Al2O3薄膜/纳米Ag颗粒复合结构的光吸收谱及增强Raman散射光谱研究

Al₂O₃介质薄膜与纳米Ag颗粒构成的复合结构,被应用于表面增强Raman散射探测实验中,其中Al₂O₃介质薄膜对纳米Ag颗粒的吸收谱及增强Raman散射光谱的影响被特别关注.该复合结构的光学特性表征出纳米Ag颗粒的偶极振荡特性.从光吸收谱中可以看到,其共振吸收谱随Al₂O₃介质薄膜厚度增加而在整个谱域上发生红移,表明纳米Ag颗粒的周围介电常数随Al₂O₃介质薄膜厚度的增加而增大.采用罗丹明6G作为探针原子,6个Raman特征峰的平均增益值作为表征表面增强Raman散射衬底增益程度的量度.实验结果表明,Al₂O₃介质薄膜层的引入提高了纳米Ag颗粒的衬底介电常数,并引起了散射共振的增强,从而使表面增强Raman散射强度提高.     

外延生长La0.7Sr0.3MnO3薄膜厚度对缺陷影响的慢正电子分析

采用脉冲激光沉积方法在(LaAlO₃)_0:3(Sr₂AlTaO₆)_0:7衬底上外延生长了La_0.7Sr_0.3MnO₃薄膜,并采用慢正电子束方法分析了薄膜在不同厚度和不同退火气氛下参数S的变化. 分析表明,薄膜中包含两种机制引入的氧空位,分别是薄膜生长气氛中氧压偏低造成薄膜的氧缺乏和由于薄膜应变引入空位型缺陷. 当薄膜厚度较薄时,应变造成的晶格畸变化比较大,当薄膜的厚度大于11 nm时,薄膜的应变驰豫已经比较完全. 原位退火的样品中正电子主要是被氧缺乏引起的氧空位捕获. 在氧气中退火的样品,S随厚度的变化反映了应变对薄膜微结构的影响.     

分子束外延生长[111]晶向CdTe的研究

本文采用分子束外延(MBE)方法在BaF₂衬底上直接外延生长了CdTe(111)薄膜. 反射高能电子衍射(RHEED)实时监控生长表面, 衍射图样揭示了CdTe(111)在BaF₂表面由二维生长向三维生长的变化过程．XRD表征验证了外延生长的CdTe薄膜的单晶性质．由红外透射光谱测量和理论拟合相结合, 得到了CdTe外延薄膜室温带隙宽度E_g=1.511 eV.     

表面缺陷对一氧化碳和甲基基团在金红石TiO2(110)表面吸附的影响

本文利用程序升温脱附技术研究了氧空位浓度对甲基基团和CO在R-TiO₂(110)表面吸附的影响. 结果表明,随着氧空位浓度的变化,吸附在桥氧位的甲基基团和吸附在五配位Ti⁴⁺位点上的CO分子的脱附温度呈现了不同的趋势,揭示了表面缺陷可能对R-TiO₂(110)不同位点上的物质吸附具有重要影响.     

甲醇在二氧化钛上的光化学性质与表面结构的相关性

通过双光子光电子的方法探测了TiO₂(011)-(2×1) 和TiO₂(110)-(1×1)表面的光催化氧化甲醇的性质. 在吸附了甲醇的二氧化钛(011)和(110)界面处探测到了一个费米能级以上2.5 eV的电子激发态,该电子激发态可作为测试二氧化钛界面还原性的探针使用. 利用此探针在甲醇/TiO₂(011)-(2×1)和甲醇/TiO₂(110)-(1×1)界面探测到了一个随光照时间的电子激发态信号变化,这一变化可以归于光催化生成的表面羟基对界面还原性的影响. 由此得出的光催化氧化甲醇的速率TiO₂(110)-(1×1)比TiO₂(011)-(2×1)快了大约11.4倍. 这可能由于表面原子结构排布的原因不同. 本工作不仅介绍了一个利用双光子光电子能谱探测到的甲醇/TiO₂界面电子结构的细节特征,还揭示了表面结构对二氧化钛光反应性质的重要影响.     

TeOx薄膜结构及短波长静态记录特性的研究

以真空蒸镀法在K9玻璃基底上制备了TeO_x单层薄膜.使用X射线光电子能谱仪(XPS)、X射线衍射仪(XRD)、原子力显微镜(AFM)对薄膜的结构进行了分析.实验结果表明,薄膜是由晶态Te分散在非晶态TeO₂基体中形成的混合体系,TeO₂基体的存在增强了Te的抗氧化性能;薄膜具有精细粒状结构和粗糙的表面;退火后薄膜的反射率增加和Te向表面的偏析、重聚集及表面粗糙度的降低有关.采用波长为514.4nm的短波长静态记录仪对薄膜静态记录性能的测试结果表明:薄膜具有良好的记录灵敏性,在记录功率1.5mW、脉宽50ns时就可产生较高的反射率衬比(度).研究结果为选择合适掺和物使TeO_x薄膜实际用作高密度光存储介质有重要意义.     

