稀土(Er, Nd, Yb, Pr, Ho, Sm)有机/无机杂化材料的制备及发光性能研究

目前，国内外对于铕和铽等稀土配合物的可见区发光和应用都有大量研究，但对具有近红外发光（800-1700 nm）性能的稀土配合物的研究还处于起步阶段。由于稀土的近红外发光在光纤通讯、激光系统及诊断学等方面应用具有特殊的优点，越来越引起人们的兴趣和重视。 稀土近红外发光配合物的致命弱点是其光、热和化学稳定性较差，从而限制了其在很多领域的实际应用。而溶胶－凝胶材料和介孔材料具有良好的光、热和化学稳定性，能改善客体分子的结构环境和化学微环境，从而能有效提高客体分子的发光性能。因此，本论文将具有优良近红外发光性能的稀土配合物分别与上述两种基质复合，从实验和理论研究稀土近红外发光杂化材料的性能和应用价值，制备出具有良好稳定性的高效稀土近红外发光杂化材料，以期为光纤通讯、激光等领域提供潜在的候选材料。围绕这一宗旨，开展了如下工作： 通过原位技术分别得到了掺杂和嫁接[Ln(dbm)3phen]化合物（Ln = Er, Nd, Yb）的杂化凝胶材料，Ln-D-P gel和Xerogel-Ln。通过对其近红外发光性能的研究，表明材料中配体能很好的保护稀土离子，并将能量有效的传递给稀土离子。采用Judd-Ofelt理论对所得部分材料进行了光谱分析，基于实验数据和理论分析表明其具有潜在的光放大和激光应用价值。 选择了两种含全氟化烷基链的β-二酮配体Hhfth和Htfnb，通过功能化的phen-Si配体，将三元配合物[Ln(hfth)3phen] (Ln = Er, Nd, Yb, Sm)和[Pr(tfnb)3phen]成功共价嫁接到介孔MCM-41和SBA-15杂化材料中，得到的衍生材料Ln(hfth)3phen–MCM-41、Pr(tfnb)3phen–MCM-41和Ln(hfth)3phen–SBA-15、Pr(tfnb)3phen–SBA-15都保持了高度有序的介孔p6mm结构，并展现出稀土离子特征的近红外发射。所得稀土配合物功能化的材料的发射光谱能完全覆盖对光通讯极具应用价值的1300-1600nm区域。 通过对Er(dbm)3phen–M41(X, Y) (X = 1~14, Y = 3, 6, 12, 18, 24 h)材料系统的比较研究，选择了X = 12, Y = 6作为合成目标材料的优化参数，通过功能化的phen-Si配体将[Ln(dbm)3phen]配合物共价嫁接于有序介孔MCM-41和SBA-15中(Ln = Er, Nd, Yb)，所得两类材料Ln(dbm)3phenM41和Ln(dbm)3phenS15都保持了很好的介孔有序性，并具有良好的近红外发光性能。通过对Ln(dbm)3phenM41和Ln(dbm)3phenS15两类材料发光行为的比较，以及两类材料中稀土离子的含量及孔结构的分析，推出以SBA-15为载体得到的材料在相对发光强度和荧光寿命上，均比以MCM-41为载体的材料有所提高。 通过对8－羟基喹啉配体进行改性，合成了具有双功能的配体Q-Si，继而合成了共价嫁接8－羟基喹啉衍生物的介孔杂化材料Q–SBA-15，其形貌均一，并具有高度有序的介孔p6mm结构。通过配体交换反应，得到了嫁接稀土喹啉配合物的具有近红外发光性能的介孔杂化材料LnQ3–SBA-15 (Ln = Er, Nd, Yb)，其仍然保持高度有序的介孔结构，且外形呈现与母体材料Q–SBA-15相似的弯曲圆柱状。激发配体的吸收，LnQ3–SBA-15材料都分别展现出相应稀土离子特征的近红外发射，并详细分析和讨论了所得介孔杂化材料的近红外发光性能。

