CN101812299B - Nanocrystal reinforced rare earth doped tellurate luminous film material and preparation method thereof - Google Patents
Nanocrystal reinforced rare earth doped tellurate luminous film material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of photoelectron information, particularly relating to a nanocrystal reinforced rare earth doped tellurate luminous film material and a preparation method thereof. The tellurate luminous film material comprises the following components: 50-95 mol% of TeO2, 0-20 mol% of TiO2, 0-10 mol% of Al2O3, 0-30 mol% of ZnO, 1-10 mol% of Na2O, 1-10 mol% of Re2O3 and 0-30 mol% of M, wherein Re is rare earth element and is one or a plurality of Pr, Nd, Sm, Eu, Tb, Ho, Er, Tm and Yb, and M is noble metal element and is one or a plurality of Ag, Au and CU. The tellurate luminous film material utilizes organic alkoxide or inorganic salt of the components through a non-hydrolysis sol-gelation method, and the tellurate luminous film material is prepared on the optical glass substrate according to the composition range and certain technical condition. The invention has simple preparation method and low cost, and the obtained film material is even and transparent, and fluorescent output can be greatly enhanced by laser pump excitation. The film material can be used in the fields, such as optical information record, display, treatment and the like.
Description
Technical field
The invention belongs to the opto-electronic information technology field, be specifically related to rare earth ion doped tellurate luminous film material of a kind of noble metal nanocrystalline enhancing and preparation method thereof.
Background technology
Luminescent material has extensive and important application in fields such as optical information storage, transmission, display and processings, for the now development of information technology provides important support.In some materials, introduce all kinds of luminophores such as rare earth, semi-conductor, metal ion and nanocrystal thereof, can obtain the luminescent properties of various uniquenesses, and compare with organic basis material, inorganic matrix material has the characteristics such as chemistry and Heat stability is good, long service life, is the important luminous substrate material of a class.
Although fluoride materials has higher quantum yield with its lower phonon energy, its chemical stability and physical strength are relatively poor, technique is made difficulty, have limited its practical application.Tellurium oxide (TeO
2) in the oxide glass material, have a minimum phonon energy, its chemical stability is better simultaneously, physical strength is higher, introducing by components such as zinc oxide, also can improve rare earth ion doped luminous efficiency, so tellurium oxide glass becomes a kind of comparatively desirable rare earth ion doped luminous substrate material.Simultaneously, the outstanding advantages such as mould material has that designability is strong, controlled, the easy practical functionization of microstructure and device, therefore, develop efficient, stable oxidation telluro luminous film material and device, optoelectronic functional materials and devices field are had important actual application value and social effect.
In addition, some noble metal nanocrystalline (such as silver, gold, copper etc.) can obviously improve the luminous intensity of luminous species with its unique surface and interface effect, quantum size effect etc., the surface of the precious metal surfaces such as i.e. utilization is silver-colored, golden or its nanocrystal strengthens fluorescent effect, such as the surface that the fluorescence species such as rare earth ion is placed the precious metal surfaces such as silver, gold, copper or its nanocrystal, can significantly improve the fluorescence quantum yield of fluorescence species, thereby improve the fluorescence output intensity.
From present published patent, RU2271593 (C2) utilizes the method for magnetron sputtering to prepare Er
3+The tungsten tellurate basal lamina material of doping fluorescent output, CN1636906A adopt traditional scorification to prepare the Er that is used for green glow output
3+/ Yb
3+Be total to oxygen-doped chlorine tellurate bulk glass material, US6859606 adopts traditional scorification to prepare Er
3+And Er
3+/ Yb
3+Doped with boron tellurate bulk glass material is used for broad band amplifier, CN101148584A then by noble metal nano particles with contain the luminophore solution phase and mix to strengthen luminous intensity.Still do not utilize sol-gel method to prepare rare earth ion doped tellurate luminous film material, and the surface fluorescence reinforcing effect of utilizing metallic nano crystal is carried out the Patents that fluorescence strengthens, therefore, developing simple, efficient, the stable rare earth ion doped tellurate luminous film material of metallic nano crystal surface enhancing of a kind of preparation technology has important practical significance.
Summary of the invention
The object of the present invention is to provide rare earth ion doped tellurate luminous film material of a kind of noble metal nanocrystalline enhancing and preparation method thereof, by preparing rare earth ion doped tellurate mould material and introducing the noble metal nano crystal, realize output and the enhancing of fluorescence, thereby a kind of luminous film material that is applied to the opto-electronic information technology field is provided.
