2,7-二辛基[1]苯并噻吩并[3,2-b]苯并噻吩在Cu(100)上的吸附生长以及能级结构演化

结合紫外光电子能谱(UPS),X射线光电子能谱(XPS),原子力显微镜(AFM)和掠入射X射线衍射谱(GIXRD)等实验手段,系统研究了2,7-二辛基[1]苯并噻吩并[3,2-b]苯并噻吩在Cu(100)基底上的吸附、生长过程以及界面能级结构.发现第一层的分子平躺吸附于Cu(100)上形成稳定的物理吸附.随膜厚增加,分子取向转为直立于薄膜平面,生长模式转为岛状生长模式.分子取向的变化导致膜厚大于16A的薄膜的能级结构发生变化.直立取向的分子在表面形成由内向外的电偶极层,引起真空能级下降,功函数降低;而轨道电离的各向异性使得分子从平躺到直立时UPS得到的分子最高占据轨道(HOMO)峰型发生变化,且HOMO起始边向深结合能端移动整体上随着膜厚的增加,真空能级向下弯曲,HOMO下移,电离能则先减小后增大下移的能带结构利于电子从界面向表面的迁移以及空穴从表面向界面的迁移.     

衬底对PTCDA薄膜结构与电荷输运特性的影响

在不同导电衬底(Au,Al和ITO)上制备了PTCDA薄膜,用XRD和AFM技术研究了PTCDA薄膜的结构和表面形貌。结果表明,薄膜中的大部分PTCDA分子平面与衬底不平行,这表明薄膜垂直方向的电流传导将以电子传输为主;在ITO和Au衬底上生长的PTCDA薄膜晶粒排列规则,在薄膜垂直方向呈现出较好的电子传输性能;而在Al衬底上生长的PTCDA薄膜晶粒排列无序,电子传输性能差。通过制备单层结构有机薄膜器件,研究了PTCDA薄膜垂直方向的电子迁移率。综合应用金属-有机界面的热电子发射理论和有机层体内空间电荷限制传导理论,并考虑电场强度对迁移率变化的影响,对ITO/PTCDA/Al器件的电流密度-电压曲线进行拟合,得到ITO衬底上生长的PTCDA薄膜在垂直方向随电场强度变化的电子迁移率数值。     

苝四甲酸二酐薄膜电子结构的同步辐射共振光电子能谱研究

利用基于同步辐射的近边X射线吸收精细结构谱(NEXAFS)和共振光电子谱(RPES)研究了苝四甲酸二酐分子(PTCDA)薄膜的电子结构.碳K边NEXAFS谱中能量小于290 eV的四个峰对应于PTCDA分子不同化学环境碳原子1s电子到未占据分子轨道的共振跃迁.RPES谱中观察到共振光电子发射和共振俄歇电子发射导致的共振峰结构,以及二次谐波激发的碳1s信号.根据电子动能对入射光能量的依赖性分别对三类峰结构进行了归属.同时,发现PTCDA分子轨道共振光电子峰的强度具有光子能量依赖性.这种能量选择性共振增强效应是由于PTCDA分子轨道空间分布差异导致的.共振俄歇峰主要源于高结合能(4.1 eV)分子轨道能级电子参与的退激发过程.明确RPES实验谱图中各个峰结构的起源有助于准确利用基于RPES的芯能级空穴时钟谱技术定量估算有机分子/电极异质界面处电子从分子未占据轨道到电极导带的超快转移时间.     

2,7-二辛基[1]苯并噻吩并[3,2-b]苯并噻吩(C8-BTBT)与MoS_2界面的能级匹配与薄膜生长

结合紫外光电子能谱(UPS)、X射线光电子能谱(XPS)和原子力显微镜(AFM)等实验手段系统研究了C8-BTBT沉积在层状Mo S2基底上的界面能级匹配、薄膜生长和分子取向。研究发现C8-BTBT分子竖直生长在Mo S2上,生长过程中界面的真空能级(VL)、最高占据态轨道(HOMO)和电离能(IP)都出现了非常规的弯曲现象。这种能级弯曲行为可归因于直立分子从界面相到体相的转变过程中,其分子倾斜角(θ)存在一定的渐变,这种渐变会在沿表面法线方向诱导出一系列的层间电偶极,最终导致能级的弯曲。同时θ的变化也会改变薄膜的表面极化强度,引起IP的逐渐减小。能级的弯曲在界面处形成类P-N结的效应会对C8-BTBT基电子器件的性能有很大的影响。     

