含钇的耐热稀土镁合金的结构和性能研究

耐热、高强和抗高温蠕变的稀土镁合金是镁合金研究与开发的重要研究课题之一。本论文主要集中于对Y和其它稀土元素复合加入镁后的镁合金结构和性能的研究。探讨了Y与其它重稀土元素如Gd、Ho复合加入镁后的镁合金的时效硬化行为和结构性能，也研究了Y与混合轻稀土金属如富铈、富镧复合加入镁后对镁合金性能的影响。还对新型Mg-Y压铸镁合金的开发为目标，探讨了这一新型合金开发的可行性。具体结果如下： 1. 研究了Y加入到Mg-10Gd-0.4Zr合金中对合金的时效硬化和性能的影响规律和Mg-10Gd-6Y-0.4Zr合金在225℃和250℃时效210h内的沉淀析出相的转变以及合金的时效硬化行为。随着Y含量的增加，合金的时效硬化反应显著增强，合金的高温拉伸强度随Y含量的增加而线性增强，其原因是合金中的β'相有好的热稳定性。 2. 研究了Y和Ho元素复合加入镁后镁合金的时效硬化反应和组织性能。研究发现，在250℃时效时，当Y和Ho元素复合加入镁后，合金固溶体的时效分解速度加快，促进了合金的时效硬化，并且，随着Y含量的增加，合金的时效硬化反应增强，力学性能也相应提高。β-Mg24Y(Ho)5和（或）β'相对合金的时效硬化起了主要的作用，而且，位错密度增加也是合金性能提高的重要原因。 3. 探讨了Y和混合轻稀土富铈（和富镧）复合加入镁后对镁合金的性能影响。富铈和富镧在镁中低的固溶度导致单独加入镁后的时效硬化反应很弱，当Y和混合轻稀土富铈（和富镧）复合加入后，合金的时效硬化反应明显增强，并随着Y含量的增加，时效硬化的反应也相应增强。富铈和富镧对Mg-Y合金固溶体的时效分解有明显的促进作用。除了基体中的沉淀强化外，仍然停留在晶界上的Mg12RE稀土相对合金的晶界也有明显的强化作用。 4. 研究开发了具有良好的力学性能和高温抗蠕变性能、低含量Y、Gd的稀土镁合金，实验结果表明该合金是一种有良好应用前景的压铸镁合金。

镁-锌-稀土系合金的组织和性能研究

　　制备了Mg-4.5wt%Zn-1～5wt%RE系合金（RE元素包括轻稀土：La、Ce、Nd、Sm；重稀土：Gd和Y），研究了铸态和热处理态合金的组织和性能。（1）适量的稀土元素均可细化合金晶粒，其中轻稀土元素的细化效果好于重稀土元素；（2）含轻稀土元素合金中的析出相主要为(Mg,Zn)17RE2和Mg4Zn7，而含重稀土元素的合金中的析出相主要为MgZnxREy(Mg3Zn6RE, Mg3RE2Zn3)和Mg4Zn7；（3）加入稀土元素后，合金的强度提高；稀土含量相同时，含轻稀土元素的强化效果较好。Mg-4.5Zn-1Ce合金具有最高的强度。T5处理态合金的抗拉强度、屈服强度和伸长率分别为236 MPa、111 MPa和15.8%，T6处理态合金分别为233 MPa、131 MPa和8.9%。强度提高的主要原因是合金中生成了大量的纳米级Mg4Zn7强化相，以及晶界沉淀相的连续性降低；（4）含重稀土元素合金的时效硬化效果高于含轻稀土元素的合金，经T6处理后，含重稀土元素合金的断裂强度和屈服强度均提高，而含轻稀土元素合金只有屈服强度提高。 　　研究了挤压变形Mg-4.5Zn-1Ce合金的组织和性能。473 K时效后峰值态合金具有较高抗拉强度和屈服强度，其值分别为291 MPa和239 MPa，比铸态分别提提高了55 MPa和128 MPa。高强度产生的原因是合金中生成了大量棒状和点状混合结构的纳米级Mg4Zn7强化相和晶粒的细化。 　　应用Edge-to-edge匹配模型成功预测了MgZn2/α-Mg体系中的位相关系，扩大了该模型的应用范围。并对模型进行了改进，主要体现在：1)确定匹配方向的平面上所有原子的中心位置需在平面上；2）匹配方向之间可任意配对。应用优化后的模型预测了Mg17Al12/α-Mg体系中的位相关系，预测结果与实验结果的吻合率为4/6，好于原模型预测的吻合率4/8。另外，使用优化后的模型，成功的预测出了理想的Burgers位相关系，从而证实了该位相关系是确实存在的，而不是near Burgers位相关系测定的误差。使用优化后的模型还成功的解释了该合金体系中稀土元素的晶粒细化机制和沉淀强化机制。

