CN101870557A - Preparation method of germanium tellurite glass optical prefabricated rod output by green ray - Google Patents

Preparation method of germanium tellurite glass optical prefabricated rod output by green ray Download PDF

Info

Publication number
CN101870557A
CN101870557A CN200910030592A CN200910030592A CN101870557A CN 101870557 A CN101870557 A CN 101870557A CN 200910030592 A CN200910030592 A CN 200910030592A CN 200910030592 A CN200910030592 A CN 200910030592A CN 101870557 A CN101870557 A CN 101870557A
Authority
CN
China
Prior art keywords
glass
preparation
green ray
conversion
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN200910030592A
Other languages
Chinese (zh)
Inventor
柳祝平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN200910030592A priority Critical patent/CN101870557A/en
Publication of CN101870557A publication Critical patent/CN101870557A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01—Manufacture of glass fibres or filaments
    • C03B37/012—Manufacture of preforms for drawing fibres or filaments
    • C03B37/01265—Manufacture of preforms for drawing fibres or filaments starting entirely or partially from molten glass, e.g. by dipping a preform in a melt
    • C03B37/01268—Manufacture of preforms for drawing fibres or filaments starting entirely or partially from molten glass, e.g. by dipping a preform in a melt by casting
    • 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
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The invention relates to a preparation method of germanium tellurite glass optical prefabricated rod output by green ray, a component formula of the glass and a preparation method. The glass material has strong up-conversion green ray luminous intensity. When the luminous strength of the green ray is the greatest, the mixture ratio of the glass is as follows: 55mol% of TeO2, 3.75mol% of GeO2, 12mol% of ZnO, 50mol% of ZnCl2, 0.75mol% of Er2O3, and 3.5mol% of Yb2O3. The oxychloride tellurite glass prepared by the melting method is transparent, has favorable devitrification resistance capability, and excellent physical or chemical property; After the oxychloride tellurite glass with different contents of ZnCl2 is pumped by utilizing a semiconductor light source in a waveband of 980nm, the up-conversion green ray luminous intensity of the glass is dramatically improved. The glass can be applied to the up-conversion fibre optical laser and the color display device output by green ray.

