磁致冷材料钆硅锗系合金中Si和Gd的重量法联测的研究

参考了HClO4脱水重量法测定Si及草酸盐重量法测定Gd的方法,建立了钆硅锗系合金中主成分Si和Gd联合测定的方法,并详细考查了共存元素及杂质元素对测定的影响。合金共存元素Ge在HCl的存在下,绝大部分可以GeCl4的形式被蒸发,达到与被测元素分离的目的。熔样过程引入的杂质元素Ni可与被测元素Gd,用氨水沉淀分离,残留Ni不足以影响Gd的测定。方法回收率在98.5%以上,Si和Gd的测量相对标准偏差分别在2.6%~3.0%和0.4%~0.5%。     

Si5H3,Si5H6,Si5Li3及Si5Na3原子簇结构的理论研究

利用Gaussian-94计算程序中的B3LYP方法，在6—311 G(2d)6d基组下，对Si5，Si5H3，Si5H6，Si5Li3和Si5Na33原子簇的几何结构进行优化和频率计算．结果表明，Si5原子簇中最稳定的具有D3h对称性的结构中，位于同一平面上的3个Si原子确实具有剩余的成键能力，可以与3个H，Li，Na原子和6个H原子形成稳定的化合物．研究还发现，虽然H，Li和Na都属同一主族，但它们与Si5原子簇中Si原子的键连方式却不同，而且它们的加入，对Si5原子簇的“三角双锥”结构也有不同的影响．     

为什么Si=Si重键难以形成?

硅是一种在地壳中仅次于氧的丰富元素,它的天然丰度大干它的同族元素碳约一百多倍。在我们周围的世界中,平均每四个原子就有一个是硅,所以硅单质及硅的化合物理应在化学领域中占有重要的地位。事实上单质硅及其化合物具有极其重要的工业价值,在许多现代工业中得到广泛应用。如水泥、陶瓷、玻璃、半导体材料等工业领域,尤其是近年来发展起来的硅珙产品,对现代工业更是有着巨大的贡献。如硅油可作织物、纸张处理剂、打光剂、消泡剂、脱模剂及润滑剂等。硅树脂可作为高级绝缘材料,用于电器及建筑方面,能耐高温、防潮、防水、防锈。硅橡胶具有优异的耐热、耐寒性和耐化学腐蚀的性能,作为性     

锂离子电池用非晶态Si/Al/Si薄膜负极材料

采用磁控溅射法在铜箔集流体上沉积了具有“三明治”结构的Si/Al/Si三层薄膜. 高分辨率透射电镜(HRTEM)和选区电子衍射(SAED)分析结果表明, 该薄膜为非晶态. 扫描电镜(SEM)和能量散射X射线能谱(EDS)结果表明, 该薄膜总厚度约为4.0 μm, 循环100周后体积膨胀率为225％. 在1.5~0.005 V(vs. Li+/Li)和0.1 mA/cm2条件下, 该薄膜电极前5周衰减较快, 而后趋于平缓. 首次放锂量为0.88 mA·h/cm2, 循环5周后, 放锂量为0.71 mA·h/cm2, 100周后的放锂量仍能保持在0.61 mA·h/cm2. 研究结果表明, Al的加入有效地抑制了Si膜的体积膨胀, 使之具有良好的循环寿命. 交流阻抗结果表明, 随着循环次数的增加, 极化电阻首先从46.9 Ω·cm2(第1周)降低到36.2 Ω·cm2(第50周), 而后又升高到47.3 Ω·cm2(第100周). Al的加入提高了Si膜的导电性, 有效地降低了其极化电阻, 改善了Si膜的电压滞后现象.     

锂离子电池用“三明治”型Si/Fe/Si薄膜负极材料的制备及其性能

采用磁控溅射法在铜箔集流体上沉积得到了具有“三明治”结构的Si/Fe/Si薄膜. 高分辨率透射电镜(HRTEM)和选区电子衍射(SAED)分析表明, 该薄膜为非晶态. 扫描电镜(SEM)和能量散射X射线能谱(EDXS)结果表明, 该薄膜循环前总厚度为3.2 μm, 循环200 周后体积膨胀率为265%. 在1.5-0.005 V(vs Li+/Li)和0.1 mA·cm-2条件下, 该薄膜电极首次吸锂量为1.85 mAh·cm-2, 70周后放锂量达最大值0.84 mAh·cm-2, 200周后放锂量仍维持在0.55 mAh·cm-2, 为最高放锂量的66%. 惰性材料铁的加入一方面提高了薄膜的导电性和电极的面积比容量, 有效抑制了电压滞后效应; 另一方面有效抑制了活性物质硅的体积膨胀, 保持了薄膜较好的循环充、放电性能.     

