CN101508527B - Nano-golden particle dispersion cobalt oxide complex optical film and preparation method - Google Patents
Nano-golden particle dispersion cobalt oxide complex optical film and preparation method Download PDFInfo
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- CN101508527B CN101508527B CN2009100782794A CN200910078279A CN101508527B CN 101508527 B CN101508527 B CN 101508527B CN 2009100782794 A CN2009100782794 A CN 2009100782794A CN 200910078279 A CN200910078279 A CN 200910078279A CN 101508527 B CN101508527 B CN 101508527B
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Abstract
The invention discloses a nano-gold particle dispersible cobalt oxide composite optical film and a preparation method thereof, belongs to the field of nanometer metal particles and inorganic non-metallic composite materials. The method adopts a sol-gel method to prepare an Aux/(CoO)1-x composite film, wherein x represents molar fraction of Au, and the value range of the x is more than or equal to 0.1 and less than or equal to 0.9. Raw materials are cobalt nitrate (Co(NO3)2.6H2O) and chlorogold acid (HAuCl4.4H2O), a solvent is ethylene glycol monomethyl ether (CH3OCH2CH2OH), the concentration of a cobalt nitrate solution is between 0.1 and 0.8 mol/L, and the annealing atmosphere is industrial nitrogen. The method has the advantages that: stoichiometric compositions of the film are easy to control due to the fact that the sol-gel method is used to prepare a precursor solution; the method has simple process, low cost, short preparation period, and energy conservation; and the nano-gold particle dispersible cobalt oxide composite optical film has good non-linear optical property, can observe an absorption peak near a wavelength of between 530 and 580 nm, and has broad application prospect in the fields such as optical switches, optical computers, light-wave separators and the like.
Description
Technical field
The invention belongs to nano-metal particle and metal oxide materials field of compound material; A kind of nano-golden particle dispersion cobalt oxide method for preparing optical thin film is provided, has related to the design and the preparation technology of a kind of nano-metal particle (Au) dispersion oxide (CoO) nonlinear optical film material.
Background technology
In the epoch of present rapid development of information technology, the optoelectronics industry development is swift and violent, to the also growth day by day of demand of photoelectric functional material.In electronic industry, need be base mateiral with the nonlinear optical material all like photoswitch, optical communication, optical information processing, optical computer, laser technology etc., therefore, nonlinear optical material have caused people's extensive concern in recent decades.Nano-metal particle dispersion medium laminated film; Because the surface plasma body resonant vibration and the local fields reinforcing effect of metallic particles; Can make film produce stronger absorption in particular range of wavelengths; Time of response that is exceedingly fast and high nonlinear factor are the good nonlinear optical materials of a kind of application prospect.That the technology of preparing of such laminated film has is ion implantation, vacuum vapour deposition, sputtering method, sol-gel method and pulsed laser deposition etc.Sol-gel method is owing to can reach the dispersion of molecular level; Can in the different media matrix, disperse multiple metal; Advantages such as having that thin film composition is prone to control, processing unit is simple, preparation cycle is short, save the energy, cost is low and thermal treatment temp is low relatively is considered at present one of the most effective masking technique.
Find that at present elements such as Au, Ag, Cu, Fe can be used as metallic nano-particle and mix in the thin film dielectrics and to improve the non-linear of material.Wherein the particle studded dielectric film of nanometer Au is owing to having good non-linear reinforcing effect and by broad research.Discover that the nonlinear optical property of laminated film not only depends on the kind of doping metals, and relevant with the selection of mounting medium.So to the different media material chosen, the investigator has done big quantity research.At the research initial stage, employing ion implantation such as R.H.Magruder prepare Au/SiO
2Film, mix Au particulate content seldom, third-order non-linear coefficient also very little [R.H.Magruder, et al., Appl.Phys.Lett., 1993,62 (15) 1730] this moment.Afterwards, employing magnetron sputtering method such as H.B.Liao has prepared Au/SiO
2Film has improved Au particulate doping greatly, makes the third-order non-linear coefficient of film that significantly raising [H.B.liao, et al., Appl.Phys.Lett., 1997,70 (1) 1] arranged.In addition, Brian J.Bozlee etc. through Prepared by Sol Gel Method the Au/ZnO film, research shows that the non-linear absorption peak intensity strengthens [Brian J.Bozlee, et al., ThinSolid Films, 2000, (378) 1] gradually along with the increasing of Au content.R.S.Sonawane etc. adopt the bigger TiO of specific refractory power
2For matrix has been studied Au/TiO
2The third-order non-linear coefficient of film has proved Au/TiO
2Film not only has bigger third-order non-linear coefficient, photocatalysis performance also increase [R.S.Sonawane, et al., Journal of Molecular Catalysis A, 2006, (243) 68].W.T.Wang etc. prepare the BaTiO that is embedded into the Au nanoparticle
3Ferroelectric membranc finds that this type material has the special optical absorption property [W.T.Wang, et al., Appl.Phys.Lett., 2003,83 (10) 1893] that is different from ferroelectric material itself.And Ferreira etc. prepare the Au/NiO laminated film as medium with transition metal oxide NiO, discover that this material also has selective light absorbent properties [F.F.Ferreira, et al., J.Phys.D:Appl.Phys., 2003, (36) 386].It is thus clear that the kind of laminated film medium is varied.CoO is a kind of broad stopband MOX, and has higher specific refractory power (2.33), has the researching value of potential nonlinear optical material.Recently; We utilize sol-gel method to prepare the Ag/CoO laminated film; Proved that nano-metal particle inlays the CoO medium and have good non-linear absorption (number of patent application: 200810223795.7), but Au particles dispersed CoO complex optical film and preparation method thereof does not also appear in the newspapers at present.
