ITO前驱物氢氧化铟In(OH)Zr3理论研究

分析了铟锡氧化物IT0（Indium Tin Oxide）前驱体氢氧化铟In(OH)3的结构，理论计算了其马德隆常数和晶格能,其值分别为2.9488和-5095.21kJ/mol, 并给出了晶核表面自由能近似公式和晶核生长率的近似表达式,进而计算了采用化学沉淀法制备In(OH)3纳米粉末时的晶核形成参数, In(OH)3晶核生长初期的生长率约为0.012nm/s. 关键词： 纳米粉末 In(OH)3 表面自由能 晶核生长     

甲醇分子(CH3OH)光谱性质的理论计算

研究了气相甲醇分子(CH3OH)基态和激发态性质。在对不同方法基组所得计算结果和实验结果进行比较之后,选用MP2(full)/6-311++G(2d,2p)理论方法进行计算,得到甲醇分子(CH3OH)基态和三重激发态的几何结构、能量以及频率信息;频率计算显示基态和三重态都为稳定构型。从三重态的结构出发,解释了三重态势能面为排斥型势能面的合理性。计算了甲醇分子单重激发态的垂直激发能,比较不同方法不同基组计算的甲醇分子单重激发态的垂直激发能,发现用TDDFT 中的b3p86方法使用6-311++G**基组的计算值和实验值符合得最好。计算得到的甲醇分子在MP2(full)/6-311++G(2d,2p)的绝热电离能和垂直电离能分别为11.18eV和11.32eV;计算得到的绝热电子亲和势与垂直电子亲和势分别为0.888eV和0.893eV。计算结果对实验研究有指导意义。     

甲醇分子(CH3OH)光谱性质的理论计算

研究了气相甲醇分子(CH3OH)基态和激发态性质。在对不同方法基组所得计算结果和实验结果进行比较之后,选用MP2(full)/6-311++G(2d,2p)理论方法进行计算,得到甲醇分子(CH3OH)基态和三重激发态的几何结构、能量以及频率信息;频率计算显示基态和三重态都为稳定构型。从三重态的结构出发,解释了三重态势能面为排斥型势能面的合理性。计算了甲醇分子单重激发态的垂直激发能,比较不同方法不同基组计算的甲醇分子单重激发态的垂直激发能,发现用TDDFT 中的b3p86方法使用6-311++G**基组的计算值和实验值符合得最好。计算得到的甲醇分子在MP2(full)/6-311++G(2d,2p)的绝热电离能和垂直电离能分别为11.18eV和11.32eV;计算得到的绝热电子亲和势与垂直电子亲和势分别为0.888eV和0.893eV。计算结果对实验研究有指导意义。     

CH3OH在Ga-Rich GaAs(001)-(4×2)表面上的吸附与解离: 团簇模型的密度泛函计算

采用简单团簇模型结合密度泛函理论研究了CH3OH在Ga-Rich GaAs(001)-(4×2)表面上的吸附与解离过程. 计算结果表明, CH3OH在Ga-Rich GaAs(001)-(4×2)表面上首先会形成两种化学吸附状态, 然后CH3OH经解离生成CH3O自由基和H原子吸附在表面不同位置上. 通过比较各个吸附解离路径, 发现解离后的H原子相对更容易吸附在位于表面第二层紧邻的As原子上.     

激光烧蚀Al等离子体与甲醇团簇反应中(CH3OH)nCH3O-的形成

激光烧蚀一分子束(LA-MB)法是研究金属离子与分子团簇反应的有效方法.在气相条件下,用飞行时间质谱观测到激光烧蚀Al等离子体与脉冲分子束超声膨胀产生的甲醇团簇碰撞反应生成的(CH30H)nCH3O-(n=3～23)团簇负离子.实验发现,此序列的团簇负离子主要生成于烧蚀激光作用于脉冲分子束的后段,(CH3OH)3CH3O-离子强度始终远远大于其后的离子,并且这些离子随尺寸大小的分布变化平缓.结合量化计算,在133LYP/6-31G(d)水平上得到(CH3OH)nCH3O-(n=1～4)的可能几何构形,并推断(CH3OH)3CH3O-为-幻数结构.     

激光烧蚀Al等离子体与甲醇团簇反应中 (CH3OH)nCH3O－的形成

激光烧蚀-分子束(LA-MB) 法是研究金属离子与分子团簇反应的有效方法。在气相条件下,用飞行时间质谱观测到激光烧蚀Al等离子体与脉冲分子束超声膨胀产生的甲醇团簇碰撞反应生成的(CH3OH)nCH3O－(n=3~23)团簇负离子。实验发现,此序列的团簇负离子主要生成于烧蚀激光作用于脉冲分子束的后段,(CH3OH)3CH3O－离子强度始终远远大于其后的离子,并且这些离子随尺寸大小的分布变化平缓。结合量化计算,在B3LYP/6-31G(d)水平上得到(CH3OH)nCH3O－(n=1~4)的可能几何构形,并推断(CH3OH)3CH3O¯为一幻数结构。     

