O(1D)和CD4反应的准经典轨线

在新的全域势能面上, 用准经典轨线方法细致地研究了O(¹D)+CD₄多通道化学反应的动力学．这个势能面是用交换不变多项式方法基于MRC+Q/aug-cc-pVTZ从头算点拟合得到的．通过计算得到了产物OD+CD₃、D+CD₂OD/CD₃O和D₂+DCOD/D₂CO的分支比、平动能分布以及角度分布,结果显示理论与实验吻合得较好, 从而说明了这个反应的同位素取代效应很小． 研究表明,O(¹D)+CD₄反应是经过陷入的抽取机理发生的： 最初主要通过D原子的抽取,并不是之前人们认为的直接C-D键的插入形成CD3OD中间物后再进而解离成各个产物通道．     

Tm3+/Yb3 :LiYF4单晶的高效近红外量子剪裁及其在光伏电池中的应用

采用改进的坩埚下降法成功地生长了Tm/Yb共掺氟化钇锂单晶. 该单晶体具有每吸收一个蓝色光子并能发射出2个1000 nm近红外光子的下转换发光效应. 测定了样品的激发光谱、发射光谱和荧光衰减曲线. 在465 nm蓝光激发下观察到由Yb³⁺：²F_5/2→²F_7/2能级跃迁所致的960～1050 nm 波段的发射带,此发光带源于Tm³ 对Yb³ 离子的能量下转换过程. 应用Inokuti-Hirayama模型,研究了晶体的能量转换过程,结果表明Tm³ 向Yb³ 的能量传递是一个电偶极子相互作用机制过程. 当Tm³ 与Yb³ 离子的掺杂浓度为0.49mol%与5.99mol%时,单晶的量子剪裁效率达到最大值167.5%.     

Characterization of Cr‐doped Sb2Te3 films and their application to phase‐change memory

Phase‐change memory (PCM) is regarded as one of the most promising candidates for the next‐generation nonvolatile memory. Its storage medium, phase‐change material, has attracted continuous exploration. Along the traditional GeTe–Sb₂Te₃ tie line, the binary compound Sb₂Te₃ is a high‐speed phase‐change material matrix. However, the low crystallization temperature prevents its practical application in PCM. Here, Cr is doped into Sb₂Te₃, called Cr–Sb₂Te₃ (CST), to improve the thermal stability. We find that, with increase of the Cr concentration, grains are obviously refined. However, all the CST films exhibit a single hexagonal phase as Sb₂Te₃ without phase separation. Also, the Cr helps to inhibit oxidation of Sb atoms. For the selected film CST_10.5, the resistance ratio between amorphous and crystalline states is more than two orders of magnitude; the temperature for 10‐year data retention is 120.8 °C, which indicates better thermal stability than GST and pure Sb₂Te₃. PCM cells based on CST_10.5 present small threshold current/voltage (4 μA/0.67 V). In addition, the cell can be operated by a low SET/RESET voltage pulse (1.1 V/2.4 V) with 50 ns width. Thus, Cr–Sb₂Te₃ with suitable composition is a promising novel phase‐change material used for PCM with high speed and good thermal stability performances. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Improvement of resistive switching fluctuations by using one step lift‐off process

Bipolar resistive switching characteristics are investigated in ZrO₂ containing Cu thin layer devices, particularly for the self‐isolated‐structure device fabricated by one step lift‐off process. Compared with the traditional‐structure device, the self‐isolated‐structure device shows more uniform resistive switching characteristics. This is because the isolation of each device cell has negligible influence on each other and thus mitigates possible crosstalk between each cell. These results suggest that the feasibility of good stabilization of the resistive switching parameters can be obtained through one step lift‐off process. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Thermal stability of amorphous SiOC/crystalline Fe composite

We examined the thermal stability of amorphous silicon oxycarbide (SiOC) and crystalline Fe composite by in situ and ex situ annealing. The Fe/SiOC multilayer thin films were grown via magnetron sputtering with controlled length scales on a surface-oxidized Si (100) substrate. These Fe/SiOC multilayers were in situ or ex situ annealed at temperature of 600 °C or lower. The thin multilayer sample (~10 nm) was observed to have a layer breakdown after 600 °C annealing. Diffusion starts from low groove angle triple junctions in Fe layers. In contrast, the thick multilayer structure (~70 nm) was found to be stable and an intermixed layer (Fe_xSi_yO_z) was observed after 600 °C annealing. The thickness of the intermixed layer does not vary as annealing time goes up. The results suggest that the Fe_xSi_yO_z layer can impede further Fe, Si and O diffusion, and assists in maintaining morphological stability.     

