新金刚石电子结构的第一性原理研究

金刚石、 石墨和卡宾碳是三种常见的碳同素异构体, 其外层轨道价电子分别是以sp³-, sp²-和sp¹-形式杂化而成的^［1］. 1991年, Hirai等^［2］在研究金刚石的形成机理时, 发现了一种新的碳同素异构体, 并将其命名为新金刚石(new diamond) ^{［3, 4］}. 在许多实验过程中虽然也曾获得过新金刚石^［5~11］, 但是这些实验获得的新金刚石的样品产量都较少, 且新金刚石的颗粒尺寸都很小(小于100 nm), 因此只能采用电子衍射(ED)的方法研究其结构. Jarkov等^［9］在分析多晶体ED图谱的基础上, 认为新金刚石是面心立方结构(FCC), 其晶格常数为0.357 nm. 2001年, Konyashin等^［1］通过ED图谱、电子能量损失谱和半经验的能量计算认定新金刚石为FCC的纯碳, 其晶格常数为0.356 3 nm. 我们曾用强磁场碳黑催化法制备出大量的新金刚石^{［3,4,12~14］}, 并对新金刚石的热稳定性进行了研究^［12］, 而对其结构和性能的研究尚未见报道.     

DMF溶液中导电玻璃上沉积类金刚石薄膜

液相法制备类金刚石膜设备简单,操作容易,能大面积成膜,越来越受到研究者们的关注．Ｎａｍｂａ［１］以乙醇为介质,在１２００Ｖ电压７０℃以下沉积膜,得到了类金刚石膜;Ｓｕｚｕｋｉ等［２］以水乙二醇溶液为介质制膜,只得到了石墨相的碳膜;以乙醇的水溶液为介质利用电解热沉积膜,得到了玻璃碳和石墨碳,同时阴极钨发生碳化有ＷＣ和Ｗ２Ｃ生成［３］;Ｎｏｖｉｋｏｖ等［４］在乙炔的液氨溶液中沉积膜,Ｒａｍａｎ谱表明他们得到了类金刚石（ＤＬＣ）膜;Ｋｗｉａｔｅｋ等［５］重复了Ｎａｍｂａ的实验,证明沉积膜主要为非晶态…     

碳氢氧体系低压金刚石非平衡定态系列相图

在碳氢体系金刚石薄膜制备取得巨大成功的同时，人们开始寻找新的原料气体来制备金刚石以改善薄膜的质量和试图降低金刚石薄膜的淀积温度并提高淀积速率。首先被人们采用的是一些含氧的化合物和氢气的混合气体作原料制备金刚石，少量氧的存在不仅改善了金刚石薄膜的质量，...     

液相电化学沉积类金刚石薄膜的研究进展

采用电化学沉积法开展液相中类金刚石薄膜的制备工艺和理论的研究,对于完善类金刚石薄膜的合成技术,开拓类金刚石薄膜的应用领域,具有很重要的理论意义和实用价值。本文概述了液相电沉积技术的基本原理和方法,重点从四个方面介绍了电化学方法制备类金刚石薄膜的研究进展,总结了该方法所制备样品的性能,并对可能的反应机制作了综合性的阐述,最后对液相电沉积类金刚石薄膜的发展前景进行了展望。     

二氧化钛超薄膜的组装

近年来LB膜技术和超微粒子研究的发展，将两者有效地结合起来组装了与量子电子学、非线性光学、光电化学、化学生物传感器有关的纳米量级无机半导体材料［‘－‘j．其中TIO。纳米薄膜材料已在太阳能电池反射膜、压电铁电薄膜、电致显示器件［‘j、可逆光电池和超导薄膜［’］研究中都显示了广阔的应用前景．这类薄膜制备多采用化学气相沉积（CVD）技术和原子层外延．也有人把LB技术应用于纳米粒子的组装来制备TIO。超薄膜［”’j二本文利用烷氧基钛在水／空气界面上发生的溶胶一凝胶化反应制备TIO。基胶态粒子及其固态凝聚膜，将其与…     

电沉积Co-Cu颗粒膜的巨磁电阻效应

从１９８８年Ｂａｉｂｉｃｈ首先在磁性Ｆｅ／Ｃｒ多层膜中发现巨磁电阻效应（ＧＭＲ）以来 ［１］,由于ＧＭＲ本身的科研价值和在磁记录、磁性传感器等方面的广泛应用前景 ,引起了人们的极大关注．继多层膜之后 ,人们在金属颗粒膜如Ｃｏ Ａｇ［２］,Ｃｏ Ｃｕ［３,４］等中也相继发现了巨磁电阻效应．颗粒膜是微颗粒镶嵌于薄膜中所构成的复合材料体系．原则上 ,颗粒的组成与薄膜的组成在制备条件上应互不固溶 ,因此颗粒膜区别于合金、化合物 ,属于非均匀相组成的材料．磁性颗粒膜是磁性粒子分布在非磁性金属材料薄膜中．在磁性颗粒与非…     