6H碳化硅衬底上硅碳锗薄膜的生长特性研究

采用低压热壁化学气相沉积法,在6H-SiC衬底(0001)面上生长了不同温度(1100—1250℃),不同GeH₄流量比(6.3%—25%)的SiCGe薄膜样品,研究了SiCGe薄膜的表面形貌、生长特性以及样品中Ge组分含量的变化. 扫描电镜测试结果表明,SiCGe薄膜在低温下倾向于岛状生长模式,随着生长温度提高,岛状生长逐渐过渡到层状生长模式,同时伴有岛形状和密度的变化. X射线光电子能谱测试得出SiCGe样品中的Ge含量约为0.15％—0.62％,在其他参数不变的情况下,样品的G 关键词： 碳化硅 化学气相沉积 反相边界 岛状生长     

载能原子沉积Au/Au(100)外延薄膜生长的计算机模拟

在分子动力学研究的基础上建立了载能原子的沉积动力学物理模型,并根据在局域环境下的表面原子扩散模型,通过运动学Monte Carlo方法研究了载能粒子沉积Au/Au(100)薄膜的初期生长过程,探讨了载能粒子沉积对薄膜生长的影响及其随基体温度的变化.通过计算机模拟发现：载能粒子沉积的Au/Au(100)薄膜生长仍然呈现层状生长-三维岛状生长-准二维层状.在薄膜生长初期,载能粒子的作用是促进表面原子的成核,增加基体表面的缺陷;在薄膜的生长阶段,载能粒子通过抑制三维岛的生长速率起着平滑薄膜表面形貌的作用.载能粒 关键词：     

F8BT薄膜表面形貌及与Al形成界面的电子结构和反应

基于共轭聚合物光电器件的性能与聚合物的表面形貌、分子取向、以及与金属电极形成的界面结构密切相关. 本文利用原子力显微镜(AFM)、同步辐射光电子能谱(SRPES)和近边X射线吸收精细结构谱(NEXAFS)等, 研究了聚(9, 9-二辛基芴并苯噻二唑)(F8BT)薄膜的表面形貌、分子取向及其与Al 电极形成界面过程的结构变化. 结果表明, 在略低于F8BT玻璃转变温度(T_g=130 ℃)条件下对F8BT薄膜进行退火, 可明显增加薄膜的表面粗糙度, 薄膜中F8BT 的分子取向角约为49°, 9, 9-二辛基芴单元(F8)与苯噻唑单元(BT)几乎在同一平面. 在Al/F8BT 界面形成过程中, Al与F8BT中的C, N和S均发生不同程度的化学反应, 并导致价带结构和未占据分子轨道(LUMO)态密度的变化. Al对F8BT进行n型掺杂引起F8BT能带弯曲的同时, 未占据能级被部分占据, 更多的电子将被注入到LUMO+1中. 通过考察价带电子结构、芯能级位移及二次截止边的变化, 绘制了清晰的Al/F8BT界面能级图.     

低覆盖度的Au/GaN(0001)界面的同步辐射研究

利用同步辐射光电子能谱研究了低覆盖度Au在GaN(0001)表面的初始生长模式,肖特基势垒高 度以及界面的电子结构.结果表明，Au沉积初始阶段有界面的化学反应,随后呈三维岛状生长 .由光电子能谱实验确定的肖特基势垒高度为14 eV. 通过对界面价带谱和Au 4f芯能级谱 的分析,确定了界面化学反应的存在.利用线性缀加平面波方法计算了GaN(0001)和Au的价带 态密度并分析了化学反应产生的机理,认为在初始阶段界面形成了Au_Ga合金. 关键词： 同步辐射 光电子能谱 Au/GaN欧姆接触 态密度     

用角分辨光电子能谱研究Co/Cu(111)外延超薄膜的电子结构

利用同步辐射角分辨光电子能谱研究了分子束外延生长的Co/Cu(111)超薄膜电子结构的变化.Cu(111)的位于表面布里渊区Γ点的表面态在覆盖度为两单层时仍然可以分辨,说明薄膜生长模式不是二维层状生长.在一单层和二单层时,动量沿Cu体布里渊区ΓΛL方向变化,Co的最明显的峰包有能量色散.在覆盖度从一单层到两单层的变化过程中,固定光子能量测谱发现Co的能带的能量调整.实验测得的Co膜的电子结构与已有理论计算的结果对比,初步确定Co原子在生长初期阶段为两层岛生长,而且在一单层时已经具有铁磁性.     