CuO/Cu2(OH)3Cl的制备及其光催化降解染料光谱性能研究

以CuCl2和NaOH为原料、微波液相加热法制得CuO/Cu2(OH)3Cl粉体作为光催化剂,XRD和FTIR进行了表征.用光度分析法测定了不同光源、溶液的酸度、催化剂的用量、光照时间等条件对染料脱色率的影响.结果表明,用太阳光作为光源照射4h,溶液的酸度为pH8,CuO/Cu3(OH)3 Cl的用量为40 mg/50 mL,氨基黑、靛蓝二磺酸钠等染料脱色率达到90%以上.加入Fe3 ,H2O2等其他物质可提高染料的脱色率.通过红外光谱和紫外光谱分析,表明染料分子在催化剂和光照条件下发生了降解.     

Ge(112)-(4×1)-In表面重构的原子结构

用扫描隧道显微镜(STM)研究了亚单层In原子引起的Ge(112)-(4×1)-In表面重构.结合随偏压极性不同而显著不同的STM图象和相应的“原子图象”,为这个重构提出了一个原子结构模型,供进一步研究参考.其中,In原子的吸附位置与它在Si(112)表面的吸附位置一致,但与Al原子和Ga原子在Si(112)表面的吸附位置不同.这个吸附位置的不同主要是由In原子较长的共价键键长引起的 关键词： 表面结构 In Ge 扫描隧道显微镜(STM)     

LaTiO3(110)薄膜分子束外延生长的精确控制和表面截止层的研究

LaTiO₃ 是一种典型的强关联电子材料, 其(110) 薄膜为通过晶格对称性、应变等的设计调控外延结构的物理性质提供了新的机会. 本文研究了SrTiO₃(110) 衬底表面金属La 和Ti 沉积所引起的微观结构变化, 进而利用电子衍射信号对分子束外延薄膜生长表面阳离子浓度的灵敏响应, 发展了原位、实时、精确控制金属蒸发源沉积速率的方法, 实现了高质量LaTiO₃(110) 薄膜的生长和对阳离子化学配比的精确控制. 由于LaTiO₃中Ti³⁺ 3d 电子的库仑排斥作用, 氧原子层截止的(110) 表面更容易实现极性补偿, 因此生长得到的薄膜表面暴露出单一类型的氧截止面.     

Synthesis and characterization of Gd(OH)3 nanobundles

Gd(OH)₃ nanobundles, which consisted of bundle-like nanorods, have been prepared through a simple and facile hydrothermal method. The crystal, purity, morphology and structural features of Gd(OH)₃ nanobundles are investigated by powder X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and energy dispersive X-ray (EDX). A possible formation mechanism of Gd(OH)₃ nanobundles is briefly discussed.     

Growth of high quality Ce~(3 ):YAP and (Ce~(3 ) Nd~(3 )): YAP single crystals

The effect of melt pretreatment of Ce~(3 ): YAP and (Ce~(3 ) Nd~(3 )): YAP and their growth ambient gases on the quality of the crystals are described. Firstly, a superheating pretreatment of YAP melt is adopted in a nitrogen atmosphere containing a little oxygen to eliminate carbon; then the YAP melt is superheated in a reduction atmosphere to fully reduce Ce~(4 ) ions into Ce~(3 ) ions in the melt. Finally, in a growth atmosphere of pure nitrogen, high quality Ce~(3 ): YAP and (Ce~(3 ) Nd~(3 )): YAP single crystals with high Ce~(3 ) concentration with only few light scattering centers were grown.     

Improved growth of solution‐deposited thin films on polycrystalline Cu(In,Ga)Se2

CdS and Zn(O,S) grown by chemical bath deposition (CBD) are well established buffer materials for Cu(In,Ga)Se₂ (CIGS) solar cells. As recently reported, a non‐contiguous coverage of CBD buffers on CIGS grains with {112} surfaces can be detected, which was explained in terms of low surface energies of the {112} facets, leading to deteriorated wetting of the chemical solution on the CIGS surface. In the present contribution, we report on the effect of air annealing of CIGS thin films prior to the CBD of CdS and Zn(O,S) layers. In contrast to the growth on the as‐grown CIGS layers, these buffer lay‐ ers grow densely on the annealed CIGS layer, even on grains with {112} surfaces. We explain the different growth behavior by increased surface energies of CIGS grains due to the annealing step, i.e., due to oxidation of the CIGS surface. Reference solar cells were processed and completed by i‐ZnO/ZnO:Al layers for CdS and by (Zn,Mg)O/ZnO:Al for Zn(O,S) buffers. For solar cells with both, CdS and Zn(O,S) buffers, air‐annealed CIGS films with improved buffer coverage resulted in higher power‐conversion efficiencies, as compared with the devices containing as‐grown CIGS layers. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

The In Situ Synthesis of Fe(OH)3 Film on Fe Foam as Efficient Anode of Alkaline Supercapacitor Based on a Promising Fe3+/Fe0 Energy Storage Mechanism

