CN101486441A - Preparation of dye / oxide semiconductor hybridized film - Google Patents
Preparation of dye / oxide semiconductor hybridized film Download PDFInfo
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- CN101486441A CN101486441A CNA2009100464999A CN200910046499A CN101486441A CN 101486441 A CN101486441 A CN 101486441A CN A2009100464999 A CNA2009100464999 A CN A2009100464999A CN 200910046499 A CN200910046499 A CN 200910046499A CN 101486441 A CN101486441 A CN 101486441A
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Abstract
The invention relates to a method for preparing dye-oxide semiconductor hybrid films, belonging to the technical field of semiconductor film materials used for photoelectric and photocatalysis effects. A liquid-phase deposition method is adopted to be combined with external field microwave irradiation to prepare oxide semiconductor hybrid films under low temperature; and organic dye molecules are taken as functional groups for decorating the oxide semiconductors and are fixedly loaded in the oxide semiconductor films by a method of electrostatic self-assembly. In the preparing process, assistant external field microwave irradiation is employed to realize the one-step low-temperature construction of the dye-oxide semiconductor hybrid films with higher degree of crystallinity. The prepared dye-oxide semiconductor hybrid films can be applied to photocatalysis, photoelectric conversion, sensor components and other aspects.
Description
Technical field
The present invention relates to a kind of preparation method of dye/oxide semiconductor hybridized film, belong to the semiconductor film material technical field that is used for photoelectric effect and photocatalytic effect.
Background technology
Semiconductor is that electrical conductivity is (10 between conductor and insulator
-10～10
4Ω cm
-1) between material.Because semiconductor has character such as special light, electricity, magnetic, thereby obtained using widely in electronics, chemical industry, medicine, aviation and military field.Along with size of semiconductor material is reduced in the nanometer scale scope, because characteristics such as the quantum size effect of its nanophase, small-size effect, skin effect, macro quanta tunnel effect, make the performance of special optics that they present conventional material and do not possess, electricity, mechanics, catalysis, biological aspect, the special photoelectric effect that particularly nano semiconductor material had makes it show great application prospect in photocatalysis, photoelectric display, opto-electronic conversion etc.
But use more nano semiconductor material (as: TiO at present
2, ZnO, SnO
2Deng) greater band gap, its utilization rate to light is lower, so the researcher attempts adopting, and approach such as ion doping, semiconductor are compound, surface deposition noble metal, dye sensitization comes the modification semi-conducting material.Wherein dye sensitization method is to have visible and near infrared region the organic functional material of very strong absorption band and fluorescence emission peak character to be arranged, as Ru part series dyes, the nano semiconductor material that sensitizing dyestufves such as phthalocyanine series dyes are modified.This method does not change the character of semi-conducting material own, and the dye molecule that only will be adsorbed on semiconductor surface improves its utilization rate to visible light to the response characteristic of visible light and the photoelectric property synergy of semi-conducting material.Chatterjee (AppliedCatalysis B:Environmental, 2001,33 (2): 119-125) wait the TiO that utilizes thionine and eosin W or W S to modify
2Degraded contains colourless organic wastewaters such as phenol, chlorophenol, dichloroethanes, and (50W tungsten lamp, irradiation wavelength have the contaminant degradation above 55-72% after 420 ~ 800nm) 5 hours, obtained good photocatalysis effect at visible light irradiation.(Catalysis Today, 2003,87 (1-4): 77-86) modify TiO such as Moon with acid red 44
2Degradation of phenol solution reaches the purpose of absorption by the conditioned reaction Property of Acid and Alkali of Solution, and thinks that dyestuff is at TiO
2The adsorptivity on surface is the principal element that influences organic dye sensitized photocatalytic activity under the visible light irradiation.As seen, utilize organic dyestuff modification semi-conducting material can improve its interests efficient, but this system cause the photosensitizer loss to environment sensitive, easy desorption, influences the performance of photoelectric properties to visible light.If can be prepared into dye/oxide semiconductor hybridized film with organic dyestuff hydridization in semiconductor substrate, can bring into play organic dyestuff to the visible light individual features, the immobilized structure of hydridization has good weatherability again, can satisfy practical application request.And this dye/oxide semiconductor hybridized film structure also will show great application prospect at aspects such as the storage of solar energy and utilization, sensor clusters.
