WO2004054938A1 - Verre d'oxyde dopé au chrome - Google Patents

Verre d'oxyde dopé au chrome Download PDF

Info

Publication number
WO2004054938A1
WO2004054938A1 PCT/GB2003/005541 GB0305541W WO2004054938A1 WO 2004054938 A1 WO2004054938 A1 WO 2004054938A1 GB 0305541 W GB0305541 W GB 0305541W WO 2004054938 A1 WO2004054938 A1 WO 2004054938A1
Authority
WO
WIPO (PCT)
Prior art keywords
mol
range
glass
oxide
concentration
Prior art date
Application number
PCT/GB2003/005541
Other languages
English (en)
Inventor
Animesh Jha
Caroline Batchelor
Woon Jin Chung
Shaoxiong Shen
Original Assignee
The University Of Leeds
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 The University Of Leeds filed Critical The University Of Leeds
Priority to AU2003298444A priority Critical patent/AU2003298444A1/en
Publication of WO2004054938A1 publication Critical patent/WO2004054938A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • C09K11/676—Aluminates; Silicates
    • 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
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • 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
    • C03C3/253—Silica-free oxide glass compositions containing germanium
    • 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
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass

Definitions

  • the present invention relates to a chromium doped oxide glass. More particular, but not exclusively, the present invention relates to a chromium doped oxide glass including a charge transfer facilitating oxide.
  • Chromium doped glasses and crystals have been studied for their spectroscopic properties for many years, in particular for their use as tunable vibronic solid-state lasers.
  • Cr 3+ - doped BeAl 2 0 4 (alexandrite) that is tunable over the range 700-850nm- (depending on the pumping conditions and the optics applied) has a lifetime of 260 ⁇ s
  • Cr 4+ -doped Mg 2 Si0 4 forsterite
  • tunable over the range l.l-1.4 ⁇ m (again depending upon the pumping conditions and optics) has a lifetime of less than 4 ⁇ s .
  • These well-known crystal hosts have much larger quantum efficiencies for Cr 4+ and Cr3+ ions than when they are present in a glass host. Crystal hosts however suffer from a major disadvantage of being bulky, which then necessitates a large pump power requirement for tunable lasers requiring an efficient cooling system for the device.
  • glass fibre lasers may be pumped using a commercially available semiconductor diode laser and therefore can be produced as compact devices.
  • Much research has been undertaken to produce both Cr 3+ and Cr 4+ containing glasses suitable for replacing the well-established laser crystals .
  • an aluminosilicate glass comprising: a) Si0 2 in the range 45 to 55 mol%; b) A1 2 0 3 in the range of 20 to 30 mol%; c) Cr 2 0 3 in the range 0.001 to 0.1 mol%; d) at least one of Li 2 0 or Na 2 0 and mixtures thereof; e) a charge transfer facilitating oxide; and f) further ingredients wherein the amounts of a + b + c + d + e + f total 100 mol% .
  • the aluminosilicate glass according to the invention has the advantage as it produces strong emissions from Cr 4+ ions when pumped in visible and near infrared wavelengths.
  • the concentration of Li 2 0 is in the range 10-25 mol%, more preferably in the range 10-20 mol%.
  • the concentration of Na 2 0 is in the range 10-25 mol%, more preferably in the range 10-20 mol%.
  • the concentration of the mixture of Li 2 0 and Na 2 0 can be in the range 10-25 mol% .
  • the aluminosilicate glass according to the invention can further comprise at least one of ZnO or Ti0 2 or mixtures ' " thereof.
  • the " concentration of ZnO or Ti0 2 " can " be in the range 0-10 mol%, preferably in the range 0.05-10 mol%, more preferably in the range 0.5-5 mol%.
  • the concentration of the mixture of ZnO and Ti0 2 can be in the range 0-10 mol%, preferably 0.05-10 mol%, more preferably 0.5-5 mol% .
  • the charge transfer facilitating oxide can be an oxide of at least one of Mn, P, As, Sb, V, Nb, Ta, Mo, W, Te, Sn, Pb and mixtures thereof.
  • the charge transfer facilitating oxide can be Bi 2 0 3 .
  • the concentration of charge facilitating oxide can be in the range 1-5 mol% .