Mg-Al-Mn-RE系合金组织与性能研究

利用金属型铸造制备了Mg-5Al-0.3Mn-xRE (x = 0~4, wt%，RE = Ce, Nd, Sm, Y和(CeLa)混合稀土)系列合金，研究了铸态合金的组织和力学性能。利用轧制和挤压技术对优化出的合金进行了变形加工处理，并研究了合金加工后的组织和力学性能。 对于铸态合金，稀土元素不仅可以细化合金的晶粒，而且形成不同类型的Al-RE化合物，含Ce的合金中生成Al11Ce3相，含Nd或Sm的合金中，主要生成Al11Nd3 (Al11Sm3)相和少量的Al2Nd (Al2Sm)相，含Y的合金中生成Al2Y相。另外，添加稀土可以改变Mg17Al12相的形貌，使其变得更加细小、弥散。添加适量的稀土可以明显提高铸态合金在室温和150℃下的力学性能，Mg-5Al-0.3Mn-1.5Ce, Mg-5Al-0.3Mn-2Nd和Mg-5Al-0.3Mn-2Sm合金在各自的体系中具有最佳的综合力学性能。合金力学性能提高的主要原因是细晶强化、Al-RE化合物第二相强化以及减弱Mg17Al12相对合金高温力学性能的不利影响。 对Mg-5Al-0.3Mn-(1.0, 1.5, 2.0)Ce，Mg-5Al-0.3Mn-2Nd，Mg-5Al-0.3Mn-1.5(CeLa)和Mg-5Al-0.3Mn-3Y合金在300-400℃下进行了热轧制或挤压变形，与铸态合金相比，轧制和挤压合金具有更高的力学性能。轧制合金的室温抗拉强度为290-340 MPa，较铸态合金提高约50％，屈服强度约为210-260 MPa，较铸态合金提高约2倍。挤压态合金的抗拉强度为260-270 MPa，屈服强度为160-190MPa，伸长率为20-22％；150℃的力学性能也得到了明显改善。 结合热力学计算、合金化元素之间的电负性差、化合物相的生成焓数据以及相图计算，阐述了稀土化合物相的生成机制，稀土元素与Al元素之间的电负性差大于其与Mg之间的电负性差，且Al-RE相的生成焓远低于Mg-RE和Mg-Al相的生成焓，因此在Mg-Al合金中加入RE后，RE优先与Al形成Al-RE化合物。从晶粒细化、化合物强化相的生成和演变、变形加工处理的位错交互作用等方面讨论了合金的强化机制，认为细晶强化、第二相强化及形变强化是提高合金力学性能的主要机制。

新型绿色荧光体ABLa(PO_4)_2:Ce, Tb研究(A = K, Na; B = Mg, Zn)

本工作完成了磷酸盐化合物ABLa(PO_4)_2的合成，这些磷盐均可在900 ℃左右合成；对其进行了结构测试与表征，发现这些磷酸盐属于单斜晶系独居石结构，与LaPO_4同构，具有很相近的晶胞参数；系统地研究了RE~(3+)离子(RE = Ce,Tb,Dy)在ABLa(PO_4)_2基质中的发光与能量传递规律，研究了Ce~(3+)、Tb~(3+)离子发光中心与基质晶格之间的相互作用，计算了这些稀土离子之间能量传递的临界距离Rc(dd)，结果表明ABLa(PO_4)_2基质中Ce~(3+)离子与基质晶格之间的相互作用属于中等程度耦合，Tb~(3+)离子与基质晶格之间的相互作用属于无辐射多声子过程，Ce~(3+)→Ce~(3+)、Ce~(3+)→Tb~(3+)能量迁移临界距离均与LaPO_4中相近，Ce~(3+) → Ce~(3+)相对于Ce~(3+) → Tb~(3+)属于快过程，Ce~(3+) → Ce~(3+)能量传递对ABLa(PO_4)_2:Ce,Tb荧光体的Tb~(3+)绿色发光起了重要的作用，ABLa(PO_4)_2基质是Ce~(3+)，Ce~(3+)-Tb~(3+)，Ce~(3+)-Dy~(3+)的优良发光基质；最后探讨了绿色荧光体ABLa(PO_4)_2:Ce，Tb的调制途径，主要研究了Ce~(3+)、Tb~(3+)离子的浓度效应，掺杂B_2O_3、Dy~(3+)、SiO_2对荧光体发光的影响及NH_4Cl的作用，结果表明Ce~(3+)、Tb~(3+)离子的适宜浓度分别为0.2～0.5和0.08～0.2，掺杂适量的B_2O_3、Dy~(3+)能很好地提高荧光体的发光，掺杂SiO_2、NH_4Cl不利荧光体发光。

