CN1361753A - Borate or aluminosilicate glass composition for optical amplfication - Google Patents

Borate or aluminosilicate glass composition for optical amplfication Download PDF

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CN1361753A
CN1361753A CN 00810615 CN00810615A CN1361753A CN 1361753 A CN1361753 A CN 1361753A CN 00810615 CN00810615 CN 00810615 CN 00810615 A CN00810615 A CN 00810615A CN 1361753 A CN1361753 A CN 1361753A
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mole
composition
glass
matrix
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Y·A·布罗谢顿
J·E·小迪肯森
D·雅各布
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
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths

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Abstract

Disclosed is a glass composition suited for use in optical amplification including a silicate which includes: at least 50 mole percent of SiO2, and at least one group III oxide, which may be selected from the group Al2O3 and B2O3, the ratio (R) of (X2O + YO) to said at least one group III oxide being less than or equal to 1.3, where X2O represents the sum of all alkali metal oxides present and YO represents the sum of all alkaline earth oxides and PbO and ZnO present. Fluorine may be included in the glass compositions. For compositions not including fluorine, it is preferred that the ratio R should be less than or equal to 1.0. The glass compositions are erbium-doped, and may be are co-doped with Yb2O3 and include dispersants such as Y2O3 and/or Gd2O3. This family of glasses possesses a flat gain characteristic in the 1545 nm region.

Description

The borate that light amplification is used or sillico aluminate glass composition
The present invention relates to glass composition, it is applicable to use the light amplification WDM telecommunication system of (specifically working as wavelength at third communication window, during namely near 1.5 microns). More specifically, the present invention relates to a class silicate glass, wherein added the oxide of at least a iii group element, better is aluminium oxide or boron oxide.
In optical fiber telecommunications system, need more and more to have the flat gain performance, especially at the amplifier material of third communication window (1525-1560nm) flat gain. At present, one of best optics amplifier material in this wave-length coverage is by ZBLAN glass (ZrF4-BaF 4-LaF 3-AlF 3-NaF) forming, (FOM=[(gains with " performance factor " FOM in its gain fluctuationMaximum-gainMinimum)/gainMinimum] * 100%) characterize, in 1.5 microns wavelength region may, the FOM of 32nm bandwidth is that the FOM of 10.6%, 35nm bandwidth is 18%. Yet ZBLAN glass is expensive, and requires specific processing conditions.
The present invention seeks to provide a class glass, the gain characteristic that it has in third communication window area, and its flatness can be comparable or better than it with ZBLAN.
By the way, FOM is at the standing part for gain characteristics, is generally that 30nm is wide or 32nm is wide part calculates. If selected 30nm or 32nm part are not to select between fixing wavelength value, but the maximum position of (this paper is 1525-1560nm) FOM value is selected in interested wavestrip, and then this FOM is defined as " unsteady () ".
The invention provides a kind of glass composition, it comprises at least 50 % by mole of SiO2With the oxide of at least a III family, better be to be selected from Al2O 3And B2O 3, it is characterized in that following proportionate relationship: R = X 2 O + YO A l 2 O 3 + B 2 O 3 A ≤ 1,3 , In the formula, X2O represents the summation of all alkali metal oxides in the composition, and YO represents to be selected from the composition summation of all oxides of alkaline earth oxide, ZnO and PbO.
Find that the glass composition of one embodiment of the invention has gain characteristic in 1.5 microns wavelength region may, its flatness can be comparable or better than it in the flatness of same band (about 30nm) with ZBLAN.
Glass composition of the present invention also is doped with the erbium of 0.005-6 weight portions usually outside 100 weight portion matrix compositions. Preferably, but these glass composition codopes have Yb2O 3, its consumption reaches 12 % by mole of matrix composition.
Preferably, in matrix composition, add such as Y2O 3And Gd2O 3And so on oxide, this helps the dispersion of erbium in matrix. The addition of these oxides reaches 3 % by mole separately, nearly 5 % by mole of total amounts. Find to add this type oxide and can also further improve gain flatness.
