CN100515943C - Method for preparing mesoporous silicon dioxide film with macroscopical ordered orientation - Google Patents
Method for preparing mesoporous silicon dioxide film with macroscopical ordered orientation Download PDFInfo
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- CN100515943C CN100515943C CNB200710040754XA CN200710040754A CN100515943C CN 100515943 C CN100515943 C CN 100515943C CN B200710040754X A CNB200710040754X A CN B200710040754XA CN 200710040754 A CN200710040754 A CN 200710040754A CN 100515943 C CN100515943 C CN 100515943C
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Abstract
This invention discloses a method for preparing highly ordered mesoporous SiO2 thin film. The method comprises: preparing periodic microscale or nanoscale groove structure on the thin film surface, preparing sol-gel precursor solution, and preparing mesoporous SiO2 thin film. The method can improve the order of the mesoporous SiO2 thin film, and has such advantages as easy operation, high controllability, and easy mass production. The mesoporous SiO2 thin film can be used as molecular separator, sensor, catalyst carrier and photoelectric material.
Description
Technical field
The present invention relates to the preparation method's in a kind of material technology field, particularly a kind of mesoporous silicon dioxide film with macroscopical ordered orientation preparation method.
Background technology
Mesoporous material is meant the poroid material of the solid of aperture between 2～50nm.Have bigger specific surface area, hydrothermal stability preferably, have very wide application prospect in the fields such as template manufacturing of support of the catalyst, molecular level chemical sensor, optical material, polymer template and noble metal line.But early stage mesoporous material mainly is to exist with the powdery granule body, arrange in the duct is direction-free, making that its application need in absorption, separation and catalytic process is intermittent carries out, and has therefore greatly limited the application of mesoporous material at aspects such as catalysis, separation, optical elements.If mesoporous material can be made continuous membrane structure, its application in these fields will be improved greatly.The powder mesoporous material is difficult to be processed into film, so must directly prepare mesoporous film from atom, molecular level.The mesopore film of early stage preparation all belongs to local orientation's film basically, mesopore orbit still lack of alignment on macroscopic view.But in production field, have only macrostructure to arrange regular directed mesopore film and just have actual using value.The preparation of macroscopic view directional property mesoporous film mainly is a principle of using liquid crystal aligning, promptly by the spatial induction effect of bottom template, makes that the micella of each diversity is qualitative on template to be deposited as macroscopical direction-sense mesoporous film.
Find by prior art documents, Fukumoto H, Nagano S, Kawatsuki N, SekiT. at " Chem.Mater " (" materials chemistry magazine "), 2006,18 phases, polymkeric substance (PPLC) with a kind of light-operated directive action prepares directed mesopore film for template method is disclosed in " Photo-alignment behavior of mesoporous silica thin film synthesized ona photo-crosslinkable polymer film " (" based on the mesoporous silica film light orientation technology of Photocrosslinkable polymeric film substrate ") of 1226-1234 page or leaf, under the irradiation of UV-light, this polymkeric substance is orientated, and utilizes crystal pulling method to prepare mesopore film on the polymkeric substance of orientation then.Because the orientation effect of template makes the mesopore film of preparing that the single-orientated of macroscopic view integral body also be arranged.But this method only can prepare the mesopore film (aperture is between 2-3nm) of aperture warp, and only limits to utilize method of pulling up to prepare mesopore film. and to the mesopore film of aperture about 10nm, this method does not then have effective alignment capability.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of preparation method of mesoporous silicon dioxide film with macroscopical ordered orientation is provided.This method not only can be used for preparing the aperture of aperture about 2-3nm through oriented mesoporous film, and to the mesopore film of aperture about 10nm, also has good orientation property.
The present invention is achieved by the following technical solutions, and concrete steps are as follows:
(1) preparation of film surface periodicity micron or nanometer channel microstructure: is 200nm-600nm with scan mode in the film surface cycle of preparing with Kapton, and the degree of depth is periodicity micron or the nano-scale trenches microstructure of 80nm-150nm.
(2) preparation of sol-gel precursor liquid: the positive tetraethyl orthosilicate in silicon source is added drop-wise in the ethanolic soln of tart tensio-active agent palmityl trimethyl ammonium chloride (perhaps being added drop-wise in the ethanolic soln of tart nonionogenic tenside PEO-PPO-PEO), pH value is 0 to 0.5, form the excessive criticality of alcohol solvent, stir, form the sol-gel precursor liquid of transparent and homogeneous.
(3) preparation of mesopore film: the Kapton of laser treatment is vertically put in the sol-gel precursor liquid for preparing, slowly vertically to lift film (perhaps rotary coating film), on film surface, form the film of macroscopic orientation, through heating and calcining or the directed mesoporous silica film of alcohol extraction preparation with groove microstructure.
