CN1262504C - Er/Yb doped tellurate oxychloride glass and its prepn process - Google Patents

Er/Yb doped tellurate oxychloride glass and its prepn process Download PDF

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CN1262504C
CN1262504C CN 200410089018 CN200410089018A CN1262504C CN 1262504 C CN1262504 C CN 1262504C CN 200410089018 CN200410089018 CN 200410089018 CN 200410089018 A CN200410089018 A CN 200410089018A CN 1262504 C CN1262504 C CN 1262504C
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glass
tellurate
mol
preparation
oxygen
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CN1636906A (en
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汪国年
戴世勋
张军杰
姜中宏
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Shanghai Institute of Optics and Fine Mechanics of CAS
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Shanghai Institute of Optics and Fine Mechanics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0071—Compositions for glass with special properties for laserable glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

The present invention relates to Er3+/Yb3+ doped tellurate oxychloride glass for outputting green light and a preparation method thereof. The tellurate oxychloride glass has the basic composition of 40 to 70 mol% of TeO2, 0 to 7.5 mol% GeO2, 4 to 20 mol% of ZnO, 0 to 50 mol% ofZnCl2, 0.5 to 1.0 mol% of Er2O3 and 2 to 5 mol% of Yb2O3. The tellurate oxychloride glass is prepared by a melt-spinning method. The preparation method has the advantages of simple process and low cost. The prepared tellurate oxychloride glass is transparent and has the advantages of good anti-devitrification ability, good physical and chemical properties and obviously increased up conversion strength of green light. The glass can be used in up converting fiber lasers, color displays, etc. for outputting green light.

