CN1180670A - 稀土元素掺杂的卤氧化物激光玻璃 - Google Patents
稀土元素掺杂的卤氧化物激光玻璃 Download PDFInfo
- Publication number
- CN1180670A CN1180670A CN97110121A CN97110121A CN1180670A CN 1180670 A CN1180670 A CN 1180670A CN 97110121 A CN97110121 A CN 97110121A CN 97110121 A CN97110121 A CN 97110121A CN 1180670 A CN1180670 A CN 1180670A
- Authority
- CN
- China
- Prior art keywords
- weight
- glass
- laser glass
- mole
- laser
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000087 laser glass Substances 0.000 title claims abstract description 46
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 30
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 11
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 53
- 239000011521 glass Substances 0.000 claims abstract description 53
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 239000011737 fluorine Substances 0.000 claims abstract description 29
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010791 quenching Methods 0.000 claims abstract description 10
- 230000000171 quenching effect Effects 0.000 claims abstract description 10
- 239000002019 doping agent Substances 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract 6
- -1 rare earth ions Chemical class 0.000 claims description 45
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 30
- 230000002688 persistence Effects 0.000 claims description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 27
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- 238000005259 measurement Methods 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 7
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims 3
- 229910044991 metal oxide Inorganic materials 0.000 claims 3
- 150000004706 metal oxides Chemical class 0.000 claims 3
- 229910052727 yttrium Inorganic materials 0.000 claims 3
- 239000013078 crystal Substances 0.000 claims 2
- 150000004820 halides Chemical class 0.000 claims 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims 1
- 235000011941 Tilia x europaea Nutrition 0.000 claims 1
- 239000010433 feldspar Substances 0.000 claims 1
- 229910001678 gehlenite Inorganic materials 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 239000004571 lime Substances 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- 125000001153 fluoro group Chemical class F* 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 abstract 6
- 229910052593 corundum Inorganic materials 0.000 abstract 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 3
