CN1269915A - Glass for high and flat gain 1.55 micros optical amplifiers - Google Patents

Glass for high and flat gain 1.55 micros optical amplifiers Download PDF

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CN1269915A
CN1269915A CN98808791A CN98808791A CN1269915A CN 1269915 A CN1269915 A CN 1269915A CN 98808791 A CN98808791 A CN 98808791A CN 98808791 A CN98808791 A CN 98808791A CN 1269915 A CN1269915 A CN 1269915A
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glass
image intensifer
weight portion
gain
medium
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M·普拉萨斯
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Corning Inc
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Corning Inc
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    • 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
    • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
    • 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
    • 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
    • H01S3/06—Construction or shape of active medium
    • H01S3/063—Waveguide lasers, i.e. whereby the dimensions of the waveguide are of the order of the light wavelength
    • H01S3/067—Fibre lasers
    • H01S3/06708—Constructional details of the fibre, e.g. compositions, cross-section, shape or tapering
    • 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
    • H01S3/06—Construction or shape of active medium
    • H01S3/063—Waveguide lasers, i.e. whereby the dimensions of the waveguide are of the order of the light wavelength
    • H01S3/067—Fibre lasers
    • H01S3/06708—Constructional details of the fibre, e.g. compositions, cross-section, shape or tapering
    • H01S3/06716—Fibre compositions or doping with active elements
    • 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
    • H01S3/1608—Solid materials characterised by an active (lasing) ion rare earth erbium
    • 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
    • H01S3/1618—Solid materials characterised by an active (lasing) ion rare earth ytterbium
    • 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
    • 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
    • H01S2301/00—Functional characteristics
    • H01S2301/04—Gain spectral shaping, flattening
    • 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
    • H01S3/173—Solid materials amorphous, e.g. glass fluoride glass, e.g. fluorozirconate or ZBLAN [ ZrF4-BaF2-LaF3-AlF3-NaF]
    • 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
    • H01S3/175—Solid materials amorphous, e.g. glass phosphate glass

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

The invention relates to a family of erbium-doped fluorophosphate glasses for use in optical signal amplification. The composition, based on 100 parts by weight, is constituted by: P2O5 15-40, A12O3 0-5, MgO 0-9, CaO 0-9, SrO 0-9, BaO 0-45, AlF3 5-25, MgF2 0-10, CaF2 0-25, SrF2 0-25, BaF2 0-20, KHF2 0-2, K2TiF6 0-2, with up to 10 parts by weight of erbium oxide. The glasses according to the present invention exhibit a high gain and a very flat spectrum over the 1550 nm bandwidth, as compared to the glasses of the figure. These glass compositions are particularly well suited for use in fiber or planar optical amplification in WDM and similar applications.

Description

The glass of 1.55 microns high and flat image intensifers is used to gain
TECHNICAL FIELD OF THE INVENTION
Present invention relates in general to the optical signal amplifier field, be specifically related to fluorphosphate glass composition as near the optical signal amplifier that 1.55 micron wave lengths, moves.
The background of invention
Optical signal amplifier is used for the optical communication network rapidly, is used to long distance especially and uses in the fiber network.Although modern silica-based optical fiber generally shows low relatively loss at 1.55 microns windows, there is certain loss in they and builds up with this loss of increase of distance.For reducing this decay, use photoelectric cell amplifying signal intensity.These elements need be transformed into the signal of telecommunication with light signal.Use known amplifying technique that the signal of telecommunication is amplified subsequently, convert light signal again to continue transmission.
