单层MXene纳米片Ti2N电磁特性的过渡金属(Sc、V、Zr)掺杂效应

二维材料MXene纳米片由于具有较大的比表面积和较高的电子迁移率而受到广泛的关注。本文采用基于密度泛函理论的第一性原理计算,对单层MXene纳米片Ti₂N电磁特性的过渡金属(Sc、V、Zr)掺杂效应进行了系统研究。结果表明,所有过渡金属掺杂体系结合能均为负值,结构均稳定;其中Ti₂N-Sc体系的形成能为-2.242 eV,结构更易形成,且保持稳定;掺杂后Ti₂N-Sc、Ti₂N-Zr体系磁矩增大;此外,Ti₂N-Sc体系中保留了较高的自旋极化率,达到84.9%,可预测该体系在自旋电子学中具有潜在的应用价值。     

一种通过梯形PPMgLN波导倍频实现带宽可调谐光源的理论研究

本文设计了一种梯形的周期极化掺镁铌酸锂(PPMgLN)波导,并通过在传播方向上引入温度梯度来拓宽其倍频(SHG)过程的泵浦光源可接收带宽。通过有限差分的光束传输法,计算波导的有效折射率,并进行波导尺寸的设计。结果表明,通过改变梯形波导不同位置的温度,使其形成一个温度梯度,可拓宽泵浦光源的波长可接收带宽。本文所设计的PPMgLN波导最大泵浦光源可接收带宽为C波段,即1 530~1 565 nm,该波导可倍频C波段,得到输出波段带宽为765~782.5 nm,温度调谐范围为30~150 ℃。     

以磷化铁为添加剂沿(111)面生长磷掺杂金刚石大单晶

掺杂是调控金刚石性能的一种重要手段。本文采用温度梯度法,在5.6 GPa、1 312 ℃的条件下,选用Fe₃P作为磷源进行磷掺杂金刚石大单晶的合成。金刚石样品的显微光学照片表明,随着Fe₃P添加比例的增加,金刚石晶体的颜色逐渐变深,包裹体数量逐渐增加,晶形由板状转变为塔状直至骸晶。金刚石晶形的变化表明Fe₃P的添加使生长金刚石的V形区向右偏移,这是Fe₃P改变触媒特性的缘故。红外光谱分析表明,Fe₃P的添加使金刚石晶体中氮含量上升,这说明磷的进入诱使氮原子更容易进入金刚石晶格中。激光拉曼光谱测试表明,随着Fe₃P添加比例的增加,所合成的掺磷金刚石的拉曼峰位变化不大,其半峰全宽(FWHM)值变大,这说明磷的进入使得金刚石晶格畸变增加。XPS测试结果显示,随着Fe₃P添加比例的增加,金刚石晶体中磷相对碳的原子百分含量也会增加,这意味着添加Fe₃P所合成的金刚石晶体中有磷存在。     

雾化辅助化学气相沉积法氧化镓薄膜生长研究

采用自主设计搭建的雾化辅助化学气相沉积系统设备,开展了Ga₂O₃薄膜制备及其特性研究工作。通过X射线衍射研究了沉积温度、系统沉积压差对Ga₂O₃薄膜结晶质量的影响。结果表明,Ga₂O₃在425~650 ℃温度区间存在物相转换关系。随着沉积温度从425 ℃升高至650 ℃,薄膜结晶分别由非晶态、纯α-Ga₂O₃结晶状态向α-Ga₂O₃、β-Ga₂O₃两相混合结晶状态改变。通过原子力显微镜表征探究了生长温度对Ga₂O₃薄膜表面形貌的影响,从475 ℃升高至650 ℃时,薄膜表面粗糙度由26.8 nm下降至24.8 nm。同时,高分辨X射线衍射仪测试表明475 ℃、5 Pa压差条件下的α-Ga₂O₃薄膜样品半峰全宽仅为190.8″,为高度结晶态的单晶α-Ga₂O₃薄膜材料。     

Evolution of electrical conductivity and semiconductor to metal transition of iron oxides at extreme conditions

Iron oxides are widely found as ores in Earth's crust and are also important constituents of its interiors. Their polymorphism, composition changes, and electronic structures play essential roles in controlling the structure and geodynamic properties of the solid Earth. While all-natural occurring iron oxides are semiconductors or insulators at ambient pressure, they start to metalize under pressure. Here in this work, we review the electronic conductivity and metallization of iron oxides under high-pressure conditions found in Earth's lower mantle. We summarize that the metallization of iron oxides is generally controlled by the pressure-induced bandgap closure near the Fermi level. After metallization, they possess much higher electrical and thermal conductivity, which will facilitate the thermal convection, support a more stable and thicker D^{$\prime\prime$} layer, and formulate Earth's magnetic field, all of which will constrain the large-scale dynamos of the mantle and core.     

