DE1955174A1 - Luminescent glass-ceramics, e.g. for laser technology - Google Patents

Luminescent glass-ceramics, e.g. for laser technology

Info

Publication number
DE1955174A1
DE1955174A1 DE19691955174 DE1955174A DE1955174A1 DE 1955174 A1 DE1955174 A1 DE 1955174A1 DE 19691955174 DE19691955174 DE 19691955174 DE 1955174 A DE1955174 A DE 1955174A DE 1955174 A1 DE1955174 A1 DE 1955174A1
Authority
DE
Germany
Prior art keywords
ceramics
glass
laser technology
ions
luminescent glass
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.)
Granted
Application number
DE19691955174
Other languages
German (de)
Other versions
DE1955174B2 (en
DE1955174C (en
Inventor
Norbert Dipl-Phys Dr Neuroth
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.)
Schott AG
Original Assignee
Jenaer Glaswerk Schott and Gen
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 Jenaer Glaswerk Schott and Gen filed Critical Jenaer Glaswerk Schott and Gen
Priority to DE19691955174 priority Critical patent/DE1955174C/en
Priority claimed from DE19691955174 external-priority patent/DE1955174C/en
Priority to NL7015894A priority patent/NL149952B/en
Priority to FR7039430A priority patent/FR2068386A5/fr
Priority to GB5207670A priority patent/GB1336321A/en
Publication of DE1955174A1 publication Critical patent/DE1955174A1/en
Publication of DE1955174B2 publication Critical patent/DE1955174B2/en
Application granted granted Critical
Publication of DE1955174C publication Critical patent/DE1955174C/en
Priority to US358224A priority patent/US3928229A/en
Expired 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
    • 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
    • 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
    • H01S3/05—Construction or shape of optical resonators; Accommodation of active medium therein; Shape of active medium
    • H01S3/08—Construction or shape of optical resonators or components thereof
    • H01S3/08072—Thermal lensing or thermally induced birefringence; Compensation thereof

Landscapes

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

Description

Lumineszierende Glaskeramik, z. B. für LasertechnikLuminescent glass-ceramic, e.g. B. for laser technology

Es sind eine große Anzahl von kristallinen Meterlallen und Gläsern bekannt, die durch Einlagerung eines oder mehrerer Arten von Aktivierungsionen lumineszieren und zur induzierten Emission angeregt werden können. Die Kristalle haben bestimmte physikalische Eigenschaften, die durch den jeweils vorliegenden Kristalltyp festgelegt werden. Bei den Gläsern kann man durch systematische Variation der chemischen Zusammensetzung die Eigenschaften stetig ändern und so gewünschte Werte annähernd erreichen.There are a large number of crystalline meter lalls and Glasses known that by storing one or more Types of activation ions luminesce and can be excited to the induced emission. The crystals have certain physical properties that are determined by the type of crystal present. With the glasses by systematically varying the chemical composition, the properties are constantly changing and so are desired values approximately reach.

Eine neue Gruppe der festen Werkstoffe stellen die Stoffe dar, die man als Glaskeramiken bezeichnet, Zur Herstellung einer Glaskeramik geht man von einem Glas bestimmter Zusammensetzung aus, das in einem zweiten Verfahrensschritt durch eine definierte Wärmebehandlung in einen glasig-kristallinen Körper umgewandelt wird. Diese heterogene Struktur bedingt besondere Eigenschaften. Man kann z. B. Glaskeramiken herstellen, deren thermische Ausdehnung praktisch null ist. Solche Materialien sind äußerst beständig gegen Wärmeschocks·The substances represent a new group of solid materials which are referred to as glass ceramics, for the production of a glass ceramic one starts with a glass of a certain composition from, which is defined in a second process step by a Heat treatment converted into a glassy crystalline body will. This heterogeneous structure requires special properties. You can z. B. produce glass ceramics whose thermal expansion is practically zero. Such materials are extremely resistant to thermal shocks

Es wurde nun gefunden, daß Glaskeramiken auch als Wirtsmaterial für Akt!vierungsionen geeignet sind. Wenn man z.B. IonenIt has now been found that glass ceramics can also be used as host material are suitable for activation ions. For example, if you have ions