多氟稀土（Sm、Tb）有机配合物的合成及发光性质的研究

本文合成了几种多氟β-二酮配合物，并将其引入无机／有机杂化基质及中孔分子筛材料中，从而制备了发光性能良好的杂化材料。选用新型的多氟β-二酮作为有机配体，合成了几种衫、试配合物，通过IR、1H NMR等手段证实了配合物的生成，并研究了其发光性质。首次得到了以4,4,5,5,6,6,6-七氟-1-2-噻吩基）-1-已二酮（HTH）为配体的衫的配合物单晶（Sm（HT）3Phen），解析了其结构，结果表明其配位多面体为三角十二面体。将多氟三元配合物Tb（Tfacac）3phen通过溶胶一凝胶过程掺杂到γ-缩水甘油丙基醚三甲氧基硅烷（GPTMS）改性的有机／无机杂化基质中，制备了有机／无机杂化发光块状材料一及其薄膜材料；研究了稀土配合物在未改性基质和改性基质中的发光性质，以及不同基质对发光性能的影响，结果发现该杂化材料最大激发峰位相对于纯配合物发生了蓝移，且激发谱带变窄；考察了两种基质中配合物掺杂浓度对杂化材料的发光强度的影响，结果表明。稀土配合物在改性基质中比在未改性基质中掺杂浓度提高了。比较了粉末材料与相应薄膜的发光性能，发现薄膜材料巴的发光强度和荧光寿命有所降低，表明材料的不同状态对其发光性能有一定的影响。制备了中孔分子筛MCM-41及GPTMS、TMSPMC改性的有机／无机杂化中孔材料。回时成功地将稀土配合物Sm（HTH）3Phen、Tb（Tfacac）3Phen组装到MCM-41及两种改性的MCM-41中，合成了担载新型稀土有机配合物的无机-有机杂化中孔发光材料。通过对稀土配合物及其在分子筛中的荧光光谱分析，发现激发光谱发生了蓝移；而且不同的改性剂对不同的稀土配合物的影响不同。并制得了发光色纯度较高的稀土-TMSPMC-MCM-41复合发光体。

M_2RSbO_6:R~(3+)复合氧化物的合成组成结构和性能的研究(M = Ba、Sr、Ca, R = La、Gd、Y、Bi, R' = Sm、Eu、Dy、Ho、Er、Tm)