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 238000006467 substitution reaction Methods 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 230000004927 fusion Effects 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000075 oxide glass Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YQLGIFUROYYGIP-UHFFFAOYSA-N [Si]([O-])([O-])([O-])[O-].[Er+3].[Si]([O-])([O-])([O-])[O-].[Si]([O-])([O-])([O-])[O-].[Er+3].[Er+3].[Er+3] Chemical compound [Si]([O-])([O-])([O-])[O-].[Er+3].[Si]([O-])([O-])([O-])[O-].[Si]([O-])([O-])([O-])[O-].[Er+3].[Er+3].[Er+3] YQLGIFUROYYGIP-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- KIVDVTOILRSCKU-UHFFFAOYSA-N aluminum oxygen(2-) trihydroxy(oxido)silane Chemical compound [O-2].[Al+3].O[Si](O)(O)[O-] KIVDVTOILRSCKU-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- FLLAMMFGTZDZDB-UHFFFAOYSA-N dialuminum fluoro hypofluorite oxygen(2-) Chemical compound O(F)F.[O-2].[Al+3].[O-2].[O-2].[Al+3] FLLAMMFGTZDZDB-UHFFFAOYSA-N 0.000 description 1
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Images
Classifications
-
- 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
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
-
- 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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- 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
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
- H01S3/16—Solid materials
- H01S3/17—Solid materials amorphous, e.g. glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2201/00—Glass compositions
- C03C2201/06—Doped silica-based glasses
- C03C2201/30—Doped silica-based glasses containing metals
- C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
- C03C2201/3476—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
-
- 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
- H01S3/17—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]
Abstract
本发明稀土元素掺杂的卤氧化物激光玻璃是用氟代替一般摩尔配料组成为50%、SiO2、25%CaO、25%Al2O3的玻璃中的氧,以改进玻璃中稀土掺杂剂的分布。本发明一般摩尔配料组成约为45—70%SiO2、15—35%CaO、10—25%Al2O3、4—15%Al2F6和0.001—2%Er2O3。将替代氟加入到2SiO2、Al2O3·CaO玻璃体系中形成Er2O3配料含量为0.01—1.2%Er2O3(500ppm,5.68重量%Er2O3)的铒掺杂的激光玻璃,它很少或不产生浓度淬灭,具有适用的荧光持续时间(约6毫秒(ms)或更长)。
Description
本发明涉及掺杂有稀土元素的卤氧化物激光玻璃。
在现有技术中已知用稀土元素掺杂石英玻璃可制得激光玻璃。这种掺杂稀土元素的激光玻璃的激光特性来自于掺杂在玻璃中受激稀土元素离子的受激发射光放大,并取决于掺杂离子的荧光持续时间。还知道激光玻璃的激光输出取决于玻璃中稀土离子的数目。
现有技术的问题在于由于浓度淬灭现象而在激光玻璃中很快达到稀土离子的最大适用浓度。浓度淬灭归因于太靠近相邻的未受激稀土离子的受激稀土离子的非辐射衰减。受激稀土离子通过偶极-偶极偶合作用将能量传递给紧密相邻的未受激稀土离子,结果不能产生净的光输出。当激光玻璃中稀土离子的浓度增加时,稀土离子会与相邻的稀土离子紧密地团聚在一起,结果没能增加可以输出激光的实际可受激稀土离子数,并且会减少稀土离子的荧光持续时间。