  • a gallogermanate glass comprising: a) Ge0 2 in the range 65 to 85 m ⁇ l%; b) Ga 2 0 3 in the range 5 to 20 mol%; c) Cr 2 0 3 in the range 0.001 to 0.01 mol%; d) at least one of Li 2 0 and Na 2 0 and mixtures thereof; e) a charge transfer facilitating oxide; and f) further ingredients wherein the amounts of a, b, c, d, e and f total 100 mol%.
  • the concentration of Li 2 0 can be in the range 0-35 mol%, preferably in the range 0.05-35 mol%, more preferably in the range 5-20 mol%.
  • the concentration of Na 2 0 can be in the range 0-20 mol%, more preferably in the range 0.05-20 mol%, more preferably in the range 5-15 mol%.
  • the concentration of the mixture of Li 2 0 and Na 2 0 can be in the range 0-35 mol%, preferably in the range 0.01 to 35 mol% the concentration of Na 2 0 not exceeding 20 mol% .
  • the charge transfer facilitating oxide can be Bi 2 0 3 .
  • the charge transfer facilitating oxide can be an oxide of at
  • the concentration of the charge transfer facilitating' oxide can be in the range 0-15 mol%, more preferably in the range 0.05-15 mol%, more preferably in the range 0.5-5 mol%.
  • the galloger anate glass according to the invention can further comprise at least one of ZnO or Ti0 2 and mixtures thereof.
  • concentration of ZnO or Ti0 2 or mixtures thereof can be in the range 0-10 mol%, more preferably in the range 0.05-7 mol%, more preferably in the range 5-10 mol%.
  • a laser or amplifier including an aluminosilicate or gallogermanate glass according to the invention.
  • Figure 1 shows a Cr 3+ and Cr 4+ and energy level diagram in aluminosilicate and gallogermanate glasses
  • Figure 2 shows absorption spectra of aluminosilicate glasses
  • Figure 3 shows emission intensity against .wavelength for an aluminosilicate glass according to the invention
  • Figure 4 shows emission intensity versus wavelength for an aluminosilicate glass according to the invention
  • Figures 5 and 6 show plots of emission intensity versus time for an aluminosilicate glass " according to the invention, pumped at 514 nm and 797 nm respectively;
  • Figures 7 and 8 show emission intensity versus wavelength for a gallogermanate glass according to the invention pumped at 514 nm and various infrared wavelengths respectively;
  • Figures 9 and 10 shows plots of emission intensity versus time for a gallogermanate glass according to the invention pumped at 502 nm and 795 nm respectively.
  • Cr 3+ -ions when doped in glass produced broad emission, which is centred around 800 nm. This broad emission is due to the ions being located in distorted low- field octahedral sites of modifier ions, which are present in the aluminosilicate and gallogermanate compositions.
  • Chromium (Cr 3+ ) ions in these low-field sites when pumped at visible wavelengths, undergo a transition: 4 A 2 ⁇ 4 T 1A which then decays nonradiatively to the 4 T 2 level . From the T 2 level, the ions emit radiation as the ions relax to the vibronic ground state via the transition 4 T 2 ⁇ 4 A 2 .
  • the radiative decay occurs from the zero-phonon level via the transition 2 E- 4 A 2 .
  • the zero-phonon level is invariably observed around 690 to 730 nm in silicate glasses and crystal hosts.
  • the Cr 4+ -ions such as those found in the forsterite crystals prefer to occupy tetrahedral sites and absorb pump power to attain the metastable state via the 3 A 2 ⁇ 3 T 1 transition.
  • the nonradiative relaxation to the 3 T 2 state lowers the energy which is then followed by the 3 T 2 ⁇ 3 A 2 NIR emission peaked - ⁇ around " 1300 " nm.
  • the 3 T " 2 " - f3 A 2 " transition is " a ' vibronic transition, which is why the emission is quite broad compared to the non-vibronic transitions in the rare-earth doped glass systems.
  • the aluminosilicate and gallogermanate glasses according to the invention include charge transfer facilitating oxides which modify the glass network.
  • the Cr + ions doped in such glasses preferably occupy low-field octahedral sites similar to the sites of the network modifying ions.
  • Light emission from such glasses is via a charge transfer process which leads to meta stable lifetimes of at least as long as 300 ⁇ s .
