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题名	镍掺杂透明微晶玻璃光学特性的研究
作者	吴伯涛
学位类别	博士
答辩日期	2008
授予单位	中国科学院上海光学精密机械研究所
导师	邱建荣
关键词	镍 透明微晶玻璃 近红外发光 宽带光放大
其他题名	Studies on optical characteristics of Ni-doped transparent glass ceramics
中文摘要	近年来，随着计算机网络及其它数据传输服务的飞速发展，长距离光通信系统对传输容量的需求正日益膨胀。而要增加光通信的传输容量一个比较有效的方法就是增加光通信系统中使用的光纤放大器的增益带宽。然而，现在广泛使用的传统石英基质掺Er光纤放大器的增益带宽由于稀土离子自身4f壳层内的禁戒跃迁使得其增益带宽很难突破100nm；虽然光纤拉曼放大器能够有效克服稀土离子掺杂的光纤放大器所固有的缺点，实现大范围内的宽带放大，但它需要多波段的泵浦并且增益效率低，而且宽带光纤拉曼放大器结构复杂，能量消耗大。因此，研制具有更宽带宽的光放大器，寻找新型具有更宽带宽的近红外发光材料已成为光纤研究领域的一个热点。最近，过渡金属Ni掺杂透明微晶玻璃受到了人们的广泛关注。这种新型Ni2+激活光学材料在近红外区域具有较长寿命和能够覆盖整个光通信窗口的宽带发光，是一种很有应用潜力的宽带光放大材料。 本论文制备了两个新的Ni2+掺杂透明微晶玻璃体系，并观察到了来自Ni2+离子的宽带近红外发光；同时根据敏化发光原理，在一些Ni2+掺杂透明微晶玻璃里分别共掺Yb2O3、Cr2O3和Bi2O3，通过能量转移使得Ni2+的近红外光谱性质得到很大改善。获得的主要结果如下： 1、制备了新的Ni2+掺杂50SiO2-16.7Al2O3-8.3Ga2O3-16.7MgO-8.3TiO2（MAGST）透明微晶玻璃。XRD、Raman和TEM分析表明该微晶玻璃析出的是含有Ga3+，Ni2+和Ti4+的MgAl2O4固溶体微晶相，其平均尺寸不超过7.2nm。吸收光谱表明Ni2+离子经热处理由玻璃中的三角双锥五配位和四面体四配位位置转变为微晶玻璃中的八面体六配位位置。在980nm激光二极管激发下，1000oC热处理2小时获得的掺杂0.30mol％NiO的MAGST微晶玻璃具有最佳的光学性质：在1050～1600nm波长区域存在一中心在1220nm的宽带发光，荧光半高宽FWHM为240nm，室温荧光寿命约260μs。光谱性质表明Ni2+掺杂MAGST透明微晶玻璃有望用作宽带光放大器和可调谐激光器的增益介质。 2、研究了(100-x) (55SiO2-18Al2O3-18MgO-9TiO2)-0.3NiO-xGa2O3 (x = 0, 2.5, 5, 7.5, 10)微晶玻璃中组分Ga2O3的作用。未添加Ga2O3的微晶玻璃析出了MgAl2O4和MgAl2Ti3O10两个纳米晶相，随Ga2O3的增加，MgAl2Ti3O10相逐渐消失，最后得到只析出尖晶石固溶体纳米晶相的微晶玻璃。随Ga2O3添加量的增加，980nm激光二极管激发下微晶玻璃中Ni2+的近红外发射强度不断增强，加入10mol％Ga2O3的微晶玻璃（即MAGST微晶玻璃）的近红外发射强度可为未添加Ga2O3的微晶玻璃的15倍，这主要是由于Ga3+离子比Ni2+离子具有高的四面体择位能，热处理后Ga3+离子进入尖晶石固溶体纳米晶里，使更多的Ni2+离子居于八面体格位，因而提高了Ni2+离子的近红外发射强度。 3、制备了新的Ni2+掺杂3.4Na2O-3.3K2O-13.3Ga2O3-80.0SiO2（NKGSN）透明微晶玻璃。XRD测试表明微晶玻璃中析出的是β-Ga2O3微晶相，TEM分析表明β-Ga2O3微晶均匀分布在微晶玻璃的玻璃基体上，其最大尺寸在3.5～5nm。吸收光谱和Ni L3边的电子能耗光谱都表明热处理后Ni2+离子进入了微晶玻璃中的β-Ga2O3纳米晶，并占据八面体六配位位置。在980nm激光二极管激发下，900oC热处理6小时获得的掺杂0.10mol％NiO的NKGSN微晶玻璃具有最佳的光学性质：在1100～1700nm波长区域存在一中心在1265nm的宽带发光，荧光半高宽FWHM为260nm，室温荧光寿命可达1220μs。Ni2+掺杂β-Ga2O3透明碱镓硅微晶玻璃优异的光谱性质使其在宽带光放大器和可调谐激光器方面有很大的应用潜力。 4、制备了不同Yb2O3浓度和0.10mol％NiO共掺的透明Li2O-Ga2O3-SiO2（LGS）微晶玻璃。在980nm激光二极管激发下，共掺0.75mol% Yb2O3的透明LGS微晶玻璃中Ni2+离子在1300nm的宽带近红外发光强度最强，约为Ni2+单掺微晶玻璃的8.5倍，其荧光半高宽FWHM为290nm，室温荧光寿命约920μs。通过Yb2O3的共掺Ni2+掺杂透明LGS微晶玻璃中的光谱性质得以改善，这归因于Yb3+离子向Ni2+离子的有效能量转移。根据Forster-Dexter无辐射能量转移模型的定性计算表明，Yb3+ → Ni2+的能量转移常数Cs-a和能量转移速率Ps-a都远远大于反向能量转移过程的。 5、室温下，在980nm光源激发下，在Yb3+单掺和Yb3+/Ni2+共掺的透明LGS微晶玻璃中分别发现来自Yb3+离子和Ni2+离子的蓝色和绿色可见上转换发光，而在单掺Ni2+的微晶玻璃中观察不到任何可见发光。Yb3+离子的蓝色可见上转换发光可归因于Yb3+离子对的合作上转换，而Ni2+离子的绿色可见发光则可以归属为两个Yb3+离子合作敏化一个Ni2+的上转换。 6、制备了0.10mol％Cr2O3和0.10mol％NiO单、共掺透明LGS微晶玻璃。吸收光谱表明Cr3+和Ni2+在LGS微晶玻璃中均进入微晶玻璃中析出的LiGa5O8纳米晶并居于八面体六配位位置。室温下，在532nm光源激发下通过Cr3+的共掺Ni2+离子在1300nm的近红外发射强度可以被提高约8.5倍。时间分辨发射光谱证明Ni2+的增强发光是由于Cr3+向Ni2+发生了有效能量转移，能量转移效率约为85％。 7、制备了不同Cr2O3掺杂浓度（0～0.30wt％）和0.10wt％NiO单、共掺的透明ZnO-Al2O3-SiO2（ZAS）微晶玻璃。吸收光谱表明Cr3+和Ni2+在ZAS微晶玻璃中均进入ZnAl2O4纳米晶并居于八面体六配位位置。室温下，在532nm光源激发下通过Cr3+的共掺Ni2+离子在1200nm的发射强度最大可以被提高约8倍。时间分辨发射光谱证明Ni2+的增强发光是由于Cr3+向Ni2+发生了能量转移，其效率约为57％。 8、制备了不同Bi2O3浓度和0.30mol％NiO共掺的透明50SiO2-16.7Al2O3-8.3Ga2O3-16.7MgO-8.3TiO2（MAGST）微晶玻璃。室温下，808nm激光二极管激发下Bi/Ni共掺MAGST微晶玻璃产生来自Bi的宽带近红外发光，其带宽大于320nm，荧光寿命可达200μs以上；980nm激光二极管激发下Bi/Ni共掺MAGST微晶玻璃产生来自Ni的增强宽带近红外发光，Ni的增强发光是由Bi向Ni的能量转移引起的。当Bi2O3掺杂浓度为0.75mol％时Ni的发光强度达到最强，约为Ni单掺微晶玻璃发射强度的4.5倍，其荧光寿命为350μs，荧光半高宽为260nm。这种Bi/Ni共掺的透明微晶玻璃有望用作宽带光放大器和可调谐激光器的增益介质。
英文摘要	In recent years, the requirement of the long distance optical communication system for communication capacity are fast increased due to the rapid development of computer network and other data-transmitting services. The most effect method of increasing the communication capacity of optical communication is broadening the gain bandwidth of optical fiber amplifiers used in optical communication system. However, the gain bandwidth of the conventional silica based Er-doped optical fiber amplifiers extensively used is hardly beyond 100 nm because the 4f-4f transitions of rare earth ions are forbidden in the inner-shell. Optical fiber Raman amplifiers can overcome the drawbacks of rare earth ions doped optical fiber amplifiers and realize broadband optical amplification. But they request multi-wavelength pumping schemes and have low gain efficiency, more complicated structure and high-power consumption. Therefore, developing optical amplifiers with broader bandwidth and novel near-infrared luminescent materials with broader bandwidth have been a focus in the fiber studies. Recently, transition metal Ni doped transparent glass ceramics (GCs) have attracted much attention for their long lifetime and broadband near-infrared luminescence covering the whole optical communication windows, which have potential applications in broadband optical amplification materials. In this thesis, two novel Ni2+-doped transparent GCs were synthesized, from which broadband near-infrared luminescence of Ni2+ was observed. According to the theory of sensitized luminescence, some Ni2+-doped transparent GCs were co-doped with Yb2O3, Cr2O3 and Bi2O3, respectively, and the near-infrared spectral properties of Ni2+ in these transparent GCs were greatly improved by energy transfer between these codoped ions and Ni2+. Main achieved results are listed as following: 1、Novel Ni2+-doped 50SiO2-16.7Al2O3-8.3Ga2O3-16.7MgO-8.3TiO2 (MAGST) transparent GCs were synthesized. XRD, Raman and TEM analysis indicated that the crystallite phase of MgAl2O4 solid solution containing Ga3+, Ni2+ and Ti4+ was precipitated in the GCs, and its average size was not beyond 7.2 nm. The absorption spectra indicated that after thermal treatment the coordination of Ni2+ transferred from trigonal bipyramid fivefold and tetrahedral fourfold in glasses to octahedral sixfold in GCs. MAGST GCs doped with 0.30 mol% NiO obtained by thermal treatment at 1000 oC for 2h had the optimal optical properties with the excitation of 980 nm laser diode (LD), which exhibited a broadband luminescence centered at 1220 nm in the region of 1050~1600 nm with full width at half maximum (FWHM) of 240 nm and lifetime of about 260 μs at room temperature. The spectral properties elucidate that Ni2+-doped MAGST GCs have potential applications as gain media of broadband optical amplifiers and tunable lasers. 2、The role of Ga2O3 in (100-x) (55SiO2-18Al2O3-18MgO-9TiO2)-0.3NiO-x Ga2O3 (x = 0, 2.5, 5, 7.5, 10) transparent GCs was studied. The MgAl2O4 and MgAl2Ti3O10 crystallite phases were precipitated in the GCs without Ga2O3, and MgAl2Ti3O10 crystallite phase gradually decreased with the increase of Ga2O3 content and finally only the crystallite phase of MgAl2O4 solid solution containing Ga3+, Ni2+ and Ti4+ was precipitated in the GCs. The near-infrared emission intensity of Ni2+ in the GCs was continuously enhanced with the increase of Ga2O3 content excited by 980 nm LD. The near-infrared emission intensity of Ni2+ in the GCs with 10 mol% Ga2O3, viz. MAGST GCs was about 15 times of that of the GCs without Ga2O3. This was mainly because the tetrahedral site preference energy of Ga3+ ions was higher than that of Ni2+ ions, and after thermal treatment Ga3+ ions entered into spinel solid solution nanocrystals, which made more Ni2+ ions entering into octahedral sites, thus the near-infrared emission intensity of Ni2+ was largely increased. 3、Novel Ni2+-doped 3.4Na2O-3.3K2O-13.3Ga2O3-80.0SiO2 (NKGSN) GCs were synthesized. XRD analysis indicated that β-Ga2O3 crystallite phase was precipitated in NKGSN GCs. TEM analysis indicated that β-Ga2O3 crystallites were homogeneously distributed in the matrices of the GCs and their largest size was 3.5~5nm. The absorption spectra and electron energy loss spectra of Ni L3 edge elucidated that after thermal treatment Ni2+ ions entered into β-Ga2O3 nanocrystals and occupied octahedral sites. NKGSN GCs doped with 0.10 mol% NiO obtained by thermal treatment at 900 oC for 6h had the optimal optical properties with the excitation of 980 nm LD, which exhibited a broadband luminescence centered at 1265 nm in the region of 1100~1700 nm with FWHM of 260 nm and lifetime of 1220 μs at room temperature. The excellent optical properties of Ni2+-doped β-Ga2O3 transparent GCs makes them very potential applications in broadband optical amplifiers and tunable lasers. 4、Transparent Li2O-Ga2O3-SiO2 (LGS) GCs codoped with different Yb2O3 concentration and 0.10 mol% NiO were synthesized. The broadband near-infrared emission intensity of Ni2+ at 1300 nm in the LGS GC co-doped with 0.75 mol% Yb2O3 was the strongest with the excitation of 980 nm LD, which was 8.5 times of that of Ni2+ single-doped GCs, and its FWHM and lifetime at room temperature were 290 nm and 920 μs, respectively. The spectral properties of Ni2+ in LGS GCs were largely improved by Yb2O3 co-doping which was attributed to efficient energy transfer from Yb3+ to Ni2+. The qualitative calculation according to the Forster-Dexter non-radiative energy transfer model indicated that the energy transfer constant Cs-a and energy transfer rate Ps-a of the energy transfer from Yb3+ to Ni2+ were much greater than in the opposite direction. 5、Blue and green visible upconversion luminescence from Yb3+ and Ni2+ were observed in Yb3+ single-doped and Yb3+/Ni2+ co-doped transparent LGS GCs, respectively, with the excitation of 980 nm laser at room temperature, but no any visible luminescence was detected in Ni2+ single-doped LGS GC. Blue visible upconversion from Yb3+ ions could be ascribed to cooperative upconversion of Yb3+-Yb3+ ion pairs, and green visible luminescence from Ni2+ ions could be attributed to upconversion luminescence of two Yb3+ ions cooperatively sensitizing one Ni2+ ion. 6、0.10 mol% Cr2O3 and 0.10 mol% NiO single- and co-doped transparent LGS GCs were prepared. The absorption spectra indicated that Cr3+ and Ni2+ ions were incorporated into LiGa5O8 nanocrystals of GCs and occupied octahedral sites. The near-infrared emission intensity of Ni2+ at 1300 nm could be increased as about 8.5 times with the excitation of 532 nm laser at room temperature. The time-resolved emission spectra confirmed that the enhanced Ni2+ luminescence was due to efficient energy transfer from Cr3+ to Ni2+, and the energy transfer efficiency was about 85%. 7、Different Cr2O3 concentration (0~0.30 wt% ) and 0.10 wt% NiO single- and co-doped transparent ZnO-Al2O3-SiO2 (ZAS) GCs were prepared. The absorption spectra indicated that Cr3+ and Ni2+ ions were incorporated into ZnAl2O4 nanocrystals of ZAS GCs and occupied octahedral sites. The near-infrared emission intensity of Ni2+ at 1200 nm could be increased as up to about 8 times with the excitation of 532 nm laser at room temperature. The time-resolved emission spectra confirmed that the enhanced Ni2+ luminescence was due to energy transfer from Cr3+ to Ni2+, and the energy transfer efficiency was about 57%. 8、Transparent 50SiO2-16.7Al2O3-8.3Ga2O3-16.7MgO-8.3TiO2 (MAGST) GCs co-doped with different Bi2O3 concentration and 0.30 mol% NiO were synthesized. At room temperature, the broadband near-infrared luminescence from Bi with FWHM of more than 320 nm and lifetime of more than 200 μs in Bi/Ni co-doped MAGST GCs was observed excited by 808 nm LD, meanwhile the enhanced broadband near-infrared luminescence from Ni2+ in Bi/Ni co-doped MAGST GCs was also observed with the excitation of 980 nm LD, which could be attributed to energy transfer from Bi to Ni2+. The emission intensity of Ni2+ was the strongest when the Bi2O3 concentration was 0.75 mol%, which was about 4.5 times of that of Ni2+ single-doped MAGST GC, and its lifetime and FWHM were 350 μs and 260 nm, respectively. It is suggested that the Bi/Ni co-doped transparent MAGST GCs have potential applications in gain media of broadband optical amplifiers and tunable lasers.
语种	中文
内容类型	学位论文
源URL	[http://ir.siom.ac.cn/handle/181231/15483]
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	吴伯涛. 镍掺杂透明微晶玻璃光学特性的研究[D]. 中国科学院上海光学精密机械研究所. 2008.

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