Optical signal amplifier need not photoelectric conversion signal with regard to scalable light signal.In image intensifer, the light signal that weakens is imported into the amplification medium part of doped with rare-earth elements ion.Light from external light source (normally semiconductor laser) excites this amplification medium, and rare earth atom is excited to higher energy level.The light that enters amplification medium with signal wavelength further excites the rare earth ion of being excited, and discharges excessive photon energy in the mode with signal pulse identical bits signal wavelength light mutually, thus amplifying optical signals.One type image intensifer uses the optical fiber of one section erbium doped.Mix the usually erbium ion of 100-500ppm magnitude of the fiber amplifier of erbium doped (EDFA).Common EDFA fiber lengths is 10-30m, and it depends on the gain that special-purpose requires.In some purposes, it is unpractical using the optical fiber of 10-30m length.Develop the planar shaped image intensifer and be used for very narrow space.The prove-in length of plane amplifier element generally is no more than 10 centimetres.In order to reach the amplification effect identical with the EDFA of 10-30m length, the plane amplifier needs amplification medium to contain the erbium ion of higher concentration, and its content is up to 4-7 weight %.
But, in the optical amplification medium of known type, when erbium ion concentration is higher, can produce a plurality of gain loss mechanism, comprise ion aggregation and collaborative same up-conversion (concentration quenching).Because erbium ion is not dissolved in the quartz substrate well, so erbium ion can assemble, and carries out energy in accumulation regions and shifts.In addition, when higher erbium ion concentration, it is more obvious that the interaction of ion and ion becomes.The ion that the energy up-conversion cancellation that produces transforms.The erbium ion energy is consumed in gathering and the cancellation process, therefore can not be used to required photon amplification process.As a result, higher erbium ion concentration descends the quantum efficiency of amplification medium fast, and amplifier gain is descended thereupon.
In addition, the amplifier of known silica based erbium doped shows obvious gain spectrum inhomogeneities.The gain spectral flat at wide bandwidth starvation can cause a plurality of problems.For example, extremely Duan light pulse has wide relatively power spectrum, if gain spectral is not flat then can not accurately amplifies.In addition, in big bandwidth purposes (as wavelength division multiplex switching (WDM)), optical fiber uses the optical transmitter of the carrier band frequency of not sharing the same light to accept the data-modulated light signal respectively from several.If the gain spectral of image intensifer is not flat in the wave-length coverage of operation, then the carrier band frequency in gain peak can be saturated, and around at this peak and peak valley place carrier band signal can not obviously amplify.The effort that gain-flattening was done mainly relies on passive or has the seedbed to filter the high gain characteristics of gain spectral.But this requires concrete amplifier and filter quite coupling and the necessary temporal variation issue that solves gain spectral.
The general introduction of invention
The present invention relates to one group of glass that is specially adapted to make optical signal amplifier.The erbium oxide of these glass doped with high concentration (up to 10 weight %) and trickle concentration quenching performance is only arranged.These glass also show higher fluorescence efficiency, have than known silicate and the more uniform amplification characteristic of Fluorozirconate glass.These glass provide high and flat amplification characteristic, are specially adapted to carry out light amplification at 1.55 microns optical wavelength windows, and are specially adapted to as wavelength division multiplex switching (WDM) system.
One aspect of the invention relates to～organizes glass, fluorphosphate glass especially, and it is particularly suitable for the rare earth ion of high concentration.An object of the present invention is to provide a kind of fluorphosphate glass medium of the oxidation erbium ion that mixes, it is used near the optical wavelength window of image intensifer 1.55 microns provides flat and high gain.Fluorphosphate glass of the present invention comprise the erbium ion (promptly near 10 weight %) of high concentration and form to ZBLAN＜-similar more uniform gain spectral, than typical silicate and phosphate glass composition tangible improvement is arranged.