  • the aluminosilicate glasses according to the invention include both low-field and high-field sites in which the Cr 3+ ions preferentially occupy.
  • the composition of the aluminosilicate glass is such that it resembles the crystal eucryptite, in which the layers of alternating A10 4 and Si0 tetrahedra are separated by Li ions.
  • Cr 3+ -ions can occupy either the low-field site between the layers, or by substituting for Al or Si ions within the high-field tetrahedral co-ordination.
  • Figure 2 shows in curve (a) the absorption spectrum of an aluminosilicate glass comprising Si0 2 , Al 2 0 3 , Li 2 0, ZnO and Cr 2 0 3 .
  • Curve (b) shows an absorption spectrum for the same glass including Bi 2 0 3 .
  • the excitation of the Cr 3+ absorption band gives rise to a small emission peak between 700 nm and 800 nm as can be seen in figure 3.
  • the larger emission peak in figure 3, between 1000 and 1400 nm is due to the Cr 4+ emission, which is evident in glass containing Bi 2 0 3 according to the invention.
  • Bi ions When Bi ions are incorporated in an aluminosilicate glass, the optical absorption and carrier properties similar to those seen in " sillenite " structures (Bi 12 G “ eO 20 and Bi 12 SiO 20 ) are observed, " see " figure 2.
  • These properties include a shoulder appearing in the absorption spectra, at around 500nm and a colour change in the samples from green for Cr 3+ -doped glasses to a brown/red for Cr + -doped glass.
  • the shoulder is reportedly due to antisite bismuth ions occupying on germanium sites. Chromium can replace bismuth in this tetrahedral germanium site to produce Cr + .
  • Figure 1 shows a representative energy level diagram indicating the charge transfer processes that are likely to occur between the levels .
  • compositional range of the aluminosilicate glasses according to the invention are shown in Table 1. Compositions outside of this range result in emission from Cr 3+ ions only.
  • X 2 is a charge transfer facilitating oxide. In one embodiment of the invention this is Bi 2 0 3 . Other oxides which participate in the charge transfer process as described below are also possible.
  • the Na 2 0 can replace Li 2 0 in part or completely.
  • the aluminosilicate glass for the invention can include Zno or
  • the Ti0 2 can replace ZnO in part or completely.
  • Shown in figures 3 and 4 are emission spectra of an aluminosilicate glass according to the invention pumped of various pump wavelengths in the visible region of the electromagnetic spectrum and at near infrared wavelengths respectively.
  • the glass was prepared from high purity starting materials (>99.99%) by melting in a platinum crucible. The melting and casting of the homogenised glass was carried out at 1600 "C for three hours in air, before being removed from the furnace and allowed to cool to room temperature. Annealing at temperatures below 500 'C yield more stable glasses as thermal stresses are removed.
  • the decay curves for Cr 4+ in the aluminosilicate glass according to the invention are shown in figures 5 and 6, pumped at 514nm and 797nm respectively.
  • the lifetime of the emission decreases when pumped at longer wavelengths due to the change in the population of the excited states.
  • the 3 T 2 ⁇ 3 A 2 level of Cr + is split into 3 further levels, each with a different lifetime profile. When the sample is pumped at longer wavelengths only the lower levels of this transition are active and participate in spontaneous emission.
  • Gallogermanate glasses are a lower temperature analogue to the aluminosilicate glasses described above.
  • X 2 is a charge transfer oxide as previously described.
  • Figures 7 and 8 show emission spectra of a gallogermanate glass according to the invention pumped in the visible region and at various near infrared wavelengths respectively.
  • the glass comprises Ge0 2 , Ga 2 0 3f Li 2 0, Bi 2 0 3 and Cr 2 0 3 .
  • the glass was melted at 1300 ° C for one hour before being removed from the furnace and being allowed to cool to room temperature. In this case the annealing was performed at 350 'C to relieve thermal stress.
  • Lifetime decays of the same glass is shown in figures 9 and 10, pumped at 502nm and 795nm respectively. Again the lifetime decreases as the pump wavelengths is increased.

