Ce~(3+)在稀土取代的卤磷酸盐中的发光与能量传递的研究

本工作用固相反方法、以炭保护或在N_2-H_2还原气氛中，两次灼烧，合成了一系列烯土取代的卤磷酸盐发光体，其反应是M_2~ICO_3 + M_3~(II)(PO_4)_2 + M_2~(III)O_3 + (NH_4)_2HPO_4 + M~(II)F_2 → M_x~IM_(10-2x)~(II)M_x~(III)(PO_4)_6F_2 + NH_3 + H_2O式中：M~I = Li~+, Na~+, K~+; M~(II) = Ca~(2+), Sr~(2+); M~(III) = Y~(3+), La~(3+), Gd~(3+); X = 0.5, 1, 2, 3。通过X－射线分析法和以Eu~(3+)作为荧光离子探针方法确定了样品的物相和晶体结构，表明它与M_(10)~(II)(PO_4)_6F_2同属六方晶系(Pb_3/m)。并用图解外推法求得样品的晶胞参数a和c分别为9.41和6.89 A。在研究了M~I, M~(II)和M~(III)为不同阳离子，X为不同值时，取代物的物相和结构变化以及对Ce~(3+)发光和能量传递影响规律的基础上，以Na_2Ca_6La_2(PO_4)_6F_2为基本体系比较详细地研究了Ce~(3+)的发光，Ce~(3+)-Mn~(2+), Ce~(3+)-Re~(3+) (Re~(3+) = Pr~(3+)、Nd~(3+)、Sm~(3+)、Tb~(3+)、Dy~(3+)、Tm~(3+)、Ho~(3+)、Er~(3+))以及Ce~(3+)-Mn~(2+)-Re~(3+) (Re~(3+) = Dy~(3+), Nd~(3+))的能量传递。实验发现，Na_2Ca_6La_2(PO_4)_6F_2:Ce~(3+)是较强的紫外光发射体，发射谱带是由338和358nm两个宽带峰组成的，相应于~2D-~2F_(5/2)和~2D-~2F_(1/2)跃迁。发射强度和~2D-~2F_(6/2)，~2D-~2F_(7/2)两种辐射跃迁几率相对大小与温度，Ce~(3+)的浓度有关；F~-含量对发射强度也有强烈的影响。我们认为，浓度和温度的影响是由于Ce~(3+)-Ce~(3+)的能量迁移作用。实验发现，Ce~(3+)能有效地敏化Mn~(2+)的发光，得到高效的黄色荧光发射体。Ce~(3+)对Re~(3+)的作用可以分为三类：A）. Ce~(3+)-Sm~(3+)、Tb~(3+)、Dy~(3+)、Tm~(3+)；B）．Ce~(3+)-Nd~(3+)，Pr~(3+)；C）. Ce~(3+)-Ho~(3+), Er~(3+)。在A，B类型中，Ce~(3+)能有效地敏化这些稀土离子，但能量传递效率(η_T)_A > (η_T)_B。在Ce~(3+)-Ho~(3+)、Ce~(3+)-Er~(3+)类型中，Ho~(3+)、Er~(3+)不产生可见辐射，Ce~(3+)的发射强度也显著降低。在Ce~(3+)-Mn~(2+)-Re~(3+)三元中心体系中，Ce~(3+)的能量可直接传递给Mn~(2+)和Re~(3+)中心，还可通过Ce~(3+)-Mn~(2+)-Re~(3+)的途径传递。通过研究中心离子的浓度效应，温度效应、测定激发光谱、荧光光谱、荧光衰减曲线的荧光寿命，能够证实：在Ce~(3+)-Mn~(2+)、Ce~(3+)-Re~(3+)、Ce~(3+)-Mn~(2+)-Re~(3+)的能量传递属于无辐射共振传递相互作用类型。符合M. Yokata等人提出的偶极－偶极相互作用扩散限制传递历程。我们还利用Ce~(3+)、Ce~(3+)-Mn~(2+)、Ce~(3+)-Re、Ce~(3+)-Mn~(2+))-Re~(3+)激活体系中Ce~(3+)的发射强度和荧光寿命等数据计算了Ce~(3+)的能量传递效率。发现两种结果相差较大，为了准确地表达Ce~(3+)的敏化效果，在分析上了产生这种误差的原因后，提出了两种传递效率表示式(η_f, η_R)。

熔盐电解法制备Al-Li合金的应用基础研究及其工艺初探

Al-Li合金是近年发展起来的新型航空材料，具有低密度、高强度的特点。目前世界上正就如何进一步提高其断裂韧性，使Al-Li合金尽早走出实验室，获得实际用进行广泛，深入的研究。熔盐电解法就是在这种情况下发展起来的。虽然此法现在尚处于研究的初级阶段，但已以其能够在较简单的设备上制备低Na高纯Al-Li合金的特点受到广泛的重视，是一种很有前途的发展方向。针对我国的技术、设备现状，在参考国外研究结果的基础上，采用熔盐电解法制备Al-Li母合金 → 应用合金的制备方法是可以尽快赶上世界发步伐的有效途径。因此，本文作为整个熔盐电解制备Al-Li合金系统研究的一部分，针对目前在此领域中很多应用基础问题，诸如：作为新的电解体系正在探索中的LiCl-KCl-LiF三元相图，Li在液体Al阴极中的扩散系数，利用熔盐电解法制备低Na高纯Al-Li合金的热力学基础及如何克服LiCl强烈的吸水性给电解工艺带来的种种不便等均未得到系统研究的现状，设计完成了一系列有关熔盐电化学和热力学实验，填补了本领域的一些研究空白，并为进一步系统研究工艺条件提供了重要的参考数据。1．用NH_4Cl氯化Li_2CO_3的研究 根据热力学从理论上论证了在200 ℃左右下述氯化反应：Li_2CO_3 + 2NN_4Cl = 2LiCl + 2NH_3~↑ + H_2O~↑ + CO_2~↑可以进行完全。利用DSC方法测定反应产物LiCl的纯度，并用离子色谱法分析反应产物中CO_3~=的含量，结果均证明：在Li_2CO_3:NH_4Cl = 1:4 (mol)时，Li_2CO_3可以定量转化为LiCl，剩余的NH_4Cl完全分解。根据热重分析结果推测NH_4Cl氯化Li_2CO_3的反应历程为：Li_2CO_3 + 2NH_4Cl = 2LiCl + 2NH_3~↑ + H_2O~↑ + CO_2~↑ NH_4Cl = HCl~↑ + NH_3~↑ 而并非是想像中的：NH_4Cl = HCl~↑ + NH_3~↑ 2HCl + Li_2CO_3 = 2LiCl + H2O~↑ + CO_2~↑利用X－射线衍射方法分析产物，结果亦说明氯化可以成功。将1:4（mol）= Li_2CO_3:NH_4Cl混合样品在差热分析反应炉中直接加热测定反应产物LiCl的溶点，并与纯LiCl样品熔点的测定结果相比较，二者完全一致。以上结果说明：不仅可用此氯化反应产物代替LiCl应用于熔盐电解制备Al-Li合金中，而且还可将其应用于LiCl体系的相图测定中。因Li_2CO_3，NH_4Cl均不吸水，极易处理，因此以上研究结果无论对于Al-Li合金的工艺研究还是其他有关LiCl体系的基础研究都是很有价值的。2．直接氯化法制备LiCl-KCl-LiF三元相图的研究。LiCl-KCl-LiF三元相图是研究此体系电解机制的重要基础。为将以上直接氯化法应用于差热分析中制作此三元体系相图，首先用直接氯化法测定了三个已知二元LiCl体系相图：LiCl－KCl；LiCl-LiF；LiCl-NaCl。