CN101353228A - Ultra-wideband near-infrared luminous transparent glass-ceramic - Google Patents

Ultra-wideband near-infrared luminous transparent glass-ceramic Download PDF

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Publication number
CN101353228A
CN101353228A CNA2008101207865A CN200810120786A CN101353228A CN 101353228 A CN101353228 A CN 101353228A CN A2008101207865 A CNA2008101207865 A CN A2008101207865A CN 200810120786 A CN200810120786 A CN 200810120786A CN 101353228 A CN101353228 A CN 101353228A
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China
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glass
transition metal
ultra
metal ions
transparent glass
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CNA2008101207865A
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周时凤
邱建荣
朱斌
杨护成
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Zhejiang University ZJU
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Zhejiang University ZJU
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Priority to CNA2008101207865A priority Critical patent/CN101353228A/en
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Abstract

The ultra wideband near infrared luminescent transparent microcrystalline glass disclosed by the invention is the glass that the glass in which transition metal ions are doped contains two or more than two kinds of 1-1,000 nano-microcrystal, and the doping concentration of the transition metal ions is 0.01-5 mol%. Compared with rare-earth ions and crystal material in which transition metal ions is doped, the ultra wideband near infrared luminescent transparent microcrystalline glass of the invention is characterized in that the processing is easy; compared with the rare-earth ions and microcrystalline glass material doping transition metal ions and only containing a single crystal phase, the ultra wideband near infrared luminescent transparent microcrystalline glass has wider infrared bandwidth. The glass of the invention can be used in ultra wideband infrared light sources, ultra wideband fibre amplifiers and tunable lasers.