Landscapes

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

Abstract

L'invention concerne un verre d'aluminosilicate comprenant: a) de 45 à 55 % molaires de Si02; b) de 20 à 30 % molaires de Al203; c) de 0,001 à 0,1 % molaires de Cr203; d) au moins l'un des éléments parmi Li20 ou Na20, et des mélanges de ceux-ci; e) un oxyde facilitant le transfert de charge; et f) d'autres ingrédients, la somme des quantités a + b + c + d + e + f représentant 100 % molaires. Un autre aspect de cette invention concerne un verre de gallogermanate comprenant: a) de 65 à 85 % molaires de GeO2; b) de 5 à 20 % molaires de Ga2O3; c) de 0,001 à 0,01 % molaires; d) au moins l'un des éléments parmi Li20 ou Na20, et des mélanges de ceux-ci; e) un oxyde facilitant le transfert de charge; et f) d'autres ingrédients, la somme des quantités a + b + c + d + e + f représentant 100 % molaires.
PCT/GB2003/005541 2002-12-18 2003-12-18 Verre d'oxyde dopé au chrome WO2004054938A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003298444A AU2003298444A1 (en) 2002-12-18 2003-12-18 Chromium doped oxide glass

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0229527.7 2002-12-18
GB0229527A GB0229527D0 (en) 2002-12-18 2002-12-18 Broad near-IR emissions at room temperature in Cr-doped oxide glasees for lasers and amplifiers

Publications (1)

Publication Number Publication Date
WO2004054938A1 true WO2004054938A1 (fr) 2004-07-01

Family

ID=9949936

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2003/005541 WO2004054938A1 (fr) 2002-12-18 2003-12-18 Verre d'oxyde dopé au chrome

Country Status (3)