At present, comparatively Chang Yong hybrid method for manufacturing thin film is colloidal sol-gel method, but this method need be used coating device, and technology is more loaded down with trivial details, can not an one-step film forming.(Adv.Mater.2000 such as Yshida in 1998,12 (16): 1219-1222) reported that the electricity consumption chemical deposition prepares the self-assembled film of ZnO and ZnO/ dyestuff, this method as substrate, prepares oxide semiconductor film with the cathode electrodeposition method with conductive matrices.(Phys.Chem.B 2004,108,8364-8370) reported with the electrochemistry self-assembly method at the synthetic eosin W or W S of FTO electro-conductive glass substrate previous step/ZnO dyestuff hybrid film for T.Oekermann etc.(photographic science and photochemistry, 2005,23 (2): 123-128) also successfully use electrochemical deposition method on ITO (tin indium oxide) electro-conductive glass, such as what Feng Yao with containing zinc chloride (ZnCl
2) doing electrolyte, the dimethyl sulphoxide solution of He perylene dyestuff prepares the dyestuff hybrid film.Compare with other method, electrochemical deposition method can prepare at normal temperatures, and can be on various baroque matrixes uniform deposition, control process conditions (as electric current, current potential, pH value of solution value, temperature, concentration, composition etc.) can accurately be controlled thickness, chemical composition and the structure etc. of sedimentary deposit.But this method must prepare on conductive substrates, and reaction is complicated, the higher needs that are difficult to satisfy the large tracts of land film forming of cost, thereby limited its application.In order to overcome existing preparation method's shortcoming and defect, efficiently utilize dye/oxide semiconductor hybridized film, be badly in need of designing the new dye/oxide semiconductor hybridized film preparation method easy, that practicality is wider.
Summary of the invention
The objective of the invention is provides a kind of technology simple, easy to operate, with low cost in order to overcome some shortcoming and defect of prior art, and can prepare the method for dye/oxide semiconductor hybridized film under cryogenic conditions.
The preparation method of a kind of dye/oxide semiconductor hybridized film of the present invention is characterized in that having following preparation process and step:
A. the cleaning of substrate and activation: being immersed in after at first with deionized water substrate being cleaned up to drip has in the ethanolic solution of hydrochloric acid, and ultrasonic processing 30 minutes, leave standstill 24 hours after, use deionized water rinsing, dry standby; Described base material is glass or PC sheet;
B. prepare reaction solution: the mixed solution of preparing certain density oxide precursor, organic dyestuff and stable compounding ingredient boric acid; Described presoma is metal oxide (NH
4)
2TiF
6Organic dyestuff is any in rhodamine B, Ru part series dyes or the phthalocyanine series dyes; Presoma (NH
4)
2TiF
6With stable compounding ingredient H
3NO
3The molal weight of consumption is than being 1:1～1:1.2; The addition of organic dyestuff by being mete-wand, is 1～2% of ammonium titanium fluoride consumption with the presoma fluotitanic acid;
C. the preparation of dye/oxide semiconductor hybridized film: adopt liquid phase deposition in conjunction with the preparation down of outfield microwave irradiation cryogenic conditions; Put into after the above-mentioned mixed solution for preparing stirred and be with the molten device of water-soluble polytetrafluoroethylene (PTFE), and the substrate of above-mentioned cleaning put in containing to respond mix the described container of shallow lake solution, water-soluble heating 30～50 minutes, heating-up temperature is 60～80 ℃, then container is put into specific microwave generating apparatus, as auxiliary heating, and under the radiation parameter of microwave outfield, system is reacted; Power 400～the 600W of microwave generating apparatus, microwave heating time is 30～40 minutes; After reaction finishes, take out substrate, wash repeatedly the back repeatedly with deionized water and ethanol then and dry naturally, finally make dye/oxide semiconductor hybridized film.
The present invention program's principle or mechanism and characteristics thereof are as described below:
Liquid deposition (LPD) method is a kind of wet chemistry film-forming method that development in recent years is got up.Its reaction mechanism is with preparation TiO
2Film is an example: (NH
4)
2TiF
6The aqueous solution exists following hydrolysising balance:
Add easy and F
-Ionic reaction also forms the H of stable complex
3BO
3, by (2) formula balanced reaction is moved right:
H
3BO
3Consume the F of non-part
-Ion, the and [Ti (OH) that generates that quickens ligand exchange reaction formula (1)
6]
2-, it and substrate surface exist-OH or [Ti (OH)
6]
2-Carry out dehydration condensation each other, on base material, separate out TiO at last
2Film.The cation organic dyestuff can with the TiO of surface fluorination
2Nanocrystalline by static self assembly approach, immobilized in TiO
2In the film.The method can be prepared this novel dyestuff/TiO by a step low temperature
2Hybrid film.
