| 题名 | 掺铒(卤)碲酸盐玻璃和重金属铋基玻璃发光性能研究 |
| 作者 | 杨建虎 |
| 学位类别 | 博士 |
| 答辩日期 | 2004 |
| 授予单位 | 中国科学院上海光学精密机械研究所 |
| 导师 | 姜中宏 |
| 关键词 | 宽带基质材料 上转换发光材料 光谱性能 |
| 其他题名 | The study of luminescent properties of Er3+ doped (halide) tellurite and bismuth-based glasses |
| 中文摘要 | 随着计算机网络及其它数据传输业务的飞速发展，人们对提高波分复用系统传输容量的需求日益增长，传统的石英基质EDFA由于其本身带宽的限制而不能满足这种需求。虽然许多物理的或结构设计的方法用来增加石英基质EDFA的传输带宽，但不能从根本上解决石英基质本身带来的限制，因此寻找合适的Ers＋掺杂基质材料，实现光信号的宽带高增益放大，对于光纤通信系统传输容量的扩展，具有非常重要的意义。另外，鉴于蓝绿光等短波长激光器在光纤通信、数据存储、激光打印、水下传输以及生物医学等方面广泛的应用，如何获得廉价、高效、小型化的蓝绿光激光器也是光电子器件和光电子材料领域研究的热点和难点。在获得蓝绿光输出的诸多方法中，利用稀土离子的上转换发光具有很多明显的优势，它有利于简单、廉价及结构紧凑小型激光器系统的发展。本论文结合当前对光通讯材料发展的需求，研究了适用于获得宽带放大的碲酸盐玻璃和重金属铋基玻璃材料中Er3＋的发光性能，总结出发光性能参数随玻璃成分变化的规律，研究了适合于获得蓝绿光激光输出的卤氧磅酸盐玻璃材料中Er3＋的发光特性，并得到发光效率和析晶稳定性能俱佳的卤氧蹄酸盐玻璃上转换发光材料。论文首先从不同玻璃网络形成体结构特征分析了Er3＋的配位环境，根据Romon光谱分析，得到不同类型玻璃中结构集团振动引起玻璃基质声子能量的变化，指出了结构中桥氧和非桥氧数目随碱金属或碱土金属含量的变化。有别于以往对无辐射跃迁与声子能量关系研究中忽略Er3＋ 4I1312→4I15/2跃迁，鉴于对获得1.5μm高发光效率的重要性，进行了4113→411012跃迁在各种基质玻璃中无辐射能量损失研究，并从声子能量、折射率以及［OH］等方面进行了分析［J ．Lumin．ZO04，106，9-14］。为了比较不同基质玻璃中稀土离子的增益和线宽性能，利用经典方程，以不存在再吸收现象的Nd3＋为例，借助于两个假设条件，定性的分析了块状玻璃中Nd3＋发射线宽和相对增益［J．opt．soc．AmB，2004，21，739-743］。论文的第二部分研究了谛酸盐玻璃中Ers＋的发光性能，不同于Wang J S等对TeoZ-znONaZo系统的研究，利用Judd-ofelt理论，重点分析了具有更好稳定性能的TeO2-ZnO-La2O3和TeO2-ZnO-Na2P-K2O玻璃中Er3＋的发光性能参数以及E尸”的浓度效应，其掺杂浓度可以达到3.3×1026m-3而不产生浓度淬灭效应。分析了蹄酸盐玻璃中Yb3＋对Er3＋的敏化效应，通过计算能量转移几率，得出了实现有效敏化的Er3＋／ Yb3＋间的比值范围。对比研究了不同的能量接受离子ce3”、Tb3＋及Eu3＋对降低Er3＋上转换发光强度以及1.5μm发光性能参数的影响，并从能量匹配以及能级结构角度出发进行了分析，得出ce3＋是改善Er3＋ 1.sm发光性能的优选离子［C hem．Phys．Lett．2004，384，295-298］。研究了磅酸盐玻璃中高声子能量玻璃网络形成体对Er3＋发光性能参数的影响，并得出wo3、Ge02及VZOS的引入并不能改善Er3＋的发光，而5102、PZos等不能与蹄酸盐玻璃成分形成良好的玻璃［J.Mater． Sci．Lett．2003，55，575-5761。为了解决磅酸盐玻璃作为光纤材料价格的昂贵性和稳定性问题，从分析折射率、膨胀系数以及软化温度出发，得到了与蹄酸盐玻璃性能匹配的并具有良好稳定性能的铅铭硅酸盐玻璃作为包层材料，为高强度低损耗蹄酸盐玻璃光纤的成功拉制提供了可能［Patent：03142112.1]。在论文的第三部分，不同于S Tanabe等对Bi2O3-SiO2-B2O3玻璃系统的研究，研究了Bi2O3-B2O3-Na2O系统中Er3＋的发光性能，并分析了BiZO3含量的变化对发光性能参数的影响，在高B2o3含量的玻璃中，Er3＋ FWHH大小可以达到81nm，而受激发射截面则随Bi2O3含量增加而增大，但荧光寿命值相比较小（最低1．sins）［J．Appl．Phys．2003，93，977-983］。在不含有BZO3的Bi203-5102-Na2O系统中，分析了Bi2o3含量变化对Er3＋发光的影响，发现Bi2o3含量的增加并不能引起FWHM的明显改变（FWHM仅为4onm左右），虽然受激发射截面和荧光寿命均有所增加［J ．Opt．Soc．AmB 2003，20，810-8151。提出了对Er3＋发光性能参数进行调整的混合形成体效应，并以B2O3、SiO2及zrF4为例进行了对比研究［Chin．Phys．Lett．2002，19，1516-1518］。在对上转换发光材料的研究中，不同于常规对氟化物玻璃以及仅含有氟化物的氧氟玻璃研究，基于磅酸盐玻璃成分，通过引入声子能量更低的卤化物，来改善蹄酸盐玻璃的声子能量大小，得到发光效率及稳定性能俱佳的卤氧磅酸盐玻璃材料，其卤化物离子含量可达40mol％。借助于Raman光谱测试，分析了卤氧磅酸盐玻璃结构基团振动的变化引起声子能量的改变以及对上转换发光强度的影响〔chem．Phys．Lett．2003，376，671-675］。利用Judd-Ofelt理论计算T卤氧磅酸盐玻璃材料中Er3＋的辐射寿命、荧光分支比以及量子效率等发光性能参数，得出卤氧蹄酸盐玻璃中Er3+非常有利于获得绿光和红光上转换发光，即使在3omw的泵浦功率下也可以用肉眼观察到明显的上转换发光现象［J ．APPI．Phys，2004，95，3020-3026］。同时通过进一步的成分调整来提高玻璃的稳定性能，使其稳定性能参数在一定范围内变化，有的样品甚至没有析晶峰的出现，得到了适合获得蓝绿光输出的卤氧磅酸盐玻璃材料组份［Patent：200410016358.x］。 |
| 英文摘要 | With the rapid development of computer networks and other data-transmitting services, the demand for the increase of transmission capacity of wavelength-division-multiplexing (WDM) system is urgent. The conventional silica based Er3+ doped fiber amplifier (EDFA) can not meet this requirement because of its intrinsic bandwidth limit. Though many physical and structural methods have been used to flatten the gain spectrum and broaden the amplification bandwidth of silica based EDFA, it is important to find another glass matrix for Er3+ doping to obtain an intrinsically broader gain bandwidth than that