酞菁铜与MoS_2(0001)范德瓦耳斯异质结研究

利用光电子能谱、原子力显微镜以及低能电子衍射等表面研究手段系统研究了真空沉积生长的酞菁铜薄膜与衬底MoS2(0001)之间的范德瓦耳斯异质结界面电子结构和几何结构.角分辨光电子能谱清楚地再现了MoS2(0001)衬底在Γ点附近的能带结构.低能电子衍射结果表明,CuPc薄膜在MoS2(0001)表面沿着衬底表面[11ˉ20],[1ˉ210]和[ˉ2110]三个晶向有序生长,反映了衬底对CuPc的影响.原子力显微镜结果表明,CuPc在MoS2衬底上遵循层状-岛状生长模式:在低生长厚度下(单层薄膜厚度约为0.3 nm),CuPc分子平面平行于MoS2表面上形成均匀连续的薄膜;在较高的沉积厚度下,CuPc沿衬底晶向形成棒状晶粒,表现出明显的各向异性.光电子能谱显示界面偶极层为0.07 eV,而且能谱在膜厚1.2 nm饱和,揭示了酞菁铜与MoS2(0001)范德瓦耳斯异质结的能级结构.     

Adsorption of 5-halouracils on Au(111)

The immobilization of 5-halouracils on Au(111) has been studied by soft X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Multilayer and monolayer films of 5-chlorouracil were deposited on the Au(111) surface by evaporation in vacuum while films of 5-bromouracil were absorbed in two modes: from the gas phase under ultrahigh vacuum conditions and from solution. The photoemission spectra of C, N and O 1s, Br 3d and Cl 2p as well as the absorption spectra at the N and O K-edges were measured for monolayers of 5-halouracil films and the nature of the bonding with the Au(111) surface has been determined. From the angular dependence of the NEXAFS spectra at the O and K-edges, we conclude that these 5-halouracils are lying nearly parallel to the Au(111) surface. Distinct chemical states and surface adsorption geometry of the 5-BrU molecules for monolayer coverage prepared in two different ways have been found.     

In-situ formation and detailed analysis of imine bonds for the construction of conjugated aromatic monolayers on Au(111)

We present the synthesis of 4′-amino-4-mercaptobiphenyl (AMB) and its deposition from solution onto Au(111) substrates. The resulting organic thin films were characterized by contact angle, infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS), and near edge X-ray absorption fine structure (NEXAFS) measurements. It is demonstrated that the majority of AMB molecules are coupled to the gold surface via S–Au covalent bonds, although only little orientational order of the AMB layer could be detected by NEXAFS. Furthermore, aromatic imine bonds between AMB and 4-hydroxybenzaldehyde (HB), 4-carboxybenzaldehyde (CB), 4-methylbenzaldehyde (MB), or 4-(trifluoromethyl) benzaldehyde (TMB) have been successfully formed. As a result of the limited order, this coupling reaction was incomplete. Nevertheless, the experimental results confirmed the formation of conjugated aromatic imine bonds.     

氧化石墨负载金催化剂在以O2为氧源的苯甲醇氧化反应中的催化性能:载体效应

对石墨氧化物经过加热处理和化学处理后担载金溶胶从而制备得到不同的Au/GO催化剂.利用X-射线光电子能谱,热脱附谱和拉曼光谱对催化剂的表面物种和结构进行了表征.结果表明,热处理和化学处理对Au/GO催化剂表面含氧物种的浓度、种类以及载体的晶体结构具有显著影响,进而导致催化剂在以O₂为氧源的液相苯甲醇选择氧化反应中的催化活性呈现明显差异.与载体表面含氧物种的浓度和种类这一因素相比,载体结构的有序程度对于Au/GO催化剂的催化活性起到更为重要的决定作用.     

PVP-capped twinned gold plates from nanometer to micrometer

PVP (poly(vinyl pyrrolidone))-capped micrometer-sized twinned gold (Au) plates with the shape of hexagon or triangle have been successfully synthesized in a large quantity by reducing hydrogen tetrachloroauric acid (HAuCl₄·3H₂O) using ethylene glycol in the presence of (PVP) molecules at 200°C under the extra condition of autogenous pressure. Clear twin boundaries in thus-obtained Au plates have been observed by scanning electron microscope (SEM). To further elucidate the mechanism of formation of the twinned Au plates, transmission electron microscopy (TEM) has been employed to characterize smaller Au nanoplates obtained simultaneously with the Au microplates, the occurrence of 1/3{422} forbidden reflections in selected area electron diffraction (SAED) can be believed to result from the presence of twinning boundary within the Au (111) plane normal to TEM electron beam. In addition, X-ray photoelectron spectroscopy (XPS) experiment has confirmed that PVP molecules exist on the surface of the Au cores, which may play a very important role in the formation and evolution of the twinned Au plates. A possible growth mechanism has been suggested to explain the Au plate evolution from nanometer to micrometer.     