与文献结果吻合很好。说明将此法应用于差热分析中制作LiCl体系相图结果是可靠的。在LiCl-KCl-LiF三元相图的测定中共做出七个垂直截面，在各截面上读出等温条件下的相界点投影到浓度三角形中，得到等温投影图。结果说明LiCl-KCl-LiF是固态完全不互溶的三元共晶体系，共有三个液－固两相区；三个液－固－固三相区；一个液－固－固－固四相区，（三元共晶平面）和一个固－固－固三相区。四相点温度为348 ℃，其组成在三相平衡线的交点处，在实验上测出近似等于：41.4KCl + 57.3LiCl + 1.3LiF (mol)。3．氯化物体系中Li~+, Na~+析出电位的比较及其去极化作用的研究。在正常电化序中，Li~+应先于Na~+析出。但在以Al作阴极电解LiCl体系时，则由于Li~+在Al上有较强的去极化作用而提前析出。这是熔盐电解法可以制备低Na，高纯Al-Li合金的基础。本文在理论上对此问题进行了较深入的研究。具体内容包括（1）。测定Li~+, Na~+在二元氯化物体系中的析出电位。通过在Al阴极，Mo阴极上二离子析出电位的比较，确认了Li~+在Al阴极上产生很强的去极化作用是能利用电解法制备低Na高纯Al-Li合金的根本原因。并为在工艺研究中选择合适的电流密度提供了参考依据。（2）．根据热力学理论推导出合金化反应产生的自由焓变化与去极化作用的关系：ΔG_x + ΔG_m = -nFΔE。揭示了产生去极化作用的原因。并根据ΔG_x（偏摩尔过剩自由焓）与合金结构的关系提出可以利用二元合金相图推测极化类型及极化大小。并根据动力学原理对温度对极化的影响提出了自己的看法。（3）．求出合金化反应的热效应，认为在一定条件下亦可利用此值作为判断去极化作用大小的标准。（4）．测定Li~+, Na~+在Al-Cu, -Al-RE合金上的析出电位。结果表明Cu，RE的存在均可加强Li~+在阴极上的去极化作用，进一步加大了Li~+, Na~+析出电位之间的差别，有利于制备更纯的Al-Li 使金。为直接生产Al-Cu-Li, Al-RE-Li三元母合金奠定了基础。（5）测定Li~+在不同组成配比的LiCl-KCl熔体中，在Al阴极上的析出电位，并求出LiCl的离子平均活度系数γ＝0.71 (T = 740 ℃), 熔体对理想状态产生负偏离。4．利用阳极计时电位法测定T＝720 ℃时Li在液体Al中的扩散系数D_(Li/Al) = 4.94 * 10~(-5)cm~2·s~(-1)，与利用Stocks-Einstan公式计算出的理论值D_(Li/Al) = 4.85 * 10~(-5)cm~2·s~(-1)吻合较好。5．在上述理论研究的基础之上进行了工艺初探，所得初步结论有：（1）．加入LiF可以提高电效。（2）．采用电流密度为1 A/cm~2时，不加搅拌亦可制备出成份均匀，含Li量为10％（w.f）的Al-Li合金。（3）．根据实验结果提出 Li在熔体中的熔解可能是影响电流效果的主要原因。

