CN101531459B - Rare earth thulium-doped aluminate fluorescent glass and preparation method thereof - Google Patents

Rare earth thulium-doped aluminate fluorescent glass and preparation method thereof Download PDF

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CN101531459B
CN101531459B CN 200910082473 CN200910082473A CN101531459B CN 101531459 B CN101531459 B CN 101531459B CN 200910082473 CN200910082473 CN 200910082473 CN 200910082473 A CN200910082473 A CN 200910082473A CN 101531459 B CN101531459 B CN 101531459B
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thulium
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glass
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CN101531459A (en
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燕路
肖志松
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北京航空航天大学
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Abstract

The invention relates to a rare earth thulium-doped aluminate fluorescent glass, and the weight proportions of the compositions are as follows: 22% to 28% of Al2O3; 30% to 37% of CaCO3; 36% to 44% of H3BO3; and 0.5% to 1.5% of Tm2O3; the preparation method is as follows: (1) extra pure reagents alumina, calcium carbonate and boric acid are weighed, and the weight percentages are respectively as follows: 22% to 28%; 30% to 37%; 36% to 44%; 0.5% to 1.5%; thulium oxide is weighed so that the ratio between the weight of thulium oxide and the total weight of the three master batches is between 0.5% and 1.5%; fluxing agent accouting for 1% to 2% of the total weight of the four extra pure reagents is weighed, and the compositions are fully mixed; (2) the mixture is loaded in a corundum crucible and is sintered in a high temperature furnace, the atmosphere is air, the sintering temperature is 1100 to 1400 DEG C, and the sintering time is 2 to 5 hours; (3) sinter is processed in an annealing furnace at the temperature of 450 to 550 DEG C, and the processing time is 30 to 60 minutes; (4) the sinter is reduced to room temperature in air, cut into required length, washed by deionized water atthe temperature of 70 to 85 DEG C, and dried at the temperature of 120 to 150 DEG C, so that the required product is obtained.

Description

一种稀土铥掺杂的铝酸盐发光玻璃及其制备方法 A rare-earth aluminate luminescent thulium-doped glass and preparation method

技术领域 FIELD

[0001] 本发明属于稀土发光和光放大材料技术领域,具体来说涉及一种以稀土铥掺杂的铝酸盐发光玻璃及其制备方法,此种稀土铥掺杂的发光玻璃可用于制备红外光源和光放大器。 [0001] The present invention belongs to the technical field of rare earth and emitting light amplifying material, particularly relates to an infrared light source was prepared luminescent aluminate glass and a method for preparing a rare earth doped thulium, thulium such rare earth doped luminescent glass can be used and optical amplifiers.