GaN薄膜的溶胶-凝胶法制备及其表征

采用溶胶凝胶法成功地制备出氮化镓薄膜.以单质镓为镓源制备镓盐溶液、柠檬酸为络合剂制备出前驱体溶胶,再甩胶于Si(111) 衬底上,在氨气氛下热处理制备出GaN薄膜.X射线衍射（XRD）分析及选区衍射分析（SAED）表明所制备的薄膜是六角纤锌矿结构GaN薄膜;XPS分析其表面,结果显示样品中的镓元素、氮元素均以化合态存在,且Ga：N约为1：1;PL谱分析结果表明所制备的薄膜具有优良的发光性能.     

Thin PTCDA films on Si(0 0 1): 2. Electronic structure

We have studied the thin film formation and the electronic structure of the organic molecular semiconductor 3,4,9,10 perylene tetracarboxylic dianhydride (PTCDA), on clean and on hydrogen-passivated Si(0 0 1) surfaces. The studies were made by means of high resolution X-ray photoelectron spectroscopy (HRXPS), angle-resolved photoelectron spectroscopy (ARPES), near edge X-ray absorption fine structure (NEXAFS) and low energy electron diffraction (LEED). On the H passivated surface the changes in the electronic structure of the substrate and the molecules with increasing film thickness are very small. The molecular orbitals show a dispersive behavior, indicating that the PTCDA layers are ordered. On the reactive clean surface the anhydride groups of the molecule interact with the substrate as indicated by changes in the core level binding energies. This results in a much lower ordering in the film compared to PTCDA on a passivated silicon surface. There is no sign of decomposition of the molecule because of the more reactive substrate.     

In situ gas-phase catalytic properties of TiC-supported size-selected gold nanoparticles synthesized by diblock copolymer encapsulation

TiC-supported size- and shape-selected Au nanoparticles with well defined interparticle distances were synthesized by diblock copolymer encapsulation. Atomic force microscopy (AFM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) have been used to investigate the correlation between the nanocatalyst morphological/electronic structure and its chemical reactivity. Using the low-temperature oxidation of CO as a model reaction, our TPD results showed an enhancement of the catalytic activity with decreasing particle size. Two desorption features were observed and assigned to kinks/steps in the gold surface and the Au-TiC interface. The role of the interparticle distance on the activity is discussed. AFM measurements showed drastic morphological changes (Ostwald ripening) on the nanoparticles after CO oxidation when the initial interparticle distance was small (∼30 nm). However, no sintering was observed for Au nanoparticles more widely spaced (∼80 nm).     

Spectroscopic analysis of the riboflavin—serum albumins interaction on silver nanoparticles

Metallic nanoparticles (NPs) supported on oxides thin films are commonly used as model catalysts for studies of heterogeneous catalysis. Several 4d and 5d metal NPs (for example, Pd, Pt and Au) grown on alumina, ceria and titania have shown strong metal support interaction (SMSI), for instance the encapsulation of the NPs by the oxide. The SMSI plays an important role in catalysis and is very dependent on the support oxide used. The present work investigates the growth mechanism and atomic structure of Rh NPs supported on epitaxial magnetite Fe₃O₄(111) ultrathin films prepared on Pd(111) using the Molecular Beam Epitaxy (MBE) technique. The iron oxide and the Rh NPs were characterized using X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction and photoelectron diffraction (PED). The combined XPS and PED results indicate that Rh NPs are metallic, cover approximately 20 % of the iron oxide surface and show height distribution ranging 3–5 ML (monolayers) with essentially a bulk fcc structure.     

Characterization of ultra-thin organic hetero-interfaces — SnPc/PTCDA/Ag(111)

Ultra-thin organic hetero-layers consisting of tin-phthalocyanine (SnPc) and 1,3,4,8-perylen-tetracarboxylicacid dianhydride (PTCDA) adsorbed on a Ag(111) surface are characterized with photoelectron spectroscopy (PES) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. If SnPc is deposited on the Ag(111) substrate, which is precovered with one monolayer of PTCDA, a well defined interface is formed with a closed SnPc wetting layer as can be derived from angle dependent core level and from valence photoelectron spectra. Moreover, X-ray absorption data show that the molecules are lying flat and that the bonding at the SnPc/PTCDA interface is weak.     

Molecular adsorption and growth of naphthalene films on Ag(1 0 0)

The adsorption of naphthalene, vacuum deposited on a Ag(1 0 0) surface, was comprehensively investigated by means of low-energy electron diffraction (LEED), temperature-programmed thermal desorption (TPD) spectroscopy, X-ray photoelectron spectroscopy (XPS), and polarization-dependent near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in the mono- and multilayer regime. A growth of long-range ordered monolayer at 140 K is observed with LEED. The polarization-dependent C 1s NEXAFS shows that the naphthalene molecules in the monolayer lie almost parallel to the Ag(1 0 0) surface. With increasing film thickness, the molecular orientation turns to upright position. Furthermore, NEXAFS measurements show that in the multilayer regime the molecular orientation depends on the substrate temperature during deposition.