CN1352624A - 玻璃组合物 - Google Patents
玻璃组合物 Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 96
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 11
- 230000003287 optical effect Effects 0.000 claims abstract 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 20
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 18
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000006862 quantum yield reaction Methods 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 18
- 239000005385 borate glass Substances 0.000 abstract description 14
- 239000000377 silicon dioxide Substances 0.000 abstract description 8
- 230000003321 amplification Effects 0.000 abstract description 6
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000005371 ZBLAN Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 6
- 229910016036 BaF 2 Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- -1 erbium ion Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000013307 optical fiber Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 101000795655 Canis lupus familiaris Thymic stromal cotransporter homolog Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 150000000917 Erbium Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000005383 fluoride glass Substances 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- 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
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Abstract
一种由掺杂铒的硼酸盐玻璃组合物组成的适用于光学放大的玻璃组合物,它至少包括30摩尔%B2O3。在约1545nm区域,该族玻璃对光学放大具有适用的带宽(50nm或更大)。一族较好的亚族玻璃含有小于或等于30摩尔%的SiO2。另一族较好的亚族玻璃含有小于或等于5摩尔%的La2O3,并且B2O3与(∑X2O+∑YO)之比大于或等于3.5,较好大于或等于4.5,其中X2O为存在的所有单价金属氧化物,YO为存在的所有二价金属氧化物。
Description
本发明涉及一族适用于WDM电信系统的新的玻璃,所述电信系统使用波长在第三电信窗(即接近1.5微米)的光学放大作用。更具体地说,本发明涉及一族掺杂铒的硼酸盐玻璃。
在光纤电信系统中,对于在越来越宽的带宽范围内(尤其在第三电信窗(1525-1560nm)和第四电信窗(1565-1615nm))具有平坦增益特性的放大器材料有日益增加的需求。目前,通常使用未改性的掺杂铒的光纤放大器(EDFA)用于光学放大,其基本材料由石英玻璃组分组成。但是,在1530-1560nm范围内EDFA的增益特性不是平坦的,从而需要使用补偿和/或滤波技术。
在波分复用(WDM)系统中,随着要传输的通信通道数的增加,对宽带宽范围内增益平坦性的要求也日益增加。例如,在设计具有载带32通信通道的系统中,目前的方法是使用掺杂铒的ZBLAN玻璃(ZrF4-BaF2-LaF3-AlF3-NaF),其在宽度接近30nm的区域内增益的波动小于7%。尽管这是良好的性能,但是使用常规石英基光纤结合已知的滤波和/或补偿技术(尽管需要增加泵功率从而提高成本)或者使用其它混合的石英光纤设计也可获得相似的性能。
本发明的目的是提供一种在1.5微米波长区具有特别平坦增益特性的玻璃组合物。
本发明的目的还在于提供一种在1.5微米波长区具有平坦增益特性的玻璃组合物,该带宽比使用石英基光纤并结合滤波技术或者石英/混合活性光纤一般所能获得的平坦增益带宽更宽。
目前,在掺杂铒的ZBLAN玻璃组合物中铒离子的发射光谱比其在石英基玻璃组合物中的发射光谱宽约20nm。本发明人发现在掺杂铒的硼酸盐玻璃中铒发射光谱具有更宽的带宽,并发现这些玻璃适合作于光学放大。
更具体地说,本发明提供一种玻璃组合物,它包括掺杂铒的硼酸盐,其中该玻璃组合物的至少30摩尔%是由B2O3构成的。
按100重量份下列组分计:SiO2 0-30摩尔% B2O3 30-90摩尔% Al2O2 0-15摩尔%GeO2 0-50摩尔% Sb2O3 0-60摩尔% TeO2 0-50摩尔%∑(X2O) 0-20摩尔% ∑(YO) 0-20摩尔% BaO 0-15摩尔%La2O3 0-5摩尔% Y2O3 0-5摩尔% Ga2O3 0-5摩尔%Ta2O5 0-5摩尔% TiO2 0-5摩尔%
本发明玻璃组合物较好包括0.01-10重量份,更好0.01-2.5重量份Er2O3和0-6重量份Yb2O3。
在本发明第一个较好的实例中,该玻璃组合物包括等于或小于30摩尔%的二氧化硅。
业已发现本发明第一个较好实例的玻璃组合物在接近50nm的带宽范围内具有平坦增益特性。该性能接近传输64信道的实用的WDM系统的要求。
使用包括完全脱水步骤(其中在干燥条件下熔融玻璃)的方法,或者使用包括采用超纯原料的玻璃纯化方法制备本发明第一个较好实例的玻璃组合物,则可改进该玻璃组合物的量子效率。
在本发明第二个较好实例中,所述玻璃组合物包括小于或等于5摩尔%的La2O3,并且B2O3与(∑X2O+∑YO)之比等于或大于3.5,较好等于或大于4.5,其中X2O表示存在的所有单价金属氧化物,YO表示存在的所有二价金属氧化物。
业已发现本发明第二个实例的玻璃组合物在特别宽的带宽(通常约80nm)范围内具有平坦增益特性。
在本发明第二个较好实例的玻璃组合物中,发现X2O较好包括Li2O,YO较好包括PbO。
当本发明第二个较好实例的玻璃组合物的制造步骤包括脱水步骤时,可改进该玻璃组合物的荧光寿命。在该玻璃组合物含有重阳离子(例如Pb、Te、Sb和Bi)的情况下,这种荧光寿命的改进效果特别明显。
通过向该玻璃组合物中选择性地加入最多5摩尔%这种组分如ZrO2、TiO2、Y2O3、Ta2O5、Gd2O3或La2O3,可改变该玻璃组合物的结构和其它性能。应理解所给出的组分并非穷举。
本发明玻璃组合物可结合已知的滤波技术一起使用,以获得更宽的适用的带宽。在本发明第二个较好实例的玻璃组合物的情况下,使用这种方法可将适用的带宽拓宽至接近100nm,对于石英基EDFA类获得的约32nm的带宽,这是巨大的改进。
由下列以实施例的方式结合附图描述的较好实例,可清楚地理解本发明的其它特征和优点。附图中:
图1是在1.5微米波长区,硼酸盐玻璃、ZBLAN玻璃、氟铝硅酸盐玻璃和硅酸锑玻璃的增益特性比较图;
图2是本发明硼酸盐玻璃的增益波动与ZBLAN玻璃组合物呈现的增益波动的比较图;
图3显示本发明第一个较好实例的玻璃组合物的第一个实施例的算得的增益特性;
图4显示本发明第一个较好实例的玻璃组合物的第二个实施例的算得的增益特性;
图5显示本发明第一个较好实例的玻璃组合物的第三个实施例的算得的增益特性;
图6显示本发明第一个较好实例的玻璃组合物的第四个实施例的算得的增益特性;
图7显示ZBLAN玻璃组合物算得的增益特性,用于比较;
图8显示氟磷酸盐玻璃组合物算得的增益特性,用于比较。
业已发现掺杂铒的硼酸盐玻璃尤其适用于接近1.5微米波长的光学放大作用。图1表示在硼酸盐玻璃中铒的发射光谱以及该发射光谱与铒在ZBLAN玻璃以及氟铝硅酸盐和硅酸锑玻璃中的发射光谱的比较情况。由图1可见,在靠近1.5微米波长区,铒在硼酸盐中的发射带宽比在ZBLAN中或者在不同的硅酸盐玻璃组合物中的带宽更宽。更具体地说,铒在硼酸盐玻璃中归一化发射谱的半宽度(FWHM)为100nm,而无硼玻璃的最佳本宽度为60nm。
图2比较了掺杂铒的硼酸盐玻璃组合物的增益波动与掺杂铒的ZBLAN玻璃组合物的增益波动。图2是根据发射和吸收截面计算模拟的增益特性得到的。由图2可见硼酸盐玻璃在64nm范围内呈现相对平的增益特性,而ZBLAN玻璃组合物仅在约30nm范围内呈现相对平的增益特性。尤其是在该64nm带宽范围内未经滤波,硼酸盐玻璃的增益波动低至13%。
当100重量份中B2O3占至少30摩尔%,并且除了该100重量份以外,该组合物还包括0.01-10重量份,较好0.01-2.5重量份Er2O3时,可观察到本发明掺杂铒的硼酸盐玻璃组合物的优良性能。
本发明硼酸盐玻璃组合物还可共掺杂Yb2O3:除了前面提到的100重量份其它组分以外,组合物还包括0-15重量份Yb2O3,更好0-6重量份Yb2O3。
根据本发明第一个较好实例,掺杂铒的硼酸盐玻璃具有低的二氧化硅含量(小于30摩尔%)。
本发明第一个较好实例的玻璃的一些组成和性能列于下表1,在该表中将其与两种已知的玻璃组合物进行比较。所示第三比较例是本发明第一个较好实例中的一种玻璃,但它比最优选的组合物含更多PbO。
表1
*在表1中构成比较例2的氟磷酸盐玻璃组合物还包括16.9重量%P2O5、5.8重量%MgF2、18.7重量%CaF2、19.7重量%SrF2、11.3重量%BaF2、19.3重量%AlF3、1.3重量%KHF2和0.6重量%K2TiF6。
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 比较例1ZBLAN | 比较例2*氟磷酸盐 | 比较例3 | |
B2O3(重量%) | 85 | 80 | 70 | 80 | 90 | 38 | ||
L2O(重量%) | 2 | |||||||
Na2O(重量%) | 15 | 20 | 30 | 5 | 0.5 | |||
K2O(重量%) | 0.9 | |||||||
BaO(重量%) | 20 | 3 | 2.7 | |||||
PbO(重量%) | 45 | |||||||
Al2O3(重量%) | 3.2 | 0.8 | ||||||
As2O3(重量%) | 0.5 | |||||||
SiO2(重量%) | 14.8 | |||||||
Er2O3(重量%) | 5 | 5 | 5 | 5 | 5 | 0.8 | 6 | 3 |
平坦度δG(1536-1560nm) | 5 | 3 | 3 | 14 | 16 | |||
平坦度δG(1524-1570nm) | 8 | 10 | ||||||
平坦度δG(1530-1580nm) | 16 | |||||||
量子效率 | 4.1 | 5.4 | 68 | 17.1 | ||||
半宽度(nm)(发射信号) | 85 | 80 | 54 | 78 | 103 | 69 | 51 | 52 |
在本文中将平坦度(δG)定义为在考虑的波长范围内最大增益和最小增益之差除以该波长范围内的最小增益。该量值一般称为F.O.M(灵敏值)。
由下列等式可计算出玻璃组合物的增益特性:
G(dB/cm)≈2.17×Nt×[σ发射(λ)×(1+D)-σ吸收(λ)×(1-D)]
其中,σ发射(λ)=以cm2为单位的发射截面;
σ吸收(λ)=以cm2为单位的吸收截面;
Nt=以cm-3为单位的Er离子总浓度;
D=(N2-N1)/Nt
在0%反转(inversion)时,D=-1
在100%反转时,D=+1
N2=高能级(4I13/2)离子群(根据波长平均)
N1=基态(I15/2)离子群(根据波长平均)
构成表1实施例1-4的玻璃组合物算得的增益特性分别如图3-图6所示。为了进行比较,将构成表1第一和第二比较例的ZBLAN和氟磷酸盐玻璃的增益特性列于图7和图8。
将图3-6与图7和图8进行比较并由表1的数据可见,本发明第一个较好实例的玻璃组合物在感兴趣的波长区(1530-1560nm)具有平坦增益特性。更具体地说,尽管在该波长范围内对于构成第一和第二比较例的ZBLAN和氟磷酸盐玻璃的F.O.M分别是14和16,但是本发明第一个较好实例的第一、第二和第四实施例的该值为5或更小。同样,当考虑更宽的带宽(即1530-1580nm)时,本发明第一个较好实例的第五实施例的增益特性的F.O.M仅达到16。