Summary of the invention
The objective of the invention is to: provide a kind of nonlinear optical property good nanometer Au particles dispersed CoO complex optical film, and prepare this film through composition, optimization sol evenning machine whirl coating and the thermal treatment process of control precursor solution.This invented technology route is simple, and required equipment is simple, and is easy to operate, and can accurately control the stoichiometric ratio of film.
The chemical formula of film provided by the invention is Au
x/ (CoO)
1-x, x representes the x of Au, its span is 0.1≤x≤0.9.
The present invention adopts sol-gel method to prepare Au
x/ (CoO)
1-xComplex optical film, concrete technology is following:
1. preparation precursor solution: at first with Xiao Suangu (Co (NO
3)
26H
2O) and hydrochloro-auric acid (HAuCl
44H
2O) be dissolved in ethylene glycol monoemethyl ether (CH respectively
3OCH
2CH
2OH) in, stirred under the room temperature 1～6 hour, (two strength of solution are 0.1～0.8mol/L) with golden transparent chlorauric acid solution to obtain the transparent CoO mother solution of pink colour; Ageing 2～8 hours mixes chlorauric acid solution and CoO mother solution according to stoichiometric ratio, stirred under the room temperature 1～6 hour, makes orange transparent Au
x/ (CoO)
1-xPrecursor solution.
2. preparation film: carry out film preparation with sol evenning machine; Substrate is glass or quartz substrate, before the whirl coating, substrate is immersed in ultrasonic cleaning in the acetone; Then solution is dripped on the substrate; With 300～1000rpm running 5～20 seconds, 1000～3000rpm running was 10～50 seconds again, and whenever even glue once carries out thermal decomposition process one time.Heat decomposition temperature is 100～400 ℃, and the time was 2～300 seconds.Behind the even glue 1～50 time sample placed and be connected with N
2Anneal in the atmosphere furnace, temperature rise rate is 1～50 ℃/min, and annealing temperature is 300～600 ℃, annealing time 10～240 minutes.
The film of the present invention preparation through X-ray diffraction analysis with TEM detection can know, diameter be the Au particles dispersed of 1～100nm in CoO phase matrix, this Au/CoO laminated film is observed absorption peak near 530～580nm wavelength, optical absorption spectra is as shown in Figure 1.
The invention has the advantages that: prepare precursor solution by sol-gel method, adopt sol evenning machine to prepare film, simple to operate, film chemical metering controllable component, cheap, temperature of reaction is low, and preparation cycle is short, saves the energy.
Description of drawings
The optical absorption spectra of the Au/CoO complex optical film that Fig. 1 designs for the present invention.
Embodiment
In the experimentation, all chemical of using are commercially available analytical pure.
Embodiment 1
0.29397g (0.001mol) Xiao Suangu and 0.4139g (0.001mol) hydrochloro-auric acid are dissolved in the 10ml ethylene glycol monoemethyl ether; Stirred 1 hour; Obtain pink colour CoO mother solution and the golden chlorauric acid solution of 0.1mol/L, ageing was got 1ml CoO mother solution and 9ml chlorauric acid solution and is mixed after 2 hours; Stirred 6 hours, and made the Au/CoO precursor solution; Before the whirl coating, substrate is immersed in successively carried out ultrasonic cleaning in acetone, the ethanol 15 minutes, then solution is dripped on the substrate, first 300rpm running 20 seconds, the 1000rpm running is 50 seconds again.Behind the even glue, with 100 ℃ of thermal decomposition process of film 2 seconds, whirl coating 1 time placed N with sample at last
2Annealing is 10 minutes in the atmosphere furnace, and temperature rise rate is 50 ℃/min, and annealing temperature is 600 ℃, prepares Au
0.9/ (CoO)
0.1Laminated film.