Description

The germanium tellurate glass preform preparation method of green glow output
Technical field
The invention relates to a kind of oxychloride tellurite glasses and preparation method thereof.The germanium tellurate glass preform preparation method who particularly relates to a kind of green glow output.
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, and this mainly is to use widely at aspects such as optical information processing technology, video demonstration, laser printing, laser medicine and surface treatments owing to it.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.In the several method that obtains blue green light output, 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; And utilize the rare earth ion up-conversion luminescence 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.The report that the up-conversion luminescence phenomenon is all arranged in materials such as rare earth ion doped crystal, glass, optical fiber, have in addition obtain the output of blue green light laser.
Allomeric material is compared, and vitreous material has a lot of advantages 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 influences its sharp rotary light performance; In addition, the spectral width of broad also provides opportunity for the development of tunable wavelength laser apparatus.Adverse factors is, stimulated emission cross section in the vitreous material is lower, cause being difficult in and realize laser output in the block glass, but by 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, thereby can 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+: ZrF4 obtains during 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, CambridgeUniversity, Press, 2003, United Kingdom; [3] P.E.-A. E.heumann, G.Huber, and B.H.T.Chai, 540mW of blue output power at 425nm generated by intracavityfrequency doubling an upconversion pumped Er:YliF 4Laser, 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 [4] 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
Polynary oxychloride tellurite glasses maximum of the present invention is characterised in that provides a kind of brand-new glass formula.Compare with up-conversion lasing substrate material in the past, this kind material has overcome oxide glass (higher phonon energy) and fluoride glass (relatively poor chemical stability) institute inherent shortcoming.Because muriatic phonon energy is lower than fluorochemical, therefore, on the basis of improving glass heat stability and chemical stability, improved Er greatly 3+Luminous efficiency.Thereby for the last conversion optical fiber laser of green glow output provides a kind of suitable substrate material.
Er of the present invention 3+/ Yb 3-The mole percentage composition of the oxychloride tellurite glasses of mixing altogether is: 55mol%TeO 2, 3.75mol%GeO 2, 12mol%ZnO, 25mol%ZnCl 2, 0.75mol%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.
Er of the present invention 3+/ Yb 3+The concrete preparation process of the oxychloride tellurite glasses of mixing altogether is as follows:
According to above-mentioned prescription, after dusty raw materials mixed, be placed in the quartz crucible of adding a cover or the platinum crucible and melt, temperature of fusion is 825 ℃ and is optimum temperature of fusion, raw material melts fully, takes out after the homogenizing clarification, rapidly glass metal is cast on the swage tool of preheating.Fast this glass is put into then and be warming up to glass transformation temperature (T g) near retort furnace in anneal.Annealing process is: at glass transformation temperature (T g) near insulation 2 hours, be cooled to 100 ℃ with 3 ℃ speed per hour then, close the retort furnace power supply then and be cooled to room temperature automatically.Glass sample is taken out in the cooling back fully.
The differential thermal curve that records by differential thermal analyzer (DSC) is estimated the calorifics stability of glass.If 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.(T in the glass system of the present invention x-T g) much larger than the minimum temperature limit (100 ℃) of fibre-optical drawing, having good calorifics stability, physical and chemical performance is good simultaneously, can satisfy the requirement of use fully.
The innovation that the present invention obtained be in: (1) is 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 oxychloride tellurite glasses reach the requirement of practicability; (2) because TeO 2In oxide compound, have minimum phonon energy, pass through ZnCl 2Mix, further reduce 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.Thereby make this kind material on device such as the upconversion laser of blue light output and color monitor and equipment, possess fabulous application prospect, among (4) the present invention owing to reduced expensive TeO 2, improved cheap ZnCl 2Content, so production cost reduces greatly; And glass is to adopt common retort furnace to found, and manufacture craft is also very simple.
Description of drawings
Different ZnCl in the oxychloride tellurite glasses 2The up-conversion luminescence strength ratio of content
Embodiment
The invention will be further described below in conjunction with embodiment.
At first determine Er 3+/ Yb 3+Be total to the prescription of oxygen-doped chlorine tellurate glass.The mole of this glass formula is formed referring to table 1.
Table 1: the oxychloride tellurite glasses prescription is formed (mol%)
The batching title Ratio range Best proportioning
??TeO 2 ??40～70 ??55
??GeO 2 ??0～7.5 ??3.75
??ZnO ??4～20 ??12
??ZnCl 2 ??0～50 ??50
??Er 2O 3 ??0.5～1.0 ??0.75
??Yb 2O 3 ??2～5 ??3.5
Concrete exemplifying embodiment:
The first step: choose suitable glass formula (seeing Table 2);
Second step: found Er 3+/ Yb 3+Be total to the technological process of oxygen-doped chlorine tellurate glass: with highly purified TeO 2, GeO 2, ZnO, ZnCl 2, Er 2O 3And Yb 2O 3After dusty raw materials mixes, found in the globars electric furnace in the platinum crucible that is placed on, temperature of fusion is 825 ℃.Feed drying nitrogen in the glass smelting process and carry out atmosphere protection, on platinum crucible, will add a cover to prevent the volatilization of Cl simultaneously.Treat that raw material melts fully, and after homogenizing clarification, come out of the stove in 650～800 ℃, glass metal is cast on the swage tool of preheating.Rapidly this glass is put into then and be warming up to material transition temperature (T g) near retort furnace in anneal.Annealing process is to be incubated 2 hours earlier near the transition temperature of this glass material, lowers the temperature 100 ℃ with 3 ℃/hour speed then, closes the retort furnace power supply then and is cooled to room temperature automatically.
7 groups of Er of table 2 specific embodiment 3+/ Yb 3+Doping oxychloride tellurite glasses prescription
Glass ingredient (mol%) The 1st The 2nd group The 3rd group The 4th group The 5th group The 6th group The 7th group The 8th group
?TeO 2 ??70 ??60 ??50 ??45 ??45 ??40 ??40 ??55
?GeO 2 ??7.5 ??7.5 ??4 ??5 ??4 ??0 ??5 ??3.75
?ZnO ??20 ??10 ??10 ??7.5 ??5 ??7.5 ??4 ??12
?ZnCl 2 ??0 ??20 ??30 ??40 ??40 ??50 ??45 ??50
Glass ingredient (mol%) The 1st The 2nd group The 3rd group The 4th group The 5th group The 6th group The 7th group The 8th group
?Er 2O 3 ??0.5 ??0.5 ??1 ??0.5 ??1 ??0.5 ??1 ??0.75
?Yb 2O 3 ??2 ??2 ??5 ??2 ??5 ??2 ??5 ??3.5
Become the glass situation Transparent Transparent Transparent Transparent Transparent Transparent Transparent Transparent
Glass transformation temperature ??336 ??319 ??308 ??295 ??299 ??281 ??292 ??328
The crystallization starting temperature ??508 ??515 ??523 ??506 ??511 ??483 ??491 ??503
Temperature head (T x-T g ??172 ??196 ??215 ??211 ??212 ??202 ??199 ??201
By the transparent no crystallization of oxychloride tellurite glasses that aforesaid method makes, physical and chemical performance is good.Show the poor (T of the minimum temperature of oxychloride tellurite glasses system of the present invention from the DSC temperature data of being surveyed x-T g) be 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 ℃).
Accompanying drawing 1 is the up-conversion luminescence intensity of specific embodiment the 1st, 2,4,6,8 assembly sides under the same test condition of table 2.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 is showing and is increasing on the green glow, works as TeO 2: 55mol%, GeO 2: 3.75mol%, ZnO:12mol%, ZnCl 2: 50mol%, Er 2O 3: 0.75mol%, Yb 2O 3: during 3.5mol%, the 8th group of glass has maximum green intensity, is conversion 25 times of intensity on the 1st group of glass green glow approximately.