MOCVD生长AlGaN薄膜的X光电子能谱

用X光电子能谱和X射线衍射谱方法分析了MOCVD生长的AlGaN薄膜的实际表面形态和晶体结构基于XPS测量结果,通过分析计算,发现实际表面除GaN外存在Ga₂O₃和Al₂O₃及其它与O有关的络合物构成的混合氧化物覆盖层,估计覆盖层厚度约1.2nmXRD结果显示生长的AlGaN薄膜为以GaN(0002)取向为主的多晶结构。     

FePc与TiO2(110)及C60界面电子结构研究

基于C₆₀受体和有机分子给体的太阳能电池是目前非常重要的一个研究热点, 利用同步辐射真空紫外光电子能谱(SRUPS) 技术研究了酞菁铁(FePc)与TiO₂(110)及C₆₀的界面电子结构, 以及FePc与C₆₀分子混合薄膜的电子结构. SRUPS价带谱显示, FePc沉积在化学计量比与还原态两种不同的TiO₂(110)表面时, FePc分子的HOMO能级均随FePc厚度的变化发生了移动, 而在化学计量比的TiO₂(110)表面位移较大, 同时发生界面能带弯曲, 说明存在从有机层向衬底的电子转移. 在FePc/C₆₀和C₆₀/FePc界面形成过程中, FePc与C₆₀分子的最高占据分子轨道(HOMO)位移大小基本相同. 由界面能级排列发现, 在FePc与C₆₀的混合薄膜中, FePc分子的HOMO与C₆₀分子的最高占据分子轨道能级差较大, 这有利于提高器件开路电压, 改善器件性能.     

CHN薄膜的制备方法与工艺研究

 采用空心阴极等离子化学气相沉积方法，以NH₃/H₂的混合气体及CH4气体为原料反应气体，成功地制备了非晶的CHN薄膜，研究了CHN薄膜的沉积速率与直流电压及反应气体流量的关系。同时用X射线光电子能谱(XPS)确定了不同条件下薄膜中N原子的百分比，用原子力显微镜(AFM)对薄膜的表面粗糙度及表面形貌进行了测量和表征。结果表明：薄膜中N原子的百分比最大为12%，薄膜的表面结构光滑、致密，表面粗糙度小于1 nm。     

Sr2CeO4电荷迁移发光的光谱结构规律研究

利用高温固相反应法分别合成了不同物相形成机理的Sr₂CeO₄，Sr ₂CeO₄∶Ca ²⁺和Sr₂CeO₄∶Ba²⁺样品，并对其光谱特性进行 了研究.结果发现，对于由SrO和CeO₂直接反应生成的Sr₂CeO₄(Ⅰ)，激发主峰位于256nm 左右；而对于SrCeO₃和SrO反应生成的Sr₂CeO₄(Ⅱ)，激发主峰位于279nm左右.在Sr₂CeO₄(Ⅰ)中掺入Ca²⁺，其激发光谱随着Ca²⁺离子浓度的增加逐渐接近于Sr₂CeO_{4(Ⅱ)的激发光谱.激发主峰带应属于CeO6八面体终端Ce⁴⁺—O^2-键的电荷迁移 带.对于激发光谱中340nm左右的弱激发峰，其峰值波长不受形成机理及Ca²⁺掺杂的影响，只是其强度 随着 激发主峰的红移而增加，它可能属于CeO6八面体平面上Ce⁴⁺—O2-键的电荷 迁移带.形成机理及Ca²⁺掺杂对发射光谱没有影响.Ca²⁺在Sr 2CeO 4(Ⅱ)与Ba²⁺在Sr2CeO4(Ⅰ)和(Ⅱ)中均难 于替代Sr²⁺的位置.}     

Development of laser photoelectron spectroscopy based on resonantly enhanced multiphoton ionization