Embodiment 2
0.58794g (0.002mol) Xiao Suangu and 0.8277g (0.002mol) hydrochloro-auric acid are dissolved in the 10ml ethylene glycol monoemethyl ether; Stirred 3 hours; Obtain pink colour CoO mother solution and the golden chlorauric acid solution of 0.2mol/L, ageing was got 3ml CoO mother solution and 7ml chlorauric acid solution and is mixed after 4 hours; Stirred 4 hours, and made the Au/CoO precursor solution; Before the whirl coating, substrate is immersed in successively carried out ultrasonic cleaning in acetone, the ethanol 20 minutes, then solution is dripped on the substrate, first 500rpm running 15 seconds, the 1500rpm running is 40 seconds again.Behind the even glue,, so repeat 5 times, at last sample is placed N 200 ℃ of thermal decomposition process of film 10 seconds
2Annealing is 30 minutes in the atmosphere furnace, and temperature rise rate is 30 ℃/min, and annealing temperature is 550 ℃, prepares Au
0.7/ (CoO)
0.3Laminated film.
Embodiment 3
0.88201g (0.003mol) Xiao Suangu and 1.2416g (0.003mol) hydrochloro-auric acid are dissolved in the 10ml ethylene glycol monoemethyl ether; Stirred 5 hours; Obtain pink colour CoO mother solution and the golden chlorauric acid solution of 0.3mol/L, ageing was got 5ml CoO mother solution and 5ml chlorauric acid solution and is mixed after 5 hours; Stirred 4 hours, and made the Au/CoO precursor solution; Before the whirl coating, substrate is immersed in successively carried out ultrasonic cleaning in acetone, the ethanol 15 minutes, then solution is dripped on the substrate, first 700rpm running 15 seconds, the 2000rpm running is 30 seconds again.Behind the even glue,, so repeat 20 times, at last sample is placed N 100 seconds of 300 ℃ of thermal decomposition process of film
2Annealing is 120 minutes in the atmosphere furnace, and temperature rise rate is 15 ℃/min, and annealing temperature is 500 ℃, prepares Ag
0.5/ (CoO)
0.5Laminated film.
Embodiment 4
1.4698g (0.005mol) Xiao Suangu and 2.0693g (0.005mol) hydrochloro-auric acid are dissolved in the 10ml ethylene glycol monoemethyl ether; Stirred 5 hours; Obtain pink colour CoO mother solution and the golden chlorauric acid solution of 0.5mol/L, ageing was got 7ml CoO mother solution and 3mi chlorauric acid solution and is mixed after 6 hours; Stirred 2 hours, and made the Au/CoO precursor solution; Before the whirl coating, substrate is immersed in successively carried out ultrasonic cleaning in acetone, the ethanol 20 minutes, then solution is dripped on the substrate, first 900rpm running 10 seconds, the 2500rpm running is 20 seconds again.Behind the even glue,, so repeat 30 times, at last sample is placed N 350 ℃ of thermal decomposition process of film 200 seconds
2Anneal is 160 minutes in the atmosphere furnace, and temperature rise rate is 10 ℃/min, and annealing temperature is 400 ℃, prepares Ag
0.3/ (CoO)
0.7Laminated film.
Embodiment 5
2.3518g (0.008mol) Xiao Suangu and 3.3109g (0.008mol) hydrochloro-auric acid are dissolved in the 10ml ethylene glycol monoemethyl ether; Stirred 6 hours; Obtain pink colour CoO mother solution and the golden chlorauric acid solution of 0.8mol/L, ageing was got 9ml CoO mother solution and 1ml chlorauric acid solution and is mixed after 8 hours; Stirred 2 hours, and made the Au/CoO precursor solution; Before the whirl coating, substrate is immersed in successively carried out ultrasonic cleaning in acetone, the ethanol 20 minutes, then solution is dripped on the substrate, first 1000rpm running 5 seconds, the 3000rpm running is 10 seconds again.Behind the even glue,, so repeat 50 times, at last sample is placed N 300 ℃ of thermal decomposition process of film 300 seconds
2Annealing is 240 minutes in the atmosphere furnace, and temperature rise rate is 5 ℃/min, and annealing temperature is 300 ℃, prepares Au
0.1/ (CoO)
0.9Laminated film.