Glass composition of the present invention preferably has the matrix composition that comprises following component: SiO250.0-90.0 % by mole GeO20.0-10.0 % by mole B2O 30.0-30.0 % by mole Al2O 30.0-30.0 % by mole Li2O 0.0-15.0 % by mole Na2O 0.0-25.0 % by mole K2O 0.0-15.0 % by mole MgO 0.0-5.0 % by mole SrO 0.0-10.0 % by mole CaO 0.0-10.0 % by mole BaO 0.0-15.0 % by mole ZnO 0.0-10.0 % by mole of PbO 0.0-10.0 % by mole Y2O 30.0-3.0 % by mole Gd2O 30.0-3.0 % by mole Yb2O 30.0-12.0 % by mole, (B2O 3+Al 2O 3) 5-35.0 % by mole X2In O 0.0-20.0 % by mole XO 0.0-15.0 % by mole and the YO 0.0-20.0 % by mole formula, X2O is the summation of all alkali metal oxides in the matrix composition, and XO is the summation of all alkaline-earth oxides in the matrix composition, and YO is the summation of all alkaline-earth oxides and ZnO and PbO in the matrix composition.
Glass composition of the present invention can comprise maximum 12 weight portion fluorine, and preferably maximum 9 weight portion fluorine join in per 100 weight portion matrix compositions.
Those do not comprise for the composition of fluorine for the present invention, and preferably ratio R should be less than or equal to 1.0. Those comprise fluorine and ratio R is less than or equal to 1.3 composition with regard to these compositions and the present invention, and the FOM that the 32nm bandwidth obtains in the wavelengths of interest zone is less than 25%.
In addition, the matrix composition of per 100 weight portions can add the chlorine of maximum 12 weight portions, the chlorine of maximum 9 weight portions preferably, is used for dry glass.
Be more preferably, glass composition of the present invention has 0.005-6.0 weight portion Er2O 3, 0.0-9.0 weight portion chlorine and 0.0-9.0 weight portion fluorine, join in the composition that 100 weight portions are comprised of following component: SiO255.0-85.0 % by mole GeO20.0-8.0 % by mole B2O 30.0-25.0 % by mole Al2O 31.5-25.0 % by mole Li2O 0.0-12.0 % by mole Na2O 0.0-20.0 % by mole K2O 0.0-12.0 % by mole MgO 0.0-3.0 % by mole SrO 0.0-5.0 % by mole CaO 0.0-8.0 % by mole BaO 0.0-10.0 % by mole ZnO 0.0-5.0 % by mole of PbO 0.0-5.0 % by mole Y2O 30.0-2.0 % by mole Gd2O 30.0-2.0 % by mole Yb2O 30.0-10.0 % by mole, (B2O 3+Al 2O 3) 5-35.0 % by mole X2In O 0.0-20.0 % by mole of XO 0.0-15.0 % by mole of YO 0.0-20.0 % by mole formula, X2O is the summation of all alkali metal oxides in the matrix composition, and XO is the summation of all alkaline-earth oxides in the matrix composition, and YO is the summation of all alkaline-earth oxides and ZnO and PbO in the matrix composition.
If necessary, can in glass composition of the present invention, add oxide, such as TiO2And/or ZrO2, to regulate the refractive index of composition. The addition of these oxides mostly is 1.0 % by mole most usually separately.
In addition, the fluorescent characteristic of glass composition of the present invention can be heat-treated and further raising after forming composition, described heat treatment for example be make sillico aluminate glass of the present invention be in 500-700 ℃ 1 hour.
Provide and by the description to better embodiment of description of drawings, can be clear that other characteristics of the present invention and advantage by embodiment from following.
