CN100366665C - Method for preparing inorganic semi-conductor/ conducting polymer composite film by photocatalyzed polymerization - Google Patents

Method for preparing inorganic semi-conductor/ conducting polymer composite film by photocatalyzed polymerization Download PDF

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CN100366665C
CN100366665C CNB200510112195XA CN200510112195A CN100366665C CN 100366665 C CN100366665 C CN 100366665C CN B200510112195X A CNB200510112195X A CN B200510112195XA CN 200510112195 A CN200510112195 A CN 200510112195A CN 100366665 C CN100366665 C CN 100366665C
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polymerization
semiconductor film
semiconductor
present
inorganic
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CN1807492A (en
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倪秀元
翁臻
王皎
赖博杰
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Fudan University
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Fudan University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The present invention belongs to the technical field of nanometer science, photochemistry and macromolecular materials, and more specifically, the present invention relates to an inorganic semiconductor /conductive polymer composite film which is prepared by photocatalysis polymerization and a preparation method thereof. Firstly, a semiconductor film is prepared on the surface of an inorganic base material; then the semiconductor film is excited by ultraviolet light, excited nanometer crystals initiate the polymerization of monomers of conducting high molecules, and thereby, a conducting polymer layer is formed on semiconductor film. The present invention prepares inorganic semiconductor/ organic conducting high molecule composite films, and the polymer layers are firmly combined with the surfaces of the semiconductor films. The composite films of the present invention can be used for photoelectric conversion devices, such as solar cells, flat panel displays, etc., and gas sensitive sensors, etc.