分子周期系

分子周期系刘秉兰（烟台师范学院化学系山东２６４０００）自１８６９年Ｍｅｎｄｅｌｅｅｖ提出元素周期表以来，对于分子周期系的研究一直是各国化学家所关注的热点，并在此领域内作出了较大贡献，取得了一定的进展。一、分子周期系的分类分子周期系通常分为两类：一是化...     

含Si—N四环的硅—硅链高聚物的研究

采用β-苯乙基甲基二氯硅烷、二苯基二氯硅烷和N,N′-双(二甲基氯硅烷基)四甲基环二硅氮烷,在甲苯中与金属钠作用缩合成两种含Si—N四环的Si—Si链聚合物。这些聚合物分子量高、熔融温度低,溶解性及热成形性好,用溶液涂膜得到具有一定强度、柔性和弹性的透明薄膜。将有机配位体加入到聚合物溶液中,其紫外光谱表明两者形成了CT复合物。     

C76Si2异构体的分子设计和光谱研究

用INDO系列方法对C76Si2的17种可能异构体进行系统理论研究, 表明最稳定异构体是由C78(C2V)沿X方向椭球长轴所穿过的六元环上的2个C原子(29, 30)被Si取代所形成, 异构体稳定性随2个Si原子沿Z方向距离增加而降低, 且取代场所附近易成为进一步反应中心; C76Si2(29, 30)电子光谱吸收峰与C78相比发生红移, 主要是由于其对称性降低和LUMO- HOMO能隙变小。     

p—Si上激光诱导局部沉积铂

现代电子工业中，电子器件基体材料多为半导体或绝缘体，因此，不用外加电源的激光诱导微区沉积技术引起了人们的重视［‘－‘j．这种高度选择性、高速沉积性、工艺简单的技术在电接插件局部镀，多芯层模块制作中的基板联线，加成法制造微带电路及其修复，半导体集成电路中布线的修复等方面有着广泛的应用前景．激光诱导液相金属沉积可在多种基体上，多种电解质溶液中进行”－“’，本课题组自90年代初从事激光镀的研究以来，已利用Ar”激光在硅片上分别实现了Ni－P合金「“］和Cll［“j的镀覆．本文采用3种不同的镀铂溶液作为电解质，在…     

Interface diffusion and chemical reaction of PZT layer/Si (111) sample during the annealing treatment in air

The interface diffusion and chemical reaction between a PZT (PbZrxTi1-xO3) layer and a Si(111) substrate during the annealing treatment in air have been studied by using XPS (X-Ray Photoelectron Spectroscopy) and AES (Auger Electron Spectroscopy). The results indicate that the Ti element in the PZT precursor reacted with residual carbon and silicon, diffused from the Si substrate, to form TiCx, TiSix species in the PZT layer during the thermal treatment. A great interface diffusion and chemical reaction took place on the interface of PZT Si also. The silicon atoms diffused from silicon substrate onto the surface of PZT layer. The oxygen atoms, which came from air, diffused into silicon substrate also and reacted with Si atoms to form a SiO2 interlayer between the PZT layer and the Si (111) substrate. The thickness of SiO2 interlayer was proportional to the square root of treatment time. The formation of the SiO2 interlayer was governed by the diffusion of oxygen in the PZT layer at low annealing tempera     

高压Na2O-SiO2系输运性质反常的分子模拟

在6000 K, 0～100 GPa范围内，对一系列Na2O-SiO2二元系进行了分子动力学模拟.这些体系包括SiO2、Na2O•10SiO2、Na2O•5SiO2、Na2O•2SiO2、Na2O•SiO2、2Na2O•SiO2.模拟结果显示，在前4个体系中，氧扩散系数随压力变化反常.在 Na2O•10SiO2, Na2O•5SiO2, Na2O•2SiO2 中，硅的扩散系数随压力变化也出现反常.在这些体系中， 20 GPa处氧的扩散系数比常压下高出一个数量级.在上述各体系中，氧扩散系数随压力变化的峰值都在20 GPa处，以前报导的SiO2体系中氧扩散系数随压力变化的峰值在30 GPa处.还观察到，在SiO2体系中，氧扩散系数最大值大致相当于硅-氧配位数以五配位为主;而在Na2O•10SiO2体系中，氧扩散系数最大值大致相当于硅-氧配位数以六配位为主.     