Fig. 1 is that the typical borosilicate glass gain of the present invention is to the graph of a relation of wavelength;
Fig. 2 is that gain fluctuation (weighing with FOM) is to (X in the typical sillico aluminate glass composition of the present invention2O+YO) with (Al2O 3+B 2O 3) graph of a relation of ratio;
Fig. 3 is that gain fluctuation (weighing with FOM) is to the graph of a relation of fluorine content in the typical sillico aluminate glass composition of the present invention;
Fig. 4 is the glass composition of table 1 embodiment 5 when having different fluorine content, and normalization fluorescence is to the graph of a relation of wavelength;
Fig. 5 is that the gain of table 1 embodiment 5 glass compositions is to the graph of a relation of wavelength;
Fig. 6 be similar to table 1 embodiment 5 glass composition after heat treatments at different, gain is to the graph of a relation of wavelength.
The present inventor finds that gain flatness can with the ZBLAN analogy or than its better optical amplifier material, can consist of by comprising the following glass composition that forms: 50 % by mole SiO at least in 1.5 micron wave length zones2, at least a III-th family oxide, better be selected from Al2O 3And B2O 3, and satisfy following proportionate relationship: R = X 2 O + YO A l 2 O 3 + B 2 O 3 A ≤ 1,3 , In the formula, X2O represents the summation of all alkali metal oxides in the composition, and YO represents to be selected from the composition summation of all oxides of alkaline earth oxide, ZnO and PbO.
Preferably, glass composition of the present invention also can comprise 0.005-6 weight portion Er beyond 100 weight portion matrix compositions2O 3, the fluorine of maximum 12 weight portions and maximum 12 weight portions chlorine (be used for dry glass and improve fluorescence lifetime), described matrix composition is made of following component: SiO250.0-90.0 % by mole GeO20.0-10.0 % by mole B2O 30.0-30.0 % by mole Al2O 30.0-30.0 % by mole Li2O 0.0-15.0 % by mole Na2O 0.0-25.0 % by mole K2O 0.0-15.0 % by mole MgO 0.0-5.0 % by mole SrO 0.0-10.0 % by mole CaO 0.0-10.0 % by mole BaO 0.0-15.0 % by mole ZnO 0.0-10.0 % by mole of PbO 0.0-10.0 % by mole Y2O 30.0-3.0 % by mole Gd2O 30.0-3.0 % by mole Yb2O 30.0-12.0 % by mole, (B2O 3+Al 2O 3) 5-35.0 % by mole X2In O 0.0-20.0 % by mole XO 0.0-15.0 % by mole and the YO 0.0-20.0 % by mole formula, X2O is the summation of all alkali metal oxides in the matrix composition, and XO is the summation of all alkaline-earth oxides in the matrix composition, and YO is the summation of all alkaline-earth oxides and ZnO and PbO in the matrix composition.
Preferably, those compositions that comprise fluorine of the present invention should satisfy: R = X 2 O + YO A l 2 O 3 + B 2 O 3 A ≤ 1,3 ,
Those not fluorine-containing compositions of the present invention should satisfy: R = X 2 O + YO A l 2 O 3 + B 2 O 3 A ≤ 1,3
More preferably, glass composition of the present invention also can comprise 0.005-6 weight portion Er beyond the matrix composition of 100 weight portions2O 3, the fluorine of maximum 9 weight portions and the chlorine of maximum 9 weight portions, described matrix composition can be comprised of following component: SiO255.0-85.0 % by mole GeO20.0-8.0 % by mole B2O 30.0-25.0 % by mole Al2O 31.5-25.0 % by mole Li2O 0.0-12.0 % by mole Na2O 0.0-20.0 % by mole K2O 0.0-12.0 % by mole MgO 0.0-3.0 % by mole SrO 0.0-5.0 % by mole CaO 0.0-8.0 % by mole BaO 0.0-10.0 % by mole ZnO 0.0-5.0 % by mole of PbO 0.0-5.0 % by mole Y2O 30.0-2.0 % by mole Gd2O 30.0-2.0 % by mole Yb2O 30.0-10.0 % by mole, (B2O 3+Al 2O 3) 5-35.0 % by mole X2O 0.0-20.0 % by mole XO 0.0-15.0 % by mole and YO 0.0-20.0 % by mole
Some typical cases that provided glass of the present invention in the following table 1 form and performance, and the details of three comparative examples.