Description

The photochemical catalysis polymerization prepares the method for inorganic semi-conductor/conducting polymer laminated film
Technical field
The invention belongs to nano science, photo chemistry technology and technical field of polymer materials, be specifically related to a kind of method of utilizing the photochemical catalysis polymerization to prepare the inorganic semi-conductor/conducting polymer laminated film.
Background technology
Opto-electronic conversion comprises the conversion (as solar cell) of luminous energy to electric energy, and electric energy is to the conversion (showing photodiode as the plane) of luminous energy.Conducting polymer mostly is black or dark material, Burroughes in nineteen ninety found conducting polymer electro optical phenomenon (Nature, 1990,347:539).It is found that subsequently inorganic semiconductor/organic conductive macromolecule matrix material has shown very strong synergy aspect photoelectric properties, have great application prospect (Science, 1995,270:315 in fields such as optics, electronics, information storage; Science, 1995,270:335).
Solar cell is an application example of inorganic semiconductor/organic conductive macromolecule matrix material, because the petroleum-based energy crisis that is on the rise, the variation of the energy is very necessary and urgent, solar cell thereby enjoy people to pay close attention to.Semiconductor material as solar cell must have suitable energy gap, could absorb sunlight effectively, produce photoelectron, and inorganic semiconductor has the broad stopband feature usually, and the visible light energy loss is big, causes photoelectric transformation efficiency low; TiO for example 2Semi-conductive energy gap can only absorbing wavelength be lower than the photon of 420nm about 3.2eV.Conductive polymers is the polymer with pi-conjugated structure, and its energy gap can be controlled by the structure of change or fine setting polymkeric substance.After inorganic semiconductor/organic conductive macromolecule matrix material was excited by sunlight, conducting polymer can produce photoelectron, and was injected into the conduction band of inorganic semiconductor rapidly, produced sensibilized to inorganic semiconductor, can improve optical efficiency (Langmuir, 2005,21:4123 significantly; High chemical journal, 1997,7:1219; Electrochemistry, 2001,7:102).
Summary of the invention
The purpose of this invention is to provide a kind of inorganic semiconductor/organic conductive macromolecule laminated film and preparation method thereof.
The present invention is at first at inorganic substrate surface preparation Nano semiconductor film, utilize the ultraviolet light irradiation semiconductor film then, the nanocrystal of film surface is stimulated, and causes the monomer generation polymerization of conducting polymer, thereby forms conductive polymer coating at semiconductor film.
What the present invention was prepared is the laminated film of inorganic semiconductor/organic conductive macromolecule, and polymer layer combines securely with the semiconductor film surface.Laminated film of the present invention can be used for electrooptical devices such as solar cell, plane demonstration, and the gas sensitization transmitter etc.
Principle of the present invention is a ultraviolet excitation inorganic semiconductor film, under the initiation of nano surface crystalline substance, the monomer generation polymerization of pi-conjugated structure at the electroconductive polymer layer of semiconductor film surface formation with surperficial mortise, obtains inorganic semiconductor/organic conductive polymer composite film.
According to the present invention, prepared inorganic semiconductor/organic conductive polymer composite film is made up of following structure:
(1) is plated on the semiconductor film on inorganic substrate surface;
(2) with the organic conductive polymer layer of semiconductor film surface bonding.
According to the present invention, can adopt conventional sol-gel process or magnetically controlled sputter method at inorganic substrate coating surface semiconductor film.The semiconductor film surface has the columnar nanometer crystal structure, and the grain crystalline substance is the 10-100 nanometer.Said semi-conductor has photocatalytic, is following one or more: TiO 2, ZnO, Fe 2O 3, WO 3, SnO 2, SrTiO 3, CdSe, CdS, ZnS, V 2O 5, MoO 3, PbS, MoSi 2, Nb 2O 5Or Bi 2O 3Sharp ore deposit type TiO 2Be preferred.When adopting sol-gel method when glass surface prepares titanium deoxid film, persursor material is a titanic acid ester, acid hydrolysis.The employing temperature programming is heat-treated, 100-200 ℃ of oven dry 30 minutes, then 500-600 ℃ of insulation 1 hour.According to atomic force microscope observation, the semiconductor film surface has the columnar nanometer crystal structure, and particle diameter is the 10-100 nanometer.
The preparation method of the said inorganic semiconductor of the present invention/organic conductive macromolecule laminated film is as follows:
(1) inorganic substrate that the surface is coated with semiconductor film is placed in the reaction solution that contains polymer monomer;
(2) with containing ultraviolet light source above-mentioned reaction system is implemented irradiation, 1 minute-10 hours time;
(3) temperature of reaction is 5-100 ℃.
Among the present invention, nanocrystalline ultraviolet excitation, the generation photo-generated carrier, thereby trigger monomer polymerization of being subjected to of semiconductor film.
