EP0914300A2 - Composition de verre presentant un spectre a phonons de faible energie, son procede de production et son utilisation - Google Patents

Composition de verre presentant un spectre a phonons de faible energie, son procede de production et son utilisation

Info

Publication number
EP0914300A2
EP0914300A2 EP98929219A EP98929219A EP0914300A2 EP 0914300 A2 EP0914300 A2 EP 0914300A2 EP 98929219 A EP98929219 A EP 98929219A EP 98929219 A EP98929219 A EP 98929219A EP 0914300 A2 EP0914300 A2 EP 0914300A2
Authority
EP
European Patent Office
Prior art keywords
glass composition
atom
rare earth
glass
composition according
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.)
Withdrawn
Application number
EP98929219A
Other languages
German (de)
English (en)
Inventor
Lothar Weber
Helmut Sautter
Jürgen Graf
Frank Gross
Peter LÖFFLER
Ingo Lang
Martin Mennig
Helmut Schmidt
Ulrich Sohling
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.)
Robert Bosch GmbH
Original Assignee
Robert Bosch GmbH
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
Priority claimed from DE19813607A external-priority patent/DE19813607A1/de
Application filed by Robert Bosch GmbH filed Critical Robert Bosch GmbH
Publication of EP0914300A2 publication Critical patent/EP0914300A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
    • H01S3/16—Solid materials
    • H01S3/17—Solid materials amorphous, e.g. 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
    • C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
    • C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
    • C03C3/323—Chalcogenide glasses, e.g. containing S, Se, Te containing halogen, e.g. chalcohalide glasses
    • 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
    • C03C4/10—Compositions for glass with special properties for infrared transmitting glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
    • H01S3/16—Solid materials
    • H01S3/1601—Solid materials characterised by an active (lasing) ion
    • H01S3/1603—Solid materials characterised by an active (lasing) ion rare earth