Table I
1(Pyrex)  2(Vycor)  3(LCD)  4(PC)  5  6 7  8  9  CE1  CE2
 SiO 2(% by mole) 82,7  68,0  67,8  60,1  64,1  69,5 69,5  64,6  64,2  80,0  74,0
 GeO 2(% by mole) 0,0  0,0  0,0  0,0  0,0  0,0 0,0  0,0  0,0  0,0  0,0
 B 2O 3(% by mole) 11,4  23,0  8,5  18,1  0,0  0,0 0,0  0,0  0,0  0,0  0,0
 Al 2O 3(% by mole) 1,5  2,0  11,5  9,5  16,9  16,0 16,0  16,9  16,8  0,0  6,0
 Li 2O (% by mole) 0,0  0,0  0,0  0,0  5,0  8,0 8,0  5,0  0,0  0,0  0,0
 Na 2O (% by mole) 4,1  7,0  0,1  2,8  5,0  3,0 3,0  5,0  5,0  20,0  20,0
 K 2O (% by mole) 0,3  0,0  0,0  9,5  0,0  0,0 0,0  0,0  5,0  0,0  0,0
MgO (% by mole) 0,0  0,0  0,0  0,0  0,0  0,0 0,0  0,0  0,0  0,0  0,0
SrO (% by mole) 0,0  0,0  1,2  0,0  0,0  0,0 0,0  0,0  0,0  0,0  0,0
CaO (% by mole) 0,0  0,0  5,3  0,0  0,0  0,0 0,0  0,0  0,0  0,0  0,0
BaO (% by mole) 0,0  0,0  4,3  0,0  3,0  0,0 0,0  3,0  3,0  0,0  0,0
ZnO (% by mole) 0,0  0,0  1,3  0,0  0,0  0,0 0,0  0,0  0,0  0,0  0,0
PbO (% by mole) 0,0  0,0  0,0  0,0  5,0  3,0 3,0  5,0  5,0  0,0  0,0
 Y 2O 3(% by mole) 0,0  0,0  0,0  0,0  0,5  0,0 0,5  0,5  0,5  0,0  0,0
 Gd 2O 3(% by mole) 0,0  0,0  0,0  0,0  0,5  0,5 0,0  0,0  0,5  0,0  0,0
 Yb 2O 3(% by mole) 0,0  0,0  0,0  0,0  0,0  0,0 0,0  0,0  0,0  0,0  0,0
Total amount 100,00 100,00  100,00  100,00  100,00  100,00 100,00  100,00  100,00  100,00  100,00
 Al 2O 3+B 2O 3(% by mole) 12,9  23,0  20,0  27,6  16,9  16,0 16,0  16,9  16,8  0,0  6,0
 X 2O (% by mole) 4,4  7,0  0,1  12,3  10,0  11,0 11,0  10,0  10,0  20,0  20,0
XO (% by mole) 0,0  0,0  10,8  0,0  3,0  0,0 0,0  3,0  3,0  0,0  0,0
YO (% by mole) 0,0  0,0  12,1  0,0  8,0  3,0 3,0  8,0  8,0  0,0  0,0
 Er 2O 3(weight portion) 3,0  3,0  3,0  3,0  1,0  1,0 1,0  1,0  1,0  1,0  1,0
Cl (weight portion) 0,0  0,0  0,0  0,0  0,0  0,0 0,0  0,0  0,0  0,0  0,0
F (weight portion) 0,0  0,0  0,0  0,0  7,0  7,0 7,0  7,0  7,0  0,0  0,0
 R 0,34  0,30  0,61  0,45  1,07  0,88 0,88  1,07  1,07  20000  3,33
FOM 32nm (floating band) 16  9  20  13  6,3  11,2 10,1  9,0  5,0  250  180
Table I (continuing)
CE3  10  11  12  13  14  15  16  17  18  19
 SiO 2(% by mole) 68,0  62,0  60,0  55,0  63,1  63,1  63,1  63,1  63,1  60,0  58,0
 GeO 2(% by mole) 0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0
 B 2O 3(% by mole) 0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  2,0
 Al 2O 3(% by mole) 12,0  18,0  20,0  25,0  16,9  16,9  16,9  16,9  16,9  20,0  20,0
 Li 2O (% by mole) 0,0  0,0  0,0  0,0  5,0  5,0  5,0  5,0  5,0  0,0  0,0
 Na 2O (% by mole) 20,0  20,0  20,0  20,0  5,0  5,0  5,0  5,0  5,0  10,0  10,0
 K 2O (% by mole) 0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0
MgO (% by mole) 0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0
SrO (% by mole) 0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0
CaO (% by mole) 0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0