Description

Ultra-wideband near-infrared luminous transparent glass-ceramic
Technical field
The present invention relates to a kind of transparent glass-ceramics, especially ultra-wideband near-infrared luminous transparent glass-ceramic.
Background technology
Bandwidth is the important parameter of broadband optical fiber amplifier and ultrashort pulse laser gain media, for a long time people always the method for seeking go to increase the bandwidth of near-infrared luminous gain media.In rare earth ion doped glass medium, can be by the component of regulation and control medium and the purpose of the method realization increase bandwidth that multiple rare earth ion is mixed altogether.But because the 4f-4f transition of electron process of rare earth ion is carried out under the shielding effect of out-shell electron, the luminous bandwidth of its correspondence has been subjected to very big restriction.Utilizing Raman effect is the another one method that increases bandwidth.Theoretically, as long as suitable pumping source is arranged, can obtain the laser of any wave band.Even so, the requirement in the structure of Ramar laser complexity and high power pump source has limited its application.
Transition metal ion 3d transition of electron is subjected to the ligand field to influence very big, stronger electronics-effect of phonon can produce the luminous of broadband, and the energy level of corresponding 3d transition of electron is also arranged at near-infrared band.Therefore select for use transition metal ion can realize near infrared broad-band illumination as light emitting ionic.In the research in the past, realized the luminous of broadband in the transition metal ion activated crystal medium, typical example such as Al 2O 3: Ti 3+And MgO:Ni 2+But the preparation cost of crystalline material is very high; On the other hand, the weakness of crystalline material poor processability has limited it and has been applied to the gain media of fiber amplifier.People also attempt the glass of doped transition metal ions is made the wideband gain material, but transition metal ion nonradiative transition in glass matrix is very strong, and luminous efficiency is very low even not luminous.
Microcrystal glass material is that a class is distributed with nanocrystalline hybrid material in the successive glassy phase.Its preparation method normally prepares the glass that designs component earlier, separates out nanocrystalline through the thermal treatment original position glass system that obtains then.If in forerunner's glass system, mix active ion, in nanocrystalline precipitation process active ion can optionally mix crystallite mutually in, show the luminescence feature similar with the active ion doped crystal.Therefore the comprehensively workability of glass and the advantage of the high-luminous-efficiency that the active ion doped crystal has of such hybrid material.In recent years, correlative study was attempting that such hybrid material was used for novel near infrared wideband gain medium.The Pinckney of Corning company etc. are at Cr 4+Adulterated Mg 2SiO 4, Zn 2SiO 4And Li 2(Zn, Mg) SiO 4Devitrified glass, and Ni 2+Realize near infrared broad-band illumination in the adulterated spinel devitrified glass.The Samson of Corning etc. are with Ni 2+Adulterated spinel devitrified glass has been made optical fiber, the application of such hybrid material in broadband optical fiber amplifier and laser apparatus is pushed away going a step further.Japan Ohishi etc. has also studied Ni in succession 2+Doping of Zn Al 2O 4And LiGa 5O 8The infraluminescence characteristics of devitrified glass.All above-mentioned researchs all center on the Ni that only contains single crystalline phase 2+The doped microcrystalline glass material carries out, and therefore the monocrystal material of the bandwidth of above-mentioned microcrystal glass material infraluminescence and doped transition metal ions is approaching, can not realize the luminous of ultra broadband.
Summary of the invention
The purpose of this invention is to provide a kind of ultra-wideband near-infrared luminous transparent glass-ceramic.
Ultra-wideband near-infrared luminous transparent glass-ceramic of the present invention is the glass that contains two or more 1～1000 nano microcrystalline in the glass of doped transition metal ions, and doped transition metal ions concentration is 0.01-5mol%.
Among the present invention, said transition metal ion is Ni 2+, Co 2+, V 3+, V 5+, Mn 6+, Cr 3+, Cr 4+, Fe 3+And Fe 2+In one or more.
Among the present invention, said two or more nano microcrystalline is Ga 2O 3, Zn 2Al 2O 4, ZnGa 2O 4, LiGa 5O 8, LiAlSiO 4NaAlSiO 4, Mg 2SiO 4, MgAl 2Si 3O 10, Zn 2SiO 4, Li 2(Zn, Mg) SiO 4And MgF 2In two or more mixture.
Among the present invention, said glass can be silicate, borate, phosphoric acid salt, borosilicate, borophosphate or silicophosphate.