本发明第一个较好实例的玻璃组合物具有低量子效率。这部分归因于其高的OH含量,部分归因于其中发生的高非辐射弛豫(硼酸盐具有高光子能量,它偏爱从4I13/2能级非辐射弛豫是众所周知的)。尽管这种低的量子效率,但是仍能发生放大作用。但是,如有必要,可采取行动改进量子效率。可改变非辐射跃迁比例。但是,通过对玻璃完全脱水(例如在干燥条件下熔融玻璃)可减少OH引起的淬灭。另外,使用超高纯原料制备玻璃可减少杂质引起的淬灭。这些措施能够改进这些玻璃组合物的量子效率(在低铒浓度下量子效率最高达50%)。
本发明第二个较好实例提供一种掺杂铒的高氧化硼含量的玻璃,与其中的单价金属氧化物或二价金属氧化物的含量相比,它具有高的B2O3含量。更具体地说,较好B2O3与(∑X2O+∑YO)之比等于或大于3.5,最好等于或大于4.5,其中X2O表示存在的所有单价金属(例如Li、Na、K、Cs、...)氧化物,YO表示存在的所有二价金属(例如Mg、Ca、Ba、Pb、Zn、...)氧化物。较好的是,这些玻璃含有最多5摩尔%La2O3。
业已发现在本发明第二个较好实例中,单价金属氧化物由Li2O组成或包括Li2O,而二价金属氧化物较好是PbO。在某些体系中(例如B/Pb、B/Te),可制得无碱金属和碱土金属的玻璃。
通过选择性加入形成玻璃的元素可改进玻璃的耐久性并控制其它性能。一般的形成玻璃的元素是SiO2、GeO2、Al2O3、Sb2O3、和TeO2。加入这种组分对带宽很少或不具有影响,只要考虑涉及玻璃组成的其它标准即可。
通过选择性地加入最多5摩尔%的这种组分如ZrO2、TiO2、Y2O3、Ta2O5、Gd2O3、La2O3,可控制玻璃组合物的结构性能(如折射率和粘度)和/或铒离子在玻璃基质中的分散性。另外,应理解这种例子是非穷举的。
本发明第二个较好实例和一些比较例(CE)玻璃的一些具体的组成和性能列于下表2。某些比较例(带星号)是本发明第二个较好实例的玻璃,但是比最佳组合物含有更多的La2O3或BaO。
表2
1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | CE1 | CE2 | 14 | CE3* | |
B2O3 | 85.5 | 85 | 72 | 63 | 54 | 36 | 90 | 90 | 90 | 90 | 85.5 | 76.5 | 70.5 | 65 | 65 | 85.5 | 81 |
Li2O | 1.9 | 2 | 1.6 | 1.4 | 1.2 | 0.8 | 2 | 2 | 2 | 2 | 1.9 | 1.7 | 1.8 | 5 | 1.9 | 1.8 | |
Na2O | 4.75 | 5 | 4 | 3.5 | 3 | 2 | 5 | 5 | 5 | 5 | 4.75 | 4.25 | 4.5 | 5 | 4.75 | 4.5 | |
CaO | 3 | 1 | |||||||||||||||
BaO | 2.85 | 3 | 2.4 | 2.1 | 1.8 | 1.2 | 3 | 2.85 | 2.55 | 2.7 | 30 | 2.85 | 2.7 | ||||
SrO | 1 | ||||||||||||||||
PbO | 1 | 3 | 30 | ||||||||||||||
Al2O3 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | ||||||||||
La2O3 | 5 | 10 | |||||||||||||||
Sb2O3 | |||||||||||||||||
As2O3 | |||||||||||||||||
SiO2 | 5 | 5 | 5 | 5 | 5 | 15 | 15 | ||||||||||
GeO2 | 10 | 20 | 30 | 50 | |||||||||||||
BaF2 | |||||||||||||||||
Na2F2 | |||||||||||||||||
Al2F6 | |||||||||||||||||
Er2O3(重量%) | 5 | 5 | 1 | 1 | 1 | 1 | 5 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
R | 9 | 8.5 | 9 | 9 | 9 | 9 | 9 | 9 | 9 | 9 | 9 | 9 | 7.8 | 1.86 | 1.86 | 8.9 | 8.9 |
半宽度 | 90 | 90 | 87 | 85 | 81 | 75 | 102 | 102 | 102 | 102 | 103 | 103 | 88 | 71 | 52.7 | 77.7 | 64.7 |
表2(续)
CE4* | 15 | 16 | CE5 | CE6 | CE7 | CE8 | 17 | CE9* | 18 | 19 | 20 | 21 | CE10 | CE11* | 22 | |