In the step (1), described scan mode is as ultraviolet source with pulsed laser.
Described scan mode, its condition is: be 10mJ/cm with the energy
2-65mJ/cm
2, sweep velocity is X-axis 0.01mm/s-0.1mm/s, Y-axis is 5mm/s-8mm/s.
Described ultraviolet source, its wavelength is: 266nm, or 355nm, or 532nm.
In the step (1), described Kapton contains the imide ring structure in the molecule of its polyimide.
In the step (2), described stirring, its whipping temp is: 20 ℃-60 ℃; Described stirring, its churning time is: 1 hour-5 hours.
In the step (3), described lifting, its speed is: 1mm/s-5mm/s.
In the step (3), described rotary coating, its speed of rotation is: 1000 rev/mins-5000 rev/mins.
The surface of inducing formation macroscopical ordered orientation mesopore film that the present invention uses is the surface with uniaxial orientation microstructure, can be applied to grind polymer surfaces, the polymer surfaces of friction treatment and the surface of the microscopic orientation microstructure that organism itself has of polymer surfaces, monochromatic light or two interference of light formation of platen press preparation.
Described tensio-active agent is a cats product, specifically: palmityl trimethyl ammonium chloride; Tensio-active agent is for also can being nonionogenic tenside as PEO-PPO-PEO P123; The silicon source can be positive tetraethyl orthosilicate, also can other metal acid and the ester compound that forms of alcohols.
Described lifting, its dip direction do not influence the degree of orientation that the duct direction still influences the duct direction.The direction in duct is only relevant with the direction of polyimide surface groove microstructure in the mesoporous silica film.
Beneficial effect of the present invention and application thereof:
Prepared the mesoporous silica film that has about wide aperture (10nm) among the present invention, degree of orientation and aperture are approaching through the degree of orientation of (2-3nm) mesopore film.Mesopore film degree of orientation height, face is visited among the result of XRD, and peak width at half height is very narrow, and about 12 degree have illustrated the degree height that is orientated.Improved the time of preparation mesopore film, the spinning solution that the present invention adopts is only with getting final product about 20 seconds.
The method of the macroscopic orientation mesopore film of the high compound with regular structure of quick preparation of the present invention, the macroscopical ordered orientation mesopore film degree of orientation that obtains is very high and arrange along single shaft, stability is very good, the film that makes is complete transparent, and this preparation method easy and simple to handle, be easy to control, required equipment simple, can scale operation, can be used for fields such as molecular separation, transmitter, support of the catalyst, photoelectric material.
Description of drawings
Fig. 1 is the X ray surface sweeping diffractogram of the present invention at θ-2 θ of the macroscopical ordered orientation mesopore film of embodiment 1 preparation.
Fig. 2 is that the present invention visits X-ray diffraction surface sweeping diffractogram at the face of the macroscopic orientation mesoporous SiO 2 film of embodiment 2 preparations.
Fig. 3 is that the face of the macroscopic orientation mesoporous SiO 2 film of the embodiment of the invention 3 preparations is visited X-ray diffraction surface sweeping diffractogram.
Fig. 4 is that the face of the macroscopic orientation mesoporous SiO 2 film of the embodiment of the invention 4 preparations is visited X-ray diffraction surface sweeping diffractogram.
Fig. 5 is that the face of the macroscopic orientation mesoporous SiO 2 film of the embodiment of the invention 5 preparations is visited X-ray diffraction surface sweeping diffractogram.
Fig. 6 is that the face of the macroscopic orientation mesoporous SiO 2 film of the embodiment of the invention 6 preparations is visited X-ray diffraction surface sweeping diffractogram.
Concrete embodiment
Below embodiments of the invention are elaborated: present embodiment has provided detailed embodiment and process being to implement under the prerequisite with the technical solution of the present invention, but protection scope of the present invention is not limited to following embodiment.
(1) 7.6mL silicon source TEOS (positive tetraethyl orthosilicate) is added drop-wise in 1.2g tensio-active agent CTAC (palmityl trimethyl ammonium chloride) ethanolic soln of acidity (PH=0), form the excessive criticality of alcohol solvent, 40 ℃ are stirred the sol-gel precursor liquid that formed transparent and homogeneous in 1 hour down.
(2) with the laser treatment Kapton of 266nm wavelength, laser energy is 10mJ/cm
2, incident angle adopts 15 degree. and sweep velocity adopts X=0.01mm/s, Y=5mm/s.The cycle of obtaining is 200nm, and the degree of depth is the surface micro-structure of 80nm.