109821/1641109821/1641

aus der Gruppe der Seltenen Erden In sie einlagert, so können diese zur Lumineszenz angeregt werden. Es wurde z. B. gefunden, daß man in eine transparente Glaskeramik mit extrem kleiner thermischer Ausdehnung Neodymionen einlagern und diese zur Lumineszenz bringen kann. Es handelt sich um Glaskeramiken, deren Herstellung ohne Aktivatoren bereits in den Anmeldungen P 15 96 855.5, P 15 96 858.8, P 15 96 860.2, P 15 96 865.7, P 16 96 062.6 beschrieben ist.from the group of the rare earths these are excited to luminescence. It was z. B. found that in a transparent glass ceramic with extremely small thermal expansion can store neodymium ions and bring them to luminescence. These are glass ceramics, their production without activators already in the applications P 15 96 855.5, P 15 96 858.8, P 15 96 860.2, P 15 96 865.7, P 16 96 062.6 is described.

In Fig. 1 ist der spektrale Verlauf der Lumineszenzemission J dargestellt. Die stärkere Emission ist bei 1060 nm, zwei schwächere Emissionsbanden treten bei 900 nm und 1330 nm auf.In Fig. 1 the spectral course of the luminescence emission J is shown. The stronger emission is at 1060 nm, two weaker emission bands occur at 900 nm and 1330 nm.

In Fig. 2 sind die Absorptionsspektren von zwei neodymhaltigen Glaskeramiken wiedergegeben. Kurve a ist von einer Glaskeramik mit 2 % Neodymoxyd, Kurve b von einer Glaskeramik mit 5 % Neodymoxyd.In Fig. 2 are the absorption spectra of two neodymium-containing Glass ceramics reproduced. Curve a is from a glass ceramic with 2% neodymium oxide, curve b from a glass ceramic with 5% Neodymium oxide.

In der Tabelle sind die Zusammensetzungen und die wichtigsten Eigenschaften von einigen lumineszierenden Glaskeramiken angegeben. Die Lumineszenzabklingzeit liegt bei den ersten drei Glaskeramiken bei über 200 Mikrosekunden, ein für die Lasertechnik erwünschter Wert. Die thermische Ausdehnung ist kleiner als die von Quarzglas. Sie ist zum Aushalten der großen Wärmeschocks, die der Laserstab beim Anregen mit den starken Blitzlampen erfährt, von großer Bedeutung.The table shows the compositions and the most important properties of some luminescent glass-ceramics. The luminescence decay time for the first three glass ceramics is over 200 microseconds, one for laser technology desired value. The thermal expansion is smaller than that of quartz glass. She is able to stand the great Thermal shocks that the laser rod receives when excited with the strong Flash lamps learns of great importance.

Die Herstellung dieser lumineszierenden Glaskeramiken erfolgt gemäß den weiter oben beschriebenen angemeldeten Verfahren, wobei man die Aktivatorionen in Form der Oxide dem Glasversatz beimengt.The production of these luminescent glass ceramics takes place according to the pending process described above, the activator ions being added to the glass offset in the form of oxides added.

109821/1641109821/1641

TabelleTabel

Eigenschaften von neodymaktivierter GlaskeramikProperties of neodymium-activated glass-ceramic

11 J- fJ- f 33 44th 67,067.0 22 64,064.0 54,254.2 SiO2 SiO 2 -- 65,065.0 5,05.0 7,77.7 P2°5 P 2 ° 5 18,518.5 -- 19,019.0 24,724.7 Al2O3 Al 2 O 3 2,82.8 17,917.9 3,23.2 3,73.7 Li2OLi 2 O 0,70.7 2,72.7 0,50.5 0,50.5 Na2ONa 2 O IfOIfO 0,70.7 0,70.7 IfO,IfO, MgOMgO 0,80.8 1,01.0 -- ; --; - CaOCaO 2,92.9 0,70.7 0,70.7 1,41.4 ZnOZnO 1,51.5 2,92.9 2,62.6 2,22.2 TiO2 TiO 2 1,81.8 1,41.4 1,81.8 1,91.9 ZrO2 ZrO 2 -- 1,71.7 0,50.5 0,70.7 As2O3 As 2 O 3 1,01.0 " ■ -"■ - -- Sb2O3 Sb 2 O 3 2,02.0 1,01.0 2,02.0 2,02.0 Nd2O3 Nd 2 O 3 5,05.0 Lumines zenz intens itatLumines zenz intens itat der Bande 1060 nmthe band 1060 nm 3030th 44th 44th (relative Werte)(relative values) 2424 LumineszenzabklingzeitLuminescence decay time 330330 240240 <C50<C50 ( λι sek)(λι sec) 220220 thermische Ausdehnungthermal expansion 2,42.4 4,04.0 0,50.5 (20 ... 300°C) «107/°C(20 ... 300 ° C) «10 7 / ° C 2,512.51 - -- - 2,512.51 2,542.54 Dichtedensity 2,562.56