BaO (% by mole) 0,0  0,0  0,0  0,0  3,0  3,0  3,0  3,0  3,0  10,0  10,0
ZnO (% by mole) 0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0
PbO (% by mole) 0,0  0,0  0,0  0,0  5,0  5,0  5,0  5,0  5,0  0,0  0,0
 Y 2O 3(% by mole) 0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0
 Gd 2O 3(% by mole) 0,0  0,0  0,0  0,0  1,0  1,0  1,0  1,0  1,0  0,0  0,0
 Yb 2O 3(% by mole) 0,0  0,0  0,0  0,0  1,0  1,0  1,0  1,0  1,0  0,0  0,0
Total amount 100,00  100,00  100,00  100,00  100,00  100,00  100,00  100,00  100,00  100,00  100,00
 Al 2O 3+B 2O 3(% by mole) 12,0  18,0  20,0  25,0  16,9  16,9  16,9  16,9  16,9  20,0  22,0
 X 2O (% by mole) 20,0  20,0  20,0  20,0  10,0  10,0  10,0  10,0  10,0  10,0  10,0
XO (% by mole) 0,0  0,0  0,0  0,0  3,0  3,0  3,0  3,0  3,0  10,0  10,0
YO (% by mole) 0,0  0,0  0,0  0,0  8,0  8,0  8,0  8,0  8,0  10,0  10,0
 Er 2O 3(weight portion) 1,0  1,0  1,0  1,0  0,2  0,2  0,2  0,2  0,2  0,7  0,7
Cl (weight portion) 0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0  0,0
F (weight portion) 0,0  0,0  0,0  0,0  0,6  2,8  4,2  5,6  7,1  0,0  0,0
 R 1,67  1,11  1,00  0,80  1,07  1,07  1,07  1,07  1,07  1,07  0,91
FOM 32nm (floating band) 150  40  19  17  23  20  13  8  5  17  15
Table I (continuing)
20  21  22  23  24  25  26
 SiO 2(% by mole) 58,0  70,0  65,0  63,0  68,0  63,0  64,6
 GeO 2(% by mole) 0,0  0,0  0,0  0,0  0,0  0,0  0,0
 B 2O 3(% by mole) 0,0  0,0  0,0  2,0  0,0  0,0  0,0
 Al 2O 3(% by mole) 20,0  15,0  17,0  17,0  15,0  17,0  16,9
 Li 2O (% by mole) 0,0  10,0  5,0  5,0  10,0  5,0  5,0
 Na 2O (% by mole) 10,0  3,0  5,0  5,0  3,0  5,0  5,0
 K 2O (% by mole) 0,0  0,0  0,0  0,0  0,0  0,0  0,0
MgO (% by mole) 0,0  0,0  0,0  0,0  0,0  0,0  0,0
SrO (% by mole) 0,0  0,0  0,0  0,0  0,0  0,0  0,0
CaO (% by mole) 0,0  0,0  0,0  0,0  0,0  0,0  0,0
BaO (% by mole) 10,0  0,0  3,0  3,0  0,0  3,0  3,0
ZnO (% by mole) 0,0  0,0  0,0  0,0  0,0  0,0  0,0
PbO (% by mole) 0,0  2,0  5,0  5,0  2,0  5,0  5,0
 Y 2O 3(% by mole) 0,0  0,0  0,0  0,0  0,0  0,0  0,0
 Gd 2O 3(% by mole) 1,0  0,0  0,0  0,0  1,0  1,0  0,5
 Yb 2O 3(% by mole) 1,0  0,0  0,0  0,0  1,0  1,0  0,0
Total amount 100,00  100,00  100,00  100,00  100,00  100,00  100,00
 Al 2O 3+B 2O 3(% by mole) 20,0  15,0  17,0  19,0  15,0  17,0  16,9
 X 2O (% by mole) 10,0  13,0  10,0  10,0  13,0  10,0  10,0
XO (% by mole) 10,0  0,0  3,0  3,0  0,0  3,0  3,0
YO (% by mole) 10,0  2,0  8,0  8,0  2,0  8,0  8,0
 Er 2O 3(weight portion) 0,7  0,7  0,7  0,7  0,7  0,7  1,0
Cl (weight portion) 0,0  0,0  0,0  0,0  0,0  0,0  0,0
F (weight portion) 0,0  0,0  0,0  0,0  0,0  0,0  0,0
 R 1,00  1,00  1,06  0,95  1,00  1,06  1,07
FOM 32nm (floating band) 13  11  13  10  10  7  6
In table 1, R represents (X2O+YO) with (B2O 3+Al 2O 3) ratio, X2O represents the summation of all alkali metal oxides of existing, and YO represents all alkaline-earth oxides of existing and the summation of ZnO and PbO.
