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.     

不锈钢基底上TiO2薄膜型光催化剂的制备和化学结构

采用钛酸正丁酯作为前驱体,通过溶胶-凝胶法在不锈钢基片上制备了TiO2纳米薄膜。利用俄歇电子能谱(AES)和紫外反射光谱等研究手段,对TIO2薄膜的化学结构及基底材料界面相互作用进行了系统研究。结果发现,在不锈钢基底上形成的TiO2薄膜与基底材料发生了明显的界面扩散反应。在TiO2薄膜的形成过程中,不锈钢中Fe元素向TiO2薄膜层扩散,并与从大气氛中扩散到界面的氧发生化学反应,形成铁氧化物界面过渡层。界面氧化过程,导致了Fe向样品表面的偏析和扩散。在高温热处理过程中,Fe可以扩散到TiO2薄膜的表面。薄膜催化剂的紫外反射光谱表明,界面扩散反应导致了Fe扩散进入TiO2薄膜的晶格,从而改变了薄膜催化剂的光吸收性能。     

Growth, structure, and stability of ceria films on Si(111) and the application of CaF2 buffer layers

The growth of ceria (CeO2) films by oxidation of evaporated Ce metal on Si(111) and on CaF2(111) epilayers on Si(111) is compared. By use of XPS, UPS, and LEED, it has been demonstrated that the application of a CaF2 buffer layer between the ceria and Si substrate prevents the formation of an amorphous oxidized Si layer at the interface and permits the growth of a well-defined epitaxial ceria layer of (111) surface orientation. The thermal stability of the CeO2/CaF2/Si(111) interface structure is limited by the solid-state reaction between CaF2 and ceria. This leads to gradual migration of fluorine into the oxide at elevated temperatures to give a solid-state solution of fluorine in the partially reduced oxide. An analysis of the composition observed after extensive annealing in a vacuum suggests that, with initial layers of CaF2 and CeO2 of similar thickness, the ultimate product may be CeOF. The onset of this solid-state reaction can, however, be significantly delayed by annealing under an oxygen atmosphere.     

Quantum-chemical cluster models for the Si(111)/SiO2 interface

The MPDP method is used to construct cluster models for the Si(111)/SiO₂ interface. The crystallochemical environment of the clusters is included by a method based on the satisfaction of the unusual cluster boundary valence by hydrogen atoms, whose locations, as far as possible, are fixed by the stoichiometry of the charge distribution on the atoms of silicon and oxygen in the model fragment. In these cluster models for the Si(111)/SiO₂ interface, considering only normal atomic displacements relative to their ideal positions, there appears a 7 Å thick transition layer encompassing four surface atomic planes of the silicon substrate and two successive Si-O and O-Si links from the SiO₂ film.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 3, pp. 268–275, May–June, 1990.The authors thank V. A. Chaplanov for stimulating our interest in this problem and for helpful discussions.     

SrS/α-SiO~2界面的XPS研究

TFEL器件中绝缘层与发光层之间的界面对电荷的输运特性、发光特性等有着十分重要的作用。本文通过XPS的测量,分析了新结构器件中SrS/α-SiO~2界面的各成分的芯电子能谱的变化和深度分布,发现Sr^2^+向SiO~2中扩散较深并以氧化物的形态存在,介质层以SiO~x(x=1.65～1.70)的形态存在。这些丰富的界面态有可能成为TFEL器件的初电子源而对SrS:Ce发光有贡献。     

金刚石颗粒表面Cr金属化及薄膜间界面扩散反应的研究

运用直流磁控溅射法可在金刚石颗粒表面沉积150nm的金属Cr层.在超高真空条件下,经300-600℃的热退火处理,可促进Cr膜与金刚石基底间的界面扩散和反应.利用俄歇电子能谱研究了Cr/金刚石颗粒界面的结合状态,发现Cr与金刚石薄膜发生了强烈的界面扩散,Cr元素渗入金刚石层达90nm,并在界面上发生化学反应形成Cr的碳化物层.对界面扩散反应动力学的研究表明,Cr/金刚石界面扩散反应的表观活化能为38.4kJ/mol,界面扩散反应主要由碳的扩散过程控制.热处理温度越高,界面扩散及反应越显著,但不利于碳化物层生成的氧化反应速度也会有所增加,界面反应产物从Cr₂C₃转变为Cr₂C物种.延长热处理时间有利于金属碳化物的生成,同样导致界面反应产物从Cr₂C₃转变为Cr₂C物种.     