Claims (3)

1. an Er3+/Yb3+ is total to oxygen-doped chlorine tellurate glass, it is characterized in that it is composed as follows:
Component molar percentage (mol%)
TeO 2???????????55
GeO 2???????????3.75
ZnO????????????12
ZnCl 2??????????50
Er 2O 3??????????0.75
Yb 2O 3??????????3.5。
2. the described Er3+/Yb3+ of claim 1 is total to the preparation method of oxygen-doped chlorine tellurate glass, it is characterized in that comprising the steps:
1.. 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, place the globars electric furnace to melt, temperature of fusion is 825 ℃;
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 (Tg) and annealed, annealing process is: insulation is 2 hours near glass transformation temperature (Tg), be cooled to 100 ℃ with 3 ℃/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..
CN200910030592A 2009-04-24 2009-04-24 Preparation method of germanium tellurite glass optical prefabricated rod output by green ray Pending CN101870557A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200910030592A CN101870557A (en) 2009-04-24 2009-04-24 Preparation method of germanium tellurite glass optical prefabricated rod output by green ray

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200910030592A CN101870557A (en) 2009-04-24 2009-04-24 Preparation method of germanium tellurite glass optical prefabricated rod output by green ray

Publications (1)

Publication Number Publication Date
CN101870557A true CN101870557A (en) 2010-10-27

Family

ID=42995664

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200910030592A Pending CN101870557A (en) 2009-04-24 2009-04-24 Preparation method of germanium tellurite glass optical prefabricated rod output by green ray

Country Status (1)

Country Link
CN (1) CN101870557A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103359939A (en) * 2012-03-27 2013-10-23 中国科学院西安光学精密机械研究所 Green light tellurate glass and its prepn
CN108640506A (en) * 2018-08-22 2018-10-12 大连工业大学 A kind of preparation method of green light glass material
CN110217986A (en) * 2019-06-28 2019-09-10 井冈山大学 A kind of high density tungsten germanium tellurate scintillation glass and preparation method thereof
CN110357425A (en) * 2019-08-07 2019-10-22 井冈山大学 High-density barium germanium tellurate scintillation glass and preparation method thereof
CN111205869A (en) * 2020-01-17 2020-05-29 西南大学 Red-green up-conversion fluorescent powder and preparation method thereof
CN115165138A (en) * 2022-07-15 2022-10-11 东北大学 Optical fiber temperature sensor for chip real-time thermal monitoring and manufacturing method and application thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103359939A (en) * 2012-03-27 2013-10-23 中国科学院西安光学精密机械研究所 Green light tellurate glass and its prepn
CN108640506A (en) * 2018-08-22 2018-10-12 大连工业大学 A kind of preparation method of green light glass material
CN110217986A (en) * 2019-06-28 2019-09-10 井冈山大学 A kind of high density tungsten germanium tellurate scintillation glass and preparation method thereof
CN110357425A (en) * 2019-08-07 2019-10-22 井冈山大学 High-density barium germanium tellurate scintillation glass and preparation method thereof
CN111205869A (en) * 2020-01-17 2020-05-29 西南大学 Red-green up-conversion fluorescent powder and preparation method thereof
CN111205869B (en) * 2020-01-17 2023-08-08 西南大学 Red-green up-conversion fluorescent powder and preparation method thereof
CN115165138A (en) * 2022-07-15 2022-10-11 东北大学 Optical fiber temperature sensor for chip real-time thermal monitoring and manufacturing method and application thereof