1,3,5-三(羧基甲氧基)苯镍配位聚合物的合成、晶体结构及性质研究

采用溶剂热法,1,3,5-三(羧基甲氧基)苯为定向配体和乙酸镍反应构筑了一个新型的金属配位聚合物[Ni(TB)₂(H₂O)₂]_n·2H₂O,其中H₃TB=1,3,5-三(羧基甲氧基)苯,通过元素分析、IR及X射线单晶衍射对配合物结构进行表征,并研究其荧光性质、热稳定性及Hirshfeld表面作用力。单晶结构分析表明,该配合物属于三斜晶系,空间群$P \overline{1}$,配合物中心离子Ni(Ⅱ)分别与来自两个水分子上的氧原子及四个不同1,3,5-三(羧基甲氧基)苯配体的羧酸氧原子配位,形成六配位的NiO₆八面体构型,并通过与1,3,5-三(羧基甲氧基)苯配体的氧原子配位不断延伸形成具有孔洞结构的一维链状构型。配合物具有良好的荧光性能和热稳定性。Hirshfeld表面作用分析表明配合物分子中O…H/H…O作用占主导且占比为39.0%,而H…H的作用力占比为25.9%,O…O的作用力占比为13.6%。     

Synthesis of flower-like WS2 by chemical vapor deposition

Flower-like tungsten disulfide (WS₂) with a diameter of 5-10 μm is prepared by chemical vapor deposition (CVD). Scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), Raman spectroscopy, and ultraviolet-visible (UV-vis) spectroscopy are used to characterize its morphological and optical properties, and its growth mechanism is discussed. The key factors for the formation of flower-like WS₂ are determined. Firstly, the cooling process causes the generation of nucleation dislocations, and then the "leaf" growth of flower-like WS₂ is achieved by increasing the temperature.     

不同退火条件对PEALD制备的Ga2O3薄膜特性的影响

利用等离子增强原子层沉积技术(PEALD)在c面蓝宝石衬底上制备了氧化镓(Ga₂O₃)薄膜,研究了退火气氛(v(N₂)∶v(O₂)=1∶1(体积比)、空气和N₂)及退火时间对Ga₂O₃薄膜晶体结构、表面形貌和光学性质的影响。研究结果表明,退火前的氧化镓处于亚稳态,不同退火气氛下退火后晶体结构发生明显改变,而且退火气氛中N₂比例增加有利于Ga₂O₃重结晶。在N₂气氛下退火达到30 min,薄膜结构已由亚稳态转变成择优取向的β-Ga₂O₃。而且表面形貌分析表明,退火30 min后表面形貌开始趋于稳定,表面晶粒密度不再增加。另外实验样品在 400~800 nm的平均透射率几乎是100%,且光吸收边陡峭。采用N₂气氛退火,对于富氧环境下沉积的Ga₂O₃更利于薄膜表面原子迁移,以及择优取向Ga₂O₃重结晶。     

Analysis on First-stage Ignition of n-Heptane at Low Temperatures with a Lumped Skeletal Mechanism

Two-stage ignition exists in the low-temperature combustion process of n-heptane and the first-stage ignition also shows a negative temperature coefficient(NTC) phenomenon. To study key reactions and understand chemical principles affecting the first-stage ignition of n-heptane, a lumped skeletal mechanism with 62 species is obtained based on the detailed NUIGMech1.0 mechanism using the directed relation graph method assisted by sensitivity analysis and isomer lumping. The lumped mechanism shows good performance on ignition delay time under wide conditions. The study revealed that the temperature after the first-stage ignition is higher and a larger amount of fuel is consumed at lower initial temperatures. The temperature at the first-stage ignition is relatively insensitive to the initial temperature. Further sensitivity analysis and reaction path analysis carried out based on the lumped mechanism show that the decomposition of RO₂ to produce alkene and HO₂is the most important reaction to inhibit the first-stage ignitions. The chain branching explosion closely related to the first-stage ignition will be terminated when the rate constant for the RO₂ decomposition is larger than that of the isomerization of RO₂ to produce QOOH. The NTC behavior as well as other characteristics of the first-stage ignition can be rationalized from the competition between these two reactions.