Metamorphic growth of 1.25-1.29 mu m InGaAs quantum well lasers on GaAs by molecular beam epitaxy

We demonstrate 1.25-1.29 mu m metamorphic laser diodes grown on GaAs by molecular beam epitaxy (MBE) using an alloy-graded buffer layer (GBL). Use of Be in the GBL is effective to reduce surface/interface roughness and improves optical quality. The RMS surface roughness of the optimized metamorphic laser is only two atomic monolayers for 1 x 1 mu m(2). Cross-sectional transmission electron microscopy (TEM) images confirm that most dislocations are blocked in the GBL. Ridge waveguide lasers with 4 mu m wide ridge were fabricated and characterized. The average threshold current under the pulsed excitation is in 170-200 mA for a cavity length of 0.9-1.5 mm. This value can be further reduced to about 100 mA by high-reflectivity coating. Lasers can work in an ambient temperature up to at least 50 degrees C. (c) 2006 Elsevier B.V. All rights reserved.

Pressure dependence of the near-band-edge photoluminescence from ZnO microrods at low temperature

The temperature and pressure dependences of band-edge photo luminescence from ZnO microrods have been investigated. The energy separation between the free exciton (FX) and its first order phonon replica (FX-1LO) decreases at a rate of k(B)T with increasing temperature. The intensity ratio of the FX-1LO to the bound exciton (BX) emission is found to decrease slightly with increasing pressure. All of the exciton emission peaks show a blue shift with increasing pressure. The pressure coefficient of the FX transition, longitudinal optical (LO) phonon energy, and binding energy of BX are estimated to be 21.4, 0.5, and 0.9 meV/GPa, respectively. (c) 2006 Elsevier Ltd. All rights reserved.

Optical characteristics of DBR with inhomogeneous graded interfaces

Optical properties of Al0.9Ga0.1As/Al gamma Ga1-gamma As/GaAs/Al chi Ga1-chi As DBR with inhomogeneous graded interfaces has been investigated by using characteristic matrix method. The refractive index model and the analytic characteristic matrix of graded interfaces are obtained. The reflectance spectrum and the reflective phase shift are calculated for GaAs/Al-0.9 Ga-0.1 As DBR and graded interfaces DBR by using characteristic matrix method. The effect of graded interfaces on the optical properties of DBR is discussed. The result shows an extra graded phase matching layer must he added in front of the graded interfaces DBR to fulfil the conditions of phase matching at central wavelength. The accurate thickness of phase matching layer is calculated by optical thickness approximation method.

High-power AlGaInP laser diodes with current-injection-free region near the laser facet

A high-power AlGaInP laser diode with current-injection-free region near the facet is successfully fabricated by metaorganic chemical vapor deposition (MOCVD) using the (100) direction n-GaAs substrates with a misorientation of 15 deg toward the (011) direction. The maximum continuous wave output power is about 90 mW for the traditional structure. In comparison, the maximum output power is enhanced by about 67%, and achieves 150 mW for LDs with current-infection-free regions. The fundamental transverse-mode operation is obtained up to 70 mW. Output characteristics at high temperatures are also improved greatly for an LD with a current-injection-free region, and the highest operation temperature is 70 C at 50 mW without kink. The threshold current is about 33 mA, the operation current and the slope efficiency at 100 mW are 120 mA and 0.9 mW/mA, respectively. The lasing wavelength is 658.4 nm at room-temperature 50 mW. (c) 2006 Society of Photo-Optical Instrumentation Engineers.

Semiconductor optical amplifier optical gate with graded strained bulk-like active structure

A novel semiconductor optical amplifier (SOA) optical gate with a graded strained bulk-like active structure is proposed. A fiber-to-fiber gain of 10 dB when the coupling loss reaches 7 dB/factet and a polarization insensitivity of less than 0.9 dB for multiwavelength and different power input signals over the whole operation current are obtained. Moreover, for our SOA optical gate, a no-loss current of 50 to 70 mA and an extinction ratio of more than 50 dB are realized when the injection current is more than no-loss current, and the maximum extinction ratio reaches 71 dB, which is critical for crosstalk suppression. (C) 2003 society of Photo-Optical Instrumentation Engineers.

A novel ultra low power temperature sensor for UHF RFID tag chip

A novel ultra low power temperature sensor for UHF RFID tag chip is presented. The sensor consists of a constant pulse generator, a temperature related oscillator, a counter and a bias. Conversion of temperature to digital output is fulfilled by counting the number of the clocks of the temperature related oscillator in a constant pulse period. The sensor uses time domain comparing, where high power consumption bandgap voltage references and traditional ADCs are not needed. The sensor is realized in a standard 0.18 mu m CMOS process, and the area is only 0.2mm(2). The accuracy of the temperature sensor is +/- 1 degrees C after calibration. The power consumption of the sensor is only 0.9 mu W.

Tunneling magnetoresistance in (Ga,Mn)As/Al-O/CoFeB hybrid structures

Tunneling magnetoresistance (TMR) in Ga(0.9)2Mn(0.08)As/Al-O/Co40Fe40B20 trilayer hybrid structure as a function of temperature from 10 to 50 K with magnetic field vertical bar H vertical bar <= 2000 Oe has been studied. TMR ratio of 1.6% at low fields at 10 K was achieved with the applied current of 1 mu A. The behavior of junction resistance was well explained by the tunneling resistance across the barrier. Strong bias dependences of magnetoresistance and junction resistance were presented. (C) 2009 American Institute of Physics. [DOI: 10.1063/1.3068418]

Enhanced photocatalytic activity of TiO2 nano-structured thin film with a silver hierarchical configuration

TiO2 sol-gels with various Ag/TiO2 molar ratios from 0 to 0.9% were used to fabricate silver-modified nano-structured TiO2 thin films using a layer-by-layer dip-coating (LLDC) technique. This technique allows obtaining TiO2 nano-structured thin films with a silver hierarchical configuration. The coating of pure TiO2 sol-gel and Ag-modified sol-gel was marked as T and A, respectively. According to the coating order and the nature of the TiO2 sol-gel, four types of the TiO2 thin films were constructed, and marked as AT (bottom layer was Ag modified, surface layer was pure TiO,), TA (bottom layer was pure TiO,, surface layer was Ag modified), TT (pure TiO, thin film) and AA (TiO, thin film was uniformly Ag modified). These thin films were characterized by means of linear sweep voltammetry (LSV), X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy and transient photocurrent (I-ph). LSV confirmed the existence of Ago state in the TiO, thin film. SEM and XRD experiments indicated that the sizes of the TiO,, nanoparticles of the resulting films were in the order of TT > AT > TA > AA, suggesting the gradient Ag distribution in the films. The SEM and XRD results also confirmed that Ag had an inhibition effect on the size growth of anatase nanoparticles. Photocatalytic activities of the resulting thin films were also evaluated in the photocatalytic degradation process of methyl orange. The preliminary results demonstrated the sequence of the photocatalytic activity of the resulting films was AT > TA > AA > TT. This suggested that the silver hierarchical configuration can be used to improve the photocatalytic activity of TiO2 thin film.

Thermal performance of a micro-combustor for micro-gas turbine system

Premixed combustion of hydrogen gas and air was performed in a stainless steel based micro-annular combustor for a micro-gas turbine system. Micro-scale combustion has proved to be stable in the micro-combustor with a gap of 2 mm. The operating range of the micro-combustor was measured, and the maximum excess air ratio is up to 4.5. The distribution of the outer wall temperature and the temperature of exhaust gas of the micro-conbustor with excess air ratio were obtained, and the wall temperature of the micro-combustor reaches its maximum value at the excess air ratio of 0.9 instead of 1 (stoichiometric ratio). The heat loss of the micro-combustor to the environment was calculated and even exceeds 70% of the total thermal power computed from the consumed hydrogen mass flow rate. Moreover, radiant hunt transfer covers a large fraction of the total heat loss. Measures used to reduce the heat loss were proposed to improve the thermal performance of the micro-combustor. The optimal operating status of the micro-combustor and micro-gas turbine is analyzed and proposed by analyzing the relationship of the temperature of the exhaust gas of the micro-combustor with thermal power and excess air ratio. The investigation of the thermal performance of the micro-combustor is helpful to design an improved microcombustor.

Multi-wavelength erbium-doped fibre lasers on assistance of high-nonlinear photonic-crystal fibres

On the basis of self-stability effect of four-wave mixings (FWMs) in high-nonlinear photonic-crystal fibres, a novel multi-wavelength erbium-doped fibre (EDF) laser is proposed and demonstrated experimentally at room temperature. The proposed lasers have the capacity of switching and tuning with excellent uniformity and stability. By means of adjusting the attenuators, the triple-, four-, or five-wavelength EDF lasers can be lasing simultaneously. With the assistance of the FWM self-stability function, the multi-wavelength spectrum is excellently stabilized with uniformity less than 0.9 dB.

超声化学法合成稀土纳米材料

稀土纳米材料因其独特的光、电、磁和催化等性能，在纳米器件和功能材料等诸多领域具有重要的应用价值。大量研究表明，纳米材料的物理和化学性质与其尺寸、成分、形貌和晶型密切相关。稀土纳米材料的合成方法有许多，然而，要真正实现这类材料的简单可控合成仍然是个艰难的课题。超声化学法由于具有操作简单、合成周期短、反应温度低、成本低廉并且产物均匀、粒径分布窄和纯度高等突出优点，已经在无机纳米材料制备领域中显示出独特的魅力。因此，本论文的工作是运用超声化学法合成有广泛应用前景的稀土纳米材料，对产物的形貌和粒径进行有效的调控，研究和分析其形成机理，并进一步考察其形貌、结构与性能之间的相互关系。 在本论文中，我们研究的体系集中在稀土磷酸盐、稀土氟化物和稀土钒酸盐三类纳米材料。 采用超声化学法得到的CePO4:Tb和CePO4:Tb/LaPO4(核/壳)纳米棒结晶完好，具有CePO4体材料的六方相结构。CePO4:Tb纳米棒直径为10-30 nm，长度为200 nm，CePO4:Tb/LaPO4(核/壳)纳米棒的LaPO4壳的厚度为2-10 nm。CePO4:Tb和CePO4:Tb/LaPO4(核/壳)纳米棒均具有Ce3+ (5d - 4f)和Tb3+ 5D4-7FJ(J = 6-3)的特征发射。与CePO4:Tb纳米棒核相比，CePO4:Tb/LaPO4(核/壳)纳米棒的光谱强度及荧光寿命均有较大的提高，这是由于形成核/壳结构后发光中心镧系金属离子与表面淬灭中心的距离增大，减少了能量传递过程中非辐射复合的路径，使能量淬灭受到抑制。 采用简单、快速、无模板辅助的超声化学法合成了稀土氟化物，并对产物的形貌和粒径进行了有效的调控。通过应用不同氟源(KBF4、NaF和NH4F)选择性合成了具有不同形貌的CeF3纳米材料，如片状、棒状和颗粒状。对具有不同形貌的CeF3样品进行了UV-Vis吸收光谱和荧光光谱测试和比较。研究结果表明不同形貌的样品，它们的光学性质存在很大差异，这说明纳米材料的光学性质与其形貌、粒径、晶体结构等因素有密切的关系。得到的EuF3单晶纳米材料具有三维花状形貌。这些纳米花的外形为球状，平均直径为0.9 μm-1.0 μm，每个花瓣的厚度约为0.14 μm。在其他实验条件不变的情况下，采用搅拌法而不经过超声辐射的对比实验只能得到二维纳米片，这表明超声辐射对花状EuF3的形成起到了至关重要的作用。基于不同反应时间的实验结果，我们提出了这种三维花状EuF3纳米材料可能的形成机理。 采用超声化学法选择性地合成了介孔及棒状CeVO4和纺锤状的YVO4:Eu3+ 纳米材料。CeVO4纳米棒的平均直径为5 nm，长度为150 nm。介孔CeVO4材料的比表面积较高(122 m2•g-1)，孔径分布窄，其催化性能有望得到提高。纺锤状的YVO4:Eu3+ 纳米粒子具有四方相锆石结构，其直径为90-150 nm，长度为250-300 nm。超声辐射对样品的形貌起着关键作用，在其他反应条件不变，未采用超声辐射的情况下只能得到团聚严重的纳米颗粒。荧光测试表明，纺锤状YVO4:Eu样品表现为Eu3+ 5D0-7FJ(J = 1- 4)的特征跃迁，以5D0-7F2电偶极跃迁(614nm)为最强峰，属于红光发射。

安培酶电极的新固定化方法和用途扩展研究

1．用溶胶-凝胶方法制备了一种新型的有机-无机杂交材料，并用这种材料制备了过氧化物酶安培酶电极。用富里叶变换红外光谱和石英晶体微天平对这种有机-无机杂交材料和用这种材料制备的酶膜进行了表征。以亚铁氰化钾为媒介体考察了传感器的电化学行为。用计时安培方法优化了pH和工作电位。传感器的响应时间为10s，线性范围的上限达3.4 mM，检测限为5 * 10~(-7)M。传感器具有高的灵敏度和好的长期稳定性。另外，还把传感器用于流动注射分析和实际样品分析来评估传感器的性能。2．利用有机修饰的溶胶-凝胶材料的优点，制备含磺酸基的功能化的溶胶，用无机-有机杂交手段制备功能化的薄膜(FIOHM)，进而制备了媒介体型过氧化氢安培生物传感器。麦尔多拉兰(MDB)通过离子交换作用被固定在膜中，MDB在FIOHM膜中的循环伏安行为比溶液中的MDB的循环伏安行为更为可逆，因而适合于作媒介体。由于磺酸基的供电子能力，MDB分子的电子密度增加，因而就变得易于氧化而难于还原，表现为阴极峰和阳极峰峰电位的负移。这是第一次用溶胶-凝胶方法制备的磺化无机-有机复合材料制备媒介体型过氧化氢传感器。响应时间小于25 s。线性范围上限达0.6mM。高的灵敏度75 nA·μM·cm~(-2)是由于高的MDB载量。检测限为0.9 μM。传感器具有灵敏的响应和满意的稳定性。3．实验证明自身成胶的接枝共聚物PVA-g-PVP是酪氨酸酶的好的固定化材料。三维氢键网络把酶包埋在聚合物膜中。这种固定化方法简单温和。4-乙烯基吡啶组分增强了膜在电极表面的附着力，所以传感器在流动体系中稳定且重现性好。酶膜组成可以调节以得到好的灵敏度或宽的线性范围以满足不同的分析要求。传感器表现出很好的重现性，稳定性和灵敏的响应。传感器在亲水有机溶剂中的线性范围加宽。制备了安培型酚传感器。固定化材料是引入了接枝共聚物PVA-g-PVP的溶胶-凝胶复合膜。酪氨酸酶有效地固定在复合膜中。对这一无机-有机复合杂交材料进行了优化。酪氨酸酶在溶胶-凝胶膜中保持了其活性，在0V(Ag/AgCl，Sat．KCl)测定了其响应。讨论了pH、氧浓度、温度对响应的影响，考察了传感器的稳定性。酶电极对儿茶酚，苯酚，对-甲苯酚的灵敏度分别为59.6，23.1，39.4μA／mM。酶电极在4℃干态保存，间歇测定3周后，其响应为初始值的73％，稳定性好于接枝共聚物PVA-g-PVP为载体的酪氨酸酶电极。5．首次用安培酶电极定量测定极性有机溶剂。初步实验证实了用酪氨酸酶电极安培法定量惰性的极性有机溶剂的可行性。酪氨酸酶电极的制备方法简单：把酪氨酸酶和共聚物的水溶液滴涂在经过抛光的洁净的玻碳电极表面上，然后置于+4℃冰箱中干燥成膜即可。电化学还原酪氨酸酶催化氧化酚生成的醌提供探测信号。此传感器可以用于定量测定甲醇，乙醇，正丁醇，丙酮，乙腈，四氢呋喃等。该方法对某有机溶剂的检测限，灵敏度，线性范围依赖于所使用的固定化材料和底物的疏水性。对所测试的有机溶剂的响应时间小于2分钟。现场计时电流-石英晶体微天平实验证实了其响应机理：加入的有机溶剂富集底物探针酚，因而降低了酶膜中的酚的浓度。增加底物探针的浓度可以增加检测的灵敏度，因而降低检测限。此方法检测极性有机溶剂的特点是简单，容易，迅速。用酪氨酸酶电极安培定量测定惰性的极性有机溶剂，大大扩展了酶电极的应用范围。用这种检测方法的优点是，可以定量测定那些还没有发现专一性的酶来构造生物传感器的有机溶剂。6．生物传感器的研究中最重要和最基本的问题是酶的固定化。我们小组提出了用低温水凝胶固定化酶方法构造有机相酶电极，但是低温水凝胶与酶的相互作用仍不清楚。我们利用肼类化合物作为探针，研究了辣根过氧化物酶与低温水凝胶的相互作用。常用的羧基捕捉剂肼和对血红素边缘有高度选择性的甲基肼不能很快地明显抑制固定在低温水凝胶中的辣根过氧化物酶的活性。原因是辣根过氧化物酶的构象可能被低温水凝胶锁定，辣根过氧化物酶的羧基和其血红素的边缘被低温水凝胶保护而免受肼类化合物的进攻。作为比较，肼类化合物与吸附在石墨电极上的辣根过氧化物酶的相互作用也用稳态电流响应和循环伏安进行了研究。对水凝胶固定化酶方法．提出了酶电极响应的动力学参数的初步理论解释，其中低温水凝胶层的厚度和电子媒介体的扩散系数不影响米氏常数K_M，但这些参数显著影响饱和响应电流I_(max)。7．六氰合铁钴(II)膜修饰的玻碳电极用于构造电流型葡萄糖传感器。以六氰合铁钴(II)膜电化学催化还原酶促反应过程中产生的过氧化氢为分析信号。明胶作为固定化材料，外涂Nafion膜。低的适加电位避免电化学氧化抗坏血酸、尿酸等干扰物。Nafion涂层靠静电斥力，阻止这些阴离子干扰物到达电极表面。得到了宽的线性范围，给出分析性能参数，进行了动力学分析。

DNA的扫描探针显微镜和电化学研究

1、在云母表面用AFM观察了不同离子对DNA形态影响。一些离子，如Mg~(2+)、Mn~(2+)、Co~(2+)等是固定和铺展DNA的较好介质，但缺陷是它们可以催化限制性内切酶对DNA的切割。在另一些离子存在下，如Co(phen)_3~(3+)和Ca~(2+)，限制酶不对DNA切割。Co(phen)_3~(3+)存在下，限制性内切酶EcoRI的星号活力位点与DNA结合。AFM直接观察到EcoRI在pBR322DNA上的星号活力图。AFM测得的星号活力物理图与理论偏差小于100 bp。获得了适于AFM观察的常规DNA铺展方法。长度大于40微米的DNA在几微米扫描范围内均匀铺展，并且云母基底表面平整干净。此铺展方法对DNA长度没有影响。这种展开的长链DNA适合于人类基因组BAC DNA的高分辨物理图制作。2、用低电流STM首次观察到金表面上自组装的ssDNA。ssDNA在局部规则区域内彼此平行排列。ssDNA链宽约为0.9纳米，其值为dsDNA的一半。在同一ssDNA链上，相邻两个亮点的距离为0.3-0.5纳米，其值与理论的ssDNA内相邻两碱基之间距离一致。电化学实验证明了自组装在Au（111）上的分子是ssDNA而不是dsDNA。讨论了传统基底-HOPG对生物样品的固定。溶菌酶被稳定地固定在氨基修饰的HOPG表面。通过低电流STM，我们观察到溶菌酶的外貌。3、侧向力显微镜对多头绒泡菌染色体的观察，我们获得了中期、前期染色体的表面精细结构和染色体的集缩过程形态。在染色体表面存在300和40纳米的细丝结构。讨论了零度扫描角的侧向力显微镜。4、研究了dsDNA和ssDNA在聚吡咯修饰电极表面的吸附行为，并通过电化学指示剂Co(phen)_3~(3+)在聚吡咯电极上区分了ssDNA和dsDNA。聚吡咯膜内掺杂的正电荷可以很好地吸附DNA分子，并且这种膜可以耐受一些变性条件的处理。再生这种电极是可能的。这些结果表明，这种新型DNA固定方法可以用于DNA传感器的研制。

喷雾热解法制备Eu~(3+)掺杂的球形发光粉

喷雾热解法对合成球形形貌的发光粉极具优势，本文用喷雾热解法（先低温喷雾干燥，在慢速升温热解）合成了正硼酸盐、氧化物和硼铝酸盐发光粉，合成过程中用柠檬酸、聚乙二醇、浓氨水等修饰喷雾前驱体溶液，以优化发光粉的形貌和发光性能，同时对相应的发光机理进行了探讨。在喷雾热解法合成Y_2O_3:Eu这种单一组分的氧化物发光粉中，PEG的分子量（分子量大小决定了分子链的长短）对所制发光粉的形貌（球形、棒状和片状）起着重要的作用。形成球形是因为分子量为10000的PEG长分子链在喷雾前驱体溶液中穿插、缠结、卷曲，并通过氢键结合柠檬酸在喷雾热解溶液中形成了相对稳定的网状结构，这使得在随后的低温喷雾干燥过程中鳌合稀土离子的柠檬酸不会因溶剂的蒸发跑到喷雾小液滴的表面而造成空心结构，从而得到实心球体，这种实心球体在随后的慢速升温热解过程中逐渐收缩、结晶，最后得到了表面光滑的实心球体；至于棒状结构，则是因为短分子链的PEG（分子量600）只能在喷雾小液滴中形成区域网状结构，这种区域网在溶剂的蒸发过程中会跑到小液滴的表面形成空心结构，由于球壳上具有PEG作为“筋”而具有一定的韧性，这使得在随后的慢速升温热解过程中球壳热解形成空心的孔洞结构，并在高温下破裂、坍塌、卷曲而形成了棒状；而片状则是因为喷雾前驱体溶液中没有PEG链使得干燥过程中，鳌合稀土离子的柠檬酸随溶剂的蒸发而跑到小液滴表面，形成了空心的球壳，这种球壳由于没有PEG链做“筋”而具有脆性，在随后的慢速升温热解过程中，这种脆性的球壳破裂成片状，并随温度的升高进一步热解、收缩，形成了最终的片状Y_2O_3:Eu。在喷雾热解法合成Y_(0.9-x)Gd_xEu_(0.1)BO_3中，聚已二醇、柠檬酸、氮气压力和前驱体溶液的浓度都严重地影响着所制发光粉的形貌。对该体系来说，获得最佳形貌（球形，实心，表面光滑，尺寸在1-3μm）的条件如下：聚已二醇I狗最佳用量是。0.004M，柠檬酸的最佳用量是两倍于溶液中总金属离子的摩尔数；最佳氮气压力为6O0atm；前驱体溶液的浓度为0.07M。Y_(0.9)Eu_(0.1)BO_3在700℃时便开始结晶，比固相法低了200℃（固相法为900℃）。随着烧结温度的提高，结晶性逐渐增强，当温度超过1100℃后，结晶性开始下降，这主要是因为和该体系有关的氧化硼熔点低（600 ℃），在高温容易挥发，造成了晶粒表面出现贫硼相，使得晶粒尺寸降低所致。在Y_(0.9-x)Gd_xEu_(0.1)BO_3中，随着X值的增大，发光强度显著增强，这是因为在Y_(0.9-x)Gd_xEu_(0.1)BO_3中存在Gd~(3+)到Eu~(3+)的能量传递，X值的增加不仅增加了Gd~(3+)-Eu~(3+)的直接能量传递几率，而且增加了Gd~(3+)-（Gd~(3+)）_n-Eu~(3+)形式的能量传递的几率，从而增强了发光强度。在硼铝酸盐Y_(0.9-x)Gd_xEu_(0.1)Al_3（BO_3）_4（0.0≤X≤0.9）体系中，用浓氨水来修饰喷雾前驱体溶液，改变其pH值，发现pH值对粒子形貌有严重影响，但对光致发光强度影响不大。当pH值为3时（不加浓氨水），所制样品形貌不规则，且团聚严重；当加入适量的浓氨水，使前驱体溶液pH值增大到4.5（此时溶液呈胶体状），所制样品呈球形，表面比较粗糙；再加浓氨水，使前驱体溶液的pH值增大到12（此时溶液呈悬浊液状），所制样品仍呈球形，表面趋于光滑，粒子尺寸降低。这三种发光粉的光致发光强度相差很小，但球形的发光粉在涂屏上具有显然的优势。在Y_(0.9-x)Gd_xEu_(0.1)Al_3（BO_3）_4发光粉中，随着X值的增大，存在两个影响发光强度的因素：一是随着X值的增大，结晶性降低，这使发光强度降低；二是随着X值的增大，Gd~(3+)-Eu~(3+)或者Gd~(3+)-（Gd~(3+)）_n-Eu~(3+)形式的能量传递效率增强，这使发光强度增加。当X值比较小时（0.0≤X≤0.3），前一因素占主导地位，当X值比较大时（0.3≤X≤0.9），后一因素占主导地位。

层状钙钛矿结构化合物的合成、电性和磁性的研究

近年来，随着金属多层膜，磁隧道结和钙钦矿锰氧化物等材料中磁阻现象的发现，以研究磁阻效应的机理和应用为目的的磁电子学迅速发展。这其中钙钦矿结构的稀土锰氧化物以其超大的磁阻值和丰富的物理内涵而备受瞩目。尽管人们对此已做了大量的工作，但是对这类氧化物的深入认识直至超大磁电阻效应物理机制的合理解释仍需做艰苦细致的努力。本论文选择层状钙钦矿稀土锰氧化物作为研究对象，系统地研究了A位，B位的变化和B位原子之间的相互作用对氧化物的结构、磁性和磁阻性质的影响。希望得到钙钦矿中磁、电性质和磁阻与结构之间的关系，能对该系列化合物中电、磁性质的变化规律和相互作用机理作出合理的解释。基于LaSr2Mn2O7的结构特殊性，我们选择了它作为母体化合物。并通过过渡金属离子Cr，Ti，Ni，Fe对Mn离子取代来研究B位原子的变化对性质的影响。结果发现，Cr3＋因为与Mn4＋具有相同的电子形态而能够参与双交换作用，使掺杂Cr3＋的系列样品的磁化强度随cr含量的增加而增加。而掺杂讨＋，Ni2＋，Fe3＋离子的化合物虽然与Mn离子之间的相互作用各不相同，但引起的磁性变化却是相同的。这四种元素的掺杂都提高了体系的磁阻和电阻率。通过对这几种过渡金属取代的比较，发现在LaS2Mn2O7中对Mn离子进行取代的离子和Mn离子之间的交换作用对磁性质的影响并不起主要作用，掺杂引起的主要作用是致使Mn位的无序度增加和对双交换作用的稀释和阻碍。值得注意的是每个系列样品中都有一个样品的磁阻在高温时出现较大的正值，且随着温度的降低转变为负值。例如，在Fe掺杂的系列样品中，只有x＝0.2的样品表现出正磁阻，且MR在28OK时达到74％。这可能是因为掺杂导致的结构变化引起的。这种正磁阻对材料的应用意义重大。电荷有序对磁阻材料是一种很重要的状态，为了提高LasrZMn2O7的电荷有序温度，我们选择了具有孤对电子的Bi3+来取代Sr2+。结果发现，单相样品只能持续到x≤0.2。样品的电荷有序温度并没有象预想的那样有所提高。这是因为体系的二维结构抑止了Bi3＋离子的作用，同时由于体系中Bi3＋的含量较少没有达到提高电荷有序温度的程度。但Tco降低的程度相对于其它离子的取代效果（如Gd）要低。目前n=3的层状钙钦矿研究较少，但是由于该化合物具有结构可变性和理论上可以解释磁转换机理，我们对（La，ca）4kMn3O10进行了深入的研究。在La3-3xCa1＋3xMn3O10（0.5≤x≤1.0）中随La3＋含量的减少，该系列化合物经历了从铁磁性到顺磁性再到反铁磁性的转变，同时在磁阻上也经历了由负磁阻（x＝0.5～0.7）到正磁阻（x=0.8-1.0）的转变。根据磁性和电性的变化规律，我们认为这种正负磁阻的转变是由于体系中超交换和双交换作用的相互竞争引起的。La3＋含量多时，Mn3十离子含量较多，双交换作用占主导地位，产生负磁阻；随着Mn3+离子含量的减少，双交换作用逐渐减弱，Mn4+离子之间的反铁磁性超交换作用逐渐增强，产生了正磁阻。在低掺杂浓度时LaxCa4-xMn3O10（x＝0-0.9）经历了顺磁性到反铁磁性的转变，为了了解其磁性变化过程，我们进一步研究了富含Mn4＋的这一区间。发现磁化强度在x≤0.2的范围内随x增加而增强，在高于0.2的掺杂范围后随x的增加而逐渐降低。这是因为这一区间的磁结构由基态时的G型-AFM向x＝0.9时的C型-AFM的转变。而且这种转变与载流子浓度密切相关。