109821/1641109821/1641

Claims (2)

Patentansprüche:Patent claims: Festkörper zur Erzeugung von Lumineszenz bzw; induzierter Emission, dadurch gekennzeichnet, daß das Wirtsmaterial für die Äktivierungsionen aus Glaskeramik besteht.Solid body for generating luminescence or; induced emission, characterized in that the host material for the activation ions consist of glass ceramic. 2. Festkörper nach Anspruch 1, dadurch gekennzeichnet, daß die Äktivierungsionen Chrom-, Mangan-, Nickel-, Kupfer-, Cer-, Praseodym-, Neodym-, Samarium-, Europium-, Gadolinium-, Terbium-, Dysprosium-, Holmium-, Erbium-, Thulium-, Ytterbiumoder Uran-Ionen oder deren Gemische sind.2. Solid body according to claim 1, characterized in that the activation ions chromium, manganese, nickel, copper, cerium, Praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or Uranium ions or mixtures thereof. 109821/1641109821/1641 Le e rs e i teBlank page
DE19691955174 1969-11-03 1969-11-03 Solid body for generating both luminescence and induced emission (laser) Expired DE1955174C (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DE19691955174 DE1955174C (en) 1969-11-03 Solid body for generating both luminescence and induced emission (laser)
NL7015894A NL149952B (en) 1969-11-03 1970-10-29 SOLID OBJECT FOR GENERATING INDUCED EMISSIONS.
FR7039430A FR2068386A5 (en) 1969-11-03 1970-11-02
GB5207670A GB1336321A (en) 1969-11-03 1970-11-02 Luminescent materials
US358224A US3928229A (en) 1969-11-03 1973-05-08 Transparent glass-ceramic laserable articles containing neodymium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19691955174 DE1955174C (en) 1969-11-03 Solid body for generating both luminescence and induced emission (laser)

Publications (3)

Publication Number Publication Date
DE1955174A1 true DE1955174A1 (en) 1971-05-19
DE1955174B2 DE1955174B2 (en) 1972-08-17
DE1955174C DE1955174C (en) 1973-03-15

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19816380C1 (en) * 1998-04-11 1999-10-07 Schott Glas Cadmium-free red glass-ceramic based starting glass for use as a red traffic light glass
DE102006062448A1 (en) 2006-12-28 2008-07-10 Schott Ag Photovoltaic module with thin electrode- and silicon layers, for solar energy collection, includes high-refraction glass or glass-ceramic converter plate containing specified dopants

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19816380C1 (en) * 1998-04-11 1999-10-07 Schott Glas Cadmium-free red glass-ceramic based starting glass for use as a red traffic light glass
DE102006062448A1 (en) 2006-12-28 2008-07-10 Schott Ag Photovoltaic module with thin electrode- and silicon layers, for solar energy collection, includes high-refraction glass or glass-ceramic converter plate containing specified dopants

Also Published As

Publication number Publication date
FR2068386A5 (en) 1971-08-20
DE1955174B2 (en) 1972-08-17
NL7015894A (en) 1971-05-05
NL149952B (en) 1976-06-15
GB1336321A (en) 1973-11-07

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Legal Events

Date Code Title Description
C3 Grant after two publication steps (3rd publication)
E77 Valid patent as to the heymanns-index 1977
8327 Change in the person/name/address of the patent owner

Owner name: SCHOTT GLASWERKE, 6500 MAINZ, DE

8339 Ceased/non-payment of the annual fee