The proposition of liquid phase deposition receives much concern because of its many advantage, but untreated titanium dioxide crystallinity is bad, so photoelectric property is unsatisfactory.The outfield microwave action can reduce the requirement to reaction temperature greatly.The microwave irradiation method is an another kind of system film wet chemistry method commonly used, and its principle is the volume heating that material causes because of dielectric loss own in electromagnetic field, can be used as a kind of novel mode of heating and is applied to the processing of material with synthetic.Its major advantage is to the reaction system heating rapidly, evenly not have thermograde, thereby the local condition of reaction is improved, and the nano particle specific area of preparation is big, particle diameter is little, Size Distribution is more even.Shine with the microwave electron line, reaction temperature only needs 60 ℃ just can make anatase type nano TiO
2Film, the sample without microwave treatment under the synthermal condition does not then almost have the anatase generation.Liquid phase deposition and outfield microwave irradiation are effectively made up in conjunction with one step of low temperature that can real dye/oxide semiconductor hybridized film.
The present invention's employing in conjunction with the outfield microwave irradiation, can directly prepare the high dye/oxide semiconductor hybridized film of degree of crystallinity with liquid phase deposition in substrate under cryogenic conditions.
Advantage of the present invention is as described below:
1) method of dye/oxide semiconductor hybridized film of the present invention, it is simple, stable, with low cost, easy to operate to have technology, but the good reproducibility film formation at low temp, and characteristics such as degree of crystallinity height;
2) adopt liquid deposition (LPD) method in conjunction with the outfield microwave irradiation, by the static self assembly effect between organic dyestuff and oxide semiconductor nanocrystalline, the step low temperature that realization has the dye/oxide semiconductor hybridized film of higher crystallinity makes up;
3) the inventive method can be on various types of substrates film forming, not limited by shapes of substrates, type and character, and the transparency is good, expanded the range of application of dye/oxide semiconductor hybridized film.
Description of drawings
Fig. 1 is the dyestuff/TiO of gained in the embodiment of the invention
2The SEM of hybrid film (SEM) photo figure.
Fig. 2 is the dyestuff/TiO of gained in the embodiment of the invention
2The X-ray diffraction of hybrid film (XRD) spectrogram.
The specific embodiment
After now specific embodiments of the invention being described in.
Embodiment 1
At first have in the ethanolic solution of hydrochloric acid being immersed in after cleaning up at the bottom of the glass chip to drip, and ultrasonic processing 30 minutes, left standstill 24 hours, use deionized water rinsing, dry standby;
Take by weighing titania precursor body ammonium titanium fluoride (NH
4)
2TiF
6, boric acid and each raw material of dyestuff rhodamine B, each raw material all measures with the molal weight number; Ammonium titanium fluoride is 40mM, and boric acid is 40mM, and the dyestuff rhodamine B is 0.8mM, the three is mixed with the mixed solution of 50mM; Put into the polytetrafluoroethylene beaker that is with water-bath after then it being stirred, and put at the bottom of the glass chip with above-mentioned cleaning in the polytetrafluoroethylene beaker that contains the mixed solution that responds, water-bath heating 30 minutes, heating-up temperature is 70 ℃.
Then beaker is put into specific microwave generating apparatus,, and under the radiation parameter of microwave outfield, system is reacted as auxiliary heating; The power of microwave generating apparatus is 500W, and heating-up temperature is 60 ℃, and microwave heating time is 35 minutes; After reaction finishes, take out at the bottom of the glass chip, dry naturally after washing three times repeatedly with deionized water and ethanol then, finally make dyestuff/titanium oxide semiconductor hybridized film.
Through observing, making product is the dyestuff Luo Ming B/TiO that surface particles is evenly distributed, crystallization degree is higher
2Hybrid film.The adding of rhodamine B makes hybrid film strengthen the absorption of the visible light in 400～500nm scope.
Dyestuff rhodamine TiO to gained in the foregoing description
2Hybrid film carries out instrument detecting, and SEM that obtains and XRD figure are seen Fig. 1 and Fig. 2.
Fig. 1 is the scanning electron microscope image (SEM) of this hybrid film.The surface particles of film is evenly distributed as can be seen from Figure, crystallization degree is higher, average grain diameter is about 15nm, certain reunion has appearred in little crystal grain, form finely dispersed aggregate, be similar to the mastoid process structure of lotus leaf surface, this structure can effectively improve the specific area of film, helps improving TiO
2The photocatalysis effect of film.Fig. 2 is dyestuff/TiO
2Hybrid film is made the XRD figure of powder.As seen from Figure 2, sample is pure anatase phase TiO
2, its angle of diffraction 2 θ are 25.42 °, 37.82 ° belong to anatase (101) mutually respectively, (004) and (200) crystal face diffraction maximum with 47.64 °.The sample crystallite dimension is 13.2nm to utilize the Scherrer formula to calculate as can be known.