Similar Documents

Publication Publication Date Title
Stevenson et al. Fluoride materials for optical applications: Single crystals, ceramics, glasses, and glass–ceramics
Serqueira et al. Judd Ofelt calculation of quantum efficiencies and branching ratios of Nd3+ doped glasses
CN111377609B (en) Preparation method of transparent glass with mid-infrared 3.9 mu m luminescence characteristic at room temperature
CN102659313B (en) Near-infrared broadband luminescence erbium and thulium-co-doped bismuthate laser glass and preparation method thereof
CN101486530A (en) 2-micron luminous rare earth ion-doped germanate laser glass and preparation method thereof
CN101870557A (en) Preparation method of germanium tellurite glass optical prefabricated rod output by green ray
Wang et al. Glass‐forming regions and enhanced 2.7 μm emission by Er3+ heavily doping in TeO2–Ga2O3–R2O (or MO) glasses
CN102211873A (en) 3-micron luminescent rare earth ion-doped fluorogermanate laser glass and preparation method thereof
CN100513339C (en) Rare earth doped gallium germanium bismuth lead luminous glass material and its preparation method and uses
CN102674690A (en) 3 mu m rare earth ion doped bismuth-germinate laser glass and preparation method thereof
Linganna et al. Longer lifetime of Er3+/Yb3+ co-doped fluorophosphate glasses for optical amplifier applications
CN103011593A (en) Erbium neodymium ion co-doped tellurium fluoride glass for emitting 2.7 microns of intermediate infrared light
CN112010557A (en) Transparent glass with middle infrared 3.5 mu m luminescence characteristic and preparation method thereof
Lakshminarayana et al. Fluorescence features of Tm3+-doped multicomponent borosilicate and borotellurite glasses for blue laser and S-band optical amplifier applications
Zaiter et al. Effect of potassium or yttrium introduction in Yb3+-doped germano-gallate glasses on the structural, luminescence properties and fiber processing
de Souza et al. Photoluminescence properties of Er 3+ and Er 3+/Yb 3+ doped tellurite glass and glass-ceramics containing Bi 2 Te 4 O 11 crystals
CN1262504C (en) Er3+/Yb3+Co-doped oxychloride tellurate glass and preparation method thereof
CN101121574B (en) Thulium adulterated germanate laser glass and preparation method thereof
Tanabe et al. Improved Fluorescence from Tm‐Ho‐and Tm‐Ho‐Eu‐Codoped Transparent PbF2 Glass‐Ceramics for S+‐Band Amplifiers
CN1233580C (en) Tm3+/Yb3+Codoped oxyfluoride tellurate glass and preparation method thereof
Yang et al. Energy transfer and frequency upconversion in Yb3+, Er3+ co-doped sodium–lead–germanate glasses
CN1562833A (en) Tm3+/Yb3+Codoped heavy metal oxyfluoride silicate glass and preparation method thereof
Cao et al. Positive influence of Sm3+ ion on the~ 2.85 µm emission in Yb3+/Ho3+ co-doped silica-germanate glass
CN103058516A (en) High-concentration erbium ion doped tellurium tungstate glass capable of emitting light at mid-infrared 2.7 microns
Iezid et al. Spectroscopic analysis of up conversion luminescence in doped halogeno-antimonite glass

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Open date: 20101027