 0.05～1.0, and the mol ratio of water and tetrabutyl titanate is 2.0～10, and carbon source additive and tetrabutyl titanate mass ratio are 0.5～2.0; Described catalyzer is acetic acid, Whitfield's ointment or ammoniacal liquor; The carbon source additive is the polyoxyethylene glycol (PEG-2000) of molecular weight 2000 or the Povidone (PVP-K30) of K30 standard;
3) with step 2) B solution dropwise add in the A solution, mix, configuration tetrabutyl titanate concentration is the colloidal sol of 0.01mol/L～0.5mol/L take ethanol as solvent;
4) with step 3) colloidal sol that obtains ageing 12h～100h at room temperature;
5) utilize the spin coating instrument that gel is spin-coated on step 1) substrate on, drying, the volatilization remove ethanol, obtain dry film;
6) with step 5) dry film that obtains heat-treats, 400 ℃～700 ℃ of thermal treatment temps, vacuum tightness is not less than 10
-3Pa, soaking time is 30min～120min.
Above-mentioned substrate can be glass slide, silica glass or silicon chip.
The thickness of titania-based selection absorbing membrane can be by spin coating number of times and rotating speed control.
For the cleaning of substrate, general step is as follows among the present invention: deionized water immersion → sonic oscillation washing → volume fraction be 15% the salt acid soak → sonic oscillation washing → acetone immersion → sonic oscillation washing → alcohol immersion → sonic oscillation washs → is stored in the ethanol stand-by.
The present invention is by using sol-gel processing plated film on substrate, then film is heat-treated the partially or completely carbonization of organism that makes in the film presoma under vacuum condition, form conductive carbon network and discrete carbon granule, wherein the carbon network has preferably electroconductibility, and low radiance is provided; Discrete carbon granule is the amorphous structure of piling up, and has good spectrum and selects absorptivity, and the high-absorbable energy is provided.Thereby the titanium dioxide base film that makes acquisition has better spectrum selects absorptivity, namely has better specific absorption in the visible range, has higher reflectivity at mid and far infrared.Present device is simple, easily on various difform substrates film forming, materials are few, cost is low, are suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the SEM section picture of the titania-based selection absorbing membrane of example 1.
Fig. 2 is the transmitted spectrum of the titania-based selection absorbing membrane of example 1.
Fig. 3 is the SEM section picture of the titania-based selection absorbing membrane of example 2.
Fig. 4 is the transmitted spectrum of the titania-based selection absorbing membrane of example 2.
Fig. 5 is the SEM section picture of the titania-based selection absorbing membrane of example 3.
Fig. 6 is the transmitted spectrum of the titania-based selection absorbing membrane of example 3.
Embodiment
Further specify the present invention below in conjunction with examples of implementation.
Embodiment 1:
1) cleans quartz base plate: quartz base plate is soaked the salt acid soak 2h of 2h → sonic oscillation washing 15min → volume fraction 15% → sonic oscillation washing 15min → acetone at deionized water soak 1h → sonic oscillation washing 15min → alcohol immersion 1h → sonic oscillation washing 15min → be stored in the ethanol stand-by;
2) tetrabutyl titanate and methyl ethyl diketone are stirred, the mol ratio of methyl ethyl diketone and tetrabutyl titanate is 0.5, obtains A solution;
PEG-2000, acetic acid and water are put into ethanol, mix, obtain B solution; The mass ratio of PEG-2000 and tetrabutyl titanate is 1.0, and the mol ratio of acetic acid and tetrabutyl titanate is 0.2, and the mol ratio of water and tetrabutyl titanate is 4;
3) with step 2) in B solution dropwise add in the A solution, mix, configuration tetrabutyl titanate concentration is the colloidal sol of 0.25mol/L take ethanol as solvent;
4) with step 3) in the colloidal sol that obtains ageing 24h at room temperature;
5) utilize the spin coating instrument that gel is spin-coated on step 1) quartz base plate on, its rotating speed is 30s under the even glue 9s of 1000r/min and the 3000r/min, at 70 ℃ of dry 10min, volatilization is removed ethanol and is obtained dry film;
6) repetition above-mentioned steps 5) 3 times, again dry film to be heat-treated under high vacuum, thermal treatment temp is 550 ℃, vacuum tightness is 10
-4Pa, soaking time is 90min.
This example obtains the titanium dioxide based conductive film with scanning electronic microscope Hitachi S-4800(SEM) observe its section picture and see Fig. 1, film thickness is about 113 nm as can be known; Use elliptic polarization spectrometer Semilab GES_5E(SE) measuring its ultraviolet-visible transmitted spectrum sees Fig. 2, and its average transmittance is lower than 30%.
