Synthesis,Structures, and Light‐Induced Transformation of Keto‐Functionalized Selenidogermanate Complexes

A double‐decker (DD) type selenidogermanate complex with C=O functionalized organic decoration, [(R¹Ge₄)Se₆] ( 1 , R¹ = CMe₂CH₂COMe), was synthesized by reaction of R¹GeCl₃ with Na₂Se, and subsequently underwent a light‐induced transformation reaction to yield [Na(thf)₂][(RGe^IV)₂(RGe^III)(Ge^IIISe)Se₅] ( 2 ). Similar to the observations reported previously for the Sn/S homologue of 1 , the product comprises a mixed‐valence complex with a newly formed Ge–Ge bond. However, different from the transformation of the tin sulfide complex, the selenidogermanate precursor did not produce a paddle‐wheel‐like dimer of the DD type structure, but led to the formation of a noradamantane (NA) type architecture, which has so far been restricted to the Si/Se and Ge/Te elemental combination.     

Estimation of inter-atomic force constants and phonon dispersion using correlation effects among thermal displacement of atoms in Ge

Neutron diffraction measurements have been performed on powder Ge at 6, 150 and 300 K. Oscillatory diffuse scattering intensity is clearly observed at 150 and 300 K. The diffuse scattering theory including correlation effects among thermal displacements of atoms is applied to background function in the Rietveld analysis. The inter-atomic distance and temperature dependence of the values of correlation effects are discussed. The force constants among the first, second and third nearest neighboring atoms in Ge are obtained from the values of correlation effects and Debye-Waller temperature parameters. A phonon dispersion spectrum in Λ [111] direction for Ge crystal has also been calculated at 80 K using inter-atomic force constants and the crystal structure.     

Theoretical study on structures and stabilities of [H,Ge,C,N

Theoretical investigations are performed for the first time on the simplest hydrogenated germanium cyanide [H,Ge,C,N], whose analogs [H,C(2),N] and [H,Si,C,N] have been detected in space and laboratory, respectively. The detailed potential energy surfaces in both singlet and triplet states are constructed at the CCSD(T)/6-311+G(3df,2p)//B3LYP/6-31G(d)+ZPVE level, including 18 minimum isomers and 26 interconversion transition states. The former three low-lying and kinetically stabilized isomers are HGeCN (1)1 (0.0 kcal/mol), HGeNC (1)2 (5.1 kcal/mol), and cyclic cCHNGe(1)7 (11.1 kcal/mol). In addition, five isomers HCNGe (1)3 (33.8), HNCGe (1)5 (29.8), cNHCGe (1)8 (37.9), HGeCN (3)1 (30.1), and HNCGe (3)5 (26.5) each have considerable barriers, despite their high energies. Future laboratory characterization and astrophysical detection of the eight [H,Ge,C,N] isomers, especially the former three low-lying species (1)1, (1)2, and (1)7, are highly recommended. The accurate spectroscopic data at the QCISD/6-311G(d,p) level are provided. For some species, the CBS-QB3 calculations are also performed. Wherever possible, comparisons with the analogous [H,C(2),N] and [H,Si,C,N] are made on the structural, energetic, and bonding properties.     

原子轰击调制离子束溅射沉积Ge量子点的生长演变

采用离子束溅射沉积的方法在Si衬底上生长Ge量子点,观察到量子点的生长随Ge原子层沉积厚度θ的增加经历了两个不同的阶段.当θ在6—10.5个单原子层(ML)范围内时,量子点的平均底宽和平均高度随θ增加同时增大,生长得到高宽比较小的圆顶形Ge量子点,伴随着量子点的生长,二维浸润层的厚度同时增大,量子点的分布密度缓慢增加;当θ在11.5一17 ML范围内时,获得高宽比较大的圆顶形Ge量子点,量子点以纵向生长为主导,二维浸润层的离解促进量子点的成核和长大,量子点的分布密度随θ的增加快速增大;量子点在θ由10.5 ML增加到11.5 ML时由一个生长阶段转变到另一个生长阶段,其分布密度同时发生6.4倍的增加.离子束溅射沉积Ge量子点的生长演变与在热平衡状态下生长的量子点不同,在量子点的不同生长阶段,其表面形貌和分布密度的变化特点是在热力学条件限制下表面原子动态演变的结果,θ的变化是引起系统自由能改变的主要因素.携带一定动能的溅射原子对生长表面的轰击促进表面原子的扩散迁移,同时压制量子点的成核,在浸润层中形成超应变状态,因而,改变体系的能量和表面原子的动力学行为,对量子点的生长起重要作用.     