This review article is mainly concerned with laser photoelectron spectroscopy based on REMPI (resonantly enhanced multiphoton ionization), consisting of two parts. One is associated with the measurement of photoelectron kinetic-energy distribution and the other is associated with the measurement of zero-kinetic-energy (ZEKE) photoelectrons in very high resolution. These two techniques are complementary to each other. During the last three decades, the author and co-workers have carried out photoelectron spectroscopic studies of molecules in the gas phase, using the HeI 584 Å resonance line and a nanosecond tunable UV–visible laser. In this article, firstly the author’s background in the field of molecular photoelectron spectroscopy is described briefly, by mentioning three topics of HeI photoelectron spectroscopy. Secondly, the principle and characteristics of laser photoelectron kinetic-energy spectroscopy and its application to several typical topics, namely, one-photon forbidden states (O₂), autoionization from a super-excited state (NO), and small van der Waals molecules (NO–Ar and the NO₂ dimer), and some others. Thirdly, the principle and characteristics of ZEKE photoelectron spectroscopy are described, together with its application to the following several topics: (1) rotational spectra of NO⁺, (2) vibrational coupling of (naphthalene)⁺, (3) large-amplitude torsional motion of (tolane)⁺, (4) rotational isomers of (cis and trans n-propylbenzene)⁺ and structural isomers of (2-hydroxypyridine)⁺, (5) proton tunneling of (tropolone)⁺ and (9-hydroxyphenalenone)⁺, (6) intramolecular vibrational redistribution of trans stilbene, and (7) cation van der Waals molecules of aniline–Ar_n (n=1,2) and azulene–Ar. All the results mentioned as examples are those obtained in the author’s laboratory.     

X-ray-induced polymerization of furan overlayers on Ru(001)

The effects of Mg K X-rays on furan overlayers on the Ru(001) surface have been investigated using X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). It was found that X-ray beams can polymerize furan multilayers condensed at 80 K, resulting in the appearance of new emission features at 532.8 eV in the O 1s XPS spectra and at 3 eV in the UPS spectra. In contrast, monolayer furan on Ru(001) at 80 K shows no signs of polymerization under the same conditions.     

Na and K on Al(100) studied by low-energy electron diffraction and high-resolution core-level spectroscopy

The temperature effects on sub-monolayers of V deposited at the TiO₂(001) surface have been studied by ultraviolet and X-ray photoelectron spectroscopies, UPS and XPS, from 300 up to 623 K.

V coverages, Θ_v, between 0.2 and 0.7 monolayers (ML) were deposited by an e-beam evaporator at 300 K. The V 2p_3/2 core line region exhibits two well-defined components whose relative intensity depends on Θ_v. These two components, assigned to different oxidation states of V, are correlated with two features, with a dominant V 3d character, detected within the TiO₂(001) band gap of the UPS valence band spectra.

UPS and XPS measurements performed after in-situ thermal treatments show unambiguous and reproducible changes of these spectral components. After annealing at 623 K only the higher binding energy component is present in the V 2p_3/2 spectra; the Ti 2_p core lines recover the typical symmetry of the clean and stoichiometric TiO₂(001) surface and the higher binding energy feature only is detected in the TiO₂ band gap. These data suggest that, within the volume probed by XPS and UPS, Ti ions have a mainly d⁰ configuration, while V has a single and stable open-shell configuration, as revealed by the significant intensity detected within the TiO₂ band gap. These annealing-induced changes are due, as suggested by the O 1s/Ti 2p core line intensity trend, to an oxygen diffusion from the TiO₂ bulk to the surface. Finally, a detailed analysis of the data indicates that different V/TiO₂(001) interfaces exhibit different behaviours after annealing treatments, depending on Θ_v. For Θ_v = 0.7 ML, V interdiffuses into the TiO₂ sub-surface layers, whereas for Θ_v = 0.2 ML it remains at the surface. This finding is consistent with a rearrangement of V atoms. which under annealing occupy first the energetically most favorable surface sites (Θ_v = 0.2 ML) before interdiffusing into the TiO₂ lattice (Θ_v = 0.7 ML).     

The formaldehyde cation: Rovibrational energy level structure and Coriolis interaction near the adiabatic ionization threshold

Rotationally resolved pulsed-field-ionization zero-kinetic-energy photoelectron spectra of the 0⁰, 6¹ and 4¹ vibrational levels of the ground electronic state of the formaldehyde cation were recorded using a resonant three-color three-photon excitation scheme. The first adiabatic ionization energy of CH₂O (87793.33(1.30) cm⁻¹) and the rigid-rotor rotational constants (A⁺ = 8.874(8) cm⁻¹, B⁺ = 1.342(15) cm⁻¹, C⁺ = 1.148(18) cm⁻¹) of the vibronic ground state of CH₂O⁺ were derived. A strong a-type Coriolis interaction between the 6¹ and 4¹ vibrational levels was observed. The Coriolis coupling parameter and the deperturbed fundamental vibrational frequencies of the in-plane-rocking mode ν₆ and the out-of-plane bending mode ν₄ were determined to be 8.70(10) cm⁻¹, 823.67(30) cm⁻¹ and 1036.50(30) cm⁻¹, respectively. The intensity distribution of the photoelectron spectra was analyzed in the realm of a simple photoionization model.     

Fe/ZnO (0001)体系界面相互作用中薄膜厚度效应的光电子能谱研究

利用同步辐射光电子能谱(SRPES)和X射线光电子能谱(XPS)技术,系统研究了室温下Fe/ZnO界面形成过程中Fe薄膜与氧结尾的ZnO(000 1 )衬底之间的相互作用,结果显示初始沉积的Fe明显被表面氧氧化为Fe²⁺离子,在Fe覆盖度为0—3 nm的范围内,分别观察到与界面电荷传输、化学反应以及薄膜磁性相关的三个有意义的临界厚度,这一结果将有助于基于Fe/ZnO界面的相关器件的设计和研发.     

The adsorption of oxygen and water on Ca and CaO films studied with MIES, UPS and XPS

Metastable induced electron spectroscopy (MIES), Ultraviolet photoelectron spectroscopy (UPS), and X-ray photoelectron spectroscopy (XPS) are employed to study the adsorption of water on Ca and CaO films as well as the adsorption of oxygen on Ca films. Ca films are prepared by evaporation of Ca onto clean Si(1 0 0) substrates. CaO films are produced by Ca evaporation in an oxygen atmosphere at a substrate temperature of 400 °C. Gas adsorption on the Ca films at room temperature, both for oxygen and water, is initiated by complete dissociation of the impinging molecules leading to the formation of Ca–O bonds. Exposure to water furthermore leads to the formation of hydroxyl groups via hydrogen abstraction from water forming a complete surface layer. Hydroxyl groups are also formed upon exposure of CaO films to water, but to a significantly smaller amount compared to Ca films exposed to water.     

Luminescence characterization and electron beam induced chemical changes on the surface of ZnAl2O4:Mn nanocrystalline phosphor

Luminescence characteristics and surface chemical changes of nanocrystalline Mn²⁺ doped ZnAl₂O₄ powder phosphors are presented. Stable green cathodoluminescence (CL) or photoluminescence (PL) with a maximum at ∼512 nm was observed when the powders were irradiated with a beam of high energy electrons or a monochromatic xenon lamp at room temperature. This green emission can be attributed to the ⁴T₁ → ⁶A₁ transitions of the Mn²⁺ ion. Deconvoluted CL spectra resulted in two additional emission peaks at 539 and 573 nm that may be attributed to vibronic sideband and Mn⁴⁺ emission, respectively. The luminescence decay of the Mn²⁺ 512 nm emission under 457 nm excitation is single exponential with a lifetime of 5.20 ± 0.11 ms. Chemical changes on the surface of the ZnAl₂O₄:Mn²⁺ phosphor during prolonged electron beam exposure were monitored using Auger electron spectroscopy. The X-ray photoelectron spectroscopy (XPS) was used to determine the chemical composition of the possible compounds formed on the surface as a result of the prolonged electron beam exposure. The XPS data suggest that the thermodynamically stable Al₂O₃ layer was formed on the surface and is possibly contributing to the CL stability of ZnAl₂O₄:Mn phosphor.     

X-ray photoelectron spectroscopy studies on core-shell structured nanocomposites

Core-shell nanostructures were grown in silica-based glasses. Copper-copper oxide and iron-iron oxide structures had diameters in the range 3-6 nm, with shell thicknesses ∼1-2 nm. Silver-lithium niobate core-shell nanostructures had diameters in the range 4.2-46 nm and thicknesses varying from 2.2 to 22 nm. X-ray photoelectron spectroscopy studies were carried out on all these specimens. The analyses of these results show the presence of Cu⁺/Cu²⁺, Fe²⁺/Fe³⁺ and Nb⁴⁺/Nb⁵⁺ valence states in the above three systems. Electrical resistivity data were fitted satisfactorily to the small polaron hopping model in the case of copper and iron-containing specimens. The presence of ions in the lithium niobate shell provides direct evidence of the formation of localized states between which variable range hopping conduction can be effected.     

Effect of hydrogenation vs. re-heating on intrinsic magnetization of Co doped In2O3

Influence of Co doping for In in In₂O₃ matrix has been investigated to study the effect on magnetic vs. electronic properties. Rietveld refinement of X-ray diffraction patterns confirmed formation of single phase cubic bixbyite structure without any parasitic phase. Photoelectron spectroscopy and refinement results further revealed that dopant Co²⁺ ions are well incorporated at the In³⁺ sites in In₂O₃ lattice and also ruled out formation of cluster in the doped samples. Magnetization measurements infer that pure In₂O₃ is diamagnetic and turns to weak ferromagnetic upon Co doping. Hydrogenation further induces a huge ferromagnetism at 300 K that vanishes upon re-heating. Experimental findings confirm the induced ferromagnetism to be intrinsic, and the magnetic moments to be associated with the point defects (oxygen vacancies V_o) or bound magnetic polarons around the dopant ions.