B2O3 | 76.5 | 80 | 81 | 70 | 69.7 | 75 | 70 | 80 | 80 | 80 | 66 | 94.9 | 92.55 | 70 | 73.5 | 85 |
Li2O | 1.7 | 2 | 1.8 | 4.3 | 4 | 10 | 1.8 | 5.1 | 7.45 | 10 | ||||||
Na2O | 4.25 | 5 | 4.5 | 30 | 13 | 8.3 | 20 | 20 | 4.5 | 15 | ||||||
K2O | 13 | 12.7 | ||||||||||||||
CaO | 20 | |||||||||||||||
BaO | 2.55 | 3 | 2.7 | 20 | 2.7 | 3.7 | ||||||||||
SrO | 9.9 | |||||||||||||||
PbO | 20 | |||||||||||||||
Al2O3 | 10 | 10 | 10 | |||||||||||||
La2O3 | 15 | 12.9 | ||||||||||||||
As2O3 | ||||||||||||||||
SiO2 | 15 | |||||||||||||||
GeO2 | ||||||||||||||||
BaF2 | ||||||||||||||||
Na2F2 | ||||||||||||||||
Al2F6 | ||||||||||||||||
Er2O3(重量%) | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
R | 8.8 | 8 | 9 | 2.3 | 2.3 | 3 | 2.3 | 4 | 4 | 4 | 7.3 | 18.6 | 12.4 | 2.3 | 5.4 | 5.7 |
半宽度 | 58.9 | 86.4 | 86.4 | 53 | 53 | 64 | 71.1 | 78 | 60.3 | 86 | 84.1 | 108 | 101 | 63 | 56.8 | 92.3 |
表2(续)
23 | 24 | 25 | 26 | 27 | 28 | CE12 | CE13 | 29 | 30 | 31 | CE14 | CE15 | 32 | 33 | CE16 | |
B2O3 | 79 | 77 | 75 | 45 | 40 | 35 | 25 | 15 | 90 | 60 | 45 | 30 | 40 | 35 | 25 | |
Li2O | 5 | 5 | 5 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
Na2O | 15 | 15 | 15 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
K2O | ||||||||||||||||
CaO | ||||||||||||||||
BaO | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | |||
SrO | ||||||||||||||||
Al2O3 | 1 | 3 | 5 | |||||||||||||
La2O3 | ||||||||||||||||
Sb2O3 | 45 | 45 | 45 | 45 | 45 | 30 | 45 | 60 | 90 | 45 | 45 | 45 | ||||
SiO2 | 5 | 10 | 20 | |||||||||||||
GeO2 | 5 | 10 | 20 | 30 | ||||||||||||
BaF2 | ||||||||||||||||
Na2F2 | ||||||||||||||||
Al2F6 | ||||||||||||||||
Er2O3(重量%) | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 4.5 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
R | 3.95 | 3.85 | 3.75 | 4.5 | 4 | 3.5 | 2.5 | 1.5 | 9 | 6 | 4.5 | 3 | 0 | 4 | 3.5 | 2.5 |
半宽度 | 88.2 | 81.2 | 88.2 | 81 | 79 | 77 | 65 | 64 | 103 | 91 | 81 | 78 | 56 | 80 | 78 | 73 |
表2(续)
34 | 35 | 36 | 37 | 38 | 39 | CE17 | CE18 | 40 | 41 | 42 | 43 | 44 | 45 | CE19 | CE20 | |
B2O3 | 85.5 | 84.5 | 82.5 | 80.5 | 45 | 47.5 | 25 | 25 | 85.5 | 85.5 | 85.5 | 75.5 | 75.5 | 75.5 | 65.5 | 65.5 |
Li2O | 1.9 | 1.9 | 1.9 | 1.9 | 2 | 1 | 1 | 1.9 | 1.9 | 1.9 | 1.9 | 1.9 | 1.9 | 1.9 | ||
Na2O | 5 | 2.5 | 2.5 | 4.75 | 7.6 | 9.5 | 4.75 | 4.75 | 4.75 | 4.75 | 4.75 | |||||
CaO | 10 | 20 | ||||||||||||||
BaO | 3 | 1.5 | 2.85 | 2.85 | 2.85 | 2.85 | 2.85 | 2.85 | ||||||||
SrO | 1.5 | 10 | ||||||||||||||
PbO | 10 | |||||||||||||||
MgO | 5 | 10 | 20 | |||||||||||||
Al2O3 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | ||||||||
Sb2O3 | 45 | 45 | ||||||||||||||
GeO2 | 45 | 47.5 | 20 | 20 | ||||||||||||
BaF2 | 2.85 | 2.85 | 2.85 | 2.85 | ||||||||||||
Na2F2 | 4.75 | 4.75 | 4.75 | 4.75 | ||||||||||||
Al2F6 | 5 | 6 | 8 | 10 | ||||||||||||
Er2O3(重量%) | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1.2 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
R | 45 | 44.5 | 43.4 | 42.4 | 4.5 | 9.5 | 2.5 | 2.5 | 9 | 9 | 9 | 3.9 | 3.9 | 3.9 | 2.2 | 2.2 |
半宽度 | 89 | 87 | 84 | 82 | 82 | 90 | 75 | 76 | 82 | 80 | 87 | 85 | 80 | 79 | 58 | 68 |
在表2中,R代表B2O3与(∑X2O+∑YO)之比。
由表2可见,本发明第二个较好实例的较好的玻璃组合物其半宽度为75或更大,显示在感兴趣的波长范围内其具有特别大的带宽。
本发明第二个较好实例的组合物中具体的荧光寿命较低,通常小于1ms。这是因为玻璃中的高水含量。使用普通的玻璃脱水技术(例如使用含卤化合物作为原料、在真空中融化玻璃、使用预锻烧的前体材料等)可改进荧光寿命。本发明第二个较好实例的含有重离子(如Pb/Te/Sb/Bi)的这些玻璃组合物对脱水更敏感,呈现优于1.5ms的荧光寿命。
为了使玻璃脱水,推荐使用含卤(氟、溴、氯...)原料,同样推荐将玻璃在控制的气氛中或在部分真空中熔融。也可使用气体(如BCl3)对熔融的玻璃混合物进行鼓泡。
特别优选的是本发明玻璃组合物可用下列组分表示:
对于100重量份下列组分:SiO2 0-30摩尔% B2O3 30-90摩尔% Al2O2 0-15摩尔%GeO2 0-50摩尔% Sb2O3 0-60摩尔% TeO2 0-50摩尔%∑(X2O) 0-20摩尔% ∑(YO) 0-20摩尔% BaO 0-15摩尔%La2O3 0-5摩尔% Y2O3 0-5摩尔% Ga2O3 0-5摩尔%Ta2O5 0-5摩尔% TiO2 0-5摩尔%
(B2O3/(∑X2O+∑YO)大于或等于3.5,较好大于或等于4.5,其中X2O为存在的所有单价金属氧化物,YO为存在的所有二价金属氧化物),
本发明玻璃组合物包括0.01-10重量份,更好0.01-2.5重量份Er2O3和0-6重量份Yb2O3。
尽管参照某些具体的实例对本发明进行了描述,但是本发明不限于这些实例的详细特征。相反,在所附权利要求的范围内可对所述实例进行各种改进和变化。
Claims (13)