Above-mentioned crystallite is 1～1000 nanometer, and nanoparticle is less than 1 nanometer, and the active ion concentration that then enters nanoparticle is low excessively, is difficult to realize efficiently luminous.If nanoparticle is too big,, then can make the sample devitrification greater than 1000 nanometers.The ionic concn of transition metal is 0.01-5mol%, low excessively be unfavorable for luminous.Too high, because concentration quenching also can make luminescent decay.
Ultra-wideband near-infrared luminous transparent glass-ceramic of the present invention, be in the glass of doped transition metal ions, optionally original position is separated out the crystallite of two kinds or two or more nanoscales, when different crystallites is separated out in glass, transition metal ion mixes respectively in the different crystallites, because the 3d transition of electron of transition metal ion is easy to be subjected to the crystal field environmental influence, therefore the transition metal ion in the different crystallites can be luminous at different-waveband, by the combination of luminous peak position, can realize the luminous of ultra broadband.
Ultra-wideband near-infrared luminous transparent glass-ceramic of the present invention is compared with the crystalline material of rare earth ion, doped transition metal ions, has easy machining characteristics; Compare with the microcrystal glass material that only contains single crystalline phase of rare earth ion, doped transition metal ions, have wideer ir bandwidth.Can be used for the ultra broadband infrared source, super-broadband fiber amplifier and tunable laser.
Embodiment
The invention will be further described below by embodiment.
Embodiment 1:
To Cr 4+Ion doping contain Li 2O, the silicate glass of MgO and ZnO is heat-treated, and original position is separated out Li 2MgSiO 4(mean sizes: 20nm) and Zn 2SiO 4(mean sizes: 20nm) crystallite, Cr 4+Ion doping concentration is 0.01mol%.Cr 4+Ion is at Li 2MgSiO 4And Zn 2SiO 4Luminous peak position in the crystallite lays respectively at 1200nm (halfwidth is 200nm) and 1350nm (halfwidth is 200nm), and by the combination of two glow peaks, obtaining halfwidth is the infrared excess broad-band illumination of 350nm.
Embodiment 2:
To V 3+Ion doping contain ZnO, Ga 2O 3And Al 2O 3Borate glass heat-treat, original position is separated out Ga 2O 3(mean sizes: 5nm) and ZnAl 2O 4(mean sizes: 30nm) crystallite, V 3+Ion doping concentration is 0.1mol%.V 3+Ion is at Ga 2O 3And ZnAl 2O 4Luminous peak position in the crystallite lays respectively at 1200nm (halfwidth is 200nm) and 1300nm (halfwidth is 200nm), and by the combination of two glow peaks, obtaining halfwidth is the infrared excess broad-band illumination of 300nm.
Embodiment 3:
To Mn 6+Ion doping contain Li 2O, Ga 2O 3And Al 2O 3Phosphate glass heat-treat, original position is separated out LiGa 5O 8(mean sizes: 3nm) and LiAlSiO 4(mean sizes: 800nm) crystallite, Mn 6+Ion doping concentration is 1mol%.Mn 6+Ion is at LiGa 5O 8And LiAlSiO 4Luminous peak position in the crystallite lays respectively at 1250nm (halfwidth is 200nm) and 1300nm (halfwidth is 200nm), and by the combination of two glow peaks, obtaining halfwidth is the infrared excess broad-band illumination of 250nm.
Embodiment 4:
To Ni 2+Ion doping contains Ga 2O 3Heat-treat with the crystallite borosilicate glass of MgO, original position is separated out Ga 2O 3(mean sizes: 3nm) and Mg 2SiO 4(mean sizes: 800nm) crystallite, Ni 2+Ion doping concentration is 1mol%.Ni 2+Ion is at Ga 2O 3And Mg 2SiO 4Luminous peak position in the crystallite lays respectively at 1200nm (halfwidth is 200nm) and 1500nm (halfwidth is 200nm), and by the combination of two glow peaks, obtaining halfwidth is the infrared excess broad-band illumination of 400nm.
Embodiment 5:
To Ni 2+Ion doping contain Ga 2O 3, MgO and MgF 2Silicon phosphate glass heat-treat, original position is separated out Ga 2O 3(mean sizes: 15nm), Mg 2SiO 4(mean sizes: 60nm) and MgF 2(mean sizes: 40nm) crystallite, Ni 2+Ion doping concentration is 5mol%.Ni 2+Ion is at Ga 2O 3And Mg 2SiO 4And MgF 2Crystallite.In luminous peak position lay respectively at 1200nm (halfwidth is 200nm), 1500nm (halfwidth is 200nm) and and 1600nm (halfwidth is 200nm), by the combination of three glow peaks, obtaining halfwidth is the infrared excess broad-band illumination of 500nm.
From above embodiment as seen, utilization of the present invention original position in the glass of doped transition metal ions is separated out two kinds or two or more devitrified glasses, the luminous peak position of transition metal ion is in different-waveband in different types of crystallite, combination by luminous peak position, can effectively increase the infraluminescence bandwidth, realize that the ultra broadband of covering overall optical communication band is luminous.