In the present invention, the rare earth ion doped tellurate luminous film material that noble metal nanocrystalline strengthens, it consists of: 50~95mol%TeO
2, 0~20mol%TiO
2, 0~10mol%Al
2O
3, 0~30mol%ZnO, 1~10mol%Na
2O, 1~10mol%Re
2O
3, 0~3mol%M, wherein Re is rare earth element, Re be Pr, Nd, Sm, Eu, Tb, Ho, Er, Tm, Yb wherein one or more; M is precious metal element, M be Ag, Au, Cu wherein one or more.
In the present invention, the tellurate luminous film material of preparation said components is take telluromercaptan salt as presoma, such as propylene glycol tellurium, ethanol tellurium etc., its thermal treatment gained TeO
2Has lower phonon energy; Introduce the titanium alkoxide, the organic alkoxide of aluminium, zinc, sodium, rare earth element and precious metal element, nitrate, acetate, halid wherein one or more.TiO
2, Al
2O
3, Na
2The introducing of the components such as O is conducive to improve the stability of network structure in the film, Re
2O
3Introducing can realize that fluorescence output, the introducing of ZnO, noble metal nano crystal (such as Ag, Au, Cu) component are conducive to strengthen fluorescence output.Take ethanol, propyl alcohol, butanols, propylene glycol or ethylene glycol monomethyl ether as solvent, and introduce polyvinylpyrrolidone or polyoxyethylene glycol to improve the viscosity of colloidal sol, introduce N, dinethylformamide or N,N-dimethylacetamide produce precipitation to prevent rare earth ion and polyvinylpyrrolidone or polyoxyethylene glycol complexing.
In the present invention, the rare earth ion doped tellurate luminous film material preparation method of noble metal nanocrystalline enhancing is as follows:
(a) according to after the selected proportioning of said components, with the organic alkoxide of zinc, sodium, aluminium, rare earth element, nitrate, acetate or halid wherein one or more are dissolved in alcoholic solvent under 60~150 ℃, obtain settled solution;
(b) mentioned solution is placed 10~50 ℃, under the environment of relative humidity about 20~50%, when stirring, slowly add successively volume ratio with alcoholic solvent and be 0.8: 1 to 1.5: 1 ethylene glycol monomethyl ether, with the volume ratio of alcoholic solvent be 1: 2 to 1: 5 N, dinethylformamide or N, the N-N,N-DIMETHYLACETAMIDE, the organic alkoxide or nitrate or the acetate that contain precious metal element, and the ratio in every liter of 50~300g adds polyvinylpyrrolidone or polyoxyethylene glycol in mentioned solution, after said components is fully dissolved, telluromercaptan salt successively when stirring, the titanium alkoxide, mentioned solution is sealed, at 10~50 ℃ of lower ageing 0.5~2h, obtain zinc, sodium, aluminium, tellurium, titanium, precious metal, each concentration of component of rare earth element is respectively 0~1mol/L, viscosity is the colloidal sol of 80~150mPas;
(c) utilize above-mentioned colloidal sol, adopt spin-coating method or crystal pulling method, apply thin film in the optical glass substrate of cleaning;
(d) said film is placed 100~130 ℃ of drying 3~5h obtain gel-film, this gel-film is heat-treated with the temperature rise rate of 0.5~2 ℃/min, be incubated 1~2h at 500 ℃, annealing with the rate of temperature fall of 1~3 ℃/min is cooled to room temperature;
(e) until cooling off rear taking-up sample fully, namely obtain the rare earth ion doped tellurate luminous film that noble metal nanocrystalline strengthens in optical glass substrate.
Technique effect of the present invention is:
(a) mould material have that designability is strong, the outstanding advantages such as controlled, the easy practical functionization of microstructure and device, efficiently, stable oxidation telluro luminous film material and device, optoelectronic functional materials and devices field are had important actual application value and social effect;
(b) TiO
2, Al
2O
3, Na
2The introducing of O component is conducive to stablize TeO
2The glass network structure, obtain the mould material of homogeneous transparent, the introducing of ZnO component and noble metal nanocrystalline is conducive to improve the luminous intensity of rare earth ion;
(c) non-hydrolytic sol of the present invention-gel technology of preparing, its method is simple, cost is low, thermal treatment process is simple and easy to control, is conducive to the actual production of this material.
Description of drawings
Fig. 1 is the transmittance curves of the embodiment of the invention 6 samples in the 300-800nm wavelength region.