Definitions

  • the invention relates to a transparent glass composition according to the preamble of claim 1, which has very good transmission properties far into the infrared range of the electromagnetic spectrum and has a phonon spectrum of low energy.
  • a method for producing this glass composition is described, as well as a method for producing thin layers from the glass composition according to the invention and their use for producing optical components.
  • gallium sulfide is present in the glass structure in the form of side-bridged GaS4 tetrahedra, in the tetrahedron gaps of which rare earth metal cations can be embedded as well as in the comparable purely oxidic glasses, which typically have a three-dimensional network of relatively ionically bound MO4 tetrahedra, in which M is a so-called “network-forming” element, for example silicon, phosphorus, aluminum, boron, etc.
  • the Pr-doped ZBLAN glasses co-doped with Yb, provide only unsatisfactory results (P. Xie and T. R. Gosnell in: Electronics Letters 1995, 31,191).
  • the highest phonon energy for example in oxide glasses, is of the order of 1100 cm " , so that only three such phonons are required to make up the difference between the 1 G 4 level and to bridge the 3 F 4 level without radiation. In extreme cases, this means that no measurable emissions can be observed at 1.3 ⁇ m.
  • ZBLAN glass matrices solve this fundamental problem by using fluorides, which change the term splitting of the rare earth metal cation and also the Reduce the maximum possible phonon energy to approx. 500 cm " . At least 6 phonons are therefore required to bridge the energy difference 1 G 4 - 3 F.
  • the glass composition according to the invention with the characterizing features of the main claim offers the surprising advantage that the combination of sulfur and halogens in the form of their anions gives rare earth-doped chalchalide glasses which have a surprisingly favorable band position of praseodymium fluorescence, a long fluorescence life and good chemical resistance, especially against moisture.
  • An important reason for the advantageous high solubility of the rare earth elements in the glass composition according to the invention lies in the use of halide anions, which moreover influence the position of the fluorescence band. Due to the addition of halides, the glass composition according to the invention shows a high level compared to analog sulfide glasses Fluorescence life of up to 460 ⁇ s.
  • the glass composition has good chemical resistance, in particular to atmospheric humidity.
  • the glass composition according to the invention for example in the case of Ge 2 2, 2 Sn 6, 4 In 3, 2 S 63, 3 C1 4, 8 doped with 1040 mol ppm praseodymium, has a fluorescence lifetime of 460 ⁇ s.
  • the glass composition according to the invention has a particularly low phonon energy, which largely prevents the quenching of the laser energy from 1 G4 to 3 F by radiation-free phonon transitions.
  • G ⁇ 24 ⁇ ln 7 S48 2 20 6 ⁇ doped with 1000 mol-ppm praseodymium has a maximum phonon energy of 436 cm " measured by Raman spectroscopy. Comparable values, described for example in the
  • sulfides of the elements of the fourth or fifth main group which have a three-dimensional tetragonal solid structure, ie. H. whose MS4 units form edge-linked tetrahedron chains. They are isostructural to corresponding oxidic glasses, in particular silicate glasses, and enable good solubilities for almost all rare earth metal cations.
  • lead, antimony or bismuth is preferred, which leads to particularly high chemical resistance and furthermore supports the further incorporation of rare earth cations.
  • the glass composition is produced in such a way that pure elements, halides or sulfides of the corresponding metals and semimetals are used as constituents. This can result in a high Purity of the substances used can be achieved without any problems, since in particular pure elements can be supplied from the corresponding manufacturers in the highest possible purity level.
  • Halides and / or sulfides may be purified by distillation or sublimation.
  • the constituents of the glass composition are mixed intimately and reacted with one another in a melting process with the exclusion of air. This prevents oxygen anions from being incorporated into the glass composition in the case of non-oxide glasses.
  • the quenching of the glass composition thus obtained is advantageously carried out either in air or in water.
  • the raw glass thus produced is comminuted to powder particles in a particularly advantageous manner and taken up in a suitable solvent.
  • a wet chemical method is used in which a colloidal solution of the powder particles taken up is used. This enables a high solids content of the solution to be achieved, which almost completely precludes later shrinking processes of the applied layers during thermal compaction.
  • the solvent used preferably an aliphatic amine, such as propylamine, n-butylamine or ethylenediamine, acts as a stabilizer for the colloidally dispersed solution of the powder particles.
  • FIG. 1 shows an energy level diagram of Pr +
  • FIG. 2 shows an energy level diagram of Yb 3 + and Pr 3+ and the energy transfer from Yb 3+ to Pr 3+ ,
  • FIG. 3 shows a fluorescence spectrum of the 1.3 ⁇ m emission band of the 1 G4 ⁇ 3 H5 transition in a glass composition according to the invention
  • Figure 4 shows the fluorescence lifetime of the 1 G4 ⁇ state of
  • FIG. 5 shows the fluorescence lifetime of the 1 G4 state of Pr 3+ as a function of the Pr 3+ doping level of a glass composition according to the invention.
  • FIG. 6 shows the excitation spectrum of a co-doped glass composition according to the invention
  • Figure 7 is a three-phase diagram of an inventive
  • Tables 1 to 5 Examples of the glass composition according to the invention are shown in Tables 1 to 5.
  • the tables show the doping levels of Pr, Er or Yb in mol ppm, based on the total concentration of cations.
  • Figure 1 shows the energy level scheme of Pr 3+ .
  • the abscissa represents the relative energy in the unit 10 3 cm -1 .
  • Pr 3+ is raised from the ground state 3 H 4 by an excitation energy of approx. 1020 nm, for example by a laser, to the laser energy level 1 G4.
  • fluorescence radiation with a wavelength of approximately 1.3 ⁇ m is emitted, in this case of 1.33 ⁇ m (1330 nm).