Near-Infrared Femtosecond Laser for Studying the Strain in Si1-xGex Alloy Films via Second-Harmonic Generation

The second-harmonic generation (SHG) from Si1-xGex alloy films has been investigated by near-infrared femtosecond laser. Recognized by s-out polarized SHG intensity versus rotational angle of sample, the crystal symmetry of the fully strained Si0.83Ge0.17 alloy is found changed from the O-h to the C-2 point group due to the inhomogeneity of the strain. Calibrated by double crystal X-ray diffraction, the strain-induced chi((2)) is estimated at 5.7 x 10(-7) esu. According to the analysis on p-in/s-out SHG, the strain-relaxed Si0.10Ge0.90 alloy film is confirmed to be not fully relaxed, and the remaining strain is quantitatively determined to be around 0.1%.

EMPIRICAL PSEUDOPOTENTIAL BAND-STRUCTURE CALCULATION FOR ZN1-XCDXSYSE1-Y QUATERNARY ALLOY

The band structure of the Zn1-xCdxSySe1-y quaternary alloy is calculated using the empirical pseudopotential method and the virtual crystal approximation. The alloy is found to be a direct-gap semiconductor for all x and y composition. Polynomial approximation is obtained for the energy gap as a function of the composition x and y. Electron and hole effective masses are also calculated along various symmetry axes for different compositions and the results agree fairly well with available experimental values.

INFLUENCES OF ALLOY DISORDER AND INTERFACE ROUGHNESS ON OPTICAL-SPECTRA OF INGAAS/GAAS STRAINED-LAYER QUANTUM-WELLS

We present studies of alloy composition and layer thickness dependences of excitonic linewidths in InGaAs/GaAs strained-layer quantum wells grown by MBE, using both photoluminescence and optical absorption. It is observed that linewidths of exciton spectra increase with indium content and well size. Using the virtual crystal approximation, the experimental data are analyzed. The results obtained show that the alloy disorder is the dominant mechanism for line broadening at low temperature. In addition, it is found that the absorption spectra related to light hole transitions have varied from a peak to a step-like structure as temperature increases. This behavior can be understood by the indirect space transitions of light holes.

Aggregation and precipitation in high dose as ion implanted Ge0.5Si0.5 alloy

Thermally stimulated redistribution and precipitation of excess arsenic in Ge0.5Si0.5 alloy has been studied by X-ray photoelectron spectroscopy (XPS), cross sectional transmission electron microscopy (XTEM) and X-ray energy disperse spectrometry (EDS). Samples were prepared by the implantation of 6 X 10(6) As+ cm(-2) and 100 keV with subsequent thermal processing at 800 degrees C and 1000 degrees C for 1 h. The XPS depth profiles from the implanted samples before and after the thermal annealing indicate that there is marked redistribution of the elements in heavily arsenic-implanted Ge0.5Si0.5 alloys during the annealing, including: (1) diffusion of As from the implanted region to the surface; (2) aggregation of Ge in the vicinity of the surface. A high density of precipitates was observed near the surface which were by XTEM and EDS identified as an arsenide. It is suggested that most of the implanted As in Ge0.5Si0.5 alloy exists in the form of GeAs.

第一性原理研究Mg,Si和Mn共掺GaN

采用基于密度泛函理论(DFT)的第一性原理平面波赝势法(PWP)计算Mg,Si和Mn共掺GaN电子结构和光学性质,分析比较计算结果.计算表明:掺杂后体系均在能隙深处产生自旋极化杂质带,具有半金属性,能产生自旋注入.与Mn掺杂GaN比较,Mg共掺后能使居里温度(TC)升高,并在1.0eV出现源于Mn4+离子基态4T1(F)到4T2(F)态跃迁的较强的光吸收,而Mn掺杂GaN时位于1.3eV处的吸收峰消失;Si共掺后没能使TC升高,且在低能区无光吸收现象.

Growth of 0.55eV-GaInAsSb Quaternary Alloy Films for a Thermophotovoltaic Device by Liquid Phase Epitaxy

Lattice matched Ga_(1-x)In_xAs_ySb_(1-y) quaternary alloy films for thermophotovoltaic cells were successfully grown on n-type GaSb substrates by liquid phase epitaxy. Mirror-like surfaces for the epitaxial layers were achieved and evaluated by atomic force microscopy. The composition of the Ga_(1-x)In_xAs_ySb_(1-y) layer was characterized by energy dispersive X-ray analysis with the result that x = 0.2, y = 0.17. The absorption edges of the Ga_(1-x)In_xAs_ySb_(1-y) films were determined to be 2. 256μm at room temperature by Fourier transform infrared transmission spectrum analysis, corresponding to an energy gap of 0.55eV. Hall measurements show that the highest obtained electron mobility in the undoped p-type samples is 512cm2~/(V·s) and the carrier density is 6. 1×10~(16)cm~(-3) at room temperature. Finally, GaInAsSb based thermophotovoltaic cells in different structures with quantum efficiency values of around 60% were fabricated and the spectrum response characteristics of the cells are discussed.

Optical and Electrical Properties of GaN.Mg Grown by MOCVD

Mg-doped GaN layers prepared by metalorganic chemical vapor deposition were annealed at temperatures between 550 and 950℃. Room temperature （RT） Hall and photoluminescence （PL） spectroscopy measurements were performed on the as-grown and annealed samples. After annealing at 850℃, a high hole concentration of 8 × 10~(17) cm~(-3) and a resistivity of 0. 8lΩ·cm are obtained. Two dominant defect-related PL emission bands in GaN.. Mg are investigated; the blue band is centered at 2. 8eV （BL） and the ultraviolet emission band is around 3.27eV （UVL）. The relative intensity of BL to UVL increases after annealing at 550℃, but decreases when theannealing temperature is raised from 650 to 850℃, and finally increases sharply when the annealing temperature is raised to 950C. The hole concentration increases with increased Mg doping, and decreases for higher Mg doping concentrations. These results indicate that the difficulties in achieving high hole concentration of 10~(18)cm~(-3) appear to be related not only to hydrogen passivation, but also to self-compensation.

Resonant Raman Scattering and Photoluminescence Emissions from Above Bandgap Levels in Dilute GaAsN Alloy

The transitions of E0 ,E0 ＋A0, and E＋ in dilute GaAs（1-x） Nx alloys with x = 0.10% ,0.22% ,0.36% ,and 0.62% are observed by micro-photoluminescence. Resonant Raman scattering results further confirm that they are from the intrinsic emissions in the studied dilute GaAsN alloys rather than some localized exciton emissions in the GaAsN alloys. The results show that the nitrogen-induced E E＋ and E0 ＋ A0 transitions in GaAsN alloys intersect at a nitrogen content of about 0.16%. It is demonstrated that a small amount of isoelectronic doping combined with micro-photoluminescence allows direct observation of above band gap transitions that are not usually accessible in photoluminescence.

MOCVD生长Mg掺杂GaN的退火研究

用MOCVD技术在50mm蓝宝石衬底(0001)面上生长了GaN∶Mg外延膜,对样品进行热退火处理并作了Hall、双晶X射线衍射(DCXRD)和室温光致发光谱(PL)测试.Hall测试结果表明,950℃退火后空穴浓度达到5×1017cm-3以上,电阻率降到2.5Ω·cm;(0002)面DCXRD测试发现样品退火前、后的半峰宽均约为4′;室温PL谱中发光峰位于2.85eV处,退火后峰的强度比退火前增强了8倍以上,表明样品中大量被H钝化的受主Mg原子在退火后被激活.

Metalorganic Chemical Vapor Deposition of GaNAs Alloy Using Dimethylhydrazine as Nitrogen Precursor

GaNAs alloy is grown by metalorganic chemical vapor deposition (MOCVD) using dimethylhydrazine (DMHy) as the nitrogen precursor. High-resolution X-ray diffraction (HRXRD) and secondary ion mass spectrometry (SIMS) are combined in determining the nitrogen contents in the samples. Room temperature photoluminescence (RTPL) measurement is also used in characterizing. The influence of different Ga precursors on GaNAs quality is investigated. Samples grown with triethylgallium (TEGa) have better qualities and less impurity contamination than those with trimethylgallium (TMGa). Nitrogen content of 5.688% is achieved with TEGa. The peak wavelength in RTPL measurement is measured to be 1278.5nm.

Characterization of Ga N_x As_(1 - x) Alloy Grownon Ga As by Molecular Beam Epitaxy

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