现有技术面临的问题是怎样提供一种玻璃组合物,在这种组合物中可掺杂比较高的稀土离子浓度,而不产生会减少稀土离子荧光持续时间的离子团聚现象。
目前,由于铒掺杂的激光玻璃可有效地放大用于光通信系统的1.55μm波长的光,所以铒是掺杂激光玻璃的常用稀土元素。钕也作为稀土掺杂剂用于激光玻璃。因此,本发明的目的是提供一种克服现有技术缺陷的激光玻璃。
本发明的目的是提供一种具有较高浓度可受激的铒离子、抗团聚的玻璃组合物,它能有利地用于激光用途,如平面光学放大器和其它在短光路长度需要高浓可受激离子的小型激光制品中。
简单地说,本发明涉及一种卤氧化物玻璃组合物,其中增加了稀土掺杂剂浓度而无浓度淬灭的不利影响。
另一方面,本发明涉及一种卤氧化物激光玻璃组合物,它能有利地分散铒离子,防止偶极-偶极偶合作用,从而提供长的荧光持续时间。
再一方面,本发明涉及一种氧氟化物-氧化铝-硅酸盐激光玻璃。
另外,本发明涉及一种氧氟化物激光玻璃,它的氟含量足以抑制浓度淬灭的不利影响。
本发明的另一个目的是揭示一种抑制稀土掺杂剂在氧化物玻璃中浓度淬灭的方法。
本发明组合物形成一种虽增大了铒离子浓度但无浓度淬灭不利影响的卤氧化物玻璃。本发明卤氧化物玻璃组合物形成一种玻璃化学结构,在这种结构中相邻的铒离子相距较远,防止铒离子相互间位置太接近时引起的偶极-偶极偶合作用导致的浓度淬灭。本发明组合物使玻璃中铒的总浓度达到最大,同时也使相邻铒离子间的距离达到最大。本发明组合物具有较高的铒浓度,同时具有适用的荧光持续时间。
本发明氟氧化物激光玻璃在于用氟代替氧化铝-硅酸盐玻璃中的氧。用Al2F6代替一般摩尔配料组成2SiO2·Al2O3·CaO中的一部分Al2O3,就可改善玻璃中铒掺杂剂的分布。本发明一般摩尔配料组成的范围约为45-70%SiO2、15-35%CaO、l0-25%Al2O3、4-15%Al2F6和0.001-2%Er2O3。在使氟氧化物玻璃至少含有6重量%F的条件下,熔融本发明配料组合物制成玻璃。
图1是荧光持续时间对于铒离子浓度的关系图。
图2是荧光持续时间对于掺杂有0.01摩尔%Er2O3玻璃实测的重量百分数的关系图。
图3是本发明重量百分数组成图。
本发明卤氧化物玻璃是用氟代替一般摩尔配料组成为50%SiO2、25%CaO、25%Al2O3的玻璃中的氧,其中约11摩尔%Al2O3以Al2F6形式配料加入来改善玻璃中铒掺杂剂的分布。本发明一般摩尔配料组成约为45-70%SiO2、15-35%CaO、10-25%Al2O3、4-15%Al2F6和0.001-2%Er2O3。本发明人将替代氟加入到2SiO2·Al2O3·CaO玻璃体系中,制得了Er2O3配料含量为0.01-1.2%Er2O3(500ppm-5.68重量%Er2O3)的铒掺杂激光玻璃,它很少或不产生浓度淬灭,具有适用的荧光持续时间(约6毫秒(ms)或更长)。
将本发明配料组合物和比较试样在盖住的铂坩埚中约1600℃熔融6小时,然后将其倒在钢板上形成尺寸为4”×4”×1/2”的玻璃块,接着在550℃退火。对这些玻璃块划痕然后敲裂取得玻璃试样,随后以毫秒(ms)为单位测定试样的荧光持续时间以决定玻璃的激光特性。
含有5-11摩尔%Al2F6(7-15重量%F)的氟配料组合物对于所用的玻璃形成条件是特别好的。本发明熔体的氟保留量为50-80%,视初始氟浓度和熔融温度而异。例如,如果配料为30重量%的F,熔融后玻璃中实际测得的氟约为15重量%。如果配料为10重量%的F,熔融后玻璃中实际测得的氟约为7重量%。保留在玻璃中的F的百分数随熔融温度降低而上升。
本发明一般配料组成的重量百分数为:
30-45重量%SiO2,
25-45重量%Al2O3,
10-25重量%CaO,
0.005-10重量%Er2O3,
7-35重量%F(以Al2F6的形式配料),使熔融后实测的氟重量百分数为6.2-20%F。
本发明较好的配料组成重量百分数为:
37-40重量%SiO2,
30-40重量%Al2O3,
15-19重量%CaO,
0.005-6重量%Er2O3,
9-30重量%F(以Al2F6的形式配料)使熔融后实测的氟重量百分数为6.5-15%F。
表1给出了本发明配料组成的重量百分数(试样1-10)。表1还给出了试样2、4、5、6、7、8、9和10在熔融形成玻璃后玻璃中实测的氟重量百分数。
表1中还列出无氟比较试样11、12、13、14、15、16、17、18和19的配料组成的百分数,制备了这些比较试样是为了与本发明含氟玻璃进行比较。
表1
试样1-19组成的重量百分数
1 2 3 4 5 6 7 8 9 10SiO2 39.4 39.4 39.4 39.4 39.4 39.1 38.7 38.3 37.9 37.2Al2O3 33.5 33.5 33.5 33.5 33.5 33.1 32.8 32.5 32.2 31.6CaO 18.4 18.4 18.4 18.4 18.4 18.2 18.0 17.9 17.7 17.4Er2O3 0.0050 0.0151 0.0251 0.0377 0.0502 0.995 0.197 2.93 3.86 5.68F(配料) 14.7 14.6 14.6 14.6 14.6 14.5 14.4 14.2 14.1 13.8F(实测) 7.1 7.7 10.2 8.4 8.3 6.7 7.4 7.5
11 12 13 14 15 16 17 18 19SiO2 43.1 43.1 43.1 43.1 43.1 42.7 42.2 39.7 41.3Al2O3 36.6 36.6 36.6 36.6 36.6 36.2 35.8 33.7 35.1CaO 20.1 20.1 20.1 20.1 20.1 19.9 19.7 18.5 19.3Er2O3 0.0055 0.0165 0.0275 0.0412 0.0549 1.09 2.15 4.05 4.21F(配料) 0 0 0 0 0 0 0 6.7 0F(实测) 4.9