The present invention relates to one group of glass that is used for light amplification, it comprises the fluorphosphate glass medium of basic oxygen-free silicon, and (promptly as the fluoride glass of optical fiber, it contains fluoride ZrF to fluoride glass by the following component of 100 weight portions 4, BaF 2, LaF 3, AlF 3And NaF) meter, it mixes up to 10 weight portions, better 0.01-10 weight portion erbium oxide:
P 2O 5 15-40 MgF 2 0-10
Al 2O 3 0-5 CaF 2 0-25
MgO 0-9 SrF 2 0-25
CaO 0-9 BaF 2 0-20
SrO 0-9 KHF 2 0-2
BaO 0-45 K 2TiF 6 0-2
AlF 35-25 is preferably, and fluorphosphate glass of the present invention has a composition, and it comprises in weight portion:
P 2O 5 16.9-24.0 MgF 2 0-7.5
Al 2O 3 1.6-3.2 CaF 2 0-18.7
MgO 0-5.0 SrF 2 0-19.7
CaO 0-5.1 BaF 2 1.5-11.3
SrO 0-8.5 KHF 2 0-1.3
BaO 2.7-43.2 K 2TiF 6 0-0.6
AlF 3 9.5-19.3
But fluorphosphate glass of the present invention also codope up to the Yb of 15 weight portions 2O 3As sensitizer so that near 980nm, improve launching efficiency.The better about 1.48-1.58 of the refractive index of fluorphosphate glass of the present invention.
The present invention relates to a kind of image intensifer that is used for the erbium doped of about 1.55 micron wavebands on the other hand, the optical amplification medium of this amplifier comprises the fluorphosphate glass composition of basic oxygen-free silicon, except that other component of 100 weight portions, said composition also comprises about 0.01-10 weight portion Er 2O 3Image intensifer of the present invention can be plane image intensifer or monomode fiber type image intensifer.
Image intensifer of the present invention comprises fluorphosphate glass, and it mixes up to 10 weight portions by the following component of 100 weight portions, better 0.01-10 weight portion erbium oxide:
P 2O 5 15-40 MgF 2 0-10
Al 2O 3 0-5 CaF 2 0-25
MgO 0-9 SrF 2 0-25
CaO 0-9 BaF 2 0-20
SrO 0-9 KHF 2 0-2
BaO 0-45 K 2TiF 6 0-2
AlF 3 5-25
Fluorphosphate glass of the present invention as image intensifer also can mix up to the Yb of 15 weight portions 2O 3As sensitizer so that near 980nm, improve launching efficiency, the better about 1.48-1.58 of its refractive index.Image intensifer of the present invention is particularly useful for wavelength division multiplex switching (WDM) system.
The accompanying drawing summary
Can learn other characteristics of the present invention and advantage by detailed description with reference to the accompanying drawings, these are described and only are used for explanation.In the accompanying drawing,
Fig. 1 and Fig. 2 are the typical performance curve of the concentration quenching of explanation binary silicate glass to fluorescence lifetime and efficient;
Fig. 3 and Fig. 4 are the fluorescence lifetime of explanation fluorosilicate glass of the present invention and the curve of efficient;
Fig. 5 is the gain shape of explanation typical quartz base glass and the relation curve of wavelength;
Fig. 6 is the gain shape of the typical ZBLAN glass of explanation and the relation curve of wavelength;
The relation curve of Fig. 7-9 for the gain shape of fluorphosphate glass of the present invention and wavelength.
The detailed description of invention
The present invention relates to one group of glass that is specially adapted to illumination (lighting), optics and electronics purposes.The unique property of this glass makes it especially to be fit to make optical signal amplifier.
A feature of these glass is that it does not contain silicon dioxide substantially.Erbium ion can not be dissolved in the quartz substrate well, thereby causes ion aggregation and gain effect is descended, and therefore removing silica based mass-energy prevents ion aggregation, thereby keeps excessive ion photon energy to be used for amplifying.Glass of the present invention contains the P of relative high concentration 2O 3The present invention relates to one group of glass that is used for light amplification, it comprises the fluorphosphate glass medium of basic oxygen-free silicon, and by other component of 100 weight portions, it mixes up to 10 weight portion erbium oxides.Table 1 has been listed the key component scope of fluorphosphate glass of the present invention.
Table 1 (weight portion)
P 2O 5 15-40 MgF 2 0-10
Al 2O 3 0-5 CaF 2 0-25
MgO 0-9 SrF 2 0-25
CaO 0-9 BaF 2 0-20
SrO 0-9 KHF 2 0-2
BaO 0-45 K 2TiF 6 0-2
AlF 3 5-25
The glass group of erbium doped of the present invention also can contain the 0.01-15 weight portion Yb that has an appointment 2O 3As sensitizer to increase near the launching efficiency the 980nm.Table 2 has been listed the narrower oxide preferably of glass of the present invention and has been formed.In this narrower scope, can obtain best optical signal amplifier performance and manufacturing property thereof.
Table 2 (weight portion)
P 2O 5 16.9-24.0 MgF 2 0-7.5
Al 2O 3 1.6-3.2 CaF 2 0-18.7
MgO 0-5.0 SrF 2 0-19.7
CaO 0-5.1 BaF 2 1.5-11.3
SrO 0-8.5 KHF 2 0-1.3
BaO 2.7-43.2 K 2TiF 6 0-0.6
AlF 3 9.5-19.3
Another feature of glass of the present invention is the erbium oxide (Er of its relative high concentration of mixing 2O 3).Under the situation that does not have silica-based glass, the erbium oxide of doped with high concentration can form good fluorescence efficiency, and it is important that this light signal to laser excitation amplifies, because reduced ion aggregation and up-conversion cancellation.This performance provides good amplification medium, and it is suitable as the image intensifer at the 1550nm wavelength.Another aspect of the present invention relates to the image intensifer of erbium doped, and it comprises that the medium that contains the fluorphosphate glass composition is used for light amplification.Be preferably, by 100 weight portion glass, the about 0.01-10 weight %Er of this fluorphosphate glass doping 2O 3, described glass contains:
Table 3 (weight portion)
P 2O 5 15-40 MgF 2 0-10
Al 2O 3 0-5 CaF 2 0-25
MgO 0-9 SrF 2 0-25
CaO 0-9 BaF 2 0-20
SrO 0-9 KHF 2 0-2
BaO 0-45 K 2TiF 6 0-2
AlF 3 5-25
According to another example of the present invention, except that erbium oxide, the image intensifer medium of erbium doped comprises the component shown in the 100 weight portion tables 4.
Table 4 (weight portion)
P 2O 5 16.9-24.0 MgF 2 0-7.5
Al 2O 3 1.6-3.2 CaF 2 0-18.7
MgO 0-5.0 SrF 2 0-19.7
CaO 0-5.1 BaF 2 1.5-11.3
SrO 0-8.5 KHF 2 0-1.3
BaO 2.7-43.2 K 2TiF 6 0-0.6
AlF 3 9.5-19.3
The image intensifer of erbium doped of the present invention also can contain the 0.01-15 weight portion Yb that has an appointment 2O 3, as sensitizer to be increased near the launching efficiency the 980nm.Image intensifer of the present invention can have different shape, as long as medium can the erbium doped ion.Described image intensifer can be a monomode fiber type image intensifer.Perhaps, described image intensifer can be the plane image intensifer.The concentration quenching effect of typical binary silica-based glass is shown in Fig. 1.At low Er 2O 3Under the concentration (less than 5E19 ion/cc, being equivalent to less than 0.5 weight portion), fluorescence lifetime is constant.Be higher than this concentration value, along with the increase fluorescence lifetime of concentration descends fast.Two characteristic concentration of definable are to distinguish glass.Concentration C QbThe starting point that is equivalent to concentration quenching.Concentration C qBe equivalent to the concentration that fluorescence lifetime reduces a half.As shown in Figure 1, concentration quenching starts from C in typical binary silicate glass Qb=7E19 ion/cc (or about 0.9 weight portion).At this point, fluorescence lifetime is about 13ms.Work as C q=3E20 ion/cc is when (or being about 3 weight portions), and fluorescence lifetime is about 7.5ms.
Fig. 2 illustrates the influence of the concentration quenching of typical silica-based glass to fluorescence efficiency.Fluorescence efficiency is defined as the 1.55 microns fluorescence of each erbium ion and the ratio of erbium concentration.In interested ion concentration level, i.e. 3-5E20 erbium ion/cc (about 4-7 weight portion), the fluorescence efficiency of silica-based glass is the 0.5-2E-19nW/ ion.