Total attenuated reflection infrared analysis of silicon-stabilized tri-calcium phosphate

Bioceramics based on silicon stabilized tricalcium phosphate [Si-TCP] have been investigated by attenuated total reflection infrared spectroscopy using an experimental preparation that ensures consistent high-quality spectral data. Phase normalized measurements show that changes in OH bands are primarily due to a decrease in the hydroxyapatite content; however, a band at 945 cm(-1) associated with dehydration of the apatite is visible and correlated with silicon doping. Changes in absorption bands with Si content associated with PO(4)(3-) differ for SiO(2) doping levels less than and greater than 0.2 mol of SiO(2)/mol of HA as the amount of Si-TCP phase saturates. Increased resolution allows the study of weak bands linked to Si at 668, 800, 863, and 892 cm(-1) and suggests that the loss of PO(4)(3-) coincides with the development of different silicate groups-SiO(4) at lower doping levels and a new silicon species at higher doping.     

Effects of Pt diffusion barrier layer on the interface reaction and electric properties of PZT film/Si (111) sample

The effects of the Pt diffusion barrier layer on the interface diffusion and reaction, crystallization, dielectric and ferroelectric properties of the PZT/Si(111) sample have been studied using XPS, AES and XRD techniques. Hie results indicate that the Pt diffusion barrier layer between the PZT layer and the Si substrate prohibits the formation of TiCx TiSix and SiO2 species in the PZT layer. The Pt barrier layer also completely interrupts the diffusion of Si from the Si substrate into the PZT layer and impedes the diffusion of oxygen from air to the Si substrate greatly. Although the Pt layer can not prevent completely the diffusion and reaction between oxygen and silicon, it can prevent the formation of a stable SiO2 interface layer on the interface of PZT/Si. The Pt layer reacts with silicon to form PtSix species on the interface of Pt/Si, which can intensify the chemical binding strength between the Pt layer and the Si substrate. To play a good role as a diffusion barrier layer, the Pt barrier layer     

Diffusion reaction of oxygen in HfO2/SiO2/Si stacks

We study the oxidation mechanism of silicon in the presence of a thin HfO2 layer. We performed a set of annealing in 18O2 atmosphere on HfO2/SiO2/Si stacks observing the 18O distribution in the SiO2 layer with time-of-flight secondary ion mass spectrometry (ToF-SIMS). The 18O distribution in HfO2/SiO2/Si stacks upon 18O2 annealing suggests that what is responsible for SiO2 growth is the molecular O2, whereas no contribution is found of the atomic oxygen to the oxidation. By studying the dependence of the oxidation velocity from oxygen partial pressure and annealing temperature, we demonstrate that the rate-determining step of the oxidation is the oxygen exchange at the HfO2/SiO2 interface. When moisture is chemisorbed in HfO2 films, the oxidation of the underlying silicon substrate becomes extremely fast and its kinetics can be described as a wet silicon oxidation process. The silicon oxidation during O2 annealing of the atomic layer deposited HfO2/Si is fast in its early stage due to chemisorbed moisture and becomes slow after the first 10 s.     

利用XPS 氩离子刻蚀表征锂离子电池Si/C负极材料中含硅的活性物质

以石墨、沥青和纳米硅粉为原料制备了锂离子电池Si/C负极材料,使用SEM/ BSE 、Raman、XRD、XPS及XPS氩离子刻蚀等方法对其硅活性物质进行了具体分析。结果表明,XRD和Raman仅判断出负极材料中含有活性物质单质Si;常规XPS结果发现近一半的Si已被氧化为惰性物质SiO2;而使用XPS氩离子刻蚀方法发现负极材料中Si存在5种化学态,包括活性物质单质Si、Si2O、SiO、Si2O3,及惰性物质SiO2;定量结果表明,复合材料的硅活性物质高于96.56%,且主要结构是低价态硅氧化物,而非单质Si。XPS氩离子刻蚀的分析方法为锂离子电池负极材料中硅活性物质的研究提供了新思路。     