背景技术 Background technique

[0002] 过去二十多年,稀土铒(Er)离子在激光器和光放大器中作为光增益媒介起着非常重要的作用,这是因为Er3+从第一激发态4Iiv2跃迁到基态4115/2时发射波长为1. 54 μ m, 恰好是光纤通讯用石英玻璃光纤的最小光吸收窗口。 [0002] Over the past twenty years, rare earth erbium (Er) ions in the laser and the optical amplifier as an optical gain medium plays an important role, because Er3 + 4Iiv2 transition from the first excited state to the ground state is emitted wavelengths 4115/2 of 1. 54 μ m, happens to be a silica glass fiber optical communications minimum light absorption window. 掺铒光纤放大器EDFA (Erbium-doped Fiber Amplifier)目前已广泛应用于光通讯领域,但其只能利用到1530-1625nm(即国际电联ITU标准中的C和L带)范围的波长资源。 Erbium doped fiber amplifier EDFA (Erbium-doped Fiber Amplifier) ​​has been widely used in optical communication field, but can only use the wavelength 1530-1625nm (i.e. ITU ITU standard C and L-band) of the resources. 相对于1.4-1. 7μπι这一光纤通讯低损耗窗口波长而言,国际电联ITU标准中的带宽资源仍有一半以上没有被开发利用,即S带(1440-1530nm)和U带(1625_1675nm)资源。 With respect to 1.4-1. 7μπι the low loss fiber communication window wavelengths, bandwidth Union ITU standards are still being developed not more than half utilized, i.e., S-band (1440-1530nm) (1625_1675nm) and with U resources. Tm3+ 因其发光带位于1. 4-1. 5 μ m和1. 6-2. 1 μ m 而受到人们关注,使得S带(1440-1530nm)和U带(1625-1675nm)的带宽应用成为可能。 Positioned with its light emitting Tm3 + 1. 4-1. 5 μ m and 1. 6-2. 1 μ m by the people concerned, such that the S-band (1625-1675nm) (1440-1530nm) and the U band bandwidth applications become may. 目前已有的掺铥光纤放大器(TDFA)只是利用了其中的S+带(1450-1480nm)资源,但仍局限于几十纳米的波长范围之内。 At present, thulium-doped fiber amplifier (the TDFA) just use one of the S + (1450-1480nm) with resources, but still confined to the wavelength range of several tens of nanometers. Tm3+固有的电子结构特性使其3H4-3F4的跃迁(即1470nm光发射)在高声子能量的基质材料(如石英玻璃〜llOOcnT1)中很容易发生多声子淬灭(MPR)。 Tm3 + unique electronic properties make transition 3H4-3F4 (i.e. 1470nm light emission) is prone to multiple phonons in the matrix material of the high acoustic phonon energy (e.g., quartz glass ~llOOcnT1) quenched (MPR). 由此,Tm掺杂声子能量相对更小的基质材料才可能获得1470nm光发射,如Tm掺杂的氟化物玻璃(〜580CHT1)已被开发出来。 Accordingly, Tm doped phonon energy of the host material relatively smaller 1470nm could obtain light emission, such as the Tm-doped fluoride glass (~580CHT1) have been developed. 但是这种玻璃由于其相对较差的化学稳定性和机械性能限制了它的进一步发展。 However, this glass because of its relatively poor mechanical properties and chemical stability limits its further development. 因此,寻找一种声子能量相对较小而机械性能性能又好的玻璃材料就成为制备Tm掺杂红外光源和光放大器的关键。 Thus, to find a relatively low phonon energy properties and good mechanical properties and a glass material has become a key preparation and Tm-doped optical amplifier infrared light source.

发明内容 SUMMARY

[0003] 本发明的目的在于提供一种稀土铥掺杂的铝酸盐发光玻璃及其制备方法,其宽谱激发(700-900nm)、发射光谱在1400_1550nm和1600-1700nm两个波段、制备工艺简单,可以克服由于相关技术限制和缺点造成的诸多问题。 [0003] The object of the present invention to provide a luminescent aluminate glass and a method for preparing a rare earth doped with thulium, its broad excitation spectrum (700-900nm), and an emission spectrum of 1600-1700nm in 1400_1550nm two bands, preparation simple, you can overcome a lot of problems due to limitations and disadvantages of the related art caused.

[0004] 本发明一种稀土铥掺杂的铝酸盐发光玻璃,其组成成分由下述化学式表示: Al2O3-CaO-B2O3-Tm2CV玻璃有效成分引入方式为高纯试剂三氧化二铝、碳酸钙、硼酸和氧化铥,其成分的重量配比如下: [0004] The thulium-doped rare earth aluminate luminescent glass of the present invention, its composition is represented by the following chemical formula: Al2O3-CaO-B2O3-Tm2CV active ingredient into the glass way purity reagents aluminum oxide, calcium carbonate , thulium oxide and boric acid, the weight ratio of its components as follows:

[0005] Al2O3 22%〜28% ;CaC03 30%〜37% ; [0005] Al2O3 22% ~28%; CaC03 30% ~37%;

[0006] H3BO3 36%〜44% ;Tm203 0. 5%〜1. 5% ; [0006] H3BO3 36% ~44%;. Tm203 0. 5% ~1 5%;

[0007] 在熔制过程中加入助熔剂,助熔剂占上述四种高纯试剂总重量比为0. 3%〜3%, 较优的为占上述四种高纯试剂总重量的〜2%。 [0007] added to the flux in the melting process, high-purity reagents of the four flux representing a total weight ratio of 0.3% ~ 3%, more accounted for ~ 2% of the total weight of the above-described four kinds of high purity reagents .

[0008] 本发明一种稀土铥掺杂的铝酸盐发光玻璃的制备方法,它包括以下步骤: [0008] The method for producing a rare earth-doped aluminates according to the present invention, thulium luminescent glass, comprising the steps of:

[0009] (1)称取高纯试剂氧化铝、碳酸钙、硼酸,其重量百分比分别为22%〜观%、 30%〜37%、36%〜44%、0. 5%〜1. 5%之间;称取氧化铥重量与上述三种玻璃母料总重量之比在0.5%〜1.5%之间;再称取占上述四种高纯试剂总重量〜2%重量的助熔剂, 将这些组分充分混勻; [0009] (1) Weigh purity reagents alumina, calcium carbonate, boric acid, its weight percentage were 22% concept%, 30% ~ 37%, 36% ~44%, 0.5% ~ 1. 5 between%; the ratio of the three said glass mother material by weight of the total weight of thulium oxide to take between 0.5% ~ 1.5%; After weighing ~ 2% of the total weight of the account of the four flux weight purity reagents, the these ingredients were thoroughly mixed;

[0010] (2)将上述混合物装入刚玉坩埚,并置于高温炉中烧结,气氛为空气,烧结温度为1100-1400°C,烧结时间为2〜5小时; [0010] (2) The above mixture was charged corundum crucible and placed in a high temperature furnace sintering atmosphere is air, the sintering temperature is 1100-1400 ° C, sintering time is 2 ~ 5 hours;

[0011] (3)将烧结物在450〜550°C的退火炉中处理,处理时间为30〜60分钟; [0011] (3) The sintering process was 450~550 ° C in an annealing furnace, the processing time is 30~60 minutes;

[0012] (4)将烧结物在空气中降到室温,切割至所需尺度,用70〜85°C去离子水洗涤, 120〜150°C温度下烘干,即得到所需产物。 [0012] (4) the sintered material in air down to room temperature, cut to the desired dimensions, using 70~85 ° C deionized water, dried at a temperature of 120~150 ° C, to obtain the desired product.

[0013]本发明中,所用的助熔剂可以是 SrF2, BaF2, NH4HF2, SrCl2, BaCl2, NH4Cl, H3BO3 中的一种或几种的混合。 [0013] In the present invention, a flux may be used SrF2 BaF2, NH4HF2, SrCl2, BaCl2, NH4Cl mixed,, of one or more of H3BO3 of.

[0014] 本发明的玻璃可被红外光激发,激发波长范围为700〜900nm,发射峰波长在1400-1550nm 和1600_1700nm 两个波段。 [0014] The glass of the present invention may be infrared light excitation, the excitation wavelength range of 700~900nm, and the emission peak wavelength in the 1400-1550nm 1600_1700nm two bands.

[0015] 根据本发明,可以得到平坦连续的1400-1550nm和1600-1700nm两个发射波段、且 [0015] According to the present invention, it is possible to obtain a flat and continuous 1400-1550nm 1600-1700nm two emission bands, and

发射强度取决于铥浓度及助熔剂种类的玻璃。 Thulium emission intensity depends on the concentration and type of glass flux. 因此,将本发明的玻璃应用于红外光源和光放大器,可用来制备国际电联ITU标准中的S和U带光源和光放大器。 Accordingly, the glass of the present invention is applied to an infrared light source and an optical amplifier, can be prepared in the ITU standard ITU S and U with the light source and the optical amplifier.

[0016] 本发明一种稀土掺杂的铝酸盐发光玻璃及其制备方法,其优点和达到的功效是: 制备的稀土元素铥掺杂的发光玻璃利用铥的特征谱带和S带U带重叠的特点,可以实现对这些波段光信号的放大,进而能够充分利用光通信低损频率窗口S和U带资源,对于宽带大容量光通讯网络的发展有重要意义。 [0016] The luminescent aluminate glass and a preparation method of the present invention, a rare earth-doped, its advantages, and efficacy is achieved: a rare earth element prepared using thulium thulium doped luminescent glass and the characteristic bands of S-band with U overlap characteristics can be achieved for these bands amplified optical signals, and further can take advantage of low-loss optical communication window S and U frequency band resources, the development of large-capacity optical wideband communication network is important. 而采用本发明的制备方法利用经过优化的具体制备条件以及后续热处理条件参数将能获得具有优良放光性能的玻璃。 Was prepared using the method of the present invention through specific production conditions and subsequent heat treatment conditions will be able to optimize the parameters to obtain a glass having excellent shine properties. 因此制备的稀土铥掺杂的发光玻璃可用于制备红外光源与光放大器。 Thus emitting rare-earth thulium-doped glass produced may be used to prepare an infrared light source and the optical amplifier.