Fig. 3 illustrates that three types of the present invention's the concentration quenching of fluorophosphoric acid alkali glass is to the influence of fluorescence lifetime.Fig. 4 illustrates the influence of the concentration quenching of three kinds of fluorophosphoric acid alkali of the present invention glass to fluorescence efficiency.As shown in Figure 3 and Figure 4, C QbAnd C qAll than high 1 order of magnitude of analog value of silica-based glass.This shows in fluorphosphate glass of the present invention, when high erbium ion concentration the concentration quenching influence less relatively, be very suitable for these glass of optical signal amplifier of short length high-gain.The composition of three kinds of fluorphosphate glasses of the present invention and typical borosilicate base glass and ZBLAN and record and calculate performance relatively list in table 5.Composition in the table 5 is the required material quantity of once-through operation.The used real composition of each time operation can comprise any raw material, oxide, fluoride or phosphate, these raw materials melt together after, change into required oxide and fluoride with suitable ratio.The example of raw material (not exhaustive) has: Ca (PO 3) 2, Ba 2P 2O 7, Al 4(P 2O 7) 3, Al (PO 3) 3, NaPO 3, K 2TiF 6, X 2O y, XF y, wherein, X is the y valence metal ion.
The expression of the listed data (as other data herein) of table 5 according to the common practice in of this area calculate glass product in the theoretical content of different component.Under the situation of oxide, theoretical content is very near actual content (that is to say, to oxide " productive rate of once-through operation " very near 100%).Mostly be that real data is a shade below theoretical value (the about 90-95% of the productive rate of once-through operation) under the situation of fluoride of shale (slatile).
Table 5
Numbering embodiment 1 embodiment 2 embodiment 3 borosilicate type glass ZBLAN2 weight portion mole %
SiO 2 66.6
B 2O 3 11.6
P 2O 5 16.9 24.0 30.9
Al 2O 3 3.2 2.7 1.6
MgF 2 5.8 7.5 0.0
CaF 2 18.7 0.5 0.0
SrF 2 19.7 17.9 0.0
BaF 2 11.3 14.4 1.5 22
AlF 2 19.3 11.3 9.5 4
ZrF 4 48
InF 3
LaF 3 3.2
NaP 22
KHF 2 1.3 0.0 0.0
K 2TiF 6 0.6 0.5 0.0
Na 2O 0.5 0.0 0.0
K 2O
CaO 0.0 5.1 0.0
SrO 0.0 2.4 8.5
BaO 2.7 13.7 43.2
MgO 0.0 0.0 4.9
ErF 3 0.8
Er 2O 36.0 4.0 1.5 2Er 2O 3(ion/cm 3) 5.84+20 4.64+20 1.6+20 1.6E+20 1.5E+20 refractive index 1.49 1.54 1.59 1.52
Density 3.62 3.83 3.976 2.552
Numbering embodiment 1 embodiment 2 embodiment 3 borosilicate type glass ZBLAN2
Weight portion mole %
9.5 87 16 fluorescence lifetimes (ms) quantum efficiencies (%) 68 95 100 39 fluorescence efficiencies (nW/ erbium 2.3 2.7 3.2 1.3 the ions) * 1E-19 cross-sectional area (cm of fluorescence lifetime 6.8 7.6 7 6.3 when hanging down erbium content 2) *
1E-21 absorbs and excites
975nm 1.9 2.3 (980nm) 0.8 2.6
1480nm 3.3 3.9 1.2 4.7 absorption signal (σ Absorb(λ))
1533nm 4.9 5.9 (1527nm) 5.6 FWHM (nm) the 65 64 15 (σ that transmits Emission(λ))
1522nm 5.3 6.5 (1537nm) 7.2 6 FWHM (nm) 51 49 17 emission/absorptions 1.1 1.1 1.3 1.1 radiation lifetimes (ms) 10 8 16 8
The once-through operation component is mixed, place platinum crucible, and Joule is heated to about 1000 ℃.After the fusion, temperature is risen to 1050-1350 ℃ to obtain glass homogeney and clarification fully.Subsequently the melt cooling is also made required shape simultaneously, at last it is transferred in the annealing furnace of about 400 ℃ of operations.Another kind of melting method comprises by the once-through operation component and forms glass, and the Er and/or the Yb raw material of this glass and required ratio is fused together again.This method can increase the homogeney of glass in some cases.