1.一种玻璃组合物,它包括掺杂铒的硼酸盐,含有至少30摩尔%B2O3。
2.如权利要求1所述的玻璃组合物,它含有少于或等于30摩尔%的SiO2。
3.如权利要求2所述的玻璃组合物,其特征在于所述玻璃组合物的制备包括在干燥条件下熔融玻璃的步骤,从而改进形成的组合物的量子效率。
4.如权利要求1所述的玻璃组合物,它含有少于或等于5摩尔%的La2O3。
5.如权利要求4所述的玻璃组合物,其特征在于B2O3与(∑X2O+∑YO)之比大于或等于3.5,其中X2O为存在的所有单价金属氧化物,YO为存在的所有二价金属氧化物。
6.如权利要求5所述的玻璃组合物,其特征在于B2O3与(∑X2O+∑YO)之比大于或等于4.5。
7.如前面任何一项权利要求所述的玻璃组合物,按100重量份下列组分计:SiO2 0-30摩尔% B2O3 30-90摩尔% Al2O2 0-15摩尔%GeO2 0-50摩尔% Sb2O3 0-60摩尔% TeO2 0-50摩尔%∑(X2O) 0-20摩尔% ∑(YO) 0-20摩尔% BaO 0-15摩尔%La2O3 0-5摩尔% Y2O3 0-5摩尔% Ga2O3 0-5摩尔%Ta2O5 0-5摩尔% TiO2 0-5摩尔%
它包括0.01-10重量份,更好0.01-2.5重量份Er2O3和0-6重量份Yb2O3。
8.如权利要求5、6或7所述的玻璃组合物,其特征在于所述X2O是Li2O。
9.如权利要求5、6、7或8所述的玻璃组合物,其特征在于所述YO是PbO。
10.如权利要求4-9中任何一项所述的玻璃组合物,其特征在于所述玻璃组合物的制备包括脱水步骤,从而改进形成的组合物的荧光寿命。
11.如权利要求10所述的玻璃组合物,它至少包括一种重阳离子,如Pb、Te、Sb和Bi。
12.如权利要求4-11中任何一项所述的玻璃组合物,它包括最多5重量%一种或多种选自ZrO2、TiO2、Y2O3、Ta2O5、Gd2O3和La2O3的金属氧化物。
13.一种光学放大器,它含有权利要求1-12中任何一项所述的玻璃组合物。
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1999
- 1999-05-06 FR FR9905761A patent/FR2793241B1/fr not_active Expired - Fee Related
-
2000
- 2000-04-28 AU AU49764/00A patent/AU4976400A/en not_active Abandoned
- 2000-04-28 EP EP00931964A patent/EP1210300A4/en not_active Withdrawn
- 2000-04-28 CA CA002370503A patent/CA2370503A1/en not_active Abandoned
- 2000-04-28 CN CN00807182.9A patent/CN1352624A/zh active Pending
- 2000-04-28 JP JP2000617140A patent/JP2002544105A/ja not_active Withdrawn
- 2000-04-28 WO PCT/US2000/011491 patent/WO2000068158A1/en not_active Application Discontinuation
- 2000-05-05 US US09/565,771 patent/US6495482B1/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
EP1210300A1 (en) | 2002-06-05 |
WO2000068158A9 (en) | 2002-06-06 |
US6495482B1 (en) | 2002-12-17 |
AU4976400A (en) | 2000-11-21 |
EP1210300A4 (en) | 2004-11-10 |
FR2793241B1 (fr) | 2002-03-08 |
WO2000068158A1 (en) | 2000-11-16 |
CA2370503A1 (en) | 2000-11-16 |
FR2793241A1 (fr) | 2000-11-10 |
JP2002544105A (ja) | 2002-12-24 |
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