Claims (1)
1, a kind of preparation method of dye/oxide semiconductor hybridized film is characterized in that having following preparation process and step:
A. the cleaning of substrate and activation: being immersed in after at first with deionized water substrate being cleaned up to drip has in the ethanolic solution of hydrochloric acid, and ultrasonic processing 30 minutes, leave standstill 24 hours after, use deionized water rinsing, dry standby; Described base material is glass or PC sheet;
B. prepare reaction solution: the mixed solution of preparing certain density oxide precursor, organic dyestuff and stable compounding ingredient boric acid; Described presoma is metal oxide (NH
4)
2TiF
6Organic dyestuff is any in rhodamine B, Ru part series dyes or the phthalocyanine series dyes; Presoma (NH
4)
2TiF
6With stable compounding ingredient H
3NO
3The molal weight of consumption is than being 1:1～1:1.2; The addition of organic dyestuff by being mete-wand, is 1～2% of ammonium titanium fluoride consumption with the presoma fluotitanic acid;
C. the preparation of dye/oxide semiconductor hybridized film: adopt liquid phase deposition in conjunction with the preparation down of outfield microwave irradiation cryogenic conditions; Put into after the above-mentioned mixed solution for preparing stirred and be with the molten device of water-soluble polytetrafluoroethylene (PTFE), and the substrate of above-mentioned cleaning put in containing to respond mix the described container of shallow lake solution, water-soluble heating 30～50 minutes, heating-up temperature is 60～80 ℃, then container is put into specific microwave generating apparatus, as auxiliary heating, and under the radiation parameter of microwave outfield, system is reacted; Power 400～the 600W of microwave generating apparatus, microwave heating time is 30～40 minutes; After reaction finishes, take out substrate, wash repeatedly the back repeatedly with deionized water and ethanol then and dry naturally, finally make dye/oxide semiconductor hybridized film.
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|---|---|---|---|
| CNA2009100464999A CN101486441A (en) | 2009-02-24 | 2009-02-24 | Preparation of dye / oxide semiconductor hybridized film |
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|---|---|---|---|
| CNA2009100464999A CN101486441A (en) | 2009-02-24 | 2009-02-24 | Preparation of dye / oxide semiconductor hybridized film |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102210917A (en) * | 2010-04-02 | 2011-10-12 | 北京化工大学 | Application of polyoxometallate containing Keplerate in carrying out heterogeneous photocatalytic degradation on rhodamine B |
| CN102503558A (en) * | 2011-11-23 | 2012-06-20 | 陕西科技大学 | Method for preparing LiFePO4 nano-film by using biomimetic method |
| CN102503553A (en) * | 2011-11-23 | 2012-06-20 | 陕西科技大学 | Sm2S3 film preparation method integrating microwave hydrothermal method and auxiliary liquid-phase self-assembling method |
-
2009
- 2009-02-24 CN CNA2009100464999A patent/CN101486441A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102210917A (en) * | 2010-04-02 | 2011-10-12 | 北京化工大学 | Application of polyoxometallate containing Keplerate in carrying out heterogeneous photocatalytic degradation on rhodamine B |
| CN102210917B (en) * | 2010-04-02 | 2012-12-12 | 北京化工大学 | Application of polyoxometallate containing Keplerate in carrying out heterogeneous photocatalytic degradation on rhodamine B |
| CN102503558A (en) * | 2011-11-23 | 2012-06-20 | 陕西科技大学 | Method for preparing LiFePO4 nano-film by using biomimetic method |
| CN102503553A (en) * | 2011-11-23 | 2012-06-20 | 陕西科技大学 | Sm2S3 film preparation method integrating microwave hydrothermal method and auxiliary liquid-phase self-assembling method |
| CN102503558B (en) * | 2011-11-23 | 2013-08-07 | 陕西科技大学 | Method for preparing LiFePO4 nano-film by using biomimetic method |
| CN102503553B (en) * | 2011-11-23 | 2013-08-14 | 陕西科技大学 | Sm2S3 film preparation method integrating microwave hydrothermal method and auxiliary liquid-phase self-assembling method |
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Open date: 20090722 |