Trapezoidal phase mask coronagraph

An angular trapezoidal phase mask used for a wideband coronagraph is proposed. The azimuthal phase of the mask is double-periodic and has both trapezoidal and constant parts in each period. This kind of continuous phase distribution can be employed to avoid the abrupt phase variation of the 6-level phase distribution we proposed previously. Numerical calculations show that this more practical phase mask can still keep its superior performance in terms of starlight elimination, small inner working angle, and good achromatism. It is of great importance that there is no singularity in this kind of mask except for a singularity at the center. This mask design is close to real manufacturing conditions, and the process technology is superior.     

Frequency-locking and threshold current-lowering effects of a quantum cascade laser and an application in gas detection field

In this paper,the frequency-locking and threshold current-lowering effects of a quantum cascade laser are studied and achieved.Combined with cavity-enhanced absorption spectroscopy,the noninvasive detection of H_2 with a prepared concentration of 500 ppm in multiple dissolved gases is performed and evaluated.The high frequency selectivity of 0.0051 cm~(-1) at an acquisition time of 1 s allows the sensitive detection of the(1-0) S(l) band of H_2 with a high accuracy of(96.53±0.29)%and shows that the detection limit to an absorption line of 4712.9046 cm~(-1) is approximately(17.26±0.63) ppm at an atmospheric pressure and a temperature of 20 ℃.     

A Novel Heterometallic Cluster-Based Coordinational Polymer with 2-[Bis-(2-hydroxy-ethyl)-Amino]-Ethanesulfonic Acid: Synthesis and Crystal Structure

A rare heterometallic cluster-based polymer [Cu₄(Hbhea)₄(μ ₂-OCH₃) K(CH₃OH))] _n ·(H₂O) _n (1) (H₃bhea = 2-[bis-(2-hydroxy-ethyl)-amino]-ethanesulfonic acid), has been synthesized and structurally determined by single crystal X-ray diffraction, elemental analysis. Crystallographic unit of 1 consists of four Cu(II), four Hbhea ligands, one methanol molecule, one methanol anion, one K ion and one crystal lattice water and formed anion cluster [Cu₄(Hbhea)₄(CH₃O)]^? which further constructed a 3-D polymer by linking the six-coordination K ions.     

Large-Scale Collision Cross-Section Profiling on a Traveling Wave Ion Mobility Mass Spectrometer

Ion mobility (IM) is a gas-phase electrophoretic method that separates ions according to charge and ion-neutral collision cross-section (CCS). Herein, we attempt to apply a traveling wave (TW) IM polyalanine calibration method to shotgun proteomics and create a large peptide CCS database. Mass spectrometry methods that utilize IM, such as HDMS^E, often use high transmission voltages for sensitive analysis. However, polyalanine calibration has only been demonstrated with low voltage transmission used to prevent gas-phase activation. If polyalanine ions change conformation under higher transmission voltages used for HDMS^E, the calibration may no longer be valid. Thus, we aimed to characterize the accuracy of calibration and CCS measurement under high transmission voltages on a TW IM instrument using the polyalanine calibration method and found that the additional error was not significant. We also evaluated the potential error introduced by liquid chromatography (LC)-HDMS^E analysis, and found it to be insignificant as well, validating the calibration method. Finally, we demonstrated the utility of building a large-population peptide CCS database by investigating the effects of terminal lysine position, via LysC or LysN digestion, on the formation of two structural sub-families formed by triply charged ions.

?     

Morphological transformations of nonequilibrium assemblies of amphiphilic diblock copolymer

Amphiphilic diblock copolymer polystyrene-block-poly(ethylene oxide) (PS-PEO) assembled into nonequilibrium bicontinuous structures or mixture of vesicles, bilayers and nanorods upon rapid micellization induced by rapid addition of selective solvent (water) into the PS-PEO solutions in a common solvent (dimethyl formamide) with different concentrations. These kinetically trapped assemblies were unstable and slowly evolved into thermodynamically favorable spheres and vesicles. The addition of non-ionic surfactant Pluronic P123 upon rapid micellization generated novel nanocages and flower-like vesicles. The nanocages spontaneously transformed into tubules capped with vesicles. These novel assemblies are beyond the classic phase diagram of block copolymer self-assemblies, especially for those primarily based on thermodynamics.