附图说明 BRIEF DESCRIPTION

[0017] 图1为本发明所提供的稀土铥掺杂的铝酸盐玻璃在1480nm发射的激发光谱图。 [0017] FIG 1 thulium-doped rare-earth aluminosilicate glass of the present invention is provided in the excitation spectrum emitted 1480nm.

[0018] 图2为本发明所提供的氧化铥含量(重量比)为的玻璃在794nm激发下的发射光谱图。 [0018] FIG. 2 of the present invention provides thulium oxide content (weight ratio) of the emission spectra of a glass at 794nm excitation.

[0019] 图3为本发明所提供的氧化铥含量(重量比)为1. 2%的玻璃在794nm激发下的发射光谱图。 [0019] FIG. 3 thulium oxide content (weight ratio) of the present invention, provided is 1.2% of the emission spectra of the glass at 794nm excitation.

具体实施方式 Detailed ways

[0020] 请参照附图1、图2、图3所示,详细说明本发明的优选实施方案。 [0020] Referring to FIG. 1, FIG 2, FIG 3, a detailed description of preferred embodiments of the present invention.

[0021]( 一)本发明一种稀土铥掺杂的铝酸盐发光玻璃,其组成成分及其重量配比如下: [0021] (a) according to the present invention, rare earth aluminate luminescent glass doped with thulium, and its composition by weight was prepared as follows:

[0022] 实施例1 : [0022] Example 1:

[0023] 称取高纯试剂氧化铝、碳酸钙、硼酸和氧化铥,其组成成分及其重量配比如下: [0023] high-purity reagents weighed alumina, calcium carbonate, boric acid and thulium oxide, and its composition by weight was prepared as follows:

[0024] Al2O3 24. 4% ;CaCO3 34% ; [0024] Al2O3 24. 4%; CaCO3 34%;

[0025] H3BO3 40. 6% ;Tm2O3 1% ; [0025] H3BO3 40. 6%; Tm2O3 1%;

[0026] 然后称取占上述四种高纯试剂总重量1. 5%重量的助熔剂,助溶剂为SrF2, BaF2, NH4HF2, SrCl2, BaCl2, NH4Cl, H3BO3中的一种或几种。 [0026] and then weighed representing 1.5% by weight of the total weight of the four high-purity flux agent, co-solvent is a SrF2, BaF2, NH4HF2, SrCl2, BaCl2, NH4Cl, H3BO3 one or several. 将它们在研钵中研磨2〜3小时,使其充分混勻。 Grind them in a mortar 2 ~ 3 hours to fully mix.

[0027] 实施例2 :[0028] 称取高纯试剂氧化铝、碳酸钙、硼酸和氧化铥,其组成成分及其重量配比如下: [0027] Example 2: [0028] high-purity reagents weighed alumina, calcium carbonate, boric acid and thulium oxide, and its composition by weight was prepared as follows:

[0029] Al2O3 25. 3% ;CaCO3 33% ; [0029] Al2O3 25. 3%; CaCO3 33%;

[0030] H3BO3 40. 5% ;Tm2O3 1. 2% ; [0030] H3BO3 40. 5%; Tm2O3 1. 2%;

[0031] 然后称取占上述四种高纯试剂总重量2%重量的助熔剂,助溶剂为SrF2, BaF2, NH4HF2, SrCl2, BaCl2, NH4Cl, H3BO3中的一种或几种。 [0031] and then weighed 2% by weight of the total weight of the four high-purity flux agent, co-solvent is a SrF2, BaF2, NH4HF2, SrCl2, BaCl2, NH4Cl, H3BO3 one or several. 将它们在研钵中研磨2〜3小时,使其充分混勻。 Grind them in a mortar 2 ~ 3 hours to fully mix.

[0032] 实施例3 : [0032] Example 3:

[0033] 称取高纯试剂氧化铝、碳酸钙、硼酸和氧化铥,其组成成分及其重量配比如下: [0033] high-purity reagents weighed alumina, calcium carbonate, boric acid and thulium oxide, and its composition by weight was prepared as follows:

[0034] Al2O3 24. 4% ;CaCO3 34% ; [0034] Al2O3 24. 4%; CaCO3 34%;

[0035] H3BO3 40. 1% ;Tm2O3 1. 5% ; [0035] H3BO3 40. 1%; Tm2O3 1. 5%;

[0036] 然后称取占上述四种高纯试剂总重量0. 5%重量的助熔剂,助溶剂为SrF2, BaF2, NH4HF2, SrCl2, BaCl2, NH4Cl, H3BO3中的一种或几种。 [0036] and then weighed representing 0.5% by weight of the total weight of the four high-purity flux agent, co-solvent is a SrF2, BaF2, NH4HF2, SrCl2, BaCl2, NH4Cl, H3BO3 one or several. 将它们在研钵中研磨2〜3小时,使其充分混勻。 Grind them in a mortar 2 ~ 3 hours to fully mix.