Fig. 2 to Fig. 5 is that embodiment of the invention 1-6 sample is through 394nm or the light activated fluorescence emission spectrum of 980nm pumping.
Embodiment
Strengthen the composition of rare earth ion doped tellurate luminous film material according to above-mentioned noble metal nanocrystalline, table 1 has provided the prescription of 6 specific embodiments of the present invention.
The specific embodiment prescription of table 1 tellurate luminous film material of the present invention
The preparation method of specific embodiment is as follows:
(a) according to each prescription in the embodiment form, the molar content conversion of each component is each raw material (telluromercaptan salt, titanium alkoxide, the organic alkoxide of aluminium, zinc, sodium, rare earth element, precious metal element, nitrate, acetate or halogenide) actual amount;
(b) organic alkoxide, nitrate, acetate or the halogenide with aluminium, zinc, sodium, rare earth element is dissolved in ethanol, propyl alcohol, butanols or propylene glycol solvent under 60~150 ℃, to remove contained crystal water in each raw material, prevent that moisture content too much causes tellurium and the too fast hydrolysis of titanium alkoxide in the system, obtain thus settled solution;
(c) mentioned solution is placed 10~50 ℃, under the environment of relative humidity about 20~50%, when stirring, slowly add successively volume ratio with alcoholic solvent and be 0.8: 1 to 1.5: 1 ethylene glycol monomethyl ether, with the volume ratio of alcoholic solvent be 1: 2 to 1: 5 N, dinethylformamide or N, the N-N,N-DIMETHYLACETAMIDE, to prevent that rare earth ion and the polyvinylpyrrolidone that adds afterwards or polyoxyethylene glycol complexing from producing precipitation, the organic alkoxide or the inorganic salt that add precious metal element make film precipitating metal in heat treatment process nanocrystalline, and add polyvinylpyrrolidone or polyoxyethylene glycol with the viscosity of adjustment colloidal sol by the ratio of every liter of 50~300g in mentioned solution; After said components is fully dissolved, when stirring, slowly add successively telluromercaptan salt and titanium alkoxide, mentioned solution is sealed, make each component polymerization at 10~50 ℃ of lower ageing 0.5~2h, obtain that zinc, sodium, aluminium, tellurium, titanium, precious metal, each concentration of component of rare earth element are respectively 0~1mol/L, viscosity is the colloidal sol of 80~150mPas;
(d) utilize above-mentioned colloidal sol, adopt spin-coating method or crystal pulling method, apply thin film in the optical glass substrate of cleaning, come the thickness of controlling diaphragm by control spin coating or the speed that lifts, also can repeat above-mentioned steps repeatedly plated film to reach thickness requirement;
(e) said film is placed 100~130 ℃ of drying 3~5h, obtain gel-film, this gel-film is heat-treated with the temperature rise rate of 0.5~2 ℃/min, at 500 ℃ of insulation 1~2h, rate of temperature fall annealing with 1~3 ℃/min also is cooled to room temperature gradually, temperature rise rate and suitable calcining temperature are conducive to the polymerization of organic eliminating and each component in the gel-film slowly, and film prevents the film cracking with the stress that furnace annealing is conducive to alleviate in the network structure.
(f) until cooling off rear taking-up sample fully, namely obtain the rare earth ion doped tellurate luminous film that noble metal nanocrystalline strengthens.
By the mould material homogeneous transparent that each prescription in above-described embodiment makes, the transmitance of embodiment 6 gained samples in the 300-800nm wavelength region as shown in Figure 1.Embodiment 1-6 gained sample is launched stronger fluorescence through 394nm or 980nm pump excitation, and its emmission spectrum is shown in Fig. 2-4; Wherein among Fig. 2 curve 1 be embodiment 1 gained sample through 394nm pump excitation gained fluorescence emission spectrum, characterized Sm
3+Fluorescent emission; Curve 2,3 is respectively embodiment 2,3 gained samples through 394nm pump excitation gained fluorescence emission spectrum among Fig. 3, has characterized Eu
3+Fluorescent emission and the silver nanoparticle crystal to its luminous enhancing; Among Fig. 4 curve 4 be embodiment 4 gained samples through 980nm pump excitation gained fluorescence emission spectrum, characterized Ho
3+/ Yb
3+Fluorescent emission; Curve 5,6 is respectively embodiment 5,6 gained samples through 980nm pump excitation gained fluorescence emission spectrum among Fig. 5, has characterized Er
3+/ Yb
3+Fluorescent emission and the silver nanoparticle crystal to its luminous enhancing.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (3)
2. tellurate luminous film material according to claim 1 is characterized in that: described rare earth element be Pr, Nd, Sm, Eu, Tb, Ho, Er, Tm, Yb wherein one or more.