Herein, a simple in situ charge/discharge activation strategy is proposed to synthesize Fe(OH)3 film on Fe foam as an efficient anode of supercapacitors. The physical characteristics of electrodes are characterized and the electrochemical energy storage performances are investigated. Importantly, it is demonstrated the as‐synthesized Fe(OH)3@Fe foam electrode adopted a novel Fe³⁺/Fe⁰ redox reaction mechanism for energy storage in alkaline electrolytes. Compared with previously reported Fe³⁺/Fe²⁺ mechanisms, the Fe³⁺/Fe⁰ redox couple shows a more promising application value (e.g., higher theoretical‐specific capacitance, excellent conductivity of its reduction state). As for supercapacitor anodes, the electrode achieves high areal capacitance of 5.55–3.94 F cm⁻² at a current range of 20–200 mA cm⁻² and shows good stability for high‐rate and long‐term cycling. The assembled single supercapacitor device gives a high energy density of 11.64–7.43 Wh m⁻² at a power density of 157–1461 W m⁻². More importantly, the as‐adopted in situ activation strategy may also have potential value for synthesizing other transition metal oxide‐based products.     

Study of surface cell Madelung constant and surface free energy of nanosized crystal grain

Surface cell Madelung constant is firstly defined for calculating the surface free energy of nanosized crystal grains, which explains the physical performance of small crystals and may be greatly beneficial to the analysis of surface states and the study of the dynamics of crystal nucleation and growth. A new approximative expression of the surface energy and relevant thermodynamic data are used in this calculation. New formula and computing method for calculating the Madelung constant α of any complex crystals are proposed, and the surface free energies and surface electrostatic energies of nanosized crystal grains and the Madelung constant of some complex crystals are theoretically calculated in this paper. The surface free energy of nanosized-crystal-grain TiO₂ and the surface electrostatic energy(absolute value) of nanosized-crystal-grain α -Al₂O₃ are found to be the biggest among all the crystal grains including those of other species.     

Cr3+:GdAl3(BO3)4晶体生长和光谱特性的研究

采用顶部籽晶法从K2 Mo3 O10 B2 O3 助熔剂体系生长出尺寸为 30mm的Cr3 :GAB晶体 ,吸收谱测试表明 :Cr3 离子在晶体中有两个宽且强的吸收带及一个微弱的吸收线 ,两宽带中心的波长为 4 2 0和 5 95nm ,对应于 4A2 →4T1和4A2 →4T2 两个具有相同的总自旋能级之间的跃迁 ,在4A2 →4T2 吸收宽带的长波边缘处有个很小的吸收峰 ,其波长为 6 81nm ,对应于 4A2 → 2 E(R线 )的跃迁。荧光测试表明 :Cr3 :GdAl3 (BO3 ) 4(CGAB)晶体荧光宽带和一个较弱的荧光线峰并存 ,宽带范围为 6 5 0～ 85 0nm ,峰值波长为 72 3nm ,对应于4T2 → 2 E ,4A2 的联合能级跃迁 ,荧光线峰波长约为 70 0nm ,其强度较弱。计算了晶场强度和Racah参数 ,其中Dq/B =2 371,晶体属于中阶场介质。研究表明 ,CGAB晶体具备可调谐激光晶体的基本光谱要求 ,且有良好的物化性能 ,可以实现宽频带可调谐激光输出。它又具有较大的倍频系数 ,有望实现 35 0nm附近紫外的自倍频激光输出。     

Synthesis and Characterization of Nano-sized Zn(OH)2 and Zn(OH)2/PVA Nano-composite

Nano-sized Zn(OH)₂ was synthesized by the co-precipitation method. Further, the structure and properties were tested with FTIR, UV-visible spectroscopy, XRD and TGA as analytical tools. The structural morphology and size of the Zn(OH)₂ synthesized by the co-precipitation method were determined by using FESEM and HRTEM techniques. The effect of the synthesized nano-sized Zn(OH)₂ on the structural and thermal properties of PVA matrix was tested and discussed.     

A reaction cell for time‐resolved in situ XAS studies during wet chemical synthesis: the Cu2(OH)3Cl case

The use of in situ time‐resolved dispersive X‐ray absorption spectroscopy (DXAS) to monitor the formation of Cu₂(OH)₃Cl particles in an aqueous solution is reported. The measurements were performed using a dedicated reaction cell, which enabled the evolution of the Cu K‐edge X‐ray absorption near‐edge spectroscopy to be followed during mild chemical synthesis. The formed Cu₂(OH)₃Cl particles were also characterized by synchrotron‐radiation‐excited X‐ray photoelectron spectroscopy, X‐ray diffraction and scanning electron microscopy. The influence of polyvinylpyrrolidone (PVP) on the electronic and structural properties of the formed particles was investigated. The results indicate clearly the formation of Cu₂(OH)₃Cl, with or without the use of PVP, which presents very similar crystalline structures in the long‐range order. However, depending on the reaction, dramatic differences were observed by in situ DXAS in the vicinities of the Cu atoms.