[0037] 实施例4 : [0037] Example 4:

[0038] 称取高纯试剂氧化铝、碳酸钙、硼酸和氧化铥,其组成成分及其重量配比如下: [0038] high-purity reagents weighed alumina, calcium carbonate, boric acid and thulium oxide, and its composition by weight was prepared as follows:

[0039] Al2O3 27. 5% ;CaCO3 35% ; [0039] Al2O3 27. 5%; CaCO3 35%;

[0040] H3BO3 37% ;Tm2O3 0. 5% ; [0040] H3BO3 37%; Tm2O3 0. 5%;

[0041] 然后称取占上述四种高纯试剂总重量2. 5%重量的助熔剂,助溶剂为SrF2, BaF2, NH4HF2, SrCl2, BaCl2, NH4Cl, H3BO3中的一种或几种。 [0041] and then weighed representing 2.5% by weight of the total weight of the four high-purity flux agent, co-solvent is a SrF2, BaF2, NH4HF2, SrCl2, BaCl2, NH4Cl, H3BO3 one or several. 将它们在研钵中研磨2〜3小时,使其充分混勻。 Grind them in a mortar 2 ~ 3 hours to fully mix.

[0042] 实施例5 : [0042] Example 5:

[0043] 称取高纯试剂氧化铝、碳酸钙、硼酸和氧化铥,其组成成分及其重量配比如下: [0043] high-purity reagents weighed alumina, calcium carbonate, boric acid and thulium oxide, and its composition by weight was prepared as follows:

[0044] Al2O3 24. 2% ;CaCO3 32% ; [0044] Al2O3 24. 2%; CaCO3 32%;

[0045] H3BO3 43% ;Tm2O3 0. 8% ; [0045] H3BO3 43%; Tm2O3 0. 8%;

[0046] 然后称取占上述四种高纯试剂总重量2%重量的助熔剂,助溶剂为SrF2, BaF2, NH4HF2, SrCl2, BaCl2, NH4Cl, H3BO3中的一种或几种。 [0046] and then weighed 2% by weight of the total weight of the four high-purity flux agent, co-solvent is a SrF2, BaF2, NH4HF2, SrCl2, BaCl2, NH4Cl, H3BO3 one or several. 将它们在研钵中研磨2〜3小时,使其充分混勻。 Grind them in a mortar 2 ~ 3 hours to fully mix.

[0047] ( 二)本发明一种稀土铥掺杂的铝酸盐发光玻璃的制备方法,其实施步骤如下: Preparation of [0047] (ii) a method of the present invention, a rare earth aluminate luminescent thulium-doped glass, the implementation steps are as follows:

[0048] 实施例1 : [0048] Example 1:

[0049] (1)为保证准确性,先将所用试剂在烘箱中处理8小时。 [0049] (1) To ensure the accuracy, the first 8 hours in an oven reagent. 称取高纯试剂氧化铝、碳酸钙、硼酸,其重量百分比分别为24. 4%,34%,40. 6% ;称取氧化铥重量与上述三种玻璃母料总重量之比为;再称取占上述四种高纯试剂总重量的1.5%重量的助熔剂,将上述玻璃成分配比实施例1中混合物在研钵中研磨3小时,使其充分混勻。 Purity reagents weighed alumina, calcium carbonate, boric acid, which percentages by weight, respectively, 24.4%, 34% and 40 6%; weighed thulium oxide weight ratio of the total weight of the above-described three kinds of glass mother material; and then Weigh 1.5% by weight of the total weight of the flux of the four high-purity reagent, the ratio of the glass component ground in a mortar for 3 hours in a mixture of Example 1, sufficiently mixed. ;