Description

Er 3+/ Yb 3+Be total to oxygen-doped chlorine tellurate glass and preparation method thereof
Technical field
The present invention relates to tellurate glass, particularly a kind of have an Er that changes on the high-level efficiency green glow 3+/ Yb 3+Be total to oxygen-doped chlorine tellurate glass and preparation method thereof.
Background technology
The short wavelength lasers such as blue green light that how to obtain cheapness, the output of efficient, small-sized and superpower are the emphasis and the difficult point of present optoelectronic functional materials and field of optoelectronic devices research, this mainly is because this kind laser apparatus is used widely at aspects such as optical information processing technology, video demonstration, laser printing, laser medicine and surface treatments, as solving the saturation problem (Jelov minimum) that the electromagnetic radiation transmission can only be operated in low frequency (100Hz) zone and 400-500nm zone in the transmission under water, realize that the big degree of depth of seabed signal is transmitted fast; In biomedicine, can simplify flow cytometry and DNA sequencer procedure; In Laser Printing equipment, improve print speed and resolving power or the like.
Obtain the several different methods that has of blue green light output, wherein utilize the frequency multiplication of non-linear optic crystal, though have beam quality preferably, need complicated non-linear parameter process carry out frequency inverted, system comparatively complexity and cost is also high; Utilize wide bandgap semiconductor materials directly to excite, though occurred and along with the prolongation of the raising of output rating and working life practicability progressively, the drawbacks limit of aspects such as its laser linewidth only is several nanometers, the drift of output light frequency is indefinite, the angle of divergence big, hot spot lack of homogeneity and the easy temperature influence of working order its direct application in a lot of fields; Utilize the rare earth ion up-conversion luminescence then to have following tangible advantage: 1) can effectively reduce the decline that photo ionization causes substrate material; 2) not high to the stability requirement of excitation wavelength, do not need strict phase matched; 3) output wavelength has certain tunability; 4) help the development of simple, cheapness and compact construction miniature laser system.
In materials such as rare earth ion doped crystal, glass, optical fiber, all have the up-conversion luminescence phenomenon to produce, have in addition obtain the output of blue green light laser.Wherein vitreous material all has more advantages than crystalline material aspect the wavelength region of the selection of pumping wavelength and laser output: the aperiodicity of vitreous material structure, make the spectrum of rare earth ion have the inhomogeneous broadening phenomenon, so the selection of pumping wavelength comparatively extensively and not influence its laser activity; In addition, the spectral width of broad also provides opportunity for the development of tunable wavelength laser apparatus.Yet, also have adverse factors: the stimulated emission cross section in the vitreous material is lower, cause being difficult in and realize laser output in the block glass, therefore need block glass material is drawn into optical fiber, pump light is limited in the small cross-section zone, under long fiber lengths, realize sufficient population inversion, to obtain stronger up-conversion lasing emission.
Realize first that in the world the output of blue green light laser is the people such as J.Y.Allain of nineteen ninety France National Communications Center under the room temperature [1]Adopt 300mW, 647nm laser pumping Ho 3+: obtain during the ZrF4 single-mode fiber, output rating is 10mW, and it is adjustable (referring to document [1] J.Y.Allain in 540～553nm scope, M.Monerie, and H.Poignant, Room temperature cw tunable greenupconversion holmium fiber laser, Electron.Lett.1990,26 (4): 261-262).Extensively carried out about the research of rare earth ion optical fiber laser afterwards, and the report of blue green light laser output is arranged in succession [2,3](referring to document [2] W.P.Risk, T.R.Gosnell, and A.V.Nurmikko, Compact blue-green lasers, Cambridge University, Press, 2003, UnitedKingdom; [3] P.E.-A.M bert, E.heumann, G.Huber, and B.H.T.Chai, 540mW of blue output power at 425nm generated by intracavity frequencydoubling an upconversion pumped Er:YliF4 laser, Appl.Phys.Lett.2003,73 (2): 139-141).
About the main result of study of rare earth ion up-conversion lasing output, the substrate material that is adopted was fluoride glass optical fiber or crystal from recent years.This mainly is because the lower phonon energy of fluoride materials can reduce the power loss that is caused by the multi-phonon relaxation, improves luminous quantum yield.But the stability of fluoride materials and bad mechanical strength, anti-laser lose shortcomings such as threshold value is low, technology is made difficulty and have limited its practical application to a great extent.Therefore people attempt to develop up-conversion luminescent material in oxide glass.Otto in 2000 etc. [4]Reported Tm under the 668nm 3+Ion is realized switching emission on the blue light (referring to document [2] A.P.Otto, K.S.Brewer, A.J.Silversmith, J.Non-Cryst.Solids 265 (2000) 176) at silicate glass.Pure oxide glass chemical stability is good, and physical strength height, but its phonon energy height make that efficiency of conversion greatly reduces on it, can not satisfy actual application at all.Therefore design a kind of physico-chemical property preferably that both had, have the glass material of very low phonon energy again, realize that at room temperature up-conversion luminescence has efficiently become the task of top priority.
Summary of the invention
The object of the present invention is to provide a kind of Er 3+/ Yb 3+Be total to oxygen-doped chlorine tellurate glass and preparation method thereof, to overcome above-mentioned the deficiencies in the prior art, particularly overcome oxide glass (higher phonon energy) and fluoride glass (relatively poor chemical stability) institute inherent shortcoming, both had physico-chemical property preferably, had very low phonon energy and higher last efficiency of conversion again.
For achieving the above object, the invention provides a kind of Er 3+/ Yb 3+Be total to oxygen-doped chlorine tellurate glass, its characteristics are that it consists of 40～70mol% TeO 2, 0～7.5mol% GeO 2, 4～20mol% ZnO, 0～50mol% ZnCl 2, 0.5～1.0mol% Er 2O 3, 2～5mol% Yb 2O 3By muriatic introducing amount of suitable adjustment and Er 3+, Yb 3+Proportioning, can obtain stronger up-conversion luminescence intensity.
The present invention also provides above-mentioned Er 3+/ Yb 3+The preparation method of oxygen-doped chlorine tellurate glass is characterized in comprising the steps: altogether
1.. after the selected proportioning of above-mentioned prescription, each raw material of weighing mixes dusty raw materials;
2.. compound is put into the quartz crucible or the Platinum crucible of adding a cover, place the globars electric furnace to melt, temperature of fusion is 700～850 ℃;
3.. complete raw material melted homogenizing clarification back is taken out, and rapidly this glass metal is cast on the mould of preheating;
4.. fast this glass is put near the retort furnace that is warming up to the glass transformation temperature and annealed, annealing process is: insulation is 2 hours near glass transformation temperature, be cooled to 100 ℃ with 2～5 ℃/hour speed then, close the retort furnace power supply then, be cooled to room temperature automatically;
5.. treat to cool off fully the back and take out glass sample.
Feed drying nitrogen in the described step melting process 2. and carry out atmosphere protection.
The calorifics stability of glass is estimated by the differential thermal curve that differential thermal analyzer (DSC) records.The crystallization of glass begins temperature (T x) and transition temperature (T g) difference big more, then anti-crystallization ability is strong more, shows that the thermostability of this glass is good more.The crystallization of glass begins the poor (T of temperature and transition temperature in the glass system of the present invention x-T g) limit (100 ℃) much larger than the minimum temperature of fibre-optical drawing, thereby have good calorifics stability, physical and chemical performance is good simultaneously, can satisfy the requirement of use fully.
Technique effect of the present invention is:
(1) by suitably adding GeO 2Improved the formation ability and the mechanical property of glass system with ZnO, improved the anti-crystallization ability of system, made the oxychloride tellurite glasses good heat stability, physical and chemical performance is good, has reached the requirement of practicability;
(2) because TeO 2In oxide compound, have minimum phonon energy, pass through ZnCl 2Mixing of (muriatic phonon energy being lower than fluorochemical) further reduced the phonon energy of system, thereby improved Er greatly 3+Last efficiency of conversion;
(3) pass through Er 3+/ Yb 3+The adjusting of doping content proportioning has drawn the best Er that has maximum up-conversion luminescence intensity in the body series glass 3+/ Yb 3+Proportioning, thus make this kind material on device such as the upconversion laser of green glow output and color monitor and equipment, possess fabulous application prospect;
(4) simultaneously, among the present invention owing to reduced expensive TeO 2, improved cheap ZnCl 2Content, so production cost reduces greatly; And this invention adopts common retort furnace to found, and manufacture craft is also very simple.
Description of drawings
Fig. 1 is different ZnCl 2The Er of the present invention of content 3+/ Yb 3+Be total to the up-conversion luminescence strength test figure of oxygen-doped chlorine tellurate glass under the same test condition.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Er of the present invention 3+/ Yb 3+The mole of the prescription of oxygen-doped chlorine tellurate glass is formed as shown in table 1 altogether.
Component Molar percentage (mol%)
TeO 2 40～70
GeO 2 0～7.5
ZnO 4～20
ZnCl 2 0～50
Er 2O 3 0.5～1.0
Yb 2O 3 2～5
Table 1: the mole of glass formula of the present invention is formed
Table 2 has been listed Er of the present invention 3+/ Yb 3+Be total to the prescription of seven groups of specific embodiments of oxygen-doped chlorine tellurate glass.
The 1st group The 2nd group The 3rd group The 4th group The 5th group The 6th group The 7th group
Glass ingredient (mol%) TeO 2 70 60 50 45 45 40 40
GeO 2 7.5 7.5 4 5 4 0 5
ZnO 20 10 10 7.5 5 7.5 4
ZnCl 2 0 20 30 40 40 50 45
Er 2O 3 0.5 0.5 1 0.5 1 0.5 1
Yb 2O 3 2 2 5 2 5 2 5
Become the glass situation Transparent Transparent Transparent Transparent Transparent Transparent Transparent
Glass transformation temperature T g (℃) 336 319 308 295 299 281 292
Crystallization starting temperature T x (℃) 508 515 523 506 511 483 491
Temperature head T x-T g (℃) 172 196 215 211 212 202 199
Table 2: the prescription of glass specific embodiment of the present invention
The preparation method of concrete exemplifying embodiment comprises the following steps:
The first step: choose glass formula by table 2, each raw material of weighing is with highly purified TeO 2, GeO 2, ZnO, ZnCl 2, Er 2O 3And Yb 2O 3Dusty raw materials mixes;
Second step: compound is put into quartz crucible or platinum crucible, place the globars electric furnace to found, temperature of fusion is 700-850 ℃, founds in the process to feed drying nitrogen and carry out atmosphere protection, will add a cover to prevent Cl on platinum crucible simultaneously -Volatilization;
The 3rd step: treat that raw material melts fully, and after homogenizing clarification, come out of the stove in 650～800 ℃, rapidly glass metal is cast on the swage tool of preheating;
The 4th step: this glass is put into be warming up to the material transition temperature T rapidly gAnneal near the retort furnace, annealing process is the transition temperature T of elder generation at this glass material gNear insulation 2 hours, be cooled to 100 ℃ with 2～5 ℃/hour speed then, close the retort furnace power supply then, be cooled to room temperature automatically;
The 5th step: treat to cool off fully the back and take out glass sample.
The Er that makes by aforesaid method 3+/ Yb 3+Be total to the transparent no crystallization of oxygen-doped chlorine tellurate glass, physical and chemical performance is good.Show that from the DSC temperature data of being surveyed the devitrification of glass of oxychloride tellurite glasses system of the present invention begins the minimum temperature difference T of temperature and transition temperature x-T gBe 172 ℃, illustrate that body series glass has the anti-crystalline range of non-constant width, the use temperature that can reach practical application requires (＞100 ℃).
Er by different ingredients of the present invention (specific embodiment the 1st, 2,4,6 assembly sides) preparation gained 3+/ Yb 3+The test result of oxygen-doped chlorine tellurate glass (by the semiconductor light source pumping of 980nm wave band) up-conversion luminescence intensity under the same test condition as shown in Figure 1 altogether.As seen from Figure 1, at fixing Er 2O 3And Yb 2O 3Be respectively under the condition of 0.5mol% and 2mol%, along with ZnCl 2The increase of content, conversion intensity enlarges markedly on the green glow, and wherein the 6th group of glass has maximum green intensity, is conversion 20 times of intensity on the 1st group of glass green glow approximately.

Claims (3)

1, a kind of Er 3+/ Yb 3+Be total to oxygen-doped chlorine tellurate glass, it is characterized in that it is composed as follows:
The component molar percentage
TeO 2 40～70
GeO 2 0～7.5
ZnO 4～20
ZnCl 2 0～50
Er 2O 3 0.5～1.0
Yb 2O 3 2～5。
2, the described Er of claim 1 3+/ Yb 3+The preparation method of oxygen-doped chlorine tellurate glass is characterized in that comprising the steps: altogether
1. according to after the selected proportioning of the described prescription of claim 1, each raw material of weighing mixes dusty raw materials;
2. compound is put into the quartz crucible or the platinum crucible of adding a cover, placed the globars electric furnace to melt, temperature of fusion is 700～850 ℃;
3. complete raw material melted homogenizing clarification back is taken out, and rapidly this glass metal is cast on the mould of preheating;
4. fast this glass being put into the retort furnace that is warming up to glass transformation temperature anneals, annealing process was: glass transformation temperature insulation 2 hours, be cooled to 100 ℃ with 2～5 ℃/hour speed then, close the retort furnace power supply then, be cooled to room temperature automatically;
5. treat to cool off fully the back and take out glass sample.
3, preparation method according to claim 2 is characterized in that feeding drying nitrogen in the described step melting process 2..
CN 200410089018 2004-12-02 2004-12-02 Er/Yb doped tellurate oxychloride glass and its prepn process Expired - Fee Related CN1262504C (en)

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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1321924C (en) * 2005-10-27 2007-06-20 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
CN101812299B (en) * 2010-04-23 2013-03-13 同济大学 Nanocrystal reinforced rare earth doped tellurate luminous film material and preparation method thereof
CN102121591B (en) * 2010-12-23 2012-07-25 大连海事大学 White LED light source and manufacturing method of phosphor thereof
CN102849943B (en) * 2012-09-21 2015-05-20 蚌埠玻璃工业设计研究院 Upconversion aluminosilicate glass for silica-base film solar battery
CN103086600B (en) * 2013-02-27 2015-03-04 中国计量学院 High erbium-doped lead-free fluoride (halide) tellurate laser glass, and preparation method and application thereof
CN104877686B (en) * 2015-06-25 2017-05-10 西南大学 Up-converting luminescence material and preparation method thereof
CN105271730B (en) * 2015-10-20 2018-01-23 宁波大学 A kind of multicolor emission tellurium bismuth titanium glass and preparation method thereof

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