3. the preparation method of claim 1 or 2 described tellurate luminous film materials, it is characterized in that: take telluromercaptan salt as presoma, take ethanol, propyl alcohol, butanols or propylene glycol wherein one or more as alcoholic solvent, introduce simultaneously titanium alkoxide, aluminium, zinc, sodium, rare earth element and precious metal element organic alkoxide, nitrate, acetate, halid wherein one or more, and introducing N, dinethylformamide or N,N-dimethylacetamide, introduce polyvinylpyrrolidone or polyoxyethylene glycol simultaneously;
Wherein above-mentioned preparation method specifically comprises:
(a) according to after the selected proportioning of described composition, with the organic alkoxide of zinc, sodium, aluminium, rare earth element, nitrate, acetate or halid wherein one or more, under 60~150 ℃, be dissolved in ethanol, propyl alcohol, butanols or propylene glycol wherein one or more, obtain settled solution;
(b) mentioned solution is placed 10~50 ℃, under the environment of relative humidity 20~50%, when stirring, slowly add successively volume ratio with alcoholic solvent and be 0.8: 1 to 1.5: 1 ethylene glycol monomethyl ether, with the volume ratio of alcoholic solvent be 1: 2 to 1: 5 N, dinethylformamide or N, the N-N,N-DIMETHYLACETAMIDE, the organic alkoxide or nitrate or the acetate that contain precious metal element, and the ratio in every liter of 50~300g adds polyvinylpyrrolidone or polyoxyethylene glycol in mentioned solution, after said components is fully dissolved, when stirring, slowly add successively telluromercaptan salt, the titanium alkoxide, mentioned solution is sealed, at 10~50 ℃ of lower ageing 0.5~2h, obtain zinc, sodium, aluminium, tellurium, titanium, precious metal, each concentration of component of rare earth element is respectively 0~1mol/L, viscosity is the colloidal sol of 80~150mPas;
(c) utilize above-mentioned colloidal sol, adopt spin-coating method or crystal pulling method, apply thin film in the optical glass substrate of cleaning;
(d) place 100~130 ℃ of drying 3~5h to obtain gel-film the film that obtains after above-mentioned (c) step, then heat-treat with the temperature rise rate of 0.5~2 ℃/min, be incubated 1~2h at 500 ℃, annealing with the rate of temperature fall of 1~3 ℃/min also is cooled to the rare earth doped tellurate luminous film that room temperature obtains nanocrystalline enhancing gradually.
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DE102013226630A1 (en) | 2013-12-19 | 2015-06-25 | Osram Gmbh | Conversion element, component and method for producing a component |
DE102013226636A1 (en) * | 2013-12-19 | 2015-06-25 | Friedrich-Schiller-Universität Jena | Glass composition, device and method of making a device |
CN104556691B (en) * | 2015-01-16 | 2017-02-22 | 浙江大学 | Optical micro-cavity based on tellurate glass and preparation method of optical micro-cavity |
CN111205869B (en) * | 2020-01-17 | 2023-08-08 | 西南大学 | Red-green up-conversion fluorescent powder and preparation method thereof |
CN112500863B (en) | 2021-02-07 | 2021-06-08 | 金陵海关技术中心 | Preparation and application of core-shell type luminescent material hidden mark of customs security inspection system |
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US5251062A (en) * | 1992-10-15 | 1993-10-05 | Bell Communications Research, Inc. | Tellurite glass and fiber amplifier |
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CN1785866A (en) * | 2005-10-27 | 2006-06-14 | 中国科学院上海光学精密机械研究所 | Yb3+/Ce3+/Er3+ codoped oxychloro tellurate glass and its preparation method |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5251062A (en) * | 1992-10-15 | 1993-10-05 | Bell Communications Research, Inc. | Tellurite glass and fiber amplifier |
CN1636906A (en) * | 2004-12-02 | 2005-07-13 | 中国科学院上海光学精密机械研究所 | Er/Yb doped tellurate oxychloride glass and its prepn process |
CN1785866A (en) * | 2005-10-27 | 2006-06-14 | 中国科学院上海光学精密机械研究所 | Yb3+/Ce3+/Er3+ codoped oxychloro tellurate glass and its preparation method |
Non-Patent Citations (1)
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