By table 5 as seen, at the quantum efficiency τ of required Er concentration value fluorphosphate glass of the present invention Obs/ τ RadBe 70-100%, and the quantum efficiency of silica-based glass is 20-35% under same concentrations.
The restriction that silica-based glass EDFA is used for the bandwidth of WDM system comprehensively is that its gain spectra is inhomogeneous.Compare with silica-based glass, another key character of the fluorophosphate composition of doped with high concentration Er of the present invention is: this fluorphosphate glass demonstrates very flat gain spectral in the bandwidth range of about 28-30nm when 1550nm.This is comparable to the ZBLAN glass fibre of doping Er.For obtain this flatness at 1528-1563nm, the fluorine content of glass medium of the present invention better is at least 18 weight portions.Use following formula can represent the shape of gain spectral and the relation of wavelength well:
G (cm -1)=[σ Emission(λ) * N 2-σ Absorb(λ) * N 1] (1)
Wherein: σ EmissionBe (λ) with cm 2Emission cross section for unit;
σ AbsorbBe (λ) with cm 2Absorption cross-section for unit;
N 2Be excitation state (upper level) ( 4I 13/2) ion clusters (average to wavelength);
N 1Be ground state ( 4I 15/2) ion clusters (average to wavelength);
N tBe Er total ion concentration (every square centimeter number of ions).
(inversion) percentage is defined as D=(N if will reverse 2-N 1)/N 1, then equation (1) can be rewritten into:
G (dB/cm) 2.15 * N t* [σ Emission(λ) * (1+D)-σ Absorb(λ) * (1-D)] (2)
Wherein: D+-1: counter-rotating percentage;
The D-1:100% counter-rotating.
Equation 2 is used to calculate the gain shape of different glass composition and the relation of wavelength, the results are shown in Fig. 5-9.
Fig. 5 explanation is used for the gain shape of the typical borosilicate type glass of optical signal amplifier.Be used near the 1550nm bandwidth of WDM, the characteristic of this gain spectral is obviously inhomogeneous.At its magnification ratio of about 1535-1565nm (scope that typically is used for WDM) is uneven.The deviation of minimum and maximum gain differs 250%.
Fig. 6 explanation is used for the gain shape of the ZBLAN glass of optical signal amplifier.With borosilicate type glassy phase ratio, ZBLAN glass has flat gain shape in the wide wave-length coverage of about 30nm.
Fig. 7 is the gain shape of first kind of fluorophosphate type glass of the present invention.Label is this glass of embodiment 1, and by other component of 100 weight portions, its Er concentration surpasses 7 weight portions, and it has flat substantially gain shape above 28nm at the 1530-1560nm wave band.
Fig. 8 is the gain shape of second kind of fluorphosphate glass of the present invention.Label is this glass of embodiment 2, and by other component of 100 weight portions, its Er concentration surpasses 4 weight portions, and it has the flat gain shape above 26nm.
Fig. 9 is the gain shape of phosphate-based glass.Label is this glass of embodiment 3, and by other component of 100 weight portions, its Er concentration is lower than 3 weight portions slightly, and it has two flat relatively gain regions, and first about 10nm is wide, and second about 9nm is wide.
Another aspect of the present invention can excite amplification medium effectively at 980nm, keeps low relatively noise level simultaneously.Light amplification need be excited to the erbium ion in the glass medium higher energy level, makes ion relaxation (relaxation) subsequently.When the erbium ion relaxation during to ground state this process send photon.The wavelength of the photon that sends in this process is identical with the wavelength of the light signal of amplification.