对于稀土与非稀土所组成的二元复合氧化物的研究国外已有较多的报导。但是，对于稀土和锑的复合氧化物只是近年来才开始有些研究工作。含锑与稀土的多元复合氧化物的报导就更少。本文在我们实验室张静筠等人三元复合氧化物研究的基础上，开展Mo—Sb_2O_5—R_2O_3—R'_2O_3—Bi_2O_3多元体系的研究工作，这对于我国丰产元素稀土和锑的应用以及利用Bi~(3+)的激活与敏化将是有益的。本文按Thornton等人的方法合成了Ba_2BiSbO_6，Ba_2GdSbO_6，按EγΦECEHKO等人的方法合成了M_2RSbO_6 (M = Ba、Sr、Ca, R = La Y)。并以M_2RSbO_6为基质，掺Sm~(3+)、Eu~(3+)、Dy~(3+)、Ho~(3+)、Er~(3+)、Tm~(3+)和Bi~(3+)，研究它们的化学组成，晶体结构与发光性能的关系及规律，Bi~(3+)的荧光和敏作用。同时研究了它们的磁学和热学性能。化学组成的分析结果表明，计算的含量与实验测得的含量符合较好，说明化学反应是按化学计量比进行的。通过X-射线粉沫物相分析和晶胞参数的理论计算确定M_2RSbO_6(M = Ba、Sr、R = La、Y、Gd、Bi)复合氧化物是属于立方钙钛太型化合物。空间群为Fm3m，点群为Oh。用计算机计算了Ca_2YSbO_6的晶胞参数并结合荧光光谱分析确定它属于畸变的单斜钙钛矿，空间群为P_(21)。用磁天平测量了样品M_2RSbO_6 (M = Ba、Sr、Ca; R = Gd、Y、Bi)的磁化率。除Ba_2GdSbO_6是顺磁性物质外共余的都是反磁性的物质。按所用原料Sb_2O_5计算的磁化率与测量值符合较好，表明在所研究的M_2RSbO_6化合物中锑是正五价的。用热重热差分析仪测量了样品在反应中的热性能，观察到在化合物形成的过程中所用原料Sb_2O_3大约在520 ℃左右氧化变为Sb_2O_5。除所用原料碳酸盐分解外没有挥发性的物质，这就进一步证明化学组成分析和磁化率测量的结果是正确的。光学测量的结果表明，所有的磷光体随着激活离子浓度的不同其光谱都发生规律性的变化。对于不同Eu~(3+)浓度的Ba_2YSbO_6:Eu~(3+)和Br_2YSbO_6:Eu~(3+), Bi~(3+)体系用254nm激发时均能观察到Eu~(3+)于595nm的尖峰发射。用基质和Bi~(3+)的激发峰325nm激发时，明显地看到敏化剂Bi~(3+)到Eu~(3+)的能量传递，使Eu~(3+)于595nm的发射大大增强，我们认为Bi~(3+)对Eu~(3+)的敏化作用是由于基质和Bi~(3+)的~1S。→ 3P_1的跃迁吸收了激发的能量，然后无辐射弛豫到Eu~(3+)的激发态~5D_0，产生~5D_0 → 7F_1的磁偶极跃迁。对于不同Eu~(3+)浓度的Sr_2YSbO_6:Eu~(3+)和Sr_2YSbO_6:Eu~(3+), Bi~(3+)体系用245nm激发时均能观察到Eu~(3+)于595nm的尖峰发射。用基质和Bi~(3+)的激发峰335nm激发时，观察到基质和Bi~(3+)对Eu~(3+)具有某种能量传递。敏化作用机理与上述的Ba_2YSbO_6:Eu~(3+)和Ba_2YSbO_6:Eu~(3+), Bi~(3+)体系相同。对于不同Eu~(3+)浓度的Ca_2YSbO_6:Eu~(3+)和Ca_2YSbO_6:Eu~(3+), Bi~(3+)体系用396nm激发时，均能观察到Eu~(3+)于613nm很强的尖峰发射。用基质和Bi~(3+)的激发峰313nm激发时，见到Bi~(3+)和基质对Eu~(3+)具有某种能量传递，这种敏化作用主要是由于基质和Bi~(3+)的3P_1 → ~1S_0的400nm的宽带发射和Eu~(3+)的~7F_0 → ~5L_6的396nm的吸收相匹配产生~5L_6→~5D_0→~7F_2的跃迁。通过对激发光谱和荧光光谱的分析给出了Ca_2Y_(0.96)Eu_(0.04)SbO_6的能级图，从实验上可见，Eu~(3+)的发光强烈地依赖于钙钛矿的结构，当Eu~(3+)在空间群为Fm3m 的Ba_2YSbO_6和Sr_2YSbO_6中处于Oh点对称性时，主要是~5D_0 → ~7F_1的磁偶极跃迁。当Eu~(3+)在空间群为P_(21)的单斜钙钛矿中时，主要是~5D_0 → ~7F_2的电偶极跃迁。对于不同掺杂浓度M_2YSbO_6:R~(13+)(M = Ba、Ca; R' = Sm、Dy、Ho、Er、Tm)体系，通过激发和荧光光谱的研究，合理地确定了谱项。发现基质对Sm~(3+)、Dy~(3+)、Ho~(3+)具有敏化作用。对不同Bi~(3+)浓度的Ca_2YSbO_6:Bi~(3+)，由激发和荧光光谱可见Bi~(3+)具有二个激发带，第一激发带位于240nm处相当于~1S_0 → ~1P_1的跃迁，第二激发带位于315nm处相当于~1S_0 → ~3P_1的跃迁。有一个很强的兰紫色发射位于400nm处相当于~3P_1 →~1S_0的跃迁。

Investigation on the strain relaxation of InGaN layer and its effects on the InGaN structural and optical properties

The evolution of strain and structural properties of thick epitaxial InGaN layers grown on GaN with different thicknesses are investigated. It is found that, with increase in InGaN thickness, plastic relaxation via misfit dislocation generation becomes a more important strain relaxation mechanism. Accompanied with the relaxation of compressive strain, the In composition of InGaN layer increases and induces an apparent red-shift of the cathodoluminescence peak of the InGaN layer. On the other hand, the plastic relaxation process results in a high defect density, which degrades the structural and optical properties of InGaN layers. A transition layer region with both strain and In composition gradients is found to exist in the 450-nm-thick InGaN layer.

CHANNELING ALIGNMENT FOR EPITAXIAL LIGHT-MASS FILM ON HEAVY-MASS SUBSTRATE

A simple procedure for obtaining a background-free backscattering spectrum of a light-mass film on a heavy-mass substrate by a normal incidence/grazing exit geometry has been described. Using this method such films can be aligned rapidly and accurately, and the impurity or defect information on the films can be obtained without need for realignment. Example is given from MeV Li-3+ analysis of a deposited film of Si on a single crystal substrate of yttria-stabilized, cubic zirconia.

EFFECT OF SURFACE-STRUCTURES UPON ULTRATHIN-FILM INTERFERENCE-FRINGES

Effect of surface structures upon ultrathin film interference fringes generated from extremely thin films or epitaxial layers grown on semiconductor wafers has been studied. Since dark regions of fringes correspond to the places where the thin films are destroyed or absent, the fringes are investigated to detect uneven surfaces with undesired structures. Therefore, surface microstructures can be detected and characterized effectively by the modification of the fringes.

EFFECT OF TOTAL HYDROGEN CONTENT IN SILICON-NITRIDE SENSITIVE FILM ON PERFORMANCE OF ISFET

Quantitative determinations of the hydrogen content and its profile in silicon nitride sensitive films by the method of resonant nuclear reaction have been carried out. At a deposition temperature of 825-degrees-C, hydrogen exists in an LPCVD silicon nitride sensitive film and the hydrogen content on its surface is in the range (8-16) x 10(21) cm-3, depending on the different deposition processes used. This hydrogen content is larger than the (2-3) x 10(21) cm-3 in its interior part, which is homogeneous. Meanwhile, we observe separate peaks for the chemical bonding configurations of Si-H and N-H bonds, indicated by the infrared absorption bands Si-O (1106 cm-1), N-H (1200 cm-1), Si-H-3 (2258 cm-1) and N-H-2 (3349 cm-1), respectively. The worse linear range of the ISFET is caused by the presence of oxygen on the surface of the silicon nitride sensitive film. The existence of chemical bonding configurations of Si-H, N-H and N-Si on its surfaces is favourable for its pH response.

ELECTRONIC SPECTROSCOPY STUDIES OF A P2S5NH4OH TREATED GAS(100) SURFACE

Microscopic characteristics of the GaAs(100) surface treated with P2S5/NH4OH solution has been investigated by using Auger-electron spectroscopy (AES) and x-ray photoemission spectroscopy (XPS). AES reveals that only phosphorus and sulfur, but not oxygen, are contained in the interface between passivation film and GaAs substrate. Using XPS it is found that both Ga2O3 and As2O3 are removed from the GaAs surface by the P2S5/NH4OH treatment; instead, gallium sulfide and arsenic sulfide are formed. The passivation film results in a reduction of the density of states of the surface electrons and an improvement of the electronic and optical properties of the GaAs surface.

EFFECT OF A SI LAYER ON THE SUPERCONDUCTIVE PROPERTIES OF A BIPBSRCACUO THIN-FILM

The Pb-doped BiSrCaCuO superconducting films were grown by the single source mixed evaporation technique. The microbridges of dimensions 50 mum x 40 mum were fabricated by standard photolithography technologies. Si films with a thickness of 2500 angstrom were deposited on the microbridge area surfaces of BiPbSrCaCuO superconducting films by rf-magnetron sputtering. A greatly lowered zero resistance temperature of the microbridge area of the BiPbSrCaCuO film after Si sputtering was found. A non-linear effect of the current-voltage (I-V) characteristics at 78 K was shown. The high-frequency capacitance-voltage (C-V) curve of this structure at 78 K was symmetrical with the maximum capacitance at V = 0, and the capacitance decreased with increasing applied bias voltage. Afl experimental results are discussed.

THIN-FILM BIPBSRCACUO DIRECT-CURRENT SUPERCONDUCTING QUANTUM INTERFERING DEVICES OPERATING AT 78-K

Direct current SQUIDs (superconducting quantum interference devices) have been successfully fabricated by using a Pb-doped BiSrCaCuO superconducting thin film made by mixed evaporation of a single source composed of related components with a resistance heater. The dc SQUID comprises a square washer with a small hole. These SQUIDs show perfectly periodic voltage-flux characteristics without magnetic shield, that is, typically, the flux noise and energy resolution at a frequency range from dc to 1 Hz and at 78 K being 1.7 x 10(-3) PHI-0/ square-root Hz and 3.6 x 10(-26) J/Hz, respectively. Meanwhile, we have found out that one of the SQUIDs still was able to operate on flux-locked mode without bias currents and showed voltage-flux second harmonic characteristics. This phenomenon is not well understood, but it may be related to I-V (current-voltage) characteristics of the dc SQUID.