真空沉积TCNQ薄膜的手性分形结构

分形是非线性科学中的一个重要分支,自１９７３年Ｍａｎｄｅｌｂｒｏｔ提出分形这一概念以来［１］,关于分形的实验和理论研究日益受到人们的重视［２,３］．自发现７,７,８,８ 四氰基对苯醌二甲烷（ＴＣＮＱ）与某些电子给体的复合物薄膜具有独特的电学特性［４,５］,至今人们对ＴＣＮＱ类薄膜器件进行了广泛的研究［６ -１０］．Ｇａｏ等［１１,１２］ 最早报导了真空离子团束 (ＩＣＢ)沉积的Ｃ６０ ＴＣＮＱ复合薄膜有独特的“海马”分形结构．由于ＩＣＢ沉积技术中的粒子有一定的荷电几率,而外加电场又会影响薄膜生长初期的分…     

聚苯胺-TCNQ复合薄膜的微观结构与电学特性

聚苯胺 (ＰＡＮＩ)作为高聚物材料 ,具有稳定性好 ,易于合成等优点．它在化学传感器、显示器、光化学电池等光电器件上有着许多潜在的应用前景．目前导电聚苯胺材料的合成、薄膜的制备与表征正在受到人们的重视．由于聚苯胺很难溶于一般的有机溶剂 ,用化学方法通过聚合物溶液用旋涂或自组装的方法成膜具有很大的局限性 ,特别是不易得到实用化的薄膜产物．而用真空蒸发沉积方法制备聚苯胺薄膜却有成膜质量高、易于控制 ,能很好与电子及微电子加工工艺相接轨等优点［１ -３］．国外已有一些关于真空蒸发沉积聚苯胺薄膜的研究报导［２ -５］,但…     

TiO2半导体薄膜的制备与特性

ＴｉＯ_２半导体薄膜的制备与特性徐明霞，徐廷献，刘宁（天津大学材料系天津３０００７２）关键词ＴｉＯ_２，半导体薄膜，制备ＴｉＯ２薄膜或涂层，作为优良的色材、氧敏传感器材料和湿式太阳电池的光电阳极材料具有广阔的应用前景［１～３］．传统制膜技术主要采用物理...     

羧基负离子型聚电解质与重氮树脂的自组装及自组装膜的光和热反应

带相反电荷的聚电解质的自组装,由于方法简单,对环境无污染,近年来备受重视［１～８］。以重氮树脂为聚正离子的聚电解质复合物,由于光照时重氮基分解,致使复合物的离子键转为共价键,溶解性发生重大改变,从而以重氮树脂为聚正离子的聚电解质复合物是一种新的光成像体系［９,１０］。张希等用重氮树脂与聚苯乙烯磺酸钠成功地制备了对极性溶剂稳定的自组装超薄膜［１１］。本文用羧基负离子聚电解质与重氮树脂进行自组装,并研究该自组装膜的光,热反应。羧基负离子聚电解质与重氮树脂的自组装超薄膜,文献上报道较少。１　聚丙烯酸钠…     

不同压力下碳氢体系低压金刚石的非平衡定态系列相图

系统压力是低压金刚石薄膜生长实验中重要的实验参数，如果采用合理的计算方法定量化地预测出压力对金刚石薄膜生长条件的影响，则可以直接用于指导其实验研究。本文报道根据非平衡热力学耦合理论模型绘制了C-H体系金刚石生长投影相图，经与大量实验结果比较相一致，并系统地计算了压力变化的碳氢体系金刚石生长非平衡定态截面相图，得到了金刚石生长区随压力变化的规律。计算得到的相图与经典平衡相图有本质不同，均有金刚石生长区，因而可以合理解决金刚石低压下连续生长而石墨被腐蚀与经典平衡热力学之间的矛盾。本文的计算结果可以为金刚石生长实验提供定量化的压力条件的选择和优化实验条件。     

添加氧影响下低压金刚石生长的条件

采用非平衡热力学耦合模型研究金刚石在CO-H₂、CO-O₂-H₂体系中的生长情况,计算不同氧含量下的金刚石生长相图,固定氧氢比考察压力变化对金刚石生长区的影响,讨论了不同氧氢含量对金刚石生长区的影响。与经典的平衡热力学理论计算所得的相图不同,本文的相图均有金刚石生长区,可以很好地解释低压下金刚石在气相中的生长,还可以用于指导低压金刚石生长的实验研究。     

氯参与的化学气相淀积金刚石的热力学分析

用非平衡热力学耦合模型研究了金刚石在CHCl体系中的生长,计算所得CHCl体系的金刚石生长的相图与大量实验结果符合良好.通过热力学分析讨论了氯的添加对提高金刚石薄膜生长速率及其质量的影响以及降低淀积温度的作用.     