Table 1 shows, the gain flatness of glass composition that the present invention satisfies ratio R≤1.3 is good.
Preferably, the ratio R of those not fluorine-containing glass compositions of the present invention≤1.0. These compositions and the composition that those comprise fluorine and satisfy R≤1.3 conditions of the present invention, the FOM (32nm) in its wavelengths of interest zone is less than 25%.
Find, form various glass according to the invention and be suitable for very much light amplification at third communication window. Embodiment 1-4 is mainly by the composition (being borosilicate) that comprises boron oxide and obtain required ratio R. Embodiment 1 is the exemplary of Pyrex (TM), and embodiment 2 is examples of Vycor (TM), and embodiment 3 is the typical glass compositions for LCD, and embodiment 4 is typical photochromic glass compositions.
These borosilicate glasses have acceptable gain flatness. Can add chlorine and fluorine (for the matrix composition of 100 weight portions, maximum 12 weight portions, preferably 9 weight portions) in these glass compositions in order to dry glass and improve its fluorescence lifetime. In addition, oxide Yb2O 3、Y 2O 3And Gd2O 3Can be advantageously used in the codope borosilicate glass or help the dispersion of erbium in glass basis.
In these borosilicates of the present invention, embodiment 2 is preferred glass compositions, not only because its smooth especially gain characteristic, and because said composition is stable and have a good viscous-elastic behaviour. A rear characteristic is so that can be with known double crucible technique by material stretched single-mode fiber easily. Fig. 1 shows the gain characteristic of glass composition in different population inversion degree situations of table 1 embodiment 2.
The embodiment 5-9 of table 1 is mainly by the glass composition (being alumino-silicate) that comprises aluminium oxide and obtain required ratio R. For these compositions, boron oxide content in matrix composition is lower than 4 % by mole, join fluorine content in the 100 weight portion matrix compositions more than or equal to 2 weight portions (preferably more than 4 weight portions), and contained Y as dispersant in this matrix composition2O 3And Gd2O 3When being at least separately 0.1 % by mole, can obtain the better gain flatness than ZBLAN. Find, add at least 0.2 % by mole Y in the glass composition of the present invention2O 3And/or Gd2O 3Can improve gain flatness.
The comparative example 1-3 of table 1 and embodiment 10-12 have illustrated and have changed the ratio of iii group element in the glass composition to the impact of gain flatness, namely changed ratio R to the impact of gain flatness.