[0050] (2)将上述混合物装入刚玉坩埚,并置于高温炉中烧结,气氛为空气,以8〜12°C/ min的速率升温到1300°C,烧结时间为2小时; [0050] (2) The above mixture was charged corundum crucible and placed in a high temperature furnace sintering atmosphere is air, at a rate of 8~12 ° C / min temperature increase to 1300 ° C, sintering time is 2 hours;

[0051] (3)取出坩埚,将熔融的玻璃液倒入800°C预热的模具中,在的退火炉中处理,处理时间为30分钟; [0051] (3) Remove the crucible, the molten glass was poured into a 800 ° C preheated mold in the annealing furnace process, the processing time was 30 minutes;

[0052] (4)将烧结物在空气中降到室温,切割至所需尺度,用70〜85°C去离子水洗涤, 120〜150°C温度下烘干,即得到所需产物。 [0052] (4) the sintered material in air down to room temperature, cut to the desired dimensions, using 70~85 ° C deionized water, dried at a temperature of 120~150 ° C, to obtain the desired product. [0053] 实施例2 : [0053] Example 2:

[0054] (1)为保证准确性,先将所用试剂在烘箱中处理8小时。 [0054] (1) To ensure the accuracy, the first 8 hours in an oven reagent. 称取高纯试剂氧化铝、碳酸钙、硼酸,其重量百分比分别为25. 3%,33%,40. 5% ;称取氧化铥重量与上述三种玻璃母料总重量之比为1. 2% ;再称取占上述四种高纯试剂总重量的2%重量的助熔剂,将上述玻璃成分配比实施例2中混合物在研钵中研磨3小时,使其充分混勻。 Purity reagents weighed alumina, calcium carbonate, boric acid, which percentages by weight, respectively, 25.3%, 33%, 40 5.%; The ratio of the three glass on the total weight of the masterbatch weighed thulium oxide to 1 wt. 2%; then weighed 2% by weight of the total weight of the flux of the four high-purity reagent, the ratio of the glass component in Example 2 mixture was ground in a mortar for 3 hours to mix thoroughly. ;

[0055] (2)将上述混合物装入刚玉坩埚,并置于高温炉中烧结,气氛为空气,以8〜12°C/ min的速率升温到1100-1400°C,烧熔2〜5小时; [0055] (2) The above mixture was charged corundum crucible and placed in a high temperature furnace sintering atmosphere is air, at a rate of 8~12 ° C / min heating to 1100-1400 ° C, 2 ~ 5 hours blow ;

[0056] (3)取出坩埚,将熔融的玻璃液倒入模具中,放入已升温至450〜550°C的退火炉中,退火30〜60分钟,再缓慢冷却至室温; [0056] (3) Remove the crucible, the molten glass was poured into a mold, has been placed was heated to 450~550 ° C in an annealing furnace, annealed 30~60 minutes, and then slowly cooled to room temperature;

[0057] (4)将烧结物在空气中降到室温,切割至所需尺度,用70〜85°C去离子水洗涤, 120〜150°C温度下烘干,即得到所需产物。 [0057] (4) the sintered material in air down to room temperature, cut to the desired dimensions, using 70~85 ° C deionized water, dried at a temperature of 120~150 ° C, to obtain the desired product.

[0058] 实施例3 : [0058] Example 3:

[0059] (1)为保证准确性,先将所用试剂在烘箱中处理8小时。 [0059] (1) To ensure the accuracy, the first 8 hours in an oven reagent. 称取高纯试剂氧化铝、碳酸钙、硼酸,其重量百分比分别为对.4%、34%、40. 1%;称取氧化铥重量与上述三种玻璃母料总重量之比为1. 5% ;再称取占上述四种高纯试剂总重量的0. 5%重量的助熔剂,将上述玻璃成分配比实施例3中混合物在研钵中研磨3小时,使其充分混勻。 Purity reagents weighed alumina, calcium carbonate, boric acid, which percentages are by weight of .4%, 34%, 401%; Weigh thulium oxide weight ratio of the total weight of the above-described three kinds of a glass mother material. 5%; re-weighed weight accounted for 0.5% of the total weight of the above-described four kinds of high purity reagents flux, the ratio of the glass component ground in a mortar for 3 hours in a mixture of Example 3, mixed sufficiently. ;

[0060] (2)将上述混合物装入刚玉坩埚,并置于高温炉中烧结,气氛为空气,以8〜12°C/ min的速率升温到1350°C,烧结时间为2小时; [0060] (2) The above mixture was charged corundum crucible and placed in a high temperature furnace sintering atmosphere is air, at a rate of 8~12 ° C / min temperature increase to 1350 ° C, sintering time is 2 hours;