Morphology and photoluminescence of ultrasmall size of Ge quantum dots directly grown on Si(0 0 1) substrate

High density and ultrasmall size of Ge quantum dots (QDs) have been achieved directly on Si(0 0 1) (2 × 1) reconstruction surface. Their detailed morphology was observed by atomic force microscope (AFM) and shows that small pyramids, small domes, huts, and multi-headed large domes coexist in the film grown at 400 °C, while small domes and multi-headed large domes formed at 450 °C. Their low temperature photoluminescence (PL) showed that a very strong non-phonon (NP) peak with a large blue shift of 0.19 eV at 14 K, which can be attributed to their very high areal density, 5.2 × 10¹¹ cm⁻², and sub-10-nm mean size, 7.6 ± 2.3 nm.     

红色Bi4 Ge3 O12晶体在低温下的发光性能

用下降法制备了Bi₄Ge₃O₁₂晶体,发现生长出来的圆柱状晶体外侧呈现淡红色。对红色Bi₄Ge₃O₁₂晶体进行了低温(至8 K)下的近红外发射光谱及衰减寿命等测试分析。发现低温时(200 K以下)红色Bi₄Ge₃O₁₂在1 150 nm等波长处有较强的发射峰,强度随温度降低而增强,衰减时间为几百μs。     

Al3+对Ge/Al-SiO2薄膜光致发光的影响

采用磁控溅射及后退火技术制备了不同组份和不同退火温度的Ge、Al共掺SiO₂薄膜。通过对样品的X射线光电子能谱(XPS)测试,确定了薄膜的成分和结构特征;同时还测试了样品的光致发光谱(PL谱),得到了峰值位于420 nm附近的紫光发射峰和峰值位于470 nm的蓝光发射峰。实验结果表明, Al的掺杂不仅可以显著地提高GeNOV中心和SiNOV中心的光发射效率,还可以促进GeNOV缺陷和SiNOV缺陷中心的形成,进而有利于薄膜的光致发光。     

脉冲激光烧蚀Ge产生等离子体特性的数值模拟

 针对激光烧蚀半导体材料Ge初期的特点,建立了1维的热传导和流体动力学模型。对波长为248 nm、脉宽为17 ns、峰值功率密度为4×10⁸ W/cm²的KrF脉冲激光在133.32 Pa氦气环境下烧蚀Ge产生等离子体的特性进行了数值模拟。结果表明：单个激光脉冲对靶的烧蚀深度达到55 nm,蒸气膨胀前端由于压缩背景气体产生压缩冲击波, 波前的速度最大,温度很高。从不同时刻的电离率分布图中得出,在靶面附近区域,Ge的1阶电离始终占优势;在中心区域,脉冲作用时间内,Ge的2阶电离率比1阶电离率大,脉冲结束后,Ge的2阶电离率下降,1阶电离率逐渐变大。     

基于BGO晶体的反射型法拉第光纤电流传感器

采用Bi4Ge3O12（BGO）晶体作为传感元件,设计了一种闭合磁环型光纤电流传感器,并对其传感特性进行了理论分析和实验研究.将BGO晶体加工成一带斜面的长方体,并在端面镀金属膜,通过光在晶体中多次临界反射来增大光程以提高测量灵敏度.实验测量得到的法拉第转角与采用倍频法测量的结果符合较好,但与实际结果存在一较大比例系数.对产生该系统误差的主要因素——传感头端面金属膜反射引起的相移及入射角偏离临界角时产生的相移进行了详细地理论分析和数值模拟.结果表明,金属膜反射和偏离临界角引起的相移对测量结果均有较大影响,但输出与作用在传感头上的磁感应强度呈很好的线性关系,可以通过将传感器的测量值乘上一个补偿系数来消除反射相移所产生的误差.