Embodiment 6
2.3518g (0.008mol) Xiao Suangu and 0.8277g (0.002mol) hydrochloro-auric acid are dissolved in the 10ml ethylene glycol monoemethyl ether; Stirred 6 hours; Obtain pink colour CoO mother solution and the golden chlorauric acid solution of 0.2mol/L of 0.8mol/L, ageing was got 5ml CoO mother solution and 5ml chlorauric acid solution and is mixed after 8 hours; Stirred 2 hours, and made the Au/CoO precursor solution; Before the whirl coating, substrate is immersed in successively carried out ultrasonic cleaning in acetone, the ethanol 20 minutes, then solution is dripped on the substrate, first 1000rpm running 5 seconds, the 3000rpm running is 10 seconds again.Behind the even glue,, so repeat 50 times, at last sample is placed N 300 ℃ of thermal decomposition process of film 300 seconds
2Annealing is 240 minutes in the atmosphere furnace, and temperature rise rate is 1 ℃/min, and annealing temperature is 300 ℃, prepares Au
0.2/ (CoO)
0..8Laminated film.
Claims (2)
1. the preparation method of a nano-golden particle dispersion cobalt oxide optics laminated film is characterized in that, the chemical formula of film is Au
x/ (Co0)
1-x, x representes the x of Au, its span is: 0.1≤x≤0.9;
With Xiao Suangu and hydrochloro-auric acid is raw material; Ethylene glycol monoemethyl ether is a solvent; Adopt the metering of sol-gel method synthetic chemistry than precursor solution accurate, uniform ingredients, film on glass or quartz substrate with sol evenning machine then, annealing obtains Au in being connected with the tube furnace of industrial nitrogen at last
x/ (CoO)
1-xComplex optical film, concrete process step is:
A, preparation precursor solution: at first be dissolved in Xiao Suangu and hydrochloro-auric acid in the ethylene glycol monoemethyl ether respectively; Stir under the room temperature and made it abundant dissolving in 1～6 hour; Obtain the CoO mother solution and the golden chlorauric acid solution of concentration pink colour, CoO mother solution and golden chlorauric acid solution concentration are 0.1～0.8mol/L; Ageing 2～8 hours mixes chlorauric acid solution and CoO mother solution according to stoichiometric ratio, stirred 1～6 hour, makes orange transparent Au
x/ (CoO)
1-xPrecursor solution;
B, preparation film: prepare film with sol evenning machine; Substrate is glass or quartz substrate, before the whirl coating, substrate is immersed in carries out ultrasonic cleaning in the acetone; Then solution is dripped on the dried substrate; With after 5～20 seconds of 300～1000rpm running, again 10～50 seconds of 1000～3000rpm running, whenever even glue once carries out thermal decomposition process one time; Heat decomposition temperature is 100～400 ℃, and the time was 2～300 seconds; Behind the even glue 1～50 time sample is placed N
2Anneal in the atmosphere furnace, temperature rise rate is 1～50 ℃/min, 300～600 ℃ of annealing temperatures, annealing time 10～240 minutes.
2. according to the preparation method of the said nano-golden particle dispersion cobalt oxide optics of claim 1 laminated film; It is characterized in that; To be 1～100nm gold grain be dispersed in the powder blue matrix with the form of simple substance diameter; And film is observed absorption peak near 530～580nm wavelength, shows good nonlinear optical properties.
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| EP2883841A4 (en) * | 2012-08-01 | 2016-07-06 | Nat Inst Of Advanced Ind Scien | Joined structure comprising cube- or quadratic prism-shaped rock salt-type oxide nanoparticle with fine metal particle, and method for producing same |
| US10384266B2 (en) | 2013-09-24 | 2019-08-20 | Heraeus Deutschland GmbH & Co. KG | Process for producing a shiny laminate structure at low temperatures |
| CN105252016B (en) * | 2015-11-11 | 2016-10-12 | 西安电子科技大学 | A kind of preparation method of gold nano grain self assembly transplantation single thin film |
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| US5688442A (en) * | 1994-03-11 | 1997-11-18 | Agency Of Industrial Science & Technology | Nonlinear optical materials and process for producing the same |
| CN101067708A (en) * | 2007-06-05 | 2007-11-07 | 北京科技大学 | Nano golden particle dispension nickel oxide optical film and producing method thereof |
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| CN101067708A (en) * | 2007-06-05 | 2007-11-07 | 北京科技大学 | Nano golden particle dispension nickel oxide optical film and producing method thereof |
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