[0061] (3)取出坩埚,将熔融的玻璃液倒入800°C预热的模具中,在的退火炉中处理,处理时间为30分钟; [0061] (3) Remove the crucible, the molten glass was poured into a 800 ° C preheated mold in the annealing furnace process, the processing time was 30 minutes;

[0062] (4)将烧结物在空气中降到室温,切割至所需尺度,用70〜85°C去离子水洗涤, 120〜150°C温度下烘干,即得到所需产物。 [0062] (4) the sintered material in air down to room temperature, cut to the desired dimensions, using 70~85 ° C deionized water, dried at a temperature of 120~150 ° C, to obtain the desired product.

[0063] 实施例4 : [0063] Example 4:

[0064] (1)为保证准确性,先将所用试剂在烘箱中处理8小时。 [0064] (1) To ensure the accuracy, the first 8 hours in an oven reagent. 称取高纯试剂氧化铝、碳酸钙、硼酸,其重量百分比分别为27. 5^^35^^37%;称取氧化铥重量与上述三种玻璃母料总重量之比为0. 5% ;再称取占上述四种高纯试剂总重量的2. 5%重量的助熔剂,将上述玻璃成分配比实施例4中混合物在研钵中研磨3小时,使其充分混勻。 Purity reagents weighed alumina, calcium carbonate, boric acid, 27.5 weight percentage of 35 ^^ ^^ 37%; thulium oxide was weighed and the ratio by weight of the total weight of the three kinds of glass mother material is 0.5% ; then weighed accounted 2.5% by weight of the total weight of the flux of the four high-purity reagent, the ratio of the glass component ground in a mortar for 3 hours in a mixture of Example 4, and sufficiently mixed. ;

[0065] (2)将上述混合物装入刚玉坩埚,并置于高温炉中烧结,气氛为空气,以8〜12°C/ min的速率升温到1400°C,烧结时间为2小时; [0065] (2) The above mixture was charged corundum crucible and placed in a high temperature furnace sintering atmosphere is air, at a rate of 8~12 ° C / min temperature increase to 1400 ° C, sintering time is 2 hours;

[0066] (3)取出坩埚,将熔融的玻璃液倒入800°C预热的模具中,在的退火炉中处理,处理时间为30分钟; [0066] (3) Remove the crucible, the molten glass was poured into a 800 ° C preheated mold in the annealing furnace process, the processing time was 30 minutes;

[0067] (4)将烧结物在空气中降到室温,切割至所需尺度,用70〜85°C去离子水洗涤, 120〜150°C温度下烘干,即得到所需产物。 [0067] (4) the sintered material in air down to room temperature, cut to the desired dimensions, using 70~85 ° C deionized water, dried at a temperature of 120~150 ° C, to obtain the desired product.

[0068] 实施例5 : [0068] Example 5:

[0069] (1)为保证准确性,先将所用试剂在烘箱中处理8小时。 [0069] (1) To ensure the accuracy, the first 8 hours in an oven reagent. 称取高纯试剂氧化铝、碳酸钙、硼酸,其重量百分比分别为对.2^^32^33%;称取氧化铥重量与上述三种玻璃母料总重量之比为0. 8% ;再称取占上述四种高纯试剂总重量的2%重量的助熔剂,将上述玻璃成分配比实施例5中混合物在研钵中研磨3小时,使其充分混勻。 Purity reagents weighed alumina, calcium carbonate, boric acid, which percentages are by weight of ^^ 32 ^ 33% .2; thulium oxide was weighed and the ratio by weight of the total weight of the three kinds of glass mother material was 0.8%; After weighing 2% by weight of the total weight of the flux of the four high-purity reagent, the ratio of the glass component ground in a mortar for 3 hours in a mixture of Example 5, sufficiently mixed. ;

[0070] (2)将上述混合物装入刚玉坩埚,并置于高温炉中烧结,气氛为空气,以8〜12°C/min的速率升温到1300°C,烧结时间为2小时; [0070] (2) The above mixture was charged corundum crucible and placed in a high temperature furnace sintering atmosphere is air, at a rate of 8~12 ° C / min temperature increase to 1300 ° C, sintering time is 2 hours;

[0071] (3)取出坩埚,将熔融的玻璃液倒入800°C预热的模具中,在的退火炉中处理,处理时间为30分钟; [0071] (3) Remove the crucible, the molten glass was poured into a 800 ° C preheated mold in the annealing furnace process, the processing time was 30 minutes;

[0072] (4)将烧结物在空气中降到室温,切割至所需尺度,用70〜85°C去离子水洗涤, 120〜150°C温度下烘干,即得到所需产物。 [0072] (4) the sintered material in air down to room temperature, cut to the desired dimensions, using 70~85 ° C deionized water, dried at a temperature of 120~150 ° C, to obtain the desired product.

[0073] 使用上述方法制备的氧化铥含量(重量比)为的玻璃在1480nm发射的激发光谱如图1所示。 [0073] was prepared using the above method thulium oxide content (weight ratio) of the glass in the excitation spectrum emitted 1480nm shown in Fig. 从图中可以看出,该玻璃在700〜900nm范围内均可以被有效激发,具有很宽的激发光谱,其中794nm有最强的激发峰。 As can be seen from the figure, both the glass can be efficiently excited in the range of 700~900nm, it has a wide spectrum of excitation, 794nm wherein the strongest excitation peak. 说明该玻璃可用普通商业化的激光光源进行激发。 Description The glass available laser light source of an ordinary commercial excited.

[0074] 上述实施例1玻璃在1.4〜1.55 μ m波长范围的光致发光谱示于图2。 [0074] In the above-described Example 1 Glass photoluminescence 1.4~1.55 μ m wavelength range spectrum is shown in FIG. 其处于1460nm的发光峰半峰宽度为123nm覆盖了国际电联ITU标准中S带(1440-1530·)的波长范围,说明这种玻璃可以用于制造S带光纤或者光波导放大器。 In which emission peak half-width of 123nm 1460nm wavelength range covering ITU ITU standard S-band (1440-1530 *), indicating that this may be used to manufacture glass fiber or waveguide amplifiers S band.

[0075] 上述实施例2玻璃在1.3〜1.8μπι波长范围内的光致发光谱示于图3。 [0075] The glass in Example 2 1.3~1.8μπι wavelength range photoluminescence spectrum is shown in FIG. 其两个发光带的半高宽分别为132和99nm,分别覆盖了国际电联ITU标准中S带(1440_1530歷) 和U带(1625-1675nm)全部的波长范围,使得这种材料可应用于制造S带和U带的光源和光放大器。 FWHM which two light strip 132 and 99nm, respectively, for respectively covering ITU ITU standard S-band (1440_1530 calendar) and the U-band (1625-1675nm) the entire wavelength range, so that such materials can be used and a light source for producing an optical amplifier with S and U bands.

Claims (2)

1. 一种稀土铥掺杂的铝酸盐发光玻璃,其特征在于:该组成成分由下述化学式表示: Al2O3-CaO-B2O3-Tm2O3 ;玻璃有效成分引入方式为高纯试剂三氧化二铝、碳酸钙、硼酸和氧化铥,其成分的重量配比如下:Al2O3 22%〜30%〜37% ; H3BO3 36%〜44% ;Tm203 0. 5%〜1. 5% ;在熔制过程中加入助熔剂,助熔剂占上述四种高纯试剂总重量比为0. 3%〜3%。 A thulium-doped rare earth aluminate luminescent glass, characterized in that: the composition represented by the following chemical formula: Al2O3-CaO-B2O3-Tm2O3; active ingredient into the glass way purity reagents aluminum oxide, calcium carbonate, boric acid and thulium oxide, the weight ratio of its components as follows: Al2O3 22% ~30% ~37%; H3BO3 36% ~44%; Tm203 0. 5% ~1 5%; added in the melting process. flux, flux representing a total of the four high-purity reagents weight ratio of 0.3% ~ 3%.
2.根据权利要求1所述的稀土铥掺杂的铝酸盐发光玻璃,其特征在于:所用的助熔剂是SrF2, BaF2, NH4HF2, SrCl2, BaCl2, NH4Cl, H3BO3 中的一种或几种的混合。 The thulium doped rare earth aluminate luminescent glass according to claim 1, wherein: the flux is used SrF2, BaF2, NH4HF2, SrCl2, BaCl2, NH4Cl, H3BO3 in one or more of mixing.
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