锂蓄电池锂合金负极的研究

锂电池是一种比能量高、工作温度范围宽的性能优良的非水电池体系。但是以纯锂作锂二次电池的负极主要存在锂枝晶以及表面惰化问题， 近年来文献上报道了不少锂合金负极材料，以期改善电极性能，但是仍不能满足实际使用的要求。在工作研制了一种新型锂铝稀土合金负极材料。首先用熔盐电解法制备铝稀合金，随后电沉积锂形成锂-铝-稀土，电解质为1M高氯酸锂/碳酸丙烯酯溶液。实际上充有氩气、且恒温在25 ± 1 ℃的手套箱中进行。在0-950 mV和-500-700 mV两个电位范围内比较了纯度为99.9%Al和99%Al形成锂铝稀土合金电极的循环伏安曲线。在9-950 mV的电位范围内99.9%Al形成的锂铝-1%稀土合金电极（这里锂是欠电位沉积）比不加稀土的阳极峰电流提高约一倍，阳极峰面积增加50～60%。峰电位负移50 mV左右。在99%Al中添加稀土元素的影响比99.9%Al的要小一些，阳极峰电流只提高30%，峰电位负移15 mV，容量略有增加。在-500-700 mV范围的循环伏安曲线，锂的沉积属于非欠电位沉积。相当的锂沉积在电极表面。但其影响趋势与0-950 mV电位范围测取的循环伏安曲线基本一致。研究了一系列稀土添加量的影响，结果表明铝合金中的稀土含量在0.4～2%时，影响最明显，稀土含量为0.1%与5%时，循环伏安曲线与不含稀土的铝锂金相近。测取和锂铝和锂-铝-稀土合金电极的充放电曲线，添加稀土元素的影响趋势与循环伏安图的基本一致。在99.9%Al中添加1%稀土效果最好，充放电效率比不加稀土的提高30%。添加0.1%稀土的电极的充放电效率几乎不起作用。在99%Al中添加稀土元素对充放电效率的影响程度比99.9%Al的要低一些。测取了不同扫描速度下的锂-铝、锂-铝-稀土合金电极的循环伏安图。发现了一些有趣的现象，在0-950 mV的电位范围内，在大于5mV/Sec时，峰电流随扫描速度的增大而增大。而在1mV/Sec-5mV/Se时，峰电流基本不变，在电位为-500-700 mV电位范围，扫描速度为1mV/Sec-10mV/Sec的范围，在第三、四周随扫描速度的增加阳极峰电流反而降低。这可能是因为随着扫描速度增加，阳极极化电流增大，新沉积的锂来不及向铝中扩散，而与溶液（PC）及其中杂质反应生成惰化膜，以致影响了它的阳极溶解过程。研究了三种不同纯度的铝（99%、99.9%、99.999%）对循环伏安曲线的影响，并用发射光谱分析了铝中杂质大致含量，由于杂质组成比较复杂，加之三种纯度铝的循环伏安图差别不大，因此难以判断不同杂质的利和弊。99.9%Al和99.9%Al+1%Re的锂合金负极与正极聚苯胺组成模拟电池，并且进行了充放电实验，容量可达5.4-6.1C/cm~2。比较了99.9%Al和99.9%Al+0.4%Re、99.9%Al+1%Re的锂合金电极在电解质溶液中放置不同时间的交流阻抗复数平面图。随着放置时间的延长，半园直径增大，表明电极表面膜随放置时间不断生长，在铝合金中添加0.4%Re或1%Re，都使表面膜生长速度减慢，但是起始反应电阻比不加稀土元素的大。电极首先阳极充电10C/cm~2，随后分别在阴极极化，阳极极化条件下，测定的交流阻抗谱表明，添加稀土元素使锂-铝电极的反应电阻降低，电容增大。未经阻极预先充电的电极，在阴极低电流密度下，阻抗谱图由两个半园组成，随着阴极电流密度增大，半园逐渐缩小，并且低频区的小半园逐渐变小以致消失。X-射线的分析结果表明用电化学方法在电极上沉积锂，其表层形成Li-Al和Li_3Al_2，在电极表面存在Li_2CO_3和LiCl。在99.9%Al添加1%稀土元素，使电极表面的Li_2CO_3量增多。用X-射线光电子能谱分析表明，电极表面有锂、铝、氧、碳和氯元素，与X-射线的分析结果一致，锂-铝-稀土合金电极表面的碳酸根含量比未加稀土元素的多。用Ar~+刻蚀后，添加稀土后表层锂元素含量比未加稀土的高。用不同方法所得实验结果都表明了锂-铝合金添加稀土元素的有益影响，可能是由于稀土元素的异质成核作用，改变了合金的结构，使得Li的扩散变得容易。根据实验结果，认为电极表面膜由两层组成，靠近电极一侧的为某种中间体；具有惰化膜的性质，靠近溶液一侧的为多孔的碳酸锂膜，按照这一模型讨论了添加稀土元素的影响。

稀土对Al-Li合金凝固组织的影响及作用机理研究

本论文借助光学显微镜、电镜、X-射线、差热等金相分析技术研究了稀土（La、Ce、Pr、Nd、MM、Ymm）在单向、自由凝固条件下对Al-Li合金凝固组织的影响，进而分析了稀土的作用机理。实验结果表明，稀土对自由凝固的晶粒及二次枝晶、单向凝固的一次枝晶均有细化作用，这种作用同稀土元素、稀土含量及凝固条件有关。分析认为，在合金凝固过程中由于稀土的富集产生“成分过冷”等作用是影响凝固组织的因素。