Country Link
AU (1) AU2003298444A1 (fr)
GB (1) GB0229527D0 (fr)
WO (1) WO2004054938A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2245113A2 (fr) * 2008-02-08 2010-11-03 University of Georgia Research Foundation Compositions phosphorescentes, procédés de préparation des compositions, et procédés d utilisation des compositions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1643489A1 (ru) * 1989-05-18 1991-04-23 Ленинградский Технологический Институт Им.Ленсовета ИК-прозрачное стекло
DE4401851A1 (de) * 1994-01-22 1995-07-27 Horst Hans Juergen Chrom- und kupferoxidhaltiges fotosensibles Lithiumalumosilikatglas
WO1995030916A1 (fr) * 1994-05-06 1995-11-16 Bay Glass Research Verre de germanate pour fibre optique medicale a infrarouge moyen
JPH11157871A (ja) * 1997-11-19 1999-06-15 Nippon Telegr & Teleph Corp <Ntt> ガラス組成物およびその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1643489A1 (ru) * 1989-05-18 1991-04-23 Ленинградский Технологический Институт Им.Ленсовета ИК-прозрачное стекло
DE4401851A1 (de) * 1994-01-22 1995-07-27 Horst Hans Juergen Chrom- und kupferoxidhaltiges fotosensibles Lithiumalumosilikatglas
WO1995030916A1 (fr) * 1994-05-06 1995-11-16 Bay Glass Research Verre de germanate pour fibre optique medicale a infrarouge moyen
JPH11157871A (ja) * 1997-11-19 1999-06-15 Nippon Telegr & Teleph Corp <Ntt> ガラス組成物およびその製造方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE INSPEC [online] THE INSTITUTION OF ELECTRICAL ENGINEERS, STEVENAGE, GB; GRINBERG M ET AL: "High-pressure luminescence of Cr/sup 3+/-doped CaO-Ga/sub 2/O/sub 3/-GeO/sub 2/ glasses", XP002279614, Database accession no. 7172035 *
DATABASE WPI Section Ch Week 199213, Derwent World Patents Index; Class L01, AN 1992-103007, XP002279615 *
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 11 30 September 1999 (1999-09-30) *
PHYSICAL REVIEW B, vol. 65, no. 6, 1 February 2002 (2002-02-01), Phys. Rev, B, Condens, Matter Mater. Phys. (USA), Physical Review B (Condensed Matter and Materials Physics), 1 Feb. 2002, APS through AIP, USA, pages 064203/1 - 9, ISSN: 0163-1829 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2245113A2 (fr) * 2008-02-08 2010-11-03 University of Georgia Research Foundation Compositions phosphorescentes, procédés de préparation des compositions, et procédés d utilisation des compositions
EP2245113A4 (fr) * 2008-02-08 2011-02-23 Univ Georgia Res Found Compositions phosphorescentes, procédés de préparation des compositions, et procédés d utilisation des compositions

Also Published As

Publication number Publication date
GB0229527D0 (en) 2003-01-22
AU2003298444A1 (en) 2004-07-09

Similar Documents

Publication Publication Date Title
US3717583A (en) Neodymium glass laser having room temperature output at wavelengths shorter than 1060 nm.
EP1180835B1 (fr) Verre amplificateur de lumière
US3714059A (en) Neodymium glass laser having room temperature output at wavelengths shorter than 1060 nm
Gonçalves et al. Rare-earth-doped transparent glass ceramics
US6599853B2 (en) Optical amplifier glass
EP1254869B1 (fr) Verre amplificateur de lumiere et procede de fabrication
US6410467B1 (en) Antimony oxide glass with optical activity
US6503860B1 (en) Antimony oxide glass with optical activity
WO2004058656A1 (fr) Composition de verre fluorescente dans la zone de longueur d&#39;onde infrarouge
JP2003283028A (ja) 赤外発光体および光増幅媒体
JPWO2006090801A1 (ja) ビスマスを含有するガラス組成物、およびこれを用いた信号光の増幅方法
WO1999033758A2 (fr) Verres tellurides presentant une solubilite amelioree des ions de terres rares
WO2004058657A1 (fr) Composition de verre fluorescente a des longueurs d&#39;onde infrarouge
US6444599B1 (en) Rare earth element-halide environments in oxyhalide glasses
WO2004054938A1 (fr) Verre d&#39;oxyde dopé au chrome
US6797657B2 (en) Tm-doped fluorophosphate glasses for 14xx amplifiers and lasers
JPS60155546A (ja) 発光ガラス
CN113387563A (zh) 掺镨红光玻璃及其制备方法
US3825500A (en) Neodymium glass laser having room temperature output at wavelengths shorter than 1060 nm
Pinckney et al. Transparent gallate spinel glass-ceramics
JP7090905B2 (ja) 透明結晶化ガラス、及び透明結晶化ガラスの製造方法
Yang et al. Thermal analysis and optical transition of Yb 3+, Er 3+ co-doped lead–germanium–tellurite glasses
Heo et al. Optoelectronics: Active Chalcogenide Glasses
MXPA00005435A (en) Rare earth element-halide environments in oxyhalide glasses
KR20020005939A (ko) 어븀 이온의 980 나노미터 여기 효율과 섬유화 특성향상을 위한 텔루라이트 유리 조성물

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP