Microstructure and ferroelectric properties of r.f. magnetron sputtering derived PZT thin films deposited on interlayer (PbO/TiO2)

Lead zirconate titanate (PZT) thin films were deposited on Pt/Ti/SiO₂/Si and interlayer/Pt/Ti/SiO₂/Si substrate by radio frequency (r.f.) magnetron sputtering with a Pb_1.1Zr_0.53Ti_0.47O₃ target. The crystallization of the PZT thin films was formed only by substrate temperature. When interlayer (PbO/TiO₂) was inserted between the PZT thin film and the Pt electrode, the grain growth and processing temperature of the PZT thin films were considerably improved. Compared to PZT/Pt structure, the dielectric constant and polarization properties of the PZT/interlayer/Pt structure were fairly improved. In particular, PZT/interlayer/Pt at the substrate temperature of 400 °C showed prevalent ferroelectric properties (_r=475.97, tanδ=0.0591, P_r=23 μC/cm²). As a result of an X-ray photoelectron spectroscopy (XPS) depth-profile analysis, it was found that PZT/interlayer/Pt deposited only by substrate temperature without the post-annealing process via r.f. magnetron sputtering method remained independent of each other regardless of substrate temperatures.     

NO在Rh(100),Rh(111)面上吸附与直接分解的密度泛函理论研究

本文应用第一性原理的密度泛函(DFT)方法,使用DMol³计算程序,对NO在Rh(100)和Rh(111)面上的吸附与分解进行量化计算,力图解决NO在Rh(100)和Rh(111)面上的优选吸附位、直接分解的过渡态和活化能等重要问题.     

PdAu(100)和PdAu(111)双金属表面的密度泛函理论研究

采用密度泛函理论(Density Functional Theory DFT)研究Au(100)和Au(111)表面含有不同Pd构型时表面的形成能.结果表明,非连续Pd构型的形成能较连续Pd构型的低,在表面易形成,其中第二临位Pd对构型被证实是乙烯与醋酸结合生成醋酸乙烯反应中催化活性最高的构型.随后计算CO在不同表面Pd原子的顶位吸附能和Pd原子的d带中心,结果显示表面Pd原子与相邻金原子之间几乎没有电子传递,并且PdAu(111)表面的Pd原子d带中心随周围Au原子个数的增加而远离费米能级,伴随着CO在其上吸附能的减小,但是同样的趋势在PdAu(100)表面不存在.最后,通过计算,CO在金属表面的吸附机理为CO成键轨道5σ的电子传递给Pd原子的d带,而Pd原子的d带电子又反馈回CO的反键轨道2π*.     

乙腈、苯基氰在Cu(111)与Pd(100)表面上的吸附与反应

用高分辨电子能量损失谱(HREELS~*)对CH_3CN(乙腈)及C_6H_5CN(苯基氰)在清洁与氧覆盖的Cu(111)及Pd(100)表面上的吸附及其反应进行了研究。从198 K时CH_3CN吸附在Cu(111)及Pd(100)表面上的高分辨电子能量损失谱(HREELS)中观察到v(C≡N)几乎消失, 并在195 meV处出现一个较弱的v(C=N)谱带, 表明CH_3CN在吸附过程中C≡N再杂化为C=N,C,N原子分别与金属表面原子键合并C=N平行于表面。从198 K时C_6H_5CN在Pd(100)及Cu(111)上的HREELS表明C_6H_5CN的环平面与CN平行于金属表面。在185K时C_6H_5CN在氧覆盖的Pd(100)表面上的HREELS与其在清洁表面上的相似。并未观察到覆盖氧增强了C_6H_5CN在Pd(100)上的吸附及其它效应。C_6H_5CN吸附在氧覆盖的Cu(111)表面上产生了C_6H_5CNO的特征谱带。     

Au单晶表面氟表面活性剂FSN自组装膜的电化学行为

研究Au(111)和Au(100)表面非离子型氟表面活性剂FSN自组装膜的电化学行为.电化学扫描隧道显微术和循环伏安法测试表明,在0～0.8 V电位区间,FSN自组装膜未发生氧化还原,均一性好,可稳定地存在于电极表面,并显著抑制硫酸根离子在电极表面的吸附和Au单晶表面的重构.在FSN自组装膜Au单晶电极的初始氧化阶段,Au(111)表面有少量突起,而Au(100)表面呈现台阶剧烈变化,但FSN自组装膜的吸附结构没有改变.与Au(100)表面相比,Au(111)表面形成的FSN自组装膜可更有效地抑制Au表面的氧化.     

Structure-relationships in electrocatalysis: oxygen reduction and hydrogen oxidation reactions on Pt(111) and Pt(100) in solutions containing chloride ions

Kinetics of the oxygen reduction reaction (orr) and the hydrogen evolution–oxidation reactions (her/hor) were studied on the Pt(111) and Pt(100) surfaces in 0.05 M H₂SO₄ containing Cl⁻. The orr is strongly inhibited on the (100) surface modified by adsorbed Cl⁻ (Cl_ad), and it occurs as a 3.5e⁻ reduction via solution phase peroxide formation. In the hydrogen adsorption (H_upd) potential region, the orr is even more inhibited, and corresponds only to a 2 e⁻ reduction at the negative potential limit where the electrode is covered by one monolayer of H_upd and some (unknown) amount of Cl_ad. On the Pt(111)---Cl_ad surface, the orr is inhibited relatively little (in addition to that caused by strong bisulfate anion adsorption on this surface), and the reaction pathway is the same as in Cl⁻ free solution. The kinetics of the hor on Pt(111) are the same in pure solution and in a solution containing Cl⁻, since Cl_ad does not affect platinum sites required for the breaking of the H---H bond. A relatively large inhibition of the hor is observed on the (100) surface, implying that strongly adsorbed Cl_ad is present on the surface even near 0 V.     

In-Au(111)和Ir-Au(111)合金表面的性质及其对巴豆醛的吸附比较

采用密度泛函理论研究了M（M=In,Ir）原子修饰的M-Au（111）合金表面的稳定性,并选其最优模型探讨了合金表面的活性及其对巴豆醛的吸附。合金的几何构型、形成能和结合能等性质表明,In-Au（111）面的稳定性随In原子的间距增大而提高,Ir-Au（111）面的稳定性随Ir原子的间距增大而降低。对于巴豆醛在MAu（111）面上的吸附,当其通过C＝O吸附于合金表面的Top_M位时,吸附能最大,吸附构型最稳定。从巴豆醛的结构变化、态密度、差分电荷密度以及Mulliken电荷布居等分析可以看出,稳定吸附构型的巴豆醛分子形变较大,电荷转移明显。其中,位于-7.04 eV至费米能级处的p、d轨道杂化,对体系的吸附具有重要贡献。分析比较In-Au（111）面与Ir-Au（111）面,发现后者的配体效应更佳,不仅具有更高的稳定性和活性,而且对于巴豆醛具有更强的吸附力。此外,相比于改性前的Au（111）面,M原子的修饰明显提升了金属表面的稳定性及吸附能力。     

Pt4(OCOCH3)4(OCOCH=CH2)4的合成及其在n型单晶硅表面的嫁接与组装

利用羧基取代法, 通过化合物Pt4(OCOCH3)8与过量的丙烯酸作用合成了配合物Pt4(OCOCH3)4(OCOCH=CH2)4. 晶体结构研究结果表明, 化合物Pt4(OCOCH3)8中的4个乙羧基能够被烯丙羧基有规律地选择性替换, 从而形成一个含双键的对称铂配合物. 利用Si—H与不饱和键的加成性质将该配合物嫁接到氢化n型单晶硅(111)表面, 发现配合物Pt4(OCOCH3)4(OCOCH=CH2)4除了能嫁接到单晶硅表面外, 还能在n型单晶硅表面进行自组装而形成许多岛状纳米粒子, 这种组装体系具有良好的热稳定性和一定的抗酸性.     

离子液体中Au(111)和Pt(111)表面Ge欠电位沉积的现场STM研究

本文研究BMIPF₆离子液体中Au(111)和Pt(111)表面Ge的电沉积行为. 循环伏安法测试结果表明,在含0.1 mol·L^-1 GeCl₄的BMIPF₆溶液Au(111)和Pt(111)表面均有两个与Ge沉积过程相关的还原峰. 第一个还原峰包含了Ge⁴⁺还原成Ge²⁺及Ge的欠电位沉积,第二个还原峰对应Ge的本体沉积. 现场扫描隧道显微镜研究结果表明,Ge在Au(111)和Pt(111)表面均有两层欠电位沉积. 第一层欠电位沉积厚度约为0.25 nm、形貌平整、带有缝隙的亚单层结构. 第二层欠电位沉积形貌相对粗糙的点状团簇结构. 该欠电位沉积过程伴随表面合金化.     

DFT Study of Thiophene Adsorption on the Pd（111） and Pt（111） Surfaces

Thiophene adsorption on the(111) surfaces of Pd and Pt have been investigated by density functional theory.The results indicate that the adsorption at the hollow sites is the most stable.To our interest,the molecular plane of thiophene ring is distorted with C=C bond being elongated to 1.450  and C-C bond being shortened to 1.347 ,and the C-H bonds tilt 13.91～44.05o away from this plane.Furthermore,analysis on population and density of states verified the calculated adsorption geometries.Finally,charge analysis suggests that thiophene molecule is an electron acceptor,reflecting the interaction between the lone pair of sulfur and the d-orbitals of metal.     

Chemical Reconstruction of Pt-Rh(100) Alloy and Pt/Rh(100), Rh/Pt(100) Bimetallic Surfaces

When Cu(110), Ni(l 10), Ag(110) surfaces are exposed to O₂ at room temperature, one dimensional metal-oxygen strings grow in the < 001 > direction of the (110) surfaces. A similar phenomenon occurs in the adsorption of H₂ on Ni( 110) surface at room temperature, where the one dimensional strings grow along the < 110 > direction. These phenomena are undoubtedly different from the adsorption induced reconstruction but are explained by the chemical reconstruction involving the formation of quasi-compounds and their self-ordering on the metal surfaces. The chemical reconstruction is indispensablly important to understand the structure and catalysis of alloy and bimetallic surfaces. Pt_0.25Rh_0.75(100) alloy surface being active for the reaction of NO with H₂ is an interesting example. When the Pt-Rh(100) alloy surface is exposed to NO or O₂ at arround 500 K, a p(3 × 1) ordered Rh-O over-layer is obtained on a Pt-enriched 2nd layer by the chemical reconstruction. Ordering of Rh-0 in the p(3 × 1) structure on the Pt(100) surface was reproduced by heating a Rh/Pt(100) bimetallic surface in O₂, and the chemical reconstruction making the p(3 × 1) Rh-O overlayer on a Pt enriched 2nd layer was also proved by heating a Pt/Rh(100) bimetallic surface in O₂ or NO. The activation mechanism of the Pt-Rh alloy and the Pt/Rh bimetallic surfaces by the chemical reconstruction was evidently shown by using a Pt deposited Rh(100), Pt/Rh(100), surface. That is, the Pt/Rh(100) is not so active for the reaction of NO with H₂, but the reconstructed p(3 × 1)Rh-O/Pt-layer/Rh(100) surface is very active for the reaction. Therefore, it was concluded that the chemical reconstruction of the Pt-Rh catalyst makes the active surface which is composed of Rh-O and a Pt layer.     

Au(111)电极上CTAB吸脱附过程的循环伏安研究

本文运用循环伏安方法研究十六烷基三甲基溴化铵(CTAB)在Au(111)电极上的吸附行为. 首次给出CTAB在Au(111)电极上的循环伏安曲线,其0.18 V、0.27 V有两对可逆的特征电流尖峰,均受扩散控制,且与卤素离子种类有关. 研究表明,烷基铵阳离子的吸脱附及吸附层相转变与Au(111)电极表面结构密切相关.     

金刚石（111）清洁／附氢表面与甲基的相互作用

利用Ａｍｌ分子轨道法计算了金刚石（１１１）清洁／附氢表面与甲基相互作用的特殊势能曲线，深入研究了清洁、附氢表面与甲基相互作用下基底弛豫重建、四甲基构型及成键能的差别，进而得到附氢表面较清洁表面更适合于甲基吸附，是更好的金刚石薄膜生长址的结论。在距基底表面０．５ｎｍ内，甲基与清洁、附氢表面皆有强烈的相互作用。     

Ru修饰前后Pd(111)面的性质及对糠醛吸附的比较研究

采用密度泛函理论研究了Pd(111)面和Ru-Pd(111)面的性质及对糠醛的吸附.原子尺寸因素、相对键长、形成能及d带中心等计算结果表明,Ru-Pd(111)面比Pd(111)面稳定且活性强,Ru的修饰优化了Pd(111)面的几何构型.糠醛在Pd(111)面及Ru-Pd(111)面的初始吸附位分别为P(top-bridge)位及P(Pd-fcc-Ru-fcc)位时,吸附能最大,吸附构型最稳定.由电荷布局和差分电荷密度可得,糠醛在Ru-Pd(111)面上电荷转移数更多,相互作用更强烈,因此吸附能更大.分析态密度可知,产生吸附的主要原因是位于-7.34 eV处至费米能级处的p,d轨道杂化.吸附于Ru-Pd(111)面后糠醛分子的p轨道向低能级偏移程度更明显,使Ru改性后的Pd催化剂具有更好的催化活性.     

乙烷在Ni(111)表面的吸附和分解

研究了乙烷在Ni(111)表面解离的可能反应机理, 使用完全线性同步和二次同步变换(complete LST/QST)方法确定解离反应的过渡态. 采用基于第一性原理的密度泛函理论与周期平板模型相结合的方法, 优化了C2H6裂解反应过程中各物种在Ni(111)表面的top, fcc, hcp和bridge位的吸附模型, 计算了能量, 并对布居电荷进行分析, 得到了各物种的有利吸附位. 结果表明, 乙烷在Ni(111)表面C—C解离的速控步骤活化能为257.9 kJ·mol-1, 而C—H解离速控步骤活化能为159.8 kJ·mol-1, 故C—H键解离过程占优势, 主要产物是C2H4和H2.     

甲基、氨基和甲胺在清洁及C(N,O)改性的Mo(100)表面的吸附

采用广义梯度近似(GGA)的密度泛函理论(DFT), 并结合平板模型, 研究了甲基、氨基和甲胺在清洁及C(N, O)改性的Mo(100)面的吸附行为. 计算结果表明, 在较低覆盖度下(θ=1/6 ML(monolayer)), 吸附物种在不同表面上的稳定吸附位的吸附能变化不大; 而在较高覆盖度下(θ=1/4 ML), 其稳定的吸附位置可能发生变化, 且吸附能有了明显的区别. 它们在改性的Mo(100)表面吸附能较清洁表面小, 并且按C、N、O的顺序降低. 究其原因可归结为C、N、O性原子的存在使得金属表面的供电子能力减弱, 从而导致金属的d带中心的下移. 通过对金属Mo的d带性质的分析, 发现d带中心只能笼统地说明改性原子对于清洁表面的性质有一定的影响, 不能很好地体现C、N、O对于清洁表面性质影响的差异, 而dz2轨道的能量中心却能很好地反映出吸附物种在改性表面上的吸附能按C、N、O的顺序依次减小这一规律.     

The bonding between NO and the NiO(100) surface

Summary The interaction between NO and different possible adsorption sites of the NiO(100) surface is studied. The Ni²⁺ cation gives a bonding to NO in reasonable agreement with experiment, but only if a crystal potential corresponding to less than completely ionic charges is assumed. The computed angle of 43° is also in good agreement with experiment. O^1– sites in both weak and strong crystal potentials also give a strong interaction with NO, 1.3 and 0.5 eV, respectively. In this case the angle is larger or around 70°. The O^2– anion and Ni¹⁺ sites do not give any significant bonding irrespective of assumed crystal potential and can be excluded as adsorption sites. The computed vibrational frequency for the adsorbed NO show shifts of +50, –85 and –200 cm^–1 for adsorption on Ni²⁺ in the weak potential, and O^1– in strong and weak potential, respectively. Only one, downwards shifted, frequency has been observed in the experiment but the most likely candidate for the experimentally observed adsorption site with a binding of 0.5 eV, is still the Ni²⁺ in a weak potential. Nitrogen core level shifts are also computed and discussed and the fully screened core-hole state is obtained for a cluster model, NiF₄O+NO, of Ni²⁺ in NiO with an ionicity lower than the standard ± 2.This work is dedicated to Prof. Inga Fischer-Hjalmars     

The structure and vibrational spectra of some ferroelectric and ferroelastic alkylammonium halogenoantimonates(III) and bismuthates(III)

Crystals from the rich family of alkylammonium halogenoantimonates(III) and bismuthates(III) containing small bioctahedra as well as infinite two- or one-dimensional polyoctahedral units attract particular attention from the point of view of possible applications. Such crystals exhibit a wealth of phase transitions including those to ferroelectric and ferroelastic phases. The analysis of vibrational spectra performed in this paper with respect to modes assigned to alkylammonium group shows that their interactions with polyanionic sublattice is of medium strength. The absorption pattern and particularly the splitting of bands on cooling very well correlates with other anomalies of physical properties and particularly with the behaviour of second moment of PMR lines and T₁ and T_1ρ relaxation times as functions of temperature. The temperature behaviour of modes is well described in terms of pseudospin–phonon coupling model that we presented for different modes in various crystals. The role of anionic dynamics is not sufficiently recognised but in one case, namely for the low temperature transition in (MA)₃Bi₂Br₉ crystal this role is predominant, according to vibrational and NQR spectra of methylammonium and isostructural caesium salt.     

PZT/P(VDF-TrFE)纤维膜的静电纺丝制备及其性能

以锆钛酸铅压电陶瓷(PZT)和聚(偏氟乙烯-三氯乙烯)(P(VDF-TrFE))共聚物为原料,利用静电纺丝的方法制备了PZT/P(VDF-TrFE)纤维膜。用扫描电子显微镜、精密阻抗测试仪和拉力试验机对纤维膜的形貌、电学性能、力学性能进行了表征。结果表明,适当地提升PZT的质量分数能有效提升纤维膜中纤维丝的均匀性。当PZT质量分数为4%时,纤维丝的均匀性最佳;静电纺丝方法能够得到低介电常数的PZT/P(VDF-TrFE)纤维膜,并且通过调节PZT的质量分数,可以保证纤维膜的介电常数在一定范围内变化。PZT颗粒的加入能够有效调节PZT/P(VDFTrFE)纤维膜的拉伸强度和断裂伸长率,当PZT质量分数为4%时,纤维膜具有最佳的综合力学性能,能够满足可穿戴设备的要求。     

Structure‐Dependent Anchoring of Organic Molecules to Atomically Defined Oxide Surfaces: Phthalic Acid on Co3O4(111), CoO(100), and CoO(111)

We have performed a model study to explore the influence of surface structure on the anchoring of organic molecules on oxide materials. Specifically, we have investigated the adsorption of phthalic acid (PA) on three different, well‐ordered, and atomically defined cobalt oxide surfaces, namely 1) Co₃O₄(111), 2) CoO(111), and 3) CoO(100) on Ir(100). PA was deposited by physical vapor deposition (PVD). The formation of the PA films and interfacial reactions were monitored in situ during growth by isothermal time‐resolved IR reflection absorption spectroscopy (TR‐IRAS) under ultrahigh vacuum (UHV) conditions. We observed a pronounced structure dependence on the three surfaces with three distinctively different binding geometries and characteristic differences depending on the temperature and coverage. 1) PA initially binds to Co₃O₄(111) through the formation of a chelating bis‐carboxylate with the molecular plane oriented perpendicularly to the surface. Similar species were observed both at low temperature (130 K) and at room temperature (300 K). With increasing exposure, chelating mono‐carboxylates became more abundant and partially replaced the bis‐carboxylate. 2) PA binds to CoO(100) in the form of a bridging bis‐carboxylate for low coverage. Upon prolonged deposition of PA at low temperature, the bis‐carboxylates were converted into mono‐carboxylate species. In contrast, the bis‐carboxylate layer was very stable at 300 K. 3) For CoO(111) we observed a temperature‐dependent change in the adsorption mechanism. Although PA binds as a mono‐carboxylate in a bridging bidentate fashion at low temperature (130 K), a strongly distorted bis‐carboxylate was formed at 300 K, possibly as a result of temperature‐dependent restructuring of the surface. The results show that the adsorption geometry of PA depends on the atomic structure of the oxide surface. The structure dependence can be rationalized by the different arrangements of cobalt ions at the three surfaces.