甲烷氧化偶联Ti-La-Li系多元氧化物催化剂的研究

本论文较详细地总结了目前文献中有关甲烷氧化偶联催化剂、活性中心及活性氧种、反应机理及动力学和甲烷氧偶联反应（OCM）的影响因素等方面的重要结果；叙述了催化剂的制备和表征方法；系统地研究了Ti-La-Li系多元氧化物催化剂关于OCM反应有关主要活性相及作用机制、催化剂的表面碱性和活性氧种的作用，探讨了Li的含稀土、过渡金属多元氧化物催化剂中的作用，考察了制备方法、焙烧温度和反应条件对OCM反应的影响，同时对催化剂的高温失活机理进行了探讨。

Harmonic Millimeter Wave Generation and Frequency Up-Conversion Using Optical Injection Locking and Brillouin Selective Sideband Amplification

Harmonic millimeter wave (mm-wave) generation and frequency up-conversion are experimentally demonstrated using optical injection locking and Brillouin selective sideband amplification (BSSA) induced by stimulated Brillouin scattering in a 10-km single-mode fiber. By using this method, we successfully generate third-harmonic mm-wave at 27 GHz (f(LO) - 9 GHz) with single sideband (SSB) modulation and up-convert the 2GHz intermediate frequency signal into the mm-wave band with single mode modulation of the SSB modes. In addition, the mm-wave carrier obtains more than 23 dB power gain due to the BSSA. The transmission experiments show that the generated mm-wave and up-converted signals indicate strong immunity against the chromatic dispersion of the fibers.

PRESSURE-DEPENDENCE OF PHOTOLUMINESCENCE IN IN(X)GA(1-X)AS/AL(Y)GA(1-Y)AS STRAINED QUANTUM-WELLS WITH DIFFERENT WIDTH

A systematic investigation on the photoluminescence (PL) properties of InxGa1-xAs/AlyGa1-xAs (x = 0.15, y = 0, 0.33) strained quantum wells (SQWs) with well widths from 1.7 to 11.0 nm has been performed at 77 K under high pressure up to 40 kbar. The experimental results show that the pressure coefficients of the exciton peaks corresponding to transitions from the first conduction subband to the heavy-hole subband increase from 10.05 meV/kbar of 11.0 nm well to 10.62 meV/kbar of 1.8 nm well for In0.15Ga0.85As/GaAs SQWs. However, the corresponding pressure coefficients slightly decrease from 9.93 meV/kbar of 9.0 nm well to 9.73 meV/kbar of 1.7 nm well for In0.15Ga0.85As/Al0.33Ga0.67As SQWs. Calculations based on the Kronig-Penney model reveal that the increased or decreased barrier heights and the increased effective masses with pressure are the main reasons of the change in the pressure coefficients.

X-RAY-SCATTERING FROM A ROUGH-SURFACE AND DAMAGED LAYER OF POLISHED WAFERS

Theoretical and experimental investigations were performed to show the application of x-ray crystal truncation rod scattering combined with x-ray reflectivity in the measurements of surface roughness and near-surface damage of mechanochemically polished wafers. By fitting the measured crystal truncation rod curves it has been shown that polished wafers are divided into three parts -irregular steps on the surface, a damaged thin layer beneath the surface and a perfect bulk. The results show that the root mean square of the surface roughness of mechanochemically polished Fe-doped and/or S-doped InP wafers is one to two atom layers, and that the lateral correlation length of the surface roughness is about 3000-7500 Angstrom. The thickness of the damaged region is found to be about 1000 atom layers.

BAND-STRUCTURE OF MG1-XZNXSYSE1-Y

The empirical pseudopotential method within the virtual crystal approximation is used to calculate the band structure of Mg1-xZnySySe1-y, which has recently been proved to be a potential semiconductor material for optoelectronic device applications in the blue spectral region. It is shown that MgZnSSe can be a direct or an indirect semiconductor depending on the alloy composition. Electron and hole effective masses are calculated for different compositions. Polynomial approximations are obtained for both the energy gap and the effective mass as functions of alloy composition at the GAMMA valley. This information will be useful for the future design of blue wavelength optoelectronic devices as well as for assessment of their properties.