Investigation of the Ti/MgCl2 interface on a Si(111) 7 × 7 substrate

Photoelectron spectroscopy with synchrotron radiation, low energy electron diffraction, and ion-scattering spectroscopy were used in order to study the Ti/MgCl(2) interface grown on an atomically clean Si(111) 7 × 7 substrate. A series of high resolution spectra after deposition of a thick MgCl(2) layer, step by step deposition of Ti and gradual annealing, indicated a very reactive interface even at room temperature. Strong interaction between the incoming Ti atoms and the MgCl(2) layer, leads to the formation of Ti(2+) and Ti(4+) oxidation states. The interfacial interaction continues even at multilayer Ti coverage mainly by the partial disruption of Mg-Cl bonds and the formation of Ti-Cl sites, rendering this interface a very promising UHV-compatible model of a pre-catalyst for olefin polymerization. After the final annealing, the MgCl(2) multilayers desorb while Ti remains on the surface forming a silicide layer on which Cl and Mg atoms are attached.     

BBDMS-PPV/ITO界面结构ADXPS研究

聚合物电致发光器件（Polymer Electroluminescent Device,PLED)已显示出广阔的应用前景^[1-6]。已往人们比较重视阴极材料的选择及相关金属与有机界面的研究^[7],而有关发光层或空穴传输层与阳极ITO膜之间的界面结构及化学问题则少见报道。事实上,ITO膜与有机层之间的作用对器件的可靠性及寿命具有更为严重的影响^[8,9]。由于异质界面的过渡层结构复杂,以纳米尺度上化学组成是非计量比的,因此对这种极薄的埋藏界面的研究方法还需进一步探索。本文通过模型试样制备和变角X射线光电子谱（ADXPS）技术,对PLED中共轭导电聚合物聚2,5－二（二甲基正丁基硅基）对苯乙烯撑（BBDMS－PPV）与阳极ITO膜所形成的界面结构进行了初步研究。     

Controlled silicon surface functionalization by alkene hydrosilylation

Immobilization of indene ligands onto two types of hydrogen-terminated surfaces, oxide-free Si [H/Si(111)] and oxidized Si [H/SiO2/Si], has been investigated by infrared absorption spectroscopy. The activity of a common catalyst (H2PtCl6) is shown to depend critically on the nature of the solvent. For instance, 2-propanol preferentially reacts with the surface, preventing any ligand attachment. Chlorobenzene is more stable, allowing some ligand attachment, but the H2PtCl6 catalyst also fosters silicon oxidation. In contrast, UV irradiation on oxide-free surfaces promotes a cleaner and more efficient reaction, leading to ligand attachment without substrate oxidation. The complete inactivity of H-terminated surfaces with a thin oxide layer [H/SiO2/Si] suggests that the UV-induced immobilization is mediated solely by the excitation of electron-hole pairs (excitons) in the substrate and is not the result of direct Si-H bond breaking.     

Ferroelectric and Pyroelectric Properties of Highly (111)-oriented Nanocrystalline Pb(Zr0:95Ti0:05)O3 Thin Films

"Lead zirconate titanate Pb(Zr0:95Ti0:05)O3 (PZT95/5) antiferroelectric thin films with 300 nm thickness were grown on Pt/Ti/SiO2/Si substrates by a sol-gel method with rapid thermal annealing processing. The X-ray diffraction results showed that the highly (111)-oriented pervoskite PZT95/5 thin films were grown on Pt/Ti/SiO2/Si substrates when annