Localized exciton dynamics in AlInGaN alloy

Carrier recombination dynamics in AlInGaN alloy has been studied by photoluminescence (PL) and time-resolved PL (TRPL) at various temperatures. The fast red-shift of PL peak energy is observed and well fitted by a physical model considering the thermal activation and transfer processes. This result provides evidence for the exciton localization in the quantum dot (QD)-like potentials in our AlInGaN alloy. The TRPL signals are found to be described by a stretched exponential function of exp[(-t/,tau)13], indicating the presence of a significant disorder in the material. The disorder is attributed to a randomly distributed QDs or clusters caused by indium fluctuations. By studying the dependence of the dispersive exponent beta on temperature and emission energy, we suggest that the exciton hopping dominate the diffusion of carriers localized in the disordered QDs. Furthermore, the localized states are found to have 0D density of states up to 250 K, since the radiative lifetime remains almost unchanged with increasing temperature. (C) 2003 Elsevier Science Ltd. All rights reserved.

Structural and optical properties of InAlGaN films grown directly on low-temperature buffer layer with (0001)sapphire substrate

Quaternary InAlGaN film has been grown directly on top of low-temperature-deposited GaN buffer layer by low-pressure metalorganic vapor phase epitaxy. High-resolution X-ray diffraction and photoluminescence (PL) results show that the film has good crystal quality and optical property. Temperature-dependent PL and time-resolved PL (TRPL) have been employed to study the carriers recombination dynamics in the film. The TRPL signals can be well fitted as a stretched exponential function exp[-(t/tau)(beta)] from 14 to 250 K, indicating that the emission is attributed to the radiative recombination of excitons localized in disorder quantum nanostructures such as quantum disks originating from indium (In) clusters or In composition fluctuation. The cross-sectional high-resolution electron microscopy measurement further proves that there exist the disorder quantum nanostructures in the quaternary. By investigating the dependence of the exponential parameter beta on the temperature, it is shown that the multiple trapping-detrapping mechanism dominates the diffusion among the localized states. The localized states are considered to have two-dimensional density of states (DOS) at 250 K, since radiative recombination lifetime tau(r) increases linearly with increasing temperature. (C) 2002 Elsevier Science B.V. All rights reserved.

Nitrogen vacancy scattering in GaN grown by metal-organic vapor phase epitaxy

Electron mobility limited by nitrogen vacancy scattering was taken into account to evaluate the quality of n-type GaN grown by metal-organic vapor phase epitaxy. Two assumptions were made for this potential for the nitrogen vacancy (1) it acts in a short range, and (2) does not diverge at the vacancy core. According to the above assumptions, a general expression to describe the scattering potential U(r) = - U-0 exp[- (r/beta)(n)], (n = 1, 2,...,infinity) was constructed, where beta is the potential well width. The mobilities for n = 1, 2, and infinity were calculated based on this equation, corresponding to the simple exponential, Gaussian and square well scattering potentials, respectively. In the limiting case of kbeta << 1 (where k is the wave vector), all of the mobilities calculated for n = 1, 2, and infinity showed a same result but different prefactor. Such difference was discussed in terms of the potential tail and was found that all of the calculated mobilities have T-1/2 temperature and beta(-6) well width dependences. A mobility taking account of a spatially complicate scattering potential was studied and the same temperature dependence was also found. A best fit between the calculated results and experimental data was obtained by taking account of the nitrogen vacancy scattering. (C) 2002 Elsevier Science Ltd. All rights reserved.

Shallow donor defect formation and its influence on semi-insulating indium phosphide after high temperature annealing with long duration

Fe-doped semi-insulating (SI) InP has become semi-conducting (SC) material completely after annealing at 900 V for 10 hours. Defects in the SC and SI InP materials have been studied by deep level transient spectroscopy (DLTS) and thermally stimulated current spectroscopy (TSC) respectively. The DLTS only detected Fe acceptor related deep level defect with significant concentration, suggesting the formation of a high concentration of shallow donor in the SC-InP TSC results confirmed the nonexistence of deep level defects in the annealed SI-InP. The results demonstrate a significant influence of the thermally induced defects on the electrical properties of SI-InP. The formation mechanism and the nature of the shallow donor defect have been discussed based on the results.

Molecular beam epitaxial growth of GaN on 3c-SiC/Si(111) substrates using a thick AIN buffer layer

Hexagonal GaN films (similar to 3 mu m) were grown on 3c-SiC/Si(111) and carbonized Si(111) substrates using a thick AlN buffer Cracks are observed on the surface of the GaN film grown on the carbonized Si(111), while no cracks are visible on the 3c-SiC/Si(111). XRD exhibits polycrystalline nature of the GaN film grown on the carbonized Si(111) due to poorer crystalline quality of this substrate. Raman spectra reveal that all GaN layers are under tensile stress, and the GaN layer grown on 3c-SiC/Si(111) shows a very low stress value of sigma(xx) = 0.65 Gpa. In low-temperature Photoluminescence spectra the remarkable donor-acceptor-pair recombination and yellow band can be attributed to the incorporation of Si impurities from the decomposition of SiC.

Growth and characterization of 4H-SiC by horizontal hot-wall CVD

4H-SiC layers have been homoepitaxially grown at 1500 degrees C with the use of a horizontal hot-wall chemical vapor deposition (CVD) system, which was built in the author's group. The typical growth rate was 2 mu m/h at a pressure of 40 Torr. The background donor concentration has been reduced to 2.3 x 10(15) cm(-3) during a prolonged growth run. It confirmed the idea that the high background concentration of thin films was caused by the impurities inside the susceptor and thermal insulator The FWHM of x-ray co-rocking curves show 9 similar to 15 aresecs in five different areas of a 32-mu m-thick 4H-SiC epilayer The free exciton peaks dominated in the near-band-edge low-temperature photoluminescence spectrum (LTPL), indicating high crystal quality.

Controlled growth of III-V compound semiconductor nano-structures and their application in quantum-devices

Various techniques on the growth of self-assembled compound semiconductor nano-structures (quantum dots, QDs) have been tried to enhance the controlling on size, density, emitting wavelength, uniformity in size and ordering in location of the QDs. Optimized growth conditions have been used in the application of the QD materials in opto-electronic devices. High-power long-lifetime quantum-dot laser-diodes (QD-LDs) emitting near 1 mu m, QD-LDs emitting in red-light range, 1.3 mu m QD-LDs on GaAs substrate and quantum-dot super-luminescent diodes (QD-SLDs) have successfully been achieved.

Molecular-beam epitaxial growth of position controlled InAs islands on cleaved edge of InGaAs/GaAs superlattice

A promising approach for positioning of InAs islands on (110)GaAs is demonstrated. By combining self-assembly of quantum dots with solid source molecular beam epitaxy (MBE) on cleaved edge of InGaAs/GaAs superlattice (SL), linear alignment of InAs islands on the InGaAs strain layers have been fabricated The cleaved edge of InGaAs/GaAs SL acts as strain nanopattern for InAs selective growth. Indium atoms incident on the surface will preferentially migrate to InGaAs regions where favorable bonding sites are available. The strain nanopattern's effect is studied by the different indium fraction and thickness of InxGa1-xAs/GaAs SL. The ordering of the InAs islands is found to depend on the properties of the underlying InGaAs strain layers.

Effect of noncoherent islands on the optical properties of the 1.3 mu m InAs/GaAs quantum dots during rapid thermal annealing

The effect of thermal annealing of InAs/GaAs quantum dots (QDs) with emission wavelength at 1.3 mu m have been investigated by photoluminescence (PL) and transmission electron microscopy (TEM measurements. There is a dramatic change in the A spectra when the annealing temperature is raised up to 800 degrees C: an accelerated blushifit of the main emission peak of QDs together with an inhomogeneous broadening of the linewidth. The TEM images shows that the lateral size of normal QDs decreases as the annealing temperature is increased, while the noncoherent islands increase their size and densit. A small fraction of the relative large QDs contain dislocations when the annealing temperature increases up to 800 degrees C. The latter leads to the strong decrease of the PL intensity.

Micro-fabricated Al0.3Ga0.7As pyramids for potential SPM applications

A novel technique of manufacturing Al0.3Ga0.7As pyramids by liquid phase epitaxy (LPE) for scanning probe microscopy (SPM) sensors is reported Four meticulously designed conditions-partial oxidation, deficient solute, air quenching and germanium doping result in defect-free homogeneous nucleation and subsequent pyramid formation. Micrometer-sized frustums and pyramids are detected by scanning electron microscopy (SEM). The sharp end of the microtip has a radius of curvature smaller than 50 nm. It is believed that such accomplishments would contribute not only to crystal growth theory, but also to miniature fabrication technology.

Raman scattering study on diluted magnetic semiconductor Ga1-xMnxAs prepared by Mn-ion implantation

Raman scattering measurements have been performed in diluted magnetic semiconductor Ga1-xMnxAs prepared by Mn-ion implantation, deposition, and post-annealing technique. It is found that the Raman spectrum measured from the implanted surface of the sample shows some new weak modes in addition to the GaAs-like modes which are observed from the unimplanted surface. The new vibrational modes observed are assigned to MnAs-like modes. The coupled LO-phonon plasmon mode, and Mn and As related vibrational modes caused by Mn-ion implantation, deposition, and post-annealing are also observed. Furthermore, the GaAs-like modes are found to be shifted by approximately 4 cm(-1) in the lower frequency side, compared with those observed from the unimplanted surface.

Edge dislocation of b=[001]/2 in the InAs nanostructure on InP(001)

The self-organized InAs/In0.52Al0.48As nanostructure were grown on InP (001) using molecular beam epitaxy (MBE). The nanostructure has been studied using transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM). The edge dislocations with the Burgers vector b = ([001]/2) and extending along the [$(110) over bar $] direction are observed. The results show that in the region near an edge dislocation, no InAs wires were formed, while in the regions free of dislocation, wire-like nanostructures were formed. The mechanisms for the formation of the [001]/2 edge dislocations were discussed.

端羟基丁二烯～丙烯腈共低聚反应中共聚物组成的控制

本工作结合水轮机涂层材料的研制，针对端羟基丁二烯～丙烯腈的共低聚反应，研究了共聚物组成的控制。根据自由基共聚反应理论，提出了一个控制共聚物组成的新计算方法。并根据这种计算方法，合成了具有均匀组成的丁腈羟液体聚合物。用Skeist公式的积分形式~((54))，对所研究的体系，进行了计算。计算结果表明：不补加单体时，丁二烯～两烯腈的共聚反应过程中，单体组成及共聚物组成的变化是显著的。为了合成组成比较均匀的共聚物，必须在反应过程中，补加消耗较快的单体——丙烯腈。根据共聚方程式和反应体系及共聚物中单体浓度的相互关系，推导出丙烯腈的补加量C_A的表示公式为：C_A = (B)_o(R-F)(1-(B)/((B)_o))式中，(B)_o是单体B的起始浓度，R为聚物中单体浓度比，F为单体浓度比。又根据共聚反应速度方程式~((31))及引发剂热分解速度公式，推导出(B)/((B)_o)与反应时间t的函数关系式为：(B)/((B)_o) = exp[K(f(I)_o/k_d)~(1/2)(l~(-k_dt/2)-1)]式中(I)_o为引发剂起始浓度，(B)为反应过程中单体B的浓度，k_d为引发剂分解速度常数，f为引发效率，K为常数。最后得到C_A的表示式为：C_A = (B)_o(R-F){1-exp[K(f(I)_o/k_d)~(1/2)(e~(k_dt/2)-1)]}按上式计算出的C_A的量，在反应过程中补加丙烯腈，这样合成的丁腈羟，实验证明，其组成是均匀的。根据Goldfinger公式~((35))，由测得的竞聚率和单体克分子比，计算了丁腈羟的序列分布。计算的结果说明：所合成的丁腈羟不仅组成是比较均匀的，其序列分布也是比较均匀的。这有利于提高丁腈羟作为水轮机涂层材料的耐磨、耐汽蚀及粘结性能。

关于半导体电极上极化成份的分解和电极反应动力学参数的确定

电极动力学在金属电极上已经发展得比较成熟，对半导体来说，由于电极反应的复杂性，还有不少问题比较模糊。其中之一是怎样根据表观的极化测量求得反映界面电荷转移的动力学参数。目前有关这方面的工作不多，还没有见到具体对极化成份进行分解以求解半导体电极反应的动力学系统的报导。本工作从一定的电极物理模型出发，在电化学测量的基础上结合电子计算技术，对这方面问题的研究提出了测量计算方法。本文提出的半导体电极的物理模型如图A所示。I，I_J, I_S, I_D, I_H均取阴极性电流方向为正，η则按电极电势的方向取阳极过电热为正，阴极过电势为负。模型中的J反映空间电荷层的Schottky结特性，其数学描述可概括（对n-型半导体）为：I_J = I_0[exp(-n_s/a)-1] I_0： 结的反向饱和电流。（a:k_T）/q或（RT）/F D反映界面电荷转移反应的特性，其数学描述适用Butler-Volmer方程：I_D = i~0[exp(-(1-β)n η_H)/a) - exp(βη-η_H/a)] i~0:交换电流。β：阳极传递系数 C_s，C_H分别表示空间电荷层和Helmholtz层的电容。R_B和R_l分别为半导体体内和溶液电阻。由于J，D二者特性不同，可以通过极化测量利用电子计算机加以鉴别。实验上针对电路主要是串联结构的特点，采用恒电流极化，利用恒电流恒电位仪实现一系列的电流阶跃（I_(K-1) I_K K = 1, 2, 3 ……）记录相应的电位随时间变化的响应曲线如图B所示。根据曲线各段的特点，利用电子计算机曲线拟合，分别求解有关参数。（1）在t = 0时，找出一系列不同I下的φ（I_K, t = 0）值，根据φ（I_K, t = 0) = φ(I = 0)-I_KR拟合求解φ（I = 0）， R。（2）找出一系列不同I下的稳态极化数据φ（I_K,t →∞），推导出电位随电流变化关系式，拟合求解I_0, j~0, β。（3）利用暂态过程的φ（I_K, t = 0) ～ t曲线，拟合求解每阶电位变化区间的C_s，C_H。由于在我们的电极模型中，D采取的是完整的Butler-Volmer表达式，没有作任何简化或近似，因而在数据处理和计算时，涉及隐式超越代数方程和隐式超越微分方程，无法通过一般解析法求解。为此我们把牛顿迭代法和Runge-Kutta法引入相应的曲线拟合计算程序中。这样做虽然计算上比较复杂困难，但方法的通用性更广泛。无论Helmholtz层处于线性极化，弱极化，或强极化区部同样适用。我们用BASIC语言编写了梯度法，线性化法联合使用的曲线拟合源程序及牛顿迭代法和Runge-Kutta法于程序。利用上述研究方法，对不同掺杂浓度的n-型GaAs电极在S~(2-)/S_x~(2-)体系中的电化学行为进行了研究。求解的电荷转移反应的动力学参数I_0, i~0, β分别在7.27 * 10~(-8) - 4.66 * 10~(-1) A/cm~2, 2.08 * 10~(-6)-4.62 * 10~(-6)A/cm~2, 0.70 - 0.78的范围之内。并于Pt电极连同一体系中的i~0，β进行了比较。i_（半导体）~0 < i_（导体）~0。但β在二种材料上差别不大。将半导体电极极化分解为空间电荷层极化和Helmholtz层极化两部分。测量了空间电荷层电学及Helmholtz层电容与电极电位的关系。从实际测量中证明，本文提出的电极模型比较恰当的反映了半导体电极的特性，本工作的测量和拟合计算方法对研究半导体电极行为是一种可行的方法。

丙烯酰胺水溶液辐射聚合 Ⅰ聚合过程中聚合物交联反应机制的探讨 Ⅱ聚丙烯酰胺的溶解 Ⅲ合成在水中易溶或速溶的丙烯酰胺聚合物和共聚物

Ⅰ. 聚合过程中聚合物交联反应机制的探讨 聚丙烯酰胺是水溶性聚合物，但一般工业生产的聚丙烯酰胺在水中很难溶解。一个重要因素是由于在聚合过程中聚合物发生了交联。Minsk (1949)认为聚丙烯酰胺大分子上的-CoNH_2的亚胺化，导致聚合物在水中难溶或不溶：Gleason (1959)和Suen (1960)分别指出活性链的链转移和在丙烯酰胺聚合过程中产生末端双键是聚合物交联的起因：AδkuH (1973)认为丙烯酰胺在浓水溶液中聚合是通过水离子作用生成网状聚合物。由于交联是一个伴随聚合的付反应，少量的交联就导致聚合物不溶，加之缺乏有效的分析手段，所以难于定量研究这一过程。一些科学工作者对交联的性质提出了各种设想，但有关交联方面的系统讨论加交联机制问题至今未见报导。本工作估算了聚丙烯酰胺的内聚能和分子间力（主要－CoNH_2间氢键作用力），说明了丙烯酰胺浓度越大，它的聚合产物越易交联；研究了聚合体系PH值对聚合交联的影响，丙烯酰胺在酸性或中性介质中用r射线引发聚合，很快出现凝胶，只有在碱性(PH > 13)介质中r射线幅照可得到水溶性聚丙烯酰胺。用酰胺基的亲核反应能力解释了原子效应，幅照生成聚合物自由基和双键是聚合物交联的潜在因素，在聚合体系加入链转移剂抗坏血酸，可有效地抑制聚合过程中聚合物的迅速交联；从红外光谱观察到交联聚丙烯酰胺的酰胺特征吸收峰从1650 cm~(-1)向亚胺特征吸收峰方向位移，聚丙烯酰胺的含N量低于理论值，交联聚丙烯酰胺含N量偏离理论值更大，以及不溶聚丙烯酰胺的交联键可以羟高温水解完全破坏，由此肯定聚合过程中聚合物交联具有亚胺结构。根据酰胺基结构特点加亲核取代反应原理，提出丙烯酰胺水溶液辐射聚合过程中聚合物的交联机制如下：1.聚合物自由基的生成。2.自由基促使－CoNH_2活化，导致-CoNH_2间亲核取代反应。3.当R_2 = -CH=CH_2即单体参与亚胺化则导致在分子链上产生悬挂双键，将引起聚合物交联。这一反应机制可以阐明丙烯酰胺水溶液辐射聚合过程中聚合交联起因和历程，可以解释键材剂。质子效应和亚胺之间联系，为制备水溶性聚丙烯酰胺提供了线索。Ⅱ. 聚丙烯酰胺的溶解 关于聚合物溶解理论前人曾从两方面进行探讨。一是Hidebrand (1949)提出以内聚能密度的平方根作为溶度参数δ来鉴别两种物互溶的可能性。Burrel (1955)把这一方法来研究聚合物的溶解。内聚能依赖于色散力、极性力和氢／键，它由三部分组成E = E_d + E_p + E_h，对应的溶度参数方程为δ~2 = δ_d~2 + δ_p~2 + δ_h~2，因此只有两种物质的溶度参数的各个分量相近时，才有可能互溶。这一方面的研究仅涉及溶解过程的热力学。另一是Ueberreiter (1968)提出溶解是一个相互扩散过程。聚合物在溶解过程中，溶解速度S和溶胀层厚度δ处于稳态。它们和溶剂在聚合物中平均扩散系数D-bar_s的关系为2S = D-bar_s/δ，比式直接反映了溶解的动力学过程。聚丙烯酰胺有极强的极性和形成氢键的能力，它只溶于水，对溶度参数的研究存在一定困难。采用扩散原理研究聚丙烯酰按的溶解速度和规律比较有利。为此目地，我们设计制作了专门溶解实验装置，借助聚丙烯酰胺存在电离基因，利用电导测定溶解速度S，并借助针入法则定溶胀层厚度δ和溶胀速度W，发现极性聚丙烯酰胺的溶解不同于Ueberreiter所研究的非极性聚合物聚苯乙烯的溶解。它是一个非稳态过程，不存在诱导期，溶解和溶胀同时进行，根据这事实和理论分析得到2S + W = （D-bar）_s/δ这一关系式与实验数据相符。此关系式可还原Ueberreinter的稳态溶解得到的关系式，并适用于交联聚合物的溶胀。聚丙烯酰胺的-CoNH_2强吸水性导致它在溶解时溶胀形成凝胶层是一个快步骤，而-CoNH_2强的形成氢键能A是溶解的主要障碍，因此溶解是一个慢过程。聚丙烯酰胺的溶解活化能E_s和水在聚合物中扩散活化能E_D都是6干卡／克分子左右；处于氢键离解能范围之内，所以聚丙烯酰胺溶解主要克服分子间氢键作用力。研究了影响聚丙烯酰胺的溶解因素：（1）聚丙烯酰胺单位时间溶解量与它们的颗粒直径2.5次方成反比。（2）聚丙烯酰胺溶解速度与分子量0.5 - 0.7次方成反比。（3）聚丙烯酰胺溶解速度对湿度的依赖关系为S = 0.278 exp[-627o/RT]（4）聚丙烯酰胺大分子中引进-CooNa，吸水性增强，溶解过程双电层形成，产生剪切应力和静电斥力，促使键移动，降低了溶解活化能，加速溶解。（5）聚合物中添加亲水性强的表面活活性剂有利于聚丙烯酰胺的溶解。Ⅲ. 合成在水中易溶或速溶丙烯酰胺聚合物和共聚物 本文强调了在丙烯酰胺水溶液辐射聚合过程中，避免聚合物交联是合成水溶性聚合物的先决条件。加NaOH的丙烯酰胺水溶液聚合和加链转移剂抗坏血酸的丙烯酰胺水溶液聚合物都可得到转化率和分子量都较高，而且不交联的丙烯酰胺的聚合物和共聚物。在单体水溶液中添加尿素对聚合物有助溶效果；添加亲水性强的表面活性剂JFC可改善聚合物颗粒的粘结和抱团。提出了两个聚合体系，合成出在水中速溶的聚丙烯酰胺和羰钠基不同含量的阴离子型 聚丙烯酰胺，聚合物颗粒小于40目，可在10分钟内完成溶解。