Although comparative example 1-3 contains the component oxide of appropriate amount, but outside the scope of the invention, because their ratio R is too large so that can't obtain smooth gain characteristic. Comparative example 1 expression does not have a mind to add the extreme case (considering the impurity content that may contain 0.1 % by mole of boron oxide or aluminium oxide, R 〉=20000) of III-th family oxide in the composition at all.
Embodiment 10-12 shows, the violent degree that improves of gain flatness when R≤1.3, embodiment 11 and 12 not fluorine-containing corresponding to composition, the preferred situation of R≤1.0.
Fig. 2 expresses the gain flatness (weighing with the FOM value) of glass composition of the present invention and the relation between the ratio R intuitively.
Find that the gain flatness of glass composition of the present invention also is subject to the impact of fluorine content in the composition. This impact can find out that from table 1 embodiment 13-17 wherein along with the increase of fluorine consumption in the matrix composition that joins constant composition, gain characteristic improves. This impact is shown in Fig. 3 intuitively, has shown when fluorine content to be increased to 4 % by weight of analyzed final composition when above, the degree that the FOM in the third communication window improves. Particularly, preferably the fluorine that comprises more than 4 weight portions of glass composition of the present invention joins in the matrix composition of per 100 weight portions.
Fig. 4 and Fig. 5 further show the dependence of glass combination physical performance of the present invention and fluorine content and ratio R. The gain characteristic that Fig. 4 illustrates the glass composition of table 1 embodiment 5 is how with the fluorine content. Fig. 5 illustrates when ratio R and fluorine and contains when measuring the value that table 1 provides the gain characteristic of the glass composition of table 1 embodiment 5. The gain spectrum of Fig. 5 is obtained by large measuring meter.
The embodiment 18-26 of table 1 shows, can change some oxides in the glass composition of the present invention and can obviously not change the gain characteristic of gained glass, and condition is the ratio R that keeps required.
As mentioned above, can in glass composition of the present invention, add such as TiO if need2And/or ZrO2And so on oxide, the refractive index that is used for regulating composition. The addition of these oxides can mostly be 1.0 % by mole of TiO most2And/or maximum 1.0 % by mole of ZrO2。
It has also been found that after glass composition of the present invention forms it is heat-treated the fluorescent characteristic that can further improve said composition, described heat treatment is to make composition be in high temperature to continue for some time. The concrete composition that heat treated duration and temperature will be suitable for heat-treating. And, in the high-temperature heat treatment short period with in the lower temperature heat treatment long period, can obtain identical effect.
Fig. 6 shows with table 1 embodiment 5 similar glass compositions respectively in the impact on its gain characteristic in 1 hour of 4 heat treatments at different. Fig. 6 also illustrates the gain characteristic without heat treated composition, is used for relatively.
The composition difference of the glass composition of Fig. 6 and table 1 embodiment 5 is that it comprises 63.1 % by mole of SiO2, 1 % by mole of Y2O 3With 1 % by mole of Gd2O 3, 2 % by mole of Na2O (is Na2And outside the matrix composition of 100 weight portions, also comprise 5 weight portion fluorine, 0.3 weight portion As the form of O (N)),2O 3With 1 weight portion Er2O 3。
As seen from Figure 6, to heat-treat after forming be favourable to glass composition of the present invention. Experiment shows that this heat treatment can not affect the transparency of glass composition.
Although the present invention is illustrated with reference to some specific embodiments, the invention is not restricted to the detail in these embodiments. On the contrary, in the scope of claims, can make many variations and change to described embodiment.

Claims (10)

1. glass composition comprises:
At least 50 % by mole of SiO2, and
At least a Al that is selected from2O 3And B2O 3The oxide of III-th family,
It is characterized in that R≤1.3, wherein R = X 2 O + YO A l 2 O 3 + B 2 O 3 A ≤ 1,3 , In the formula, X2O represents the summation of all alkali metal oxides in the composition, and YO represents to be selected from the composition summation of all oxides of alkaline-earth oxide, ZnO and PbO.