Adsorption of silanes bearing nitrogenated Lewis bases on SiO2/Si (100) model surfaces

The present paper describes the one-pot procedure for the formation of self-assembled thin films of two silanes on the model oxidized silicon wafer, SiO2/Si. SiO2/Si is a model system for other surfaces, such as glass, quartz, aerosol, and silica gel. MALDI-TOF MS with and without a matrix, XPS, and AFM have confirmed the formation of self-assembled thin films of both 3-imidazolylpropyltrimethoxysilane (3-IPTS) and 4-(N-propyltriethoxysilane-imino)pyridine (4-PTSIP) on the SiO2/Si surface after 30 min. Longer adsorption times lead to the deposition of nonreacted 3-IPTS precursors and the formation of agglomerates on the 3-IPTS monolayer. The formation of 4-PTSIP self-assembled layers on SiO2/Si is also demonstrated. The present results for the flat SiO2/Si surface can lead to a better understanding of the formation of a stationary phase for affinity chromatography as well as transition-metal-supported catalysts on silica and their relationship with surface roughness and ordering. The 3-IPTS and 4-PTSIP modified SiO2/Si wafers can also be envisaged as possible built-on-silicon thin-layer chromatography (TLC) extraction devices for metal determination or N-heterocycle analytes, such as histidine and histamine, with "on-spot" MALDI-TOF MS detection.     

共沉淀法掺杂SiO_2对V_2O_5-WO_3/TiO_2催化剂SCR性能的影响

通过共沉淀法将SiO_2组分掺入到V2O5-WO3/SiO_2-TiO_2催化剂TiO_2载体中,并通过多种物理化学手段,考察了不同SiO_2掺杂量对催化剂结构、表面性质与SCR性能的影响.结果表明,SiO_2掺入到TiO_2中,Si与Ti形成Si—O—Ti键,使催化剂比表面积增加.Si—O—Ti键的生成以及Si Ox物种上的-OH基团使催化剂表面Br?nsted酸增加,但新增的Br?nsted酸对SCR反应不利,并且SiO_2的掺杂也使得V~(5+)含量降低,Si—O—V键合作用使分散的VOx物种更难还原.Si组分以共沉淀法掺入到V_2O_5-WO_3/TiO_2催化剂会造成脱硝活性的显著下降.     

Nanometer-scale wetting of the silicon surface by its equilibrium oxide

Despite the extremely broad technical applications of the Si/SiO2 structure, the equilibrium wetting properties of silicon oxide on silicon are poorly understood. Here, we produce new results in which a solid-state buffer method is used to systematically titrate oxygen activity about the Si/SiO2 coexistence value. The equilibrium morphology at the Si(001) surface over >8 decades of PO2 about coexistence is revealed to be a uniform sub-stoichiometric SiOx film of sub-nanometer thickness, coexisting with secondary island structures which coarsen with annealing time. A new thermodynamic method using chemical potential to stabilize and control surficial oxides in nanoscale devices is suggested.     

两亲性PS-b-PEG嵌段共聚物刷的合成及响应行为

利用原子转移自由基聚合(ATRP)和点击化学(Click)反应, 在硅基底上制备了聚苯乙烯-b-聚乙二醇(PS-b-PEG)两亲性嵌段共聚物刷. 首先, 利用ATRP方法在表面改性的硅片引发苯乙烯单体(St)的聚合, 得到PS-Br均聚刷, 然后通过叠氮化钠(NaN₃)将均聚刷末端功能化为PS-N₃, 再与炔基聚乙二醇甲醚(Alkynyl-PEG)发生Click反应, 得到PS-b-PEG嵌段共聚物刷. 通过X射线光电子能谱(XPS)和接触角测量仪表征了聚合物刷的表面化学组成和表面亲疏水性质, 证明在硅基底上接枝了嵌段共聚物刷. 用原子力显微镜(AFM)观察了PS-b-PEG嵌段共聚物刷在不同溶剂处理后的形态结构变化, 研究了其响应行为.