of silica based EDFA, which is beneficial to the enlargement of transmission capacity. Besides, owing to its potential applications in the fields of color display, optical data strorage, biomedical diagnostics and undersea transmission of blue and green lasers, how to obtain cheap, high-efficient, and compact visible lasers are now becoming hot topics and challenges in the fields of optoelectronic materials and components. Among the several methods of obtaining blue and green light output, many advantages are expected by using the upeonversion emission of rare earth ions. Based on the requirements of the development of optoelectronic materials, the luminescent properties of Er3+ doped tellurite and bismuth-based glasses suitable for broadband and high gain amplification were studied and the optical parameters change with the glass composition were discussed. Besides, the upeonversion properties of Er3+ doped halide modified tellurite glasses, which has potential applications in the fields of upeonversion laser materials, were also studied. In the dissertation, the local ligand environment of Er3+ was discussed based on the structural characteristics of different glass formers. From the Raman measurements, the vibrations of different kinds of structural group cause the difference of maximum phonon energies in different glasses. The variations of the number of bridging and nonbridging oxygens with the alkali and/or alkali-earth ions were also pointed out. Instead of the neglection of Er3+ 4I13/2→4I15/2 in conventional discussion of the correlations between nonradiative transition and phonon energy of the glass matrix, to the importance of. 1.5μm emission with high efficiency, the nonradiative losses of the 4I13/2→4I15/2 transition in different glasses were discussed from the viewpoints of phonon energy, refractive index, and the existence of [OH] groups [J. Lumin. 2004, 106, 9-14]. In order to compare the gain and bandwidth performance of rare earth ions in different glasses, on the basis of classic equations, without the influence of reabsorption, the relative emission bandwidth and gain values were discussed qualitatively [J. Opt. Soc. Am B, 2004, 21, 739-743], In the second part of the dissertation, the luminescent properties of Er3+ doped tellurite glasses were discussed, instead of the composition of TeO2-ZnO-Na2O studied by Wang J S, by using Judd-Ofelt theory, the optical parameters and concentration effects of Er3+ were analyzed in TeO2-ZnO-La2Os and TeOj-ZnO- glasses with good glass stability. The Er3+ doping concentration can be arrived at 3.3 X 102 m'3 while no concentration quenching occurs. The sensitization of Yb3+ to Er3+ in tellurite glasses was analyzed, by the calculation of energy transfer rate, the Er3+/Yb3+ ratio range was obtained to realize effective sensitization. The influence of different energy acceptors, Ce3+, Tb3+, and Eu3+, on the upconversion intensities and 1.5(j,m optical parameters of Er3+ was discussed from the energy match and energy level structure points [Chem. Phys. Lett. 2004, 384, 295-298]. Besides, the effects of different glass formers with higher phonon energies than tellurite glass on the luminescent properties of Er3+ were also discussed, which was found that the introduction of WO3, GeO2, and V2O5 can not improve the parameters of Er3+, while the existence of S1O2 and P2O5 in the tellurite glass composition can not form good transparent glasses either the corundum or the Pt crucibles was used [J. Mater. Sci. Lett. 2003, 55, 575-576]. In order to solve the expensive price and glass stability of tellurite glass materials, from the analyzation of refractive index, thermal expansion coefficients, and the softening tempertature, the Pb-Bi-slicate glasses matched with the tellurite glass properties was obtained, which provides the possibility of the successful preparation of high strength and low loss tellurtie glass fiber [Patent: 03142112.1]. Different from the properties of Bi2O3-SiO2-B2O3 glasses studied by S Tanabe, in the third part of the dissertation, the study of luminescent properties of Er3+ doped Bi203-B203-Na2O glasses were performed, and the compositional dependence of optical parameters of Er3+ on B2O3 content were discussed. With the increase of B2O3 content, the FWHM increases monotonically, while the stimulated emission cross section and lifetime of 4Ii3/2 decrease [J. Appl. Phys. 2003, 93, 977-983]. The optical properties of Er3+ in Bi2O3-SiO2-Na2O glasses without B2O3 were also studied, and the changes of optical parameters with B12O3 content were discussed, which was found that the increase of Bi2O3 content causes the increase of stimulated emission cross section, but the FWHM almost does not change, and the lifetime of 4Ii3/2 level decreases slightly [J. Opt. Soc. Am B 2003, 20, 810-815]. The mixed former effect for the adjustment of Er3+ luminescent parameters was mentioned, and was exampled by using B2O3, SiO2, and ZrF4 as the former compositions [Chin. Phys. Lett. 2002, 19, 1516-1518]. For the investigation of upconversion materials, instead of the study of conventional fluoride materials and fluoride modified oxide glasses, based on tellurite glasses, by introducing halide ions with low phonon energies to improve the phonon energy value of tellurite glasses, the halide modified tellurite glasses with low phonon energy and good glass stability was obtained, where the halide ion content can be arrived at 40mol%. From Raman measurements, the variations of phonon energy and the upconversion intensity attributed to the changes of structural units in halide modified tellurite glasses were discussed [Chem. Phys. Lett. 2003, 376, 671-675]. The optical parameters such as radiative lifetime, branching ratio, and quantum efficiency were calculated according to Judd-Ofelt theory. The upconversion signal was so bright that can be observed by the naked eye even at the pumping power as low as 30mW [J. Appl. Phys. 2004, 95, 3020-3026]. The glass stability was also improved by further composition adjustment, the glass stability parameters can be varied in a wide range. The halide modified tellurite glasses with high luminescent efficiency and good glass stability suitable for blue and green light output were obtained [Patent: 200410016358.x]. |
| 语种 | 中文 |
| 内容类型 | 学位论文 |
| 源URL | [http://ir.siom.ac.cn/handle/181231/15409]  |
| 专题 | 上海光学精密机械研究所_学位论文 |
| 推荐引用方式 GB/T 7714 | 杨建虎. 掺铒(卤)碲酸盐玻璃和重金属铋基玻璃发光性能研究[D]. 中国科学院上海光学精密机械研究所. 2004. |
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