2. glass composition as claimed in claim 1, R is less than or equal to 1.3 when it is characterized in that composition is fluorine-containing, and R was not less than or equal to 1.0 when composition was fluorine-containing.
3. glass composition as claimed in claim 2 is characterized in that the matrix composition for per 100 weight portions, also comprises the fluorine greater than 4 weight portions.
4. such as claim 1,2 or 3 described glass compositions, it is characterized in that matrix composition comprises at least 0.2 % by mole Y2O 3And/or Gd2O 3。
5. such as claim 1,2,3 or 4 described glass compositions, it is characterized in that this glass composition beyond 100 weight portion matrix compositions, also comprises 0.005-6 weight portion Er2O 3, maximum 12 weight portion fluorine and maximum 12 weight portion chlorine, described matrix composition comprises: SiO250.0-90.0 % by mole GeO20.0-10.0 % by mole B2O 30.0-30.0 % by mole Al2O 30.0-30.0 % by mole Li2O 0.0-15.0 % by mole Na2O 0.0-25.0 % by mole K2O 0.0-15.0 % by mole MgO 0.0-5.0 % by mole SrO 0.0-10.0 % by mole CaO 0.0-10.0 % by mole BaO 0.0-15.0 % by mole ZnO 0.0-10.0 % by mole of PbO 0.0-10.0 % by mole Y2O 30.0-3.0 % by mole Gd2O 30.0-3.0 % by mole Yb2O 30.0-12.0 % by mole, (B2O 3+Al 2O 3) 5-35.0 % by mole X2In O 0.0-20.0 % by mole of XO 0.0-15.0 % by mole of YO 0.0-20.0 % by mole formula, X2O is the summation of all alkali metal oxides in the matrix composition, and XO is the summation of all alkaline-earth oxides in the matrix composition, and YO is the summation of all alkaline-earth oxides and ZnO and PbO in the matrix composition.
6. glass composition as claimed in claim 5 is characterized in that described matrix composition comprises and is less than or equal to 5.0 % by mole (Y2O 3+Gd 2O 3)。
7. such as claim 1,2,3 or 4 described glass compositions, it is characterized in that this glass composition beyond 100 weight portion matrix materials, also comprises 0.005-6.0 weight portion Er2O 3, the fluorine of maximum 9.0 weight portions and the chlorine of maximum 9.0 weight portions, described matrix material comprises: SiO255.0-85.0 % by mole GeO20.0-8.0 % by mole B2O 30.0-25.0 % by mole Al2O 31.5-25.0 % by mole Li2O 0.0-12.0 % by mole Na2O 0.0-20.0 % by mole K2O 0.0-12.0 % by mole MgO 0.0-3.0 % by mole SrO 0.0-5.0 % by mole CaO 0.0-8.0 % by mole BaO 0.0-10.0 % by mole ZnO 0.0-5.0 % by mole of PbO 0.0-5.0 % by mole Y2O 30.0-2.0 % by mole Gd2O 30.0-2.0 % by mole Yb2O 30.0-10.0 % by mole, (B2O 3+Al 2O 3) 5-35.0 % by mole X2In O 0.0-20.0 % by mole of XO 0.0-15.0 % by mole of YO 0.0-20.0 % by mole formula, X2O is the summation of all alkali metal oxides in the matrix composition, and XO is the summation of all alkaline-earth oxides in the matrix composition, and YO is the summation of all alkaline-earth oxides and ZnO and PbO in the matrix composition.
8. such as the described glass composition of above each claim, it is characterized in that said composition also comprises maximum 1 % by mole TiO2And/or maximum 1 % by mole ZrO2。
9. such as the described glass composition of above each claim, it is characterized in that after forming described composition, it being heat-treated.
10. an optical amplifier comprises each described glass composition among the claim 1-9.
CN 00810615 1999-07-21 2000-06-16 Borate or aluminosilicate glass composition for optical amplfication Pending CN1361753A (en)

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