用氩离子激光束(514nm)激发试样,测定试样1-19的荧光持续时间。用Ge光电二极管探测由试样发出的荧光辐射,由此计算荧光持续时间。图1表示试样1-19铒离子的荧光持续时间(毫秒)对于试样1-19铒掺杂剂密度(铒离子数/厘米3)的关系。与试样11-试样19曲线所示的无氟试样相比,图1清楚地表明了本发明玻璃的优良荧光持续时间特性。如图1所示,当铒的含量由试样11的0.0055重量%Er2O3增加至试样19的4.21重量%Er2O3(由小于108增加至大于1020铒离子数/厘米3),荧光持续时间由7.5毫秒呈指数下降至3毫秒。在相同的铒浓度变化范围内,本发明含氟试样的荧光持续时间长得多。本发明组合物能使铒掺杂剂的密度大于1020离子/厘米3,同时保持6毫秒或更长的适用荧光持续时间。就本发明组合物而言,当铒浓度由试样1(配料0.005重量%Er2O3)增加至试样6(配料0.995重量%Er2O3),荧光持续时间仍保持上升趋势。当铒掺杂剂超出1020离子/厘米3时,荧光持续时间的变化在8-9毫秒范围变得平坦起来,并然后下降至6毫秒(试样10)。试样10的6毫秒荧光持续时间仍然是可用的,特别是考虑到其很高的铒浓度。将比较试样18(配料4.05重量%Er2O3,配料6.7重量%F,实测4.9重量%F)与试样8、9、10比较表明,试样18中实测的4.9重量%氟在这种高的铒浓度下不足以抑制浓度淬灭。
表2和图2显示本发明玻璃形成后其实测的氟含量与增加的荧光持续时间间的关系和本发明抑制浓度淬灭的能力。表2列出了试样20-24和来自表1的试样15和5的配料组成重量百分数,所有这些试样的配料组成均含0.01摩尔%Er2O3。图2清楚地显示出玻璃的含氟量与其荧光持续时间的关系。
表2
15 20 21 22 5 23 24SiO2 43.1 42.0 41.4 39.7 39.4 36.8 35.6Al2O3 36.6 35.7 35.1 39.1 33.5 31.3 30.2CaO 20.1 19.6 19.3 15.6 18.4 17.2 16.6Er2O3 0.0549 0.0535 0.0527 0.0506 0.0502 0.0469 0.0453F(配料) 0 4.26 6.98 9.38 14.6 24.9 30F(实测) 3.61 6.17 7.04 10.2 12.8 14.2
当0.01摩尔%Er2O3配料组合物的实测氟重量百分数由试样15(不含氟)增加至试样21(6.17重量%F)时,荧光持续时间稳定在6.8-7毫秒的范围内。此后增加约1重量%的F(试样22),荧光持续时间跳升至8毫秒。随着试样5、23和24氟百分数的增加,荧光持续时间进一步增长。在氟重量百分数为6%和7%之间的这个阈值与试样18的4.9重量%F和试样8的6.7重量%F之间的氟含量阈值相关。
本发明组合物能抑制铒离子的浓度淬灭是由于形成铒离子相互有利地隔开分布的玻璃化学结构。本发明组合物的氟含量使得其玻璃在增加铒离子浓度的同时,仍具有适用的荧光持续时间。
如图3的重量百分组成图所示,本发明一般的氧化物玻璃组成区域101与钙长石(CaO·Al2O3·2SiO2)和钙黄长石(2CaO·Al2O3·SiO2)这两个结晶相的化学计量范围对应,但加入铒和氟,为的是给出适当荧光持续时间的激光特性。
本发明人用ZnO、碱金属氧化物和碱土金属氧化物(如MgO、BaO和Na2O)代替配料组成中的CaO,制成铒掺杂的氧氟化物-氧化铝-硅酸盐玻璃。这种玻璃组合物拥有本发明含氟抑制稀土离子浓度淬灭的好处,应能显示出相似的激光特性。
本发明玻璃组合物还包括用Ga2O3代替配料组成中的Al2O3。在配料组成中的Al2O3可全部用氧化镓代替。本发明玻璃配料组成中可含有0-25摩尔%Ga2O3。
本发明玻璃组合物还包括用GeO2代替配料组成中的SiO2。在配料组成中的SiO2可全部用氧化锗代替。本发明玻璃配料组成中可含有0-50摩尔%GeO2。
本发明玻璃组合物还包括用B2O3代替配料组成中的Al2O3。在配料组成中的铝可用硼所代替。本发明玻璃配料组成中可含有0-15摩尔%B2O3。
除了上述实施方案以外,显然对本领域中具有熟练技艺的人来说,在不偏离本发明精神和范围的情况下,可对本发明进行许多改进和变化。
Claims (20)
1.掺杂有许多稀土离子的卤氧化物激光玻璃,所述玻璃的荧光持续时间至少为6毫秒,其特征在于所述玻璃的卤化物浓度足以抑制所述稀土离子的浓度淬灭。
2.如权利要求1所述的激光玻璃,其特征在于所述卤化物浓度至少为6.2重量%F。
3.如权利要求1所述的激光玻璃,其特征在于所述稀土离子是铒。
4.如权利要求1所述的卤氧化物激光玻璃,其特征在于所述卤氧化物激光玻璃是氧氟化物-氧化铝-硅酸盐激光玻璃。
5.稀土元素掺杂的激光玻璃,所述激光玻璃的摩尔配料组成为:
45-70摩尔%SiO2;
15-35摩尔%X;
15-35摩尔%Y;
其中X是一种金属氧化物,选自碱金属氧化物、碱土金属氧化物和ZnO;
Y是选自氧化铝和卤化铝的铝化合物,其中至少10摩尔%的Y是卤化铝。
6.如权利要求5所述的激光玻璃,其特征在于所述激光玻璃掺杂有铒。
7.如权利要求5所述的激光玻璃,其特征在于X是CaO。
8.如权利要求5所述的激光玻璃,其特征在于卤化铝是Al2F6。
9.如权利要求5所述的激光玻璃,其特征在于所述激光玻璃的荧光持续时间至少为6毫秒。
10.一种激光玻璃,其配料组成重量百分数为:
30-45重量%SiO2;
25-45重量%Al2O3;
10-25重量%CaO;
0.005-10重量%Er2O3;
7-35重量%F,
其中所述玻璃实测的氟重量百分数至少为6.2重量%F。
11.如权利要求10所述的激光玻璃,其特征在于F以Al2F6的形式配料。
12.一种激光玻璃,其配料组成重量百分数基本上为:
