CN101456675B - Glass-ceramics for emitting bright white light through up-conversion - Google Patents

Glass-ceramics for emitting bright white light through up-conversion Download PDF

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Publication number
CN101456675B
CN101456675B CN2007100099820A CN200710009982A CN101456675B CN 101456675 B CN101456675 B CN 101456675B CN 2007100099820 A CN2007100099820 A CN 2007100099820A CN 200710009982 A CN200710009982 A CN 200710009982A CN 101456675 B CN101456675 B CN 101456675B
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moles
glass
conversion
white light
mol ratio
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CN101456675A (en
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陈大钦
王元生
余运龙
黄萍
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Fujian Institute of Research on the Structure of Matter of CAS
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Fujian Institute of Research on the Structure of Matter of CAS
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Abstract

The invention discloses transparent glass ceramic for transmitting bright white light through up-conversion and a preparation method thereof, and relates to the field of luminous material. The glass ceramic comprises the following components according to mol ratio: 44 moles of SiO2, 28 moles of Al2O3, 17 moles of YF3, w moles of NaF, x moles of ReF3, y moles of TmF3, and z moles of YbF3, wherein Re is Er or Ho, x is 0 to 0.5, y is 0 to 0.5, z is 0 to 1.0, and w is 11-x-y-z. The glass ceramic is prepared by adopting a sharp quenching method for fused mass. The glass ceramic has the property ofup-conversion white light transmission.

Description

Glass-ceramic through last switching emission bright white light
Technical field
The present invention relates to the solid luminescent material field, especially relate to a kind of rare earth doping transparent glass-ceramic and preparation technology thereof that can realize efficiently going up the conversion of white light emission.
Background technology
In recent years, owing to having broad application prospects at aspects such as solid-state polychrome 3-D display and backlights, white light source causes the extensive concern of scientific circles.One of method that produces white light is to change on the frequency, and it is transformed into multicolor visible light with near infrared light through multiphoton process.La rear earth ion has the profuse electronic level and the narrow spectral line of emission, therefore very is suitable as the up-conversion luminescence center.Obtain efficient, at a low price and durable last conversion of white light source need satisfy following requirement: stable matrix, cheap excitaton source (like 976 nanometer lasers), exciting light is effectively absorbed and controlled red green blue tricolor is launched.1996; People such as Downing have realized the conversion of white light emission in rear-earth-doped heavy metal fluoride glass; But it needs the exciting light pumping simultaneously of two wavelength could realize [E.Downing, L.Hesselink, J.Ralston; And R.MacFarlane, Science 1996 (273): 1185-1189].Oxyfluoride glass ceramic is the matrix material that comprises oxide glass phase and crystal of fluoride, makes it crystal particle scale through control fluorochemical crystallization and remains on below the 30nm, and be uniformly distributed in the silica glass matrix, can obtain transparent glass-ceramic.This glass-ceramic has fluorochemical phonon energy low and oxide compound machinery intensity and the high advantage of thermostability concurrently, is novel luminescent material, has great application prospect at photoelectric field.The present invention is thulium doped ion, erbium or holmium ion and ytterbium ion in the novel nanocrystalline glass-ceramic of fluorinated yttrium, makes rare earth ion get in the yttrium-fluoride nanocrystalline in a large number through the control heat-treat condition; Through adjusting rear-earth-doped concentration, can under 976 nanometer laser pumping conditions, make the strong red green blue tricolor light of material emission, thereby obtain bright last conversion of white light.
Summary of the invention
The present invention proposes a kind of Re 3+/ Tm 3+/ Yb 3+The component and the preparation technology thereof of the fluorinated yttrium nano crystal transparent glass ceramic of (Re=Er or Ho) ternary codoped, purpose are to prepare Stability Analysis of Structures, can realize efficiently going up the solid luminescent material of conversion of white light emission.
Transparent glass ceramics component of the present invention is (mol ratio): 44SiO 2-28Al 2O 3-17YF 3-wNaF-xReF 3-yTmF 3-zYbF 3, Re=Er, and Ho (x=0～0.5, y=0～0.5, z=0～1.0, w=11-x-y-z).
The present invention adopts and is prepared as follows technology: powder raw material is mixed according to certain set of dispense ratio; Grinding evenly is placed in the crucible, in resistance furnace, is heated to 1300～1500 ℃ and makes it fusion, and be incubated 0～5 hour; Then, glass melt is poured in the copper mold of 300 ℃ of preheatings fast be shaped; The forerunner's glass that obtains is put into resistance furnace annealing to eliminate internal stress; Glass after the annealing continues 550～750 ℃ of heat tracings 1～10 hour, makes it to take place partially-crystallized, obtains transparent glass ceramics.
Adopt above glass ingredient and preparation technology, successfully obtained in the oxide glass matrix, to contain the transparent glass ceramics of equally distributed rare earth ion doped yttrium-fluoride nanocrystalline.Through regulating rear-earth-doped concentration, be under the 976 nanometer laser shooting conditionss of 0.1W, respectively at Er at power 3+/ Tm 3+, Re 3+/ Yb 3+(Re=Er or Ho) and Tm 3+/ Yb 3+Observe switching emission on the strong red, green, blue in the codoped glass-ceramic; And at Re 3+/ Tm 3+/ Yb 3+Observe bright white light emission in the glass-ceramic of (Re=Er or Ho) ternary doping, the equal-energy white emission of its chromaticity coordinate value and standard is very approaching.
Glass-ceramic preparation technology of the present invention is simple, with low cost, and being expected exploitation becomes a kind of new type of solid state three-dimensional light demonstration and backlight material.
Embodiment
Instance 1: with analytically pure SiO 2, Al 2O 3, NaF, YF 3With purity be 99.99% TmF 3With YbF 3Powder is pressed 0.1TmF 3: 0.5YbF 3: 44SiO 2: 28Al 2O 3: 10.4NaF: 17YF 3The accurate weighing of the proportioning of (mol ratio) is placed in the agate mortar; Make its uniform mixing more than grinding half a hour, and be placed in the platinum crucible, in program control high temperature box type resistance furnace, be heated to 1400 ℃ after insulation 0.5 hour; Then, glass melt is poured in the copper mold of 300 ℃ of preheatings fast be shaped; The forerunner's glass that obtains is put into resistance furnace, 500 ℃ of annealing after 2 hours furnace cooling to eliminate internal stress; Glass after the annealing is made it to take place crystallization in 2 hours 670 ℃ of insulations, obtain the colourless transparent glass pottery.Transmission electron microscope (TEM) research shows that the YF that is of a size of 20-30nm is in a large number arranged in this glass-ceramic 3Uniform crystal particles is distributed in the oxide glass matrix; Electron Energy Disperse Spectroscopy (EDS) analysis revealed rare earth ion gathers in nanocrystalline partially.Sample carries out indoor temperature measurement with the FLS920 XRF through surface finish, at power be observe under the 976 nanometer laser shooting conditionss of 0.1W strong blue up-conversion luminous.
Instance 2: with analytically pure SiO 2, Al 2O 3, NaF, YF 3With purity be 99.99% YbF 3And ErF 3Powder is pressed 0.1ErF 3: 0.5YbF 3: 44SiO 2: 28Al 2O 3: 10.4NaF: 17YF 3The accurate weighing of the proportioning of (mol ratio) after the preparation and heat treatment process identical with instance 1, obtains the transparent glass ceramics of redness.Sample carries out indoor temperature measurement through surface finish with the FLS920 XRF, is under the 976 nanometer laser shooting conditionss of 0.1W at power, observes strong green up-conversion luminescence.
Instance 3: with analytically pure SiO 2, Al 2O 3, NaF, YF 3With purity be 99.99% ErF 3And TmF 3Powder is pressed 0.2TmF 3: 0.1ErF 3: 44SiO 2: 28Al 2O 3: 10.7NaF: 17YF 3The accurate weighing of the proportioning of (mol ratio) after the preparation and heat treatment process identical with instance 1, obtains the transparent glass ceramics of redness.Sample carries out indoor temperature measurement through surface finish with the FLS920 XRF, is under the 976 nanometer laser shooting conditionss of 0.1W at power, observes strong red up-conversion luminescence.
Instance 4: with analytically pure SiO 2, Al 2O 3, NaF, YF 3With purity be 99.99% ErF 3, YbF 3And TmF 3Powder is pressed 0.1TmF 3: 0.02ErF 3: 0.5YbF 3: 44SiO 2: 28Al 2O 3: 10.38NaF: 17YF 3The accurate weighing of the proportioning of (mol ratio) after the preparation and heat treatment process identical with instance 1, obtains pink transparent glass ceramics.Sample carries out indoor temperature measurement through surface finish with the FLS920 XRF, is under the 976 nanometer laser shooting conditionss of 0.1W at power, observes strong cyan up-conversion luminescence.
Instance 5: with analytically pure SiO 2, Al 2O 3, NaF, YF 3With purity be 99.99% ErF 3, YbF 3And TmF 3Powder is pressed 0.1TmF 3: 0.1ErF 3: 0.5YbF 3: 44SiO 2: 28Al 2O 3: 10.3NaF: 17YF 3The accurate weighing of the proportioning of (mol ratio) after the preparation and heat treatment process identical with instance 1, obtains the transparent glass ceramics of redness.Sample carries out indoor temperature measurement through surface finish with the FLS920 XRF, is under the 976 nanometer laser shooting conditionss of 0.1W at power, observes strong yellow up-conversion luminescence.
Instance 6: with analytically pure SiO 2, Al 2O 3, NaF, YF 3With purity be 99.99% ErF 3, YbF 3And TmF 3Powder is pressed 0.1TmF 3: 0.2ErF 3: 0.5YbF 3: 44SiO 2: 28Al 2O 3: 10.2NaF: 17YF 3The accurate weighing of the proportioning of (mol ratio) after the preparation and heat treatment process identical with instance 1, obtains the transparent glass ceramics of redness.Sample carries out indoor temperature measurement through surface finish with the FLS920 XRF, is under the 976 nanometer laser shooting conditionss of 0.1W at power, observes strong orange up-conversion luminescence.
Instance 7: with analytically pure SiO 2, Al 2O 3, NaF, YF 3With purity be 99.99% ErF 3, YbF 3And TmF 3Powder is pressed 0.1TmF 3: 0.05ErF 3: 0.5YbF 3: 44SiO 2: 28Al 2O 3: 10.35NaF: 17YF 3The accurate weighing of the proportioning of (mol ratio) after the preparation and heat treatment process identical with instance 1, obtains pink transparent glass ceramics.Sample carries out indoor temperature measurement through surface finish with the FLS920 XRF, is under the 976 nanometer laser shooting conditionss of 0.1W at power, observes bright white up-conversion luminescence.
Instance 8: with analytically pure SiO 2, Al 2O 3, NaF, YF 3With purity be 99.99% HoF 3, YbF 3With TmF 3Powder is pressed 0.1TmF 3: 0.03HoF 3: 0.5YbF 3: 44SiO 2: 28Al 2O 3: 10.37NaF: 17YF 3The accurate weighing of the proportioning of (mol ratio) after the preparation and heat treatment process identical with instance 1, obtains flaxen transparent glass ceramics.Sample carries out indoor temperature measurement through surface finish with the FLS920 XRF, is under the 976 nanometer laser shooting conditionss of 0.1W at power, observes bright white up-conversion luminescence.

Claims (2)

1. go up conversion of white light emission transparent glass ceramics, it is characterized in that: its chemical composition mol ratio is 44SiO 2-28Al 2O 3-17YF 3-10.35NaF-0.05ErF 3-0.1TmF 3-0.5YbF 3, and 44SiO 2-28Al 2O 3-17YF 3-10.37NaF-0.03HoF 3-0.1TmF 3-0.5YbF 3
2. the preparation method of the glass-ceramic of a claim 1 is characterized in that: adopt SiO 2, Al 2O 3, YF 3, NaF, YbF 3, TmF 3And ReF 3Powder is as raw material, and wherein Re=Er or Ho with the mol ratio of its chemical composition, mix post-heating to 1300-1500 ℃ and be incubated 0-5 hour, then, melting liquid are made vitreum; This vitreum continues to be heated to 550-750 ℃ and be incubated 1-10 hour after internal stress is eliminated in annealing.
CN2007100099820A 2007-12-11 2007-12-11 Glass-ceramics for emitting bright white light through up-conversion Expired - Fee Related CN101456675B (en)

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Publication number Priority date Publication date Assignee Title
CN109761501A (en) * 2019-03-08 2019-05-17 福建师范大学 A kind of glass ceramics can be used for up-conversion lasing solid-state lighting and preparation method thereof and solid-state lighting device

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US20130069005A1 (en) * 2010-06-08 2013-03-21 Ocean's King Lighting Science & Technology Co., Ltd. Transparent glass ceramic emitting white light and preparation method thereof
EP2597071B1 (en) 2010-07-22 2016-10-19 Ocean's King Lighting Science&Technology Co., Ltd. White light emitting glass-ceramic and production method thereof
CN102344247B (en) * 2010-08-02 2014-07-23 海洋王照明科技股份有限公司 Glass luminescent material and preparation method thereof
CN102775990B (en) * 2011-09-09 2013-08-28 太原理工大学 Method for quickly preparing ultraviolet phosphors
CN102503139B (en) * 2011-11-10 2016-08-17 中国科学院福建物质结构研究所 A kind of up-conversion luminous transparent glass ceramic and preparation method thereof
CN102491642A (en) * 2011-12-06 2012-06-13 中国科学院福建物质结构研究所 Up-conversion white light emission glass ceramic and preparation method thereof
CN102992630A (en) * 2012-12-12 2013-03-27 中国科学院福建物质结构研究所 Nano-structure glass ceramic with up / down conversion luminescent property and preparation method thereof
CN103073190B (en) * 2013-02-21 2014-12-24 山东轻工业学院 Spontaneously-crystallized up-converting luminescent transparent ceramic glass
CN105948481A (en) * 2016-06-21 2016-09-21 海南中航特玻科技有限公司 Method for improving upconversion luminescence efficiency of silicate glass
CN110002761A (en) * 2019-03-04 2019-07-12 昆明理工大学 A kind of upper conversion LED fluorescent glass-ceramics and preparation method thereof

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