RADIATIVE RECOMBINATION IN N-TYPE AND P-TYPE GAAS COMPENSATED WITH LI

We report fundamental changes of the radiative recombination in a wide range of n-type and p-type GaAs after diffusion with the group-I element Li. These optical properties are found to be a bulk property and closely related to the electrical conductivity of the samples. In the Li-doped samples the radiative recombination is characterized by emissions with excitation-dependent peak positions which shift to lower energies with increasing degree of compensation and concentration of Li. These properties are shown to be in qualitative agreement with fluctuations of the electrostatic potential in strongly compensated systems. For Li-diffusion temperatures above 700-800-degrees-C semi-insulating conditions with electrical resistivity exceeding 10(7) OMEGA cm are obtained for all conducting starting materials. In this heavy Li-doping regime, the simple model of fluctuating potentials is shown to be inadequate for explaining the. experimental observations unless the number of charged impurities is reduced through complexing with Li. For samples doped with low concentrations of Li, on the other hand, the photoluminescence properties are found to be characteristic of impurity-related emissions.

ELECTRONIC-STRUCTURES OF THE ALKALI-CONTAINING BUCKMINSTERFULLERENES (A-DELTA-C60) (A=LI,NA,K,RB,CS) AND THE HALOGEN-CONTAINING BUCKMINSTERFULLERENES (H-DELTA-C60) (H=F,CL,BR,I)

The geometrical parameters and electronic structures of C60, (A partial derivative C60) (A = Li, Na, K, Rb, Cs) and (H partial derivative C60) (H = F, Cl, Br, I) have been calculated by the EHMO/ASED (atom superposition and electron delocalization) method. When putting a central atom into the C60 cage, the frontier and subfrontier orbitals of (A partial derivative C60) (A = Li, Na, K, Rb, Cs) and (H partial derivative C60) (H = F, Cl) relative to those of C60 undergo little change and thus, from the viewpoint of charge transfer, A (A = Li, Na, K, Rb, Cs) and H (H = F, Cl) are simply electron donors and acceptors for the C60 cage resPeCtively. Br is an electron acceptor but it does influence the frontier and subfrontier MOs for the C60 cage, and although there is no charge transfer between I and the C60 cage, the frontier and subfrontier MOs for the C60 cage are obviously influenced by I. The stabilities DELTAE(X) (DELTAE(X) = (E(X) + E(C60)) - E(x partial derivative C60)) follow the sequence I < Br < None < Cl < F < Li < Na < K < Rb < Cs while the cage radii r follow the inverse sequence. The stability order and the cage radii order have been explained by means of the (exp-6-1) potential.

SHIFTING PHOTOLUMINESCENCE BANDS IN HIGH-RESISTIVITY LI-COMPENSATED GAAS

It is shown that Li diffusion of GaAs can give rise to semi-insulating samples with electrical resistivity as high as 10(7) OMEGAcm in undoped, n-type, and p-type starting materials. The optical properties of the compensated samples are correlated with the depletion of free carriers caused by the Li diffusion. The radiative recombination of the Li-compensated samples is dominated by emissions with excitation-dependent peak positions that shift to lower energies with increasing compensation. The photoluminescence properties are characteristic of fluctuations of the electrostatic potential in strongly doped, compensated crystals.

A NEW TYPE OF SILICON-ON-INSULATOR WITH A PERFECT SURFACE SILICON LAYER

A novel silicon structure consisting of a silicon-on-defect layer (SODL), with enhanced surface Hall mobility in the surface layer on a buried defect layer (DL), has been discovered [J. Li, Nucl. Instr. and Meth. B59/60 (1991) 1053]. SODL material was formed by using proton implantation and subsequent two-step annealing. The implantation was carried out with a Varian 350D ion implanter. Based on the discovery, a standard measurement method (current-voltage curve method) was adopted to measure the true resistivity value of the DL in order to replace the spreading resistivity measurement by which the true resistivity in seriously defective silicon cannot be obtained. By adopting the current-voltage current method, the true resistivity value of the DL is measured to be 4.2 x 10(9) OMEGA cm. The SODL material was proved to be a silicon-on-insulator substrate.

A COMPARATIVELY LOW-QUALITY SILICON MATERIAL IMPROVED FOR SOLAR-CELL FABRICATION

A comparatively low-quality silicon wafer (with a purity of almost-equal-to 99.9%) was adopted to form a silicon-on-defect-layer (SODL) structure featuring improved crystalline silicon near the defect layer (DL) by means of proton implantation and subsequent annealing. Thus, the SODL technique provides an opportunity to enable low-quality silicon wafers to be used for fabrication of low-cost solar cells.