  • FIG. 2 shows the energy level diagram for the energy transfer of a praseodymium chalchalide glass composition according to the invention co-doped with Yb 3+ .
  • the abscissa represents the relative energy in the unit 10 3 cm ⁇ 1 .
  • Yb is first 3+ 7 2 transferred from the ground state 2 F by a power supply, for example by a laser diode of 980 nanometers in the F 5/2 state, the spin-forbidden its energy nonradiative on the emitting 1 G 4 state of Pr 3+ transmits.
  • the desired wavelength is emitted by falling back of the now excited Pr 3+ from ⁇ 4 to 3 H5.
  • the emission maximum is between 1325 and 1345 nm.
  • Figure 3 shows the fluorescence wavelength of the glass composition Ge28 ⁇ -n6 s 56 c -'- 10 ( s - Table 1), doped with 1000 mol-ppm praseodymium with excitation with 1025 nm, the 1.3 ⁇ m fluorescence of the Pr 3+ Transition is at 1338 nm.
  • the abscissa shows the fluorescence intensity in relative units and the ordinate the wavelength in nm.
  • Table 1 Glass composition based on sulfide and sulfide chloride.
  • FIG. 4 with the associated table 4 shows the fluorescence lifetime in ⁇ s of the 1 G state of Pr 3+ as a function of the chloride content in the glass composition Ge22 Sn 6 4 In 3 2 s 67-x c - L x is clearly recognizable that an optimum between 6 and 13 atomic% chloride content is achieved based on the total anions.
  • the maxima are between 6.5 and 10 atom% chloride content based on the total anions. From a chloride content of 25 atomic% based on the total anions of the glass composition, the glass decomposes and in particular hydrolyses.
  • Figure 5 shows the fluorescence lifetime in microseconds of the 1 G4 state of Pr 3+ on the abscissa as a function of the Pr doping level on the ordinate in the glass composition Ge 2 gIng_ x Pr x S5 I 1 o. It can be seen here that low doping with praseodymium leads to longer fluorescence lifetimes. The maximum lifetime is achieved with the composition Ge28 ⁇ - n 6 s 56 I 10 doped with 1000 mol ppm Pr 3+ .
  • Figure 6 shows the excitation spectrum of the glass composition Ge 2 5 7 t> ⁇ 9 (In + Yb) 5/7 Sg 0 4Clg g (s. Table 2), which ppm molar of 5000 mol ppm of Pr 3+ and 10000 Yb 3 + is doped or co-doped.
  • the abscissa indicates the fluorescence intensity in relative units and the ordinate that
  • FIG. 6 shows the difference in the fluorescence intensity of the 1.3 ⁇ m fluorescence of Pr 3+ when excited with different wavelengths. Excitation of the Yb 3+ ions with 987.7 nm shows that the transferred energy becomes a
  • compositions have the shape
  • FIG. 7 shows a three-phase diagram for a glass composition according to the invention which contains Ga2S3, Sb2S3 and GeS2 as essential constituents.
  • Area 1 includes the prior art disclosed in U.S. Patent 5,392,376 for such mixtures.
  • the invention Glass composition comprises area 2, which is identified by points A, B, C and D.
  • All the exemplary embodiments of the glass composition according to the invention have in common a long fluorescence lifetime ⁇ eff of up to 460 ⁇ s.
  • the phonon energy of the glass composition according to the invention is generally very low.
  • l In 7, l s 48 2 I 20 6 doped with 1000 mol ppm Pr 3+ , ⁇ eff 309 ⁇ s and the phonon energy is 436 cm.
  • Table 3 Glass composition with 2 different halides.
  • the glass composition according to the invention characterized by a few exemplary embodiments, also has good temperature stability, indicated by the glass transition temperature T g .
  • the glass composition according to the invention has a very high moisture resistance.
  • the glass composition according to the invention is produced, for example, by melting the constituents in cleaned, evacuated silica glass ampoules and then quenching them in air or in ice water.
  • Starting materials are used in the highest commercially available degrees of purity. If necessary, the starting materials by sublimation or
  • the starting materials in particular high-purity germanium, indium, tin, erbium, Pr2S3, Yb2S3, Er2S3 and PbCl2, were obtained from Chempur, GeBr4, Sb and iodine from Alfa, Johnson Matthey, purified sulfur from Vitron, InCl3 from Strem and SrS from Cerac.
  • Thin glass film layers are produced from the glass composition according to the invention by means of the new method according to the invention.
  • substrates can be coated with colloidal solutions with a high solids content.
  • the raw glass is pulverized and colloidally dissolved in a solvent, preferably an aliphatic amine, for example propylamine, n-butylamine or ethylenediamine.
  • a solvent preferably an aliphatic amine, for example propylamine, n-butylamine or ethylenediamine.
  • the Solvents also act as stabilizers for the colloids, which is ensured by the aliphatic amines used.
  • the colloidal solutions in aliphatic amines can be diluted with suitable inert solvents, for example acetone, ethanol, propanols or acetonitrile.
  • colloidal solutions using solvents which are a mixture of alphatic amines and the inert solvents.
  • solvents which are a mixture of alphatic amines and the inert solvents.
  • the colloidal solutions obtained in this way are used to produce praseodymium-doped chalcogenide and chalcohalide glass layers by means of a known immersion or spin-on process on a substrate, for example ITO (indium tin oxide), plastics or other suitable substrates, and then by thermal Aftertreatment compacted.
  • ITO indium tin oxide
  • These layers are then laterally structured in a simple manner by processes known per se, for example ion etching or UV exposure.
  • AS2S3 glasses are dissolved in 1 ml propylamine and stirred at 20 ° C for 1 h. After filtration through a filter with an average pore size of 0.5 ⁇ m, a clear yellow solution is obtained.
  • This can be used to produce coatings on glass substrates by dip coating, spin coating or spray coating. The thermal compression takes place at 130 ° C.
  • the coating solution can be spin-coated at 1000 rpm for 30 seconds and then compacted at 130 ° C. Produce layers with a thickness of 0.5 ⁇ m on which the 1.3 ⁇ m fluorescence can be detected.
  • the glass composition according to the invention is thus used in the form of fiber lasers, fiber amplifiers, glass lasers, planar waveguide lasers, planar waveguide amplifiers, etc.
  • Table 4 Variation of the chloride content in atomic% of the anions.
  • Table 5 Variation of the Pr 3+ doping level with a Ge-In-SI glass composition.