Described reaction solution is formed (weight percent) by following ingredients:
(1) polymerization single polymerization monomer: 0.1-100%
(2) thinner; 0-99.9%
Among the present invention, monomer content (weight percent) is 100% o'clock, shows it is to adopt mass polymerization.
The said polymerization single polymerization monomer of the present invention is the compound that has pi-conjugated structure, and formed polymkeric substance is called conducting polymer.
The compound of the said pi-conjugated structure of the present invention can be but be not limited to one or more of following compounds: pyrroles, aniline, thiophene, O-Phenylene Diamine, thioxene, trimethylthiophene or contain substituent derivative.Pyrroles, aniline are preferred.
Thinner in the reaction solution is a kind of of water, methyl alcohol, ethanol, propyl alcohol, butanols, acetone, ether, toluene or dimethylbenzene, or wherein several mixtures.Water and ethanol water mixed solvent are preferred.
The present invention's employing contains ultraviolet light source reaction system is carried out irradiation, and wherein ultraviolet light source can be high voltage mercury lamp, medium pressure mercury lamp, low pressure mercury lamp, xenon lamp, luminescent lamp, halogen tungsten lamp or sunlight.Said ultraviolet ray is that wavelength is the monochromatic ray or the multifrequency light of 200-450 nanometer.Wavelength is that the monochromatic ray or the multifrequency of 300-450 nanometer is only preferred.
Among the present invention, light source can be positioned over the reactor outside or place inside reactor.
After reacting as stated above, the inorganic substrate print to be taken out from reaction solution, electroconductive polymer layer is contained on the print surface, promptly obtains inorganic semiconductor/organic conductive macromolecule laminated film.The original color of print color and conducting polymer is identical or approaching.
By the inorganic semiconductor/organic conductive macromolecule laminated film of the present invention's preparation, in conjunction with firm, print boils in water or adopts organic solvent to soak, and electroconductive polymer layer does not come off, the print nondiscoloration.
Among the present invention, the direct trigger monomer polymerization of semiconductor film does not need to add any other organic or inorganic initiator, and technology is easy, and prepared conductive polymer film and inorganic semiconductor surface mortise.
Embodiment
Embodiment 1
Tetrabutyl titanate is mixed with ethanol, water, and add a small amount of hydrolysis catalyst concn hydrochloric acid, be mixed with colloid.Adopt the proofing crystal pulling method at glass print surface preparation TiO 2Coating.The glass print 100 ℃ of down oven dry 30 minutes, 500 ℃ of sintering temperatures 1 hour, is obtained transparent print, titanium dioxide (TiO then 2) surface thickness 120 nanometers of film, the equal particle diameter of nano surface Jinping is the 10-100 nanometer.
Reactor is furnished with whipping appts, recycle pump and nitrogen protection.With mass concentration is that 1% pyrroles adds in the reactor, and thinner is a water, stirs then.The glass print that is coated with titanium dioxide is placed glass reactor, sealed reactor.Logical nitrogen was opened ultraviolet and is placed the outer high voltage mercury lamp of reactor after 10 minute, and temperature is controlled at 40 ℃, reacts and takes out print after 5 hours, and print is a light/dark balance.(LabRam-1B Dilor) has confirmed that the upper layer material is a polypyrrole to use infrared spectra (Magna-IRTM550) and Raman spectrum.With scanning electron microscopic observation print section structure, the mean thickness that obtains polypyrrole layer is 115 nanometers.
Embodiment 2
Pyrroles's mass concentration is 20% in the reaction solution, reacts 5 hours, and other condition is identical with embodiment 1 with step.Made print is a black, and the mean thickness of polypyrrole layer is 235 nanometers.
Embodiment 3
Pyrroles's mass concentration is 100% (being mass polymerization) in the reaction solution, and the reaction times is 10 minutes, and other condition is identical with step embodiment 1.Made print is a black, and the mean thickness of polypyrrole layer is 560 nanometers.
Embodiment 4
Pyrroles's mass concentration is 1% in the reaction solution, and the glass print that is coated with CdS is placed glass reactor, and the reaction times is 2 hours, and other condition is identical with embodiment 1 with step.Made print is a black, and the mean thickness of polypyrrole layer is 175 nanometers.
Embodiment 5
With aniline is monomer, and the mass concentration in reaction solution is 5%, and thinner is an ethanol, will be coated with TiO 2The glass print place glass reactor, reacted 5 hours, other condition is identical with step embodiment 1.Made print is a deep yellow, uses infrared spectra and has confirmed that the upper layer material is a polyaniline.With scanning electron microscopic observation print section structure, the mean thickness of polyaniline layer is 150 nanometers.
Embodiment 6
With the thiophene is monomer, mass concentration in reaction solution is 1.5%, thinner is a water, the glass print that the surface is coated with ZnO places glass reactor, and temperature is controlled at 25 ℃, reacts 5 hours, other condition is identical with step embodiment 1, made print is a light/dark balance, and infrared spectroscopy has confirmed that the upper layer material is a Polythiophene, and the mean thickness of Polythiophene layer is 740 nanometers.