The resistivity of film adopts the method for four point probe to measure, and its instrument model is ST-2258A type digital multifunctional four point probe tester, its test result such as table 1, and the resistivity of film reaches 10
-3The Ω cm order of magnitude illustrates that this film has good conductivity, can ensure lower radiant ratio.
Table 1: four probe method is surveyed the electrical properties that characterizes its film
| Annealing atmosphere | Square resistance (Ω/) | Thickness (nm) | Resistivity (Ω cm) |
| 10 -4Pa | 95 | 113 | 1.07*10 -3 |
Embodiment 2:
1) cleans quartz base plate: quartz base plate is soaked the salt acid soak 2h of 2h → sonic oscillation washing 15min → volume fraction 15% → sonic oscillation washing 15min → acetone at deionized water soak 1h → sonic oscillation washing 15min → alcohol immersion 1h → sonic oscillation washing 15min → be stored in the ethanol stand-by;
2) tetrabutyl titanate and dimethyl formamide are stirred, the mol ratio of dimethyl formamide and tetrabutyl titanate is 0.2, obtains A solution;
PVP-K30, Whitfield's ointment and water are put into ethanol, mix, obtain B solution; The mass ratio of PVP-K30 and tetrabutyl titanate is 0.5, and the mol ratio of Whitfield's ointment and tetrabutyl titanate is 1.0, and the mol ratio of water and tetrabutyl titanate is 2;
3) with step 2) in B solution dropwise add in the A solution, mix, configuration tetrabutyl titanate concentration is the colloidal sol of 0.5mol/L take ethanol as solvent;
4) with step 3) in the colloidal sol that obtains ageing 12h at room temperature;
5) utilize the spin coating instrument that gel is spin-coated on step 1) quartz base plate on, its rotating speed is 30s under the even glue 9s of 1000r/min and the 3000r/min, at 70 ℃ of dry 10min, volatilization is removed ethanol and is obtained dry film;
6) repetition above-mentioned steps 5) 3 times, again dry film to be heat-treated under high vacuum, thermal treatment temp is 400 ℃, vacuum tightness is 10
-4Pa, soaking time is 30min.
This example obtains the titanium dioxide based conductive film and observes its section picture with SEM and see Fig. 3, and film thickness is about 350 nm as can be known; Use SE to measure its ultraviolet-visible transmitted spectrum and see Fig. 4, its average transmittance is lower than 15%.
The resistivity of film adopts the method for four point probe to measure, its test result such as table 2, and the resistivity of film reaches 10
-3The Ω cm order of magnitude illustrates that this film has good conductivity, can ensure lower radiant ratio.
Table 2: four probe method is surveyed the electrical properties that characterizes its film
| Annealing atmosphere | Square resistance (Ω/) | Thickness (nm) | Resistivity (Ω cm) |
| 10
-4 |
60 | 350 | 2.1*10 -3 |
Embodiment 3:
1) cleans quartz base plate: quartz base plate is soaked the salt acid soak 2h of 2h → sonic oscillation washing 15min → volume fraction 15% → sonic oscillation washing 15min → acetone at deionized water soak 1h → sonic oscillation washing 15min → alcohol immersion 1h → sonic oscillation washing 15min → be stored in the ethanol stand-by;
2) tetrabutyl titanate and methyl ethyl diketone are stirred, the mol ratio of methyl ethyl diketone and tetrabutyl titanate is 1.0, obtains A solution;
PVP-K30, ammoniacal liquor and water are put into ethanol, mix, obtain B solution; The mass ratio of PVP-K30 and tetrabutyl titanate is 2.0, and the mol ratio of ammoniacal liquor and tetrabutyl titanate is 0.05, and the mol ratio of water and tetrabutyl titanate is 10;
3) with step 2) in B solution dropwise add in the A solution, mix, configuration tetrabutyl titanate concentration is the colloidal sol of 0.01mol/L take ethanol as solvent;
4) with step 3) in the colloidal sol that obtains ageing 100h at room temperature;
5) utilize the spin coating instrument that gel is spin-coated on step 1) quartz base plate on, its rotating speed is 30s under the even glue 9s of 1000r/min and the 3000r/min, at 70 ℃ of dry 10min, volatilization is removed ethanol and is obtained dry film;
6) repetition above-mentioned steps 5) 3 times, again dry film to be heat-treated under high vacuum, thermal treatment temp is 700 ℃, vacuum tightness is 10
-4Pa, soaking time is 120min.