Claims (4)

1. ultra-wideband near-infrared luminous transparent glass-ceramic is characterized in that containing the glass of two or more 1～1000 nano microcrystalline in the glass of doped transition metal ions, doped transition metal ions concentration is 0.01-5mol%.
2. ultra-wideband near-infrared luminous transparent glass-ceramic according to claim 1 is characterized in that transition metal ion is Ni 2+, Co 2+, V 3+, V 5+, Mn 6+, Cr 3+, Cr 4+, Fe 3+And Fe 2+In one or more.
3. ultra-wideband near-infrared luminous transparent glass-ceramic according to claim 1 is characterized in that said two or more nano microcrystalline is Ga 2O 3, Zn 2Al 2O 4, ZnGa 2O 4, LiGa 5O 8, LiAlSiO 4NaAlSiO 4, Mg 2SiO 4, MgAl 2Si 3O 10, Zn 2SiO 4, Li 2(Zn, Mg) SiO 4And MgF 2In two or more mixture.
4. ultra-wideband near-infrared luminous transparent glass-ceramic according to claim 1 is characterized in that said glass is silicate, borate, phosphoric acid salt, borosilicate, borophosphate or silicophosphate.
CNA2008101207865A 2008-09-05 2008-09-05 Ultra-wideband near-infrared luminous transparent glass-ceramic Pending CN101353228A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
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CN103450895A (en) * 2013-10-05 2013-12-18 上海科润光电技术有限公司 Method for manufacturing infrared luminous material
CN103466949A (en) * 2013-08-21 2013-12-25 中国计量学院 Glass-ceramic precipitating Zn1.7SiO4 nanocrystalline and preparation method thereof
CN103539358A (en) * 2013-09-26 2014-01-29 中国计量学院 Method for controllably precipitating crystal phase of transparent glass ceramics for ultra-wide-band fiber amplifiers
CN104310786A (en) * 2014-10-09 2015-01-28 华南理工大学 Microcrystal glass material with ultra wide band near-infrared light emission and preparation method of microcrystal glass material
CN106244140A (en) * 2016-07-26 2016-12-21 华南理工大学 Near-infrared long-persistence nano material that a kind of bivalent nickel ion activates and its preparation method and application
CN106746622A (en) * 2016-12-19 2017-05-31 温州大学 A kind of Mn2+White light glass of activation and preparation method thereof
CN110342824A (en) * 2019-08-01 2019-10-18 电子科技大学 A kind of low-loss low thermal expansion magnalium silicon-based microcrystal glass material and preparation method thereof
CN113087397A (en) * 2021-04-13 2021-07-09 泰山学院 Double-phase transparent glass ceramic with ultra-wideband fluorescence emission characteristic and preparation method thereof
CN114075039A (en) * 2020-08-18 2022-02-22 中国科学院大连化学物理研究所 Gallium silicate glass composite material and preparation and application thereof

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103466949A (en) * 2013-08-21 2013-12-25 中国计量学院 Glass-ceramic precipitating Zn1.7SiO4 nanocrystalline and preparation method thereof
CN103466949B (en) * 2013-08-21 2015-10-28 中国计量学院 A kind of precipitation Zn 1.7siO 4nanocrystalline devitrified glass and preparation method thereof
CN103539358B (en) * 2013-09-26 2016-03-02 中国计量学院 The method of the controlled precipitation of a kind of super-broadband fiber amplifier transparent glass-ceramics crystalline phase
CN103539358A (en) * 2013-09-26 2014-01-29 中国计量学院 Method for controllably precipitating crystal phase of transparent glass ceramics for ultra-wide-band fiber amplifiers
CN103450895A (en) * 2013-10-05 2013-12-18 上海科润光电技术有限公司 Method for manufacturing infrared luminous material
CN103450895B (en) * 2013-10-05 2015-07-15 上海科润光电技术有限公司 Method for manufacturing infrared luminous material
CN104310786A (en) * 2014-10-09 2015-01-28 华南理工大学 Microcrystal glass material with ultra wide band near-infrared light emission and preparation method of microcrystal glass material
CN106244140A (en) * 2016-07-26 2016-12-21 华南理工大学 Near-infrared long-persistence nano material that a kind of bivalent nickel ion activates and its preparation method and application
CN106244140B (en) * 2016-07-26 2019-08-20 华南理工大学 A kind of near-infrared long-persistence nano material and its preparation method and application of bivalent nickel ion activation
CN106746622A (en) * 2016-12-19 2017-05-31 温州大学 A kind of Mn2+White light glass of activation and preparation method thereof
CN110342824A (en) * 2019-08-01 2019-10-18 电子科技大学 A kind of low-loss low thermal expansion magnalium silicon-based microcrystal glass material and preparation method thereof
CN114075039A (en) * 2020-08-18 2022-02-22 中国科学院大连化学物理研究所 Gallium silicate glass composite material and preparation and application thereof
CN114075039B (en) * 2020-08-18 2023-05-16 中国科学院大连化学物理研究所 Gallium silicate glass composite material and preparation and application thereof
CN113087397A (en) * 2021-04-13 2021-07-09 泰山学院 Double-phase transparent glass ceramic with ultra-wideband fluorescence emission characteristic and preparation method thereof

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