Claims (3)

1. the preparation method of an inorganic semi-conductor/conducting polymer laminated film is characterized in that concrete steps are as follows:
(1) inorganic substrate that the surface is coated with semiconductor film places the reaction solution that contains polymer monomer;
(2) with containing ultraviolet light source above-mentioned reaction system is carried out irradiation, 1 minute-10 hours time;
(3) temperature of reaction 5-100 ℃;
Wherein, reaction solution one-tenth is grouped into by weight percentage and is:
(1) polymerization single polymerization monomer: 0.1-100%
(2) thinner: 0-99.9%;
Described polymerization single polymerization monomer is one or more of following compounds: pyrroles, aniline, thiophene, O-Phenylene Diamine, thioxene or trimethylthiophene;
The material of said semiconductor film is one or more of following compounds: TiO 2, ZnO, Fe 2O 3, WO 3, SnO 2, SrTiO 3, CdSe, CdS, ZnS, V 2O 5, MoO 3, PbS, MoSi 2, Nb 2O 5Or Bi 2O 3
2. preparation method according to claim 1 is characterized in that said thinner is a kind of of water, methyl alcohol, ethanol, propyl alcohol, butanols, or several mixtures.
3. preparation method according to claim 1 is characterized in that said ultraviolet ray is that wavelength is the monochromatic ray or the multifrequency source of 200-450 nanometer.
CNB200510112195XA 2005-12-29 2005-12-29 Method for preparing inorganic semi-conductor/ conducting polymer composite film by photocatalyzed polymerization Expired - Fee Related CN100366665C (en)

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US8206537B2 (en) 2008-08-27 2012-06-26 Carnegie Mellon University Method for forming a conducting multi-polymer nanostructure
CN101747574B (en) * 2008-11-28 2012-01-18 复旦大学 Transparent fluorescent film, preparation method and application thereof
CN102431255B (en) * 2011-09-20 2014-12-24 奇瑞汽车股份有限公司 Composite material having solar cell and production method thereof
CN102418170B (en) * 2011-09-20 2013-04-03 吉林大学 Method of controllable preparation of conducting polymer in semiconductor nano fiber
CN102941124B (en) * 2012-11-21 2014-09-03 江南大学 Visible-light reaction polypyrrole/Bi2WO6 composite catalyst and preparation method thereof
CN102998344B (en) * 2012-12-11 2014-11-26 清华大学 Novel nanosheet film for sensor and preparation method thereof
CN103242513A (en) * 2013-05-15 2013-08-14 复旦大学 Preparation method of conjugated polymer/graphene oxide compounded material
CN103913497A (en) * 2014-04-17 2014-07-09 常州联德电子有限公司 Lead-poisoning-resistant protective coating of automotive oxygen sensor and preparation method of coating
CN108671963B (en) * 2018-03-16 2021-10-22 浙江大学宁波理工学院 Preparation method of micro/nano structured cadmium sulfide/aniline oligomer composite material

Citations (4)

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Publication number Priority date Publication date Assignee Title
JPS6361284A (en) * 1986-09-01 1988-03-17 オムロン株式会社 Conducting high polymer electronic element
EP0917208A1 (en) * 1997-11-11 1999-05-19 Universiteit van Utrecht Polymer-nanocrystal photo device and method for making the same
CN1243849A (en) * 1999-07-12 2000-02-09 武汉工业大学 nm-class composite polyphenylamine-Fe2O3 material and its preparing process
CN1194031C (en) * 2002-10-08 2005-03-23 吉林大学 Method for mfg. controllable structure inorganic nanoparticle/polymer composite superthin film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6361284A (en) * 1986-09-01 1988-03-17 オムロン株式会社 Conducting high polymer electronic element
EP0917208A1 (en) * 1997-11-11 1999-05-19 Universiteit van Utrecht Polymer-nanocrystal photo device and method for making the same
CN1243849A (en) * 1999-07-12 2000-02-09 武汉工业大学 nm-class composite polyphenylamine-Fe2O3 material and its preparing process
CN1194031C (en) * 2002-10-08 2005-03-23 吉林大学 Method for mfg. controllable structure inorganic nanoparticle/polymer composite superthin film

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