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

Abstract

L'invention concerne la production d'une composition de verre à base de verres de chalcogénure et de chalcohalogénure dopés par des métaux rares, avec ou sans codopage, un procédé de production de cette composition, ainsi qu'un procédé de production de couches de verres minces transparentes et leur utilisation pour la formation de composants optiques. La composition de verre comprend au moins un élément du troisième groupe principal, au moins un élément du quatrième groupe principal, au moins un élément des halogénures et au moins un élément des métaux rares comme additifs de dopage, ainsi que du soufre.
EP98929219A 1997-04-15 1998-04-09 Composition de verre presentant un spectre a phonons de faible energie, son procede de production et son utilisation Withdrawn EP0914300A2 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE19715578 1997-04-15
DE19715578 1997-04-15
DE19726388 1997-06-21
DE19726388 1997-06-21
DE19813607A DE19813607A1 (de) 1997-04-15 1998-03-27 Glaszusammensetzung mit einem Phonenspektrum niedriger Energie, Verfahren zu deren Herstellung sowie deren Verwendung
DE19813607 1998-03-27
PCT/DE1998/001013 WO1998046538A2 (fr) 1997-04-15 1998-04-09 Composition de verre presentant un spectre a phonons de faible energie, son procede de production et son utilisation

Publications (1)

Publication Number Publication Date
EP0914300A2 true EP0914300A2 (fr) 1999-05-12

Family

ID=27217302

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98929219A Withdrawn EP0914300A2 (fr) 1997-04-15 1998-04-09 Composition de verre presentant un spectre a phonons de faible energie, son procede de production et son utilisation

Country Status (3)

Country Link
EP (1) EP0914300A2 (fr)
JP (1) JP2000512611A (fr)
WO (1) WO1998046538A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4240720B2 (ja) * 2000-01-26 2009-03-18 旭硝子株式会社 光増幅ガラス
KR100341212B1 (ko) * 2000-07-31 2002-06-20 오길록 1.6 미크론미터 대역 광 증폭 시스템
JP5339720B2 (ja) * 2007-12-28 2013-11-13 五鈴精工硝子株式会社 モールド成型用赤外線透過ガラス
US10099957B2 (en) * 2015-06-17 2018-10-16 Schott Corporation Infrared transmission chalcogenide glasses
JP7181495B2 (ja) 2017-04-07 2022-12-01 日本電気硝子株式会社 カルコゲナイドガラス

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5389584A (en) * 1994-04-11 1995-02-14 Corning Incorporated Ga- and/or In-containing AsGe sulfide glasses
US5392376A (en) * 1994-04-11 1995-02-21 Corning Incorporated Gallium sulfide glasses

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9846538A3 *

Also Published As

Publication number Publication date
JP2000512611A (ja) 2000-09-26
WO1998046538A3 (fr) 1999-01-21
WO1998046538A2 (fr) 1998-10-22

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