For first three energy level of erbium, between energy level 2 (metastable state) and energy level 1 (ground state), produce the emission that is suitable for.For obtain population inversion (in the population of energy level 2 more than or equal to 50%) and and then obtain gain, must be with outer light source activation amplification medium.In general, amplify, excite amplification medium with the diode laser of 980nm or 1480nm for light signal.When using the 980nm diode laser, electron transition to the three-level ( 4I 11/12), dielectric relaxation to the second energy level and subsequently relaxation send 1.55 microns photon to ground state.When using the diode laser of 1480nm, electronics directly transits to laser levels (2), and relaxation is sent 1.55 microns photon to ground state subsequently.The most effective and reliable light amplification is that 980nm excites.But, because the 980nm exciting method is electron transition to the three-level, should be very short in the life-span of three-level, be preferably in the microsecond order of magnitude, otherwise electronics can be excited to higher energy level, thereby reduce launching efficiency.In fact when exciting with 980nm, this phenomenon occurs in the ZBLAN shape glass medium, because it relatively grows (about 9 milliseconds) in the life-span of energy level (3).Therefore, when exciting with the 980nm diode laser, ZBLAN shape amplification medium is so effective not as fluorphosphate glass of the present invention.
As with 980nm light activated amplification medium, the mix fluorphosphate glass of Er of the present invention is more favourable than the fluoride of other doping Er.ZBLAN shape (100% fluoride, oxygen-free) composition because 4I 11/12Excitation level has high fluorescence lifetime (9ms), so launching efficiency is low.Therefore ZBLAN shape composition excites at 1480nm usually.But, have shortcoming at this long-wavelength excitation.For example, can not reverse fully, and the noise of amplifier rises at this energy level population.On the contrary, fluorphosphate glass medium of the present invention can effectively excite at 980nm, because 4I 11/12Life-span is the 10-70 microsecond.
Fig. 5-9 shows that the fluorphosphate glass of the present invention that uses 980nm to excite shows the flat gain characteristic similar to ZBLAN, has compared tangible improvement with phosphate with silicate.Glass composition of the present invention has high and flat gain characteristic in the image intensifer of short length, thereby can be used for making plane amplifier and/or the short length monomode fiber that has the gain of ZBLAN shape and be applicable to WDM and other similar purposes.

Claims (13)

1. the fluorphosphate glass of 1.55 microns high and flat image intensifers that is used to gain is characterized in that by the following component of 100 weight portions, it contains 0.01-10 weight portion Er 2O 3:
P 2O 5 15-40 MgF 2 0-10
Al 2O 3 0-5 CaF 2 0-25
MgO 0-9 SrF 2 0-25
CaO 0-9 BaF 2 0-20
SrO 0-9 KHF 2 0-2
BaO 0-45 K 2TiF 6 0-2
AlF 3 5-25 。
2. fluorphosphate glass as claimed in claim 1 is characterized in that it also comprises 0.01-15 weight portion Yb 2O 3
3. fluorphosphate glass as claimed in claim 1 or 2 is characterized in that comprising in its chemical composition of weight portion:
P 2O 5 16.9-24.0 MgF 2 0-7.5
Al 2O 3 1.6-3.2 CaF 2 0-18.7
MgO 0-5.0 SrF 2 0-19.7
CaO 0-5.1 BaF 2 1.5-11.3
SrO 0-8.5 KHF 2 0-1.3
BaO 2.7-43.2 K 2TiF 6 0-0.6
AlF 3 9.5-19.3 。
4. as any one described fluorphosphate glass among the claim 1-3, it is characterized in that its content of fluoride is the 7-88 weight portion.
5. fluorphosphate glass as claimed in claim 4 is characterized in that its content of fluoride is more than or equal to 18 weight portions.
6. the image intensifer of an erbium doped, it comprises the medium that is used for light amplification, it is characterized in that described medium comprises the fluorphosphate glass composition, by the following component of 100 weight portions, it contains 0.01-10 weight portion Er 2O 3:
P 2O 5 15-40 MgF 2 0-10
Al 2O 3 0-5 CaF 2 0-25
MgO 0-9 SrF 2 0-25
CaO 0-9 BaF 2 0-20
SrO 0-9 KHF 2 0-2
BaO 0-45 K 2TiF 6 0-2
AlF 3 5-25 。
7. the image intensifer of erbium doped as claimed in claim 6 is characterized in that described medium comprises in the chemical composition of weight portion:
P 2O 5 16.9-24.0 MgF 2 0-7.5
Al 2O 3 1.6-3.2 CaF 2 0-18.7
MgO 0-5.0 SrF 2 0-19.7
CaO 0-5.1 BaF 2 1.5-11.3
SrO 0-8.5 KHF 2 0-1.3
BaO 2.7-43.2 K 2TiF 6 0-0.6
AlF 3 9.5-19.3 。
8. as the image intensifer of claim 6 or 7 described erbium doped, it is characterized in that it comprises about 0.01-15 weight portion Yb 2O 3
9. as the image intensifer of any one described erbium doped among the claim 6-8, it is characterized in that described image intensifer is the planar shaped image intensifer.
10. as the image intensifer of any one described erbium doped among the claim 6-8, it is characterized in that described image intensifer is a monomode fiber type image intensifer.
11. as the image intensifer of any one described erbium doped among the claim 6-10, the content of fluoride that it is characterized in that it is the 7-88 weight portion.
12. the image intensifer of erbium doped as claimed in claim 11 is characterized in that its content of fluoride is more than or equal to 18 weight portions.
13. an image intensifer is characterized in that it comprises:
Active light medium with input and output, described active light medium is doped with fluorescent dopants, and it accepts the light signal that wavelength is about 1525-1570nm at its input; With
Excitation source, it provides the luminous energy that excites of the about 980nm of wavelength to described active light medium, this exciting light is used to excite described fluorescent dopants, make it ballistic phonon, in the spectral region of about 1525-1565nm, be amplified in described light signal in the wide wave-length coverage of about 20-30nm with flat substantially gain spectral less than about 13% change in gain, it is about 65% that the quantum efficiency of wherein said active light medium surpasses, and described quantum efficiency is the fluorescence lifetime of described active light medium and the ratio between the emission lifetime.
CN98808791A 1997-09-05 1998-08-12 Glass for high and flat gain 1.55 micros optical amplifiers Pending CN1269915A (en)

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FR9711054A FR2768143B1 (en) 1997-09-05 1997-09-05 ERBIUM DOPED FLUOROPHOSPHATE GLASS AND OPTICAL AMPLIFIER INCLUDING THIS GLASS
FR97/11054 1997-09-05

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CN1313404C (en) * 2005-08-24 2007-05-02 中国科学院上海光学精密机械研究所 Low-refractive-index erbium-doped fluorophosphate glass and preparation method thereof
CN100358151C (en) * 2003-07-17 2007-12-26 松下电器产业株式会社 Optical component and manufacture method of the same

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US7989376B2 (en) * 2001-06-26 2011-08-02 Afo Research, Inc. Fluorophosphate glass and method for making thereof
JP4655553B2 (en) * 2003-09-05 2011-03-23 住友電気工業株式会社 Optical amplifying waveguide, optical amplifying module, and optical communication system
US10393887B2 (en) 2015-07-19 2019-08-27 Afo Research, Inc. Fluorine resistant, radiation resistant, and radiation detection glass systems

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CN100358151C (en) * 2003-07-17 2007-12-26 松下电器产业株式会社 Optical component and manufacture method of the same
CN1313404C (en) * 2005-08-24 2007-05-02 中国科学院上海光学精密机械研究所 Low-refractive-index erbium-doped fluorophosphate glass and preparation method thereof

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KR20010023640A (en) 2001-03-26
EP1010220A4 (en) 2001-07-04
CA2297331A1 (en) 1999-03-18
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EP1010220A1 (en) 2000-06-21
JP2001516958A (en) 2001-10-02

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