37-40重量%SiO2;
30-40重量%Al2O3;
0.005-6重量%Er2O3;
9-30重量%F,
其特征在于所述玻璃实测的氟重量百分数至少为6.5重量%F。
13.掺杂有许多铒离子的卤氧化物激光玻璃,所述铒离子的浓度至少为1×1017离子/厘米3,所述玻璃的实测氟重量百分数至少为6.2重量%F,其中所述玻璃的荧光持续时间至少为7.6毫秒。
14.如权利要求13所述的激光玻璃,其特征在于所述铒离子的浓度至少为1×1020离子/厘米3。
15.一种卤氧化物玻璃,其配料组成为:
至少13重量%F、
至少2重量%Er2O3,
其特征在于所述玻璃的荧光持续时间至少为6毫秒。
16.如权利要求15所述的激光玻璃,其特征在于所述激光玻璃具有钙长石晶体相和钙黄长石晶体相的化学计量。
17.由配料组成重量百分数为30-45重量%SiO2,25-45重量%Al2O3,10-25重量%CaO,0.005-10重量%Er2O3以及7-35重量%F的激光玻璃制成的光学放大器,其特征在于所述玻璃实测含氟量至少为6.2重量%氟。
18.一种抑制在玻璃中稀土掺杂剂浓度淬灭的方法,所述方法是用卤离子代替激光玻璃中的氧离子。
19.一种稀土元素掺杂的激光玻璃,所述激光玻璃的摩尔配料组成主要为:
45-70摩尔%SiO2;
15-35摩尔%X;
15-35摩尔%Y;
其中X是一种金属氧化物,选自碱金属氧化物、碱土金属氧化物和ZnO;
Y是选自氧化铝和卤化铝的铝化合物,其中至少10摩尔%的Y是卤化铝。
20.一种稀土元素掺杂的激光玻璃,所述激光玻璃的摩尔配料组成为:
45-70摩尔%A;
15-35摩尔%X;
15-35摩尔%Y;
其中A选自SiO2和GeO2;
X是一种金属氧化物,选自碱金属氧化物、碱土金属氧化物和ZnO;
Y选自氧化铝、卤化铝、Ga2O3和B2O3,其中至少10摩尔%的Y是卤化铝。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US1580196P | 1996-04-17 | 1996-04-17 | |
US60/015801 | 1996-04-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1180670A true CN1180670A (zh) | 1998-05-06 |
Family
ID=21773723
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN97110121A Pending CN1180670A (zh) | 1996-04-17 | 1997-04-17 | 稀土元素掺杂的卤氧化物激光玻璃 |
Country Status (9)
Country | Link |
---|---|
US (1) | US5798306A (zh) |
EP (1) | EP0802169B1 (zh) |
JP (1) | JPH1067536A (zh) |
KR (1) | KR970069923A (zh) |
CN (1) | CN1180670A (zh) |
AU (1) | AU1775697A (zh) |
CA (1) | CA2201576A1 (zh) |
DE (1) | DE69702417T2 (zh) |
TW (1) | TW404934B (zh) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1101349C (zh) * | 2000-12-14 | 2003-02-12 | 中国科学院长春应用化学研究所 | 稀土黄绿色长余辉玻璃的制备方法 |
CN1326790C (zh) * | 2005-10-28 | 2007-07-18 | 宁波大学 | 稀土离子掺杂的yag微晶玻璃及其制备方法 |
CN100389086C (zh) * | 2005-05-11 | 2008-05-21 | 浙江大学 | 稀土掺杂的透明氟氧化物玻璃陶瓷及其制备方法 |
CN101870555A (zh) * | 2010-06-11 | 2010-10-27 | 陕西科技大学 | 高掺量铒含钡磷酸盐激光玻璃的制备方法 |
Families Citing this family (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6766183B2 (en) | 1995-11-22 | 2004-07-20 | Medtronic Minimed, Inc. | Long wave fluorophore sensor compounds and other fluorescent sensor compounds in polymers |
US6356699B1 (en) * | 1997-09-24 | 2002-03-12 | Corning Incorporated | Rare earth doped optical glasses |
JP2001524448A (ja) | 1997-12-02 | 2001-12-04 | コーニング インコーポレイテッド | オキシハライドガラスにおける稀土類・ハライド環境 |
GB9805800D0 (en) * | 1998-03-19 | 1998-05-13 | Univ Leeds | Erbium doped optical glass |
JP2000086283A (ja) * | 1998-09-08 | 2000-03-28 | Ohara Inc | 発光性ガラス |
US6077799A (en) * | 1999-03-12 | 2000-06-20 | Corning Inc. | SPCVD silicate glasses |