This example obtains the titanium dioxide based conductive film and observes its section picture with SEM and see Fig. 5, and film thickness is about 240 nm as can be known; Use SE to measure its ultraviolet-visible transmitted spectrum and see Fig. 6, its average transmittance is lower than 20%.
The resistivity of film adopts the method for four point probe to measure, its test result such as table 3, and the resistivity of film reaches 10
-3The Ω cm order of magnitude illustrates that this film has good conductivity, can ensure lower radiant ratio.
Table 3: four probe method is surveyed the electrical properties that characterizes its film
| Annealing atmosphere | Square resistance (Ω/) | Thickness (nm) | Resistivity (Ω cm) |
| 10
-4 |
70 | 240 | 1.68*10 -3 |
Claims (2)
1. the preparation method of a titania-based selection absorbing membrane is characterized in that may further comprise the steps:
1) base-plate cleaning is clean;
2) tetrabutyl titanate and additive are mixed, additive and tetrabutyl titanate mol ratio are 0.2～1.0, obtain solution A; Described additive is methyl ethyl diketone or dimethyl formamide;
Catalyzer, water and carbon source additive are put into ethanol, mix, obtain B solution; The mol ratio of catalyzer and tetrabutyl titanate is 0.05～1.0, and the mol ratio of water and tetrabutyl titanate is 2.0～10, and carbon source additive and tetrabutyl titanate mass ratio are 0.5～2.0; Described catalyzer is acetic acid, Whitfield's ointment or ammoniacal liquor; The carbon source additive is the polyoxyethylene glycol of molecular weight 2000 or the Povidone of K30 standard;
3) with step 2) B solution dropwise add in the A solution, mix, configuration tetrabutyl titanate concentration is the colloidal sol of 0.01mol/L～0.5mol/L take ethanol as solvent;
4) with step 3) colloidal sol that obtains ageing 12h～100h at room temperature;
5) utilize the spin coating instrument that gel is spin-coated on step 1) substrate on, drying, the volatilization remove ethanol, obtain dry film;
6) with step 5) dry film that obtains heat-treats, 400 ℃～700 ℃ of thermal treatment temps, vacuum tightness is not less than 10
-3Pa, soaking time is 30min～120min.
2. the preparation method of titania-based selection absorbing membrane according to claim 1 is characterized in that described substrate is glass slide, silica glass or silicon chip.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753336A (en) * | 2016-01-25 | 2016-07-13 | 浙江大学 | Carbon-nickel oxide composite thin film with array porous structure on surface and preparation method of thin film |
| WO2021082261A1 (en) * | 2019-10-31 | 2021-05-06 | 山东大学 | Method for preparing micro structure on glass surface with titanium dioxide nanoparticles assisted by infrared nanosecond laser |
| CN113913898A (en) * | 2021-09-16 | 2022-01-11 | 浙江大学 | TiO 22Reflection type electrochromic film and preparation method thereof |
| CN115677234A (en) * | 2022-10-25 | 2023-02-03 | 华东理工大学 | Preparation method of near-infrared laser radar high-wear-resistance antireflection film and antireflection film |
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| CN1563490A (en) * | 2004-04-20 | 2005-01-12 | 清华大学 | Titania thin film possessing high catalytic activity under visible light and preparation method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753336A (en) * | 2016-01-25 | 2016-07-13 | 浙江大学 | Carbon-nickel oxide composite thin film with array porous structure on surface and preparation method of thin film |
| CN105753336B (en) * | 2016-01-25 | 2018-01-16 | 浙江大学 | A kind of surface has carbon-oxidation nickel composite film of array loose structure and preparation method thereof |
| WO2021082261A1 (en) * | 2019-10-31 | 2021-05-06 | 山东大学 | Method for preparing micro structure on glass surface with titanium dioxide nanoparticles assisted by infrared nanosecond laser |
| US11952307B2 (en) | 2019-10-31 | 2024-04-09 | Shandong University | Method for preparing microstructure on surface of glass by titanium oxide nanoparticle-assisted infrared nanosecond laser |
| CN113913898A (en) * | 2021-09-16 | 2022-01-11 | 浙江大学 | TiO 22Reflection type electrochromic film and preparation method thereof |
| CN115677234A (en) * | 2022-10-25 | 2023-02-03 | 华东理工大学 | Preparation method of near-infrared laser radar high-wear-resistance antireflection film and antireflection film |
| CN115677234B (en) * | 2022-10-25 | 2024-04-19 | 华东理工大学 | Preparation method of near-infrared laser radar high-wear-resistance antireflection film and antireflection film |
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Application publication date: 20130123 |