CO(NH2)2-H3BO3-H2O体系相平衡研究

农作物不仅需要吸收C、H、O、N、P、K、Ca、Mg等营养元素,而且还需要吸收B、Mn、Zn等营养元素,以维持它们正常生长的需要.尿素是一种含氮量很高(46.60%)、性能很好的氮肥,而硼化合物又是一种很重要的微量元素肥料.因此,研究尿素与硼化合物间的相互作用,以得到既含氮又含硼的一种化合物,是一种很有意义的工作。目前,国外已开展了尿素与硼酸间相互作用的研究工作.研究结果表明,在一定条     

Measured and Predicted Solubility Phase Diagrams of Quaternary Systems LiBr-NaBr-MgBr2-H2O and LiBr-KBr-MgBr2-H2O at 298.15 K

The stable phase equilibria of quaternary systems LiBr-NaBr-MgBr₂-H₂O and LiBr-KBr-MgBr₂-H₂O at 298.15 K were studied by both experimental measurement(isothermal solution saturation method) and theoretical prediction(Pitzer model). The solubilities of the saturated solution have been determined experimentally and two stable phase diagrams and relevant water diagrams of the two quaternary systems were obtained. Results show that quaternary system LiBr-NaBr-MgBr₂-H₂O is hydrate II type as NaBr and NaBr·2H₂O coexistence. Its phase diagram consists of only one invariant point, four univariant curves, and five crystallization fields. The quaternary system LiBr-KBr-MgBr₂-H₂O is a complex type as the double salt KBr·MgBr₂·6H₂O formed. In addition to this double salt, the three single salts LiBr·2H₂O, KBr and MgBr₂·6H₂O also crystallize. In this paper, the solubilities of phase equilibria in above quaternary systems were also calculated by the Pitzer's electrolyte solution model. All the needed parameters can be obtained from the literature or be fitted by experimental data. On the Basis of the experimental and calculated results, the phase diagram of the quaternary system was plotted for comparison. It shows that the calculation results are consistent with the experimental ones.     

Recent studies of phase equilibria at high pressures

In its first part the present review considers the dependence of phase transition temperatures of some selected liquid crystals on pressure up to 300 MPa with differential thermal analysis (DTA) and diamond anvil techniques; here also pressure-induced phases as well as tricritical and reentrant phenomena will be discussed. In the second part the most important types of high-pressure phase diagrams of fluid mixtures are shortly reviewed. Here recent results on binary systems (containing trifluoromethane, tetrafluoromethane, nitrogen etc) will be presented and compared with data that are calculated from an equation of state. The results will be discussed in relation to some applications e.g. in fluid extraction and supercritical fluid chromatography (SFC).     

A molecular theory including hard rod interactions of liquid crystalline phases exhibited by highly polar compounds

We extend our molecular mean field model of highly polar compounds to include hard rod interactions to develop a hybrid model. The latter interactions are restricted to second virial terms, following a method developed by Koda and Kimura. This allows us to calculate pressure-temperature phase diagrams. Depending on the model parameters used, the phase diagrams exhibit the following features: nematic-nematic phase transition, bounded SmA_d region, double reentrance, reentrant nematic lake surrounded by the smectic A phase (the reentrant nematic lake merging with the main nematic sea) as well as the possibility of quadruple reentrance. We compare the calculated phase diagrams with the available experimental data.     

A molecular theory including hard rod interactions of liquid crystalline phases exhibited by highly polar compounds

We extend our molecular mean field model of highly polar compounds to include hard rod interactions to develop a hybrid model. The latter interactions are restricted to second virial terms, following a method developed by Koda and Kimura. This allows us to calculate pressure-temperature phase diagrams. Depending on the model parameters used, the phase diagrams exhibit the following features: nematic-nematic phase transition, bounded SmA_d region, double reentrance, reentrant nematic lake surrounded by the smectic A phase (the reentrant nematic lake merging with the main nematic sea) as well as the possibility of quadruple reentrance. We compare the calculated phase diagrams with the available experimental data.     

Semiempirical dynamic phase diagrams of nanocrystalline products during copper (II) acetylacetonate vapour decomposition

Nanoparticle production by Cu(acac)₂ vapour decomposition was studied. The composition of the produced particles varied from Cu to Cu₂O depending on experimental conditions. In order to explain the crystalline phase behaviour, a kinetic model to build a semiempirical dynamic phase diagram of the products was proposed. Prevailing role of copper dimers in the processes of copper and copper (I) oxide particle growth was demonstrated. The composition of products was determined by reactions on the surface of growing particles and depended on the ratio of gaseous species. The calculated dynamic phase diagrams were in excellent agreement with the experimental results.