US6235666B1 (en) | 1999-03-29 | 2001-05-22 | Guardian Industries Corporation | Grey glass composition and method of making same |
FR2796637B1 (fr) * | 1999-07-21 | 2002-06-07 | Corning Inc | Verre borosilicate ou aluminosilicate pour amplification optique |
KR100340047B1 (ko) | 1999-10-11 | 2002-06-12 | 오길록 | 할로겐이 첨가된 다성분계 산화물 조성의 광증폭기 및 레이저용 유리 |
EP1139518A1 (en) * | 2000-03-30 | 2001-10-04 | Optical Technologies Italia S.p.A. | Active optical fibre doped with rare earth elements |
US6587633B2 (en) | 2000-03-30 | 2003-07-01 | Corning Oti, Inc. | Active optical fibre doped with rare earth elements |
US6466365B1 (en) * | 2000-04-07 | 2002-10-15 | Corning Incorporated | Film coated optical lithography elements and method of making |
US6611372B1 (en) | 2000-06-09 | 2003-08-26 | The Arizona Board Of Regents On Behalf Of The University Of Arizona | Erbium and ytterbium co-doped phosphate glass optical fiber amplifiers using short active fiber length |
KR100340686B1 (ko) * | 2000-09-19 | 2002-06-15 | 오길록 | 다중 호스트 컴퓨터와 레이드 사이의 중복연결을 위한 장치 |
US6636347B1 (en) * | 2000-11-08 | 2003-10-21 | Corning Incorporated | Phosphorus-silicate fibers suitable for extended band amplification |
US6927246B2 (en) * | 2001-02-15 | 2005-08-09 | Medtronic Minimed, Inc. | Polymers functionalized with fluorescent boronate motifs and methods for making them |
JP2005503453A (ja) * | 2001-02-26 | 2005-02-03 | ザ・トラステイーズ・オブ・ザ・ユニバーシテイ・オブ・ペンシルベニア | 発光性多色発色団系 |
US20020173416A1 (en) * | 2001-04-06 | 2002-11-21 | Ellison Adam J. | Dispersal of optically active ions in glass |
JP2004528598A (ja) * | 2001-05-30 | 2004-09-16 | スリーエム イノベイティブ プロパティズ カンパニー | 制御されたモードフィールド径膨張の整合を有する光ファイバー融着接続 |
US6690868B2 (en) | 2001-05-30 | 2004-02-10 | 3M Innovative Properties Company | Optical waveguide article including a fluorine-containing zone |
US20030024276A1 (en) * | 2001-05-30 | 2003-02-06 | 3M Innovative Properties Company | Method of manufacture of an optical waveguide article including a fluorine-containing zone |
US7045361B2 (en) | 2001-09-12 | 2006-05-16 | Medtronic Minimed, Inc. | Analyte sensing via acridine-based boronate biosensors |
US7003981B2 (en) | 2001-10-02 | 2006-02-28 | University Of Southhampton | Low phonon energy gain medium and related active devices |
US20040067198A1 (en) * | 2002-02-26 | 2004-04-08 | Therien Michael J | Emissive multichromophoric systems |
US20050100073A1 (en) * | 2003-11-10 | 2005-05-12 | Hughes Lawrence C.Jr. | Cladding-pumped quasi 3-level fiber laser/amplifier |