The Kapton with periodic micro structure that (3) will prepare is vertically put in the sol solutions, lifts out the glass plate with the speed of 5mm/s, makes to form one deck mesopore film on the glass plate.As shown in Figure 1, be the X ray surface sweeping diffractogram that 360 ° of faces of the macroscopical ordered orientation mesopore film of this examples preparation are visited, the mesopore film orientation degree of acquisition is 95.1%, mesoporous aperture is 3.0nm.
Embodiment 2
Present embodiment 2 is implemented under following implementation condition and technical requirements condition:
(1) 7.6mL silicon source TEOS (positive tetraethyl orthosilicate) is added drop-wise in 1.2g tensio-active agent CTAC (palmityl trimethyl ammonium chloride) ethanolic soln of acidity (PH=0.4), form the excessive criticality of alcohol solvent, 60 ℃ are stirred the sol-gel precursor liquid that formed transparent and homogeneous in 3 hours down.
(2) with the laser treatment Kapton of 355nm wavelength, laser energy is 65mJ/cm
2, incident angle adopts 15 degree. and sweep velocity adopts X=0.01mm/s, Y=8mm/s.The cycle of obtaining is 380nm, and the degree of depth is the surface micro-structure of 105nm.
The Kapton with periodic micro structure that (3) will prepare is vertically put in the sol solutions, lifts out the glass plate with the speed of 1 mm/second, makes to form one deck mesopore film on the glass plate.As shown in Figure 2, be the X ray surface sweeping diffractogram that 360 ° of faces of the macroscopical ordered orientation mesopore film of this examples preparation are visited, the mesopore film orientation degree of acquisition is 95.1%, mesoporous aperture is 3.0nm.
Embodiment 3
Present embodiment 3 is implemented under following implementation condition and technical requirements condition:
(1) 1.9mL silicon source TEOS (positive tetraethyl orthosilicate) is added drop-wise in the 5ml ethanol-hydrochloric acid soln of acidity (PH=0.5). simultaneously 0.5g nonionogenic tenside P123 is dissolved in the 5ml ethanol, form the excessive criticality of alcohol solvent, 20 ℃ are stirred the sol-gel precursor liquid that formed transparent and homogeneous in 5 hours down.
(2) with the laser treatment Kapton of 532nm wavelength, laser energy is 40mJ/cm
2, incident angle adopts 15 degree. and sweep velocity adopts X=0.1mm/s, Y=8mm/s.The cycle of obtaining is 600nm, and the degree of depth is the surface micro-structure of 150nm.
The Kapton with periodic micro structure that (3) will prepare is vertically put in the sol solutions, lifts out the glass plate with the speed of 3 mm/second, makes to form one deck mesopore film on the glass plate.Referring to Fig. 3, be the X ray surface sweeping diffractogram that 360 ° of faces of the macroscopical ordered orientation mesopore film of this examples preparation are visited, the mesopore film orientation degree of acquisition is 95.0%, mesoporous aperture is 3.0nm.
Embodiment 4
Present embodiment 4 is implemented under following implementation condition and technical requirements condition:
(1) 7.6mL silicon source TEOS (positive tetraethyl orthosilicate) is added drop-wise in 1.2g tensio-active agent CTAC (palmityl trimethyl ammonium chloride) ethanolic soln of acidity (PH=0.4), form the excessive criticality of alcohol solvent, 60 ℃ are stirred the sol-gel precursor liquid that formed transparent and homogeneous in 3 hours down.
(2) with the laser treatment Kapton of 355nm wavelength, laser energy is 65mJ/cm
2, incident angle adopts 15 degree. and sweep velocity adopts X=0.01mm/s, Y=8mm/s.The cycle of obtaining is 380nm, and the degree of depth is the surface micro-structure of 105nm.
(3) the sol-gel precursor liquid with configuration drips the polyimide substrate surface that has micro nano structure on the surface, and spin-coating, rotating speed are chosen as 1000 rev/mins, 20s.Referring to shown in Figure 4, be the X ray surface sweeping diffractogram that 360 ° of faces of the macroscopical ordered orientation mesopore film of this examples preparation are visited, the mesopore film orientation degree of acquisition is 93.1%, mesoporous aperture is 3.0nm.
Embodiment 5
Present embodiment 5 is implemented under following implementation condition and technical requirements condition:
(1) 1.9mL silicon source TEOS (positive tetraethyl orthosilicate) is added drop-wise in the 5ml ethanol-hydrochloric acid soln of acidity (PH=0.5). simultaneously 0.5g nonionogenic tenside P123 is dissolved in the 5ml ethanol, form the excessive criticality of alcohol solvent, 20 ℃ are stirred the sol-gel precursor liquid that formed transparent and homogeneous in 3 hours down.
(2) with the laser treatment Kapton of 355nm wavelength, laser energy is 65mJ/cm
2, incident angle adopts 15 degree. and sweep velocity adopts X=0.01mm/s, Y=5mm/s.The cycle of obtaining is 380nm, and the degree of depth is the surface micro-structure of 105nm.
(3) the sol-gel precursor liquid with configuration drips the polyimide substrate surface that has micro nano structure on the surface, and spin-coating, rotating speed are chosen as 5000 rev/mins, 20s.As Fig. 5, be the X ray surface sweeping diffractogram that 360 ° of faces of the macroscopical ordered orientation mesopore film of this examples preparation are visited, the mesopore film orientation degree of acquisition is 94.5%, mesoporous aperture is 9.6nm.
Embodiment 6
Present embodiment 6 is implemented under following implementation condition and technical requirements condition:
(1) 1.9mL silicon source TEOS (positive tetraethyl orthosilicate) is added drop-wise in the 5ml ethanol-hydrochloric acid soln of acidity (PH=0.5). simultaneously 0.5g nonionogenic tenside P123 is dissolved in the 5ml ethanol, form the excessive criticality of alcohol solvent, 20 ℃ are stirred the sol-gel precursor liquid that formed transparent and homogeneous in 3 hours down.
(2) with the laser treatment Kapton of 355nm wavelength, laser energy is 65mJ/cm
2, incident angle adopts 15 degree. and sweep velocity adopts X=0.03mm/s, Y=5mm/s.The cycle of obtaining is 380nm, and the degree of depth is the surface micro-structure of 105nm.
(3) the sol-gel precursor liquid with configuration drips the polyimide substrate surface that has micro nano structure on the surface, and spin-coating, rotating speed are chosen as 3000 rev/mins, 20s.As Fig. 6, be the X ray surface sweeping diffractogram that 360 ° of faces of the macroscopical ordered orientation mesopore film of this examples preparation are visited, the mesopore film orientation degree of acquisition is 94.6%, mesoporous aperture is 9.6nm.
Claims (7)
1. the preparation method of a mesoporous silicon dioxide film with macroscopical ordered orientation is characterized in that, comprises the steps:
(1) the periodically preparation of micron or nanometer channel microstructure of film surface: to be 200nm-600nm as the scan mode of ultraviolet source in the film surface cycle of preparing with pulsed laser, the degree of depth is periodicity micron or the nano-scale trenches microstructure of 80nm-150nm with Kapton;
(2) preparation of sol-gel precursor liquid: the positive tetraethyl orthosilicate in silicon source is added drop-wise in the ethanolic soln of tart tensio-active agent palmityl trimethyl ammonium chloride or is added drop-wise in the ethanolic soln of tart nonionogenic tenside PEO-PPO-PEO, the pH value is 0 to 0.5, form the excessive criticality of alcohol solvent, stir, form the sol-gel precursor liquid of transparent and homogeneous;
(3) preparation of mesopore film: will vertically put in the sol-gel precursor liquid for preparing through the Kapton that step (1) is handled, slowly vertically to lift film or rotary coating film, on film surface, form the film of macroscopic orientation, through heating and calcining or the directed mesoporous silica film of alcohol extraction preparation with groove microstructure.
2. the preparation method of mesoporous silicon dioxide film with macroscopical ordered orientation as claimed in claim 1 is characterized in that, described scan mode, and its condition is: it is 10mJ/cm that pulsed laser is arranged to energy
2～65mJ/cm
2, sweep velocity is X-axis 0.01mm/s～0.1mm/s, Y-axis is 5mm/s～8mm/s.
3. the preparation method of mesoporous silicon dioxide film with macroscopical ordered orientation as claimed in claim 1 is characterized in that, in the step (1), described Kapton contains the imide ring structure in the molecule of its polyimide.
4. the preparation method of mesoporous silicon dioxide film with macroscopical ordered orientation as claimed in claim 1 is characterized in that, in the step (2), and described stirring, its whipping temp is: 20 ℃-60 ℃.
5. as the preparation method of claim 1 or 4 described mesoporous silicon dioxide film with macroscopical ordered orientation, it is characterized in that, described stirring, its churning time is: 1 hour-5 hours.
6. the preparation method of mesoporous silicon dioxide film with macroscopical ordered orientation as claimed in claim 1 is characterized in that, in the step (3), and described lifting, its speed is: 1mm/s-5mm/s.
7. the preparation method of mesoporous silicon dioxide film with macroscopical ordered orientation as claimed in claim 1 is characterized in that, in the step (3), and described rotary coating, its speed of rotation is: 1000 rev/mins-5000 rev/mins.
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