WO2008048974A1 (en) * | 2006-10-17 | 2008-04-24 | Rensselaer Polytechnic Institute | Process for making rare earth containing glass |
DE102013015934A1 (de) | 2013-09-18 | 2015-03-19 | Friedrich-Schiller-Universität Jena | Seltenerd-dotierte Aluminosilicatgläser, insbesondere zur Verwendung als aktives Lasermaterial in Hochleistungs-Bulklasern |
US11476634B2 (en) * | 2018-05-07 | 2022-10-18 | The Board Of Trustees Of The University Of Illinois | Rare earth-doped multicomponent fluorosilicate optical fiber for optical devices |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4142986A (en) * | 1978-04-20 | 1979-03-06 | Owens-Illinois, Inc. | Glasses suitable for laser application |
DE3524605A1 (de) * | 1985-01-22 | 1987-01-15 | Schott Glaswerke | Lichtwellenleiter, hergestellt aus speziellen hoch-aluminiumhaltigen substratglaesern durch ionenaustausch gegen cs+-ionen |
FR2638854B1 (fr) * | 1988-11-10 | 1992-09-04 | Comp Generale Electricite | Amplificateur laser a fibre optique dopee |
JPH02186685A (ja) * | 1989-01-13 | 1990-07-20 | Tosoh Corp | 固体レーザー発振装置 |
US4962995A (en) * | 1989-06-16 | 1990-10-16 | Gte Laboratories Incorporated | Glasses for high efficiency erbium (3+) optical fiber lasers, amplifiers, and superluminescent sources |
US4962067A (en) * | 1989-07-14 | 1990-10-09 | Kigre, Inc. | Erbium laser glass compositions |
CA2051104C (en) * | 1990-02-05 | 1996-05-14 | Akira Oyobe | Quartz glass doped with rare earth element and production thereof |
US5200029A (en) * | 1991-04-25 | 1993-04-06 | At&T Bell Laboratories | Method of making a planar optical amplifier |
EP0535798B1 (en) * | 1991-08-26 | 1997-12-29 | Nippon Telegraph and Telephone Corporation | Optical fiber for optical amplifier |
JP2694859B2 (ja) * | 1992-01-20 | 1997-12-24 | セントラル硝子株式会社 | 1.3μm帯光増幅ファイバ用プリフォーム |
US5475528A (en) * | 1994-03-25 | 1995-12-12 | Corning Incorporated | Optical signal amplifier glasses |
US5655046A (en) * | 1994-12-14 | 1997-08-05 | Nippon Telegraph And Telephone Corporation | Glass composition, optical fiber made of same, and method for preparing glasses |
JPH08198637A (ja) * | 1995-01-17 | 1996-08-06 | Nippon Telegr & Teleph Corp <Ntt> | ガラス組成物 |
-
1997
- 1997-04-02 CA CA002201576A patent/CA2201576A1/en not_active Abandoned
- 1997-04-07 AU AU17756/97A patent/AU1775697A/en not_active Abandoned
- 1997-04-09 DE DE69702417T patent/DE69702417T2/de not_active Expired - Fee Related
- 1997-04-09 EP EP97105868A patent/EP0802169B1/en not_active Expired - Lifetime
- 1997-04-14 US US08/835,899 patent/US5798306A/en not_active Expired - Lifetime
- 1997-04-16 KR KR1019970014093A patent/KR970069923A/ko not_active Application Discontinuation
- 1997-04-17 CN CN97110121A patent/CN1180670A/zh active Pending
- 1997-04-17 JP JP9100092A patent/JPH1067536A/ja active Pending
- 1997-04-24 TW TW086105592A patent/TW404934B/zh not_active IP Right Cessation
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1101349C (zh) * | 2000-12-14 | 2003-02-12 | 中国科学院长春应用化学研究所 | 稀土黄绿色长余辉玻璃的制备方法 |
CN100389086C (zh) * | 2005-05-11 | 2008-05-21 | 浙江大学 | 稀土掺杂的透明氟氧化物玻璃陶瓷及其制备方法 |
CN1326790C (zh) * | 2005-10-28 | 2007-07-18 | 宁波大学 | 稀土离子掺杂的yag微晶玻璃及其制备方法 |
CN101870555A (zh) * | 2010-06-11 | 2010-10-27 | 陕西科技大学 | 高掺量铒含钡磷酸盐激光玻璃的制备方法 |
CN101870555B (zh) * | 2010-06-11 | 2011-12-07 | 陕西科技大学 | 高掺量铒含钡磷酸盐激光玻璃的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JPH1067536A (ja) | 1998-03-10 |
MX9702816A (es) | 1998-06-28 |
US5798306A (en) | 1998-08-25 |
DE69702417T2 (de) | 2001-01-25 |
KR970069923A (ko) | 1997-11-07 |
AU1775697A (en) | 1997-10-23 |
CA2201576A1 (en) | 1997-10-17 |
DE69702417D1 (de) | 2000-08-10 |
TW404934B (en) | 2000-09-11 |
EP0802169A1 (en) | 1997-10-22 |
EP0802169B1 (en) | 2000-07-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1180670A (zh) | 稀土元素掺杂的卤氧化物激光玻璃 | |
US5173456A (en) | Phosphate glass useful in high energy lasers | |
US7637124B2 (en) | Bismuth containing fluorophosphate glass and method for making thereof | |
US6503860B1 (en) | Antimony oxide glass with optical activity | |
US6410467B1 (en) | Antimony oxide glass with optical activity | |
EP1180835A2 (en) | Optical amplifying glass | |
CA2346851C (en) | Optical fiber for light amplifier | |
US6413891B1 (en) | Glass material suitable for a waveguide of an optical amplifier | |
US5240885A (en) | Rare earth-doped, stabilized cadmium halide glasses | |
JPH0228525B2 (zh) | ||
Tanabe et al. | Improved Fluorescence from Tm‐Ho‐and Tm‐Ho‐Eu‐Codoped Transparent PbF2 Glass‐Ceramics for S+‐Band Amplifiers | |
AU659339B2 (en) | Rare earth-doped, stabilized cadmium halide glasses | |
US6344425B1 (en) | Fluorotellurite, amplifier glasses | |
Tanabe | Development of rare-earth doped fiber amplifiers for broad band wavelength-division-multiplexing telecommunication | |
JPS6341858B2 (zh) | ||
KR20040095485A (ko) | 광 증폭기용 셀레나이드 유리 조성물 | |
JPH08217490A (ja) | 波長変換ガラス材 | |
JPH08217489A (ja) | 波長変換ガラス材 | |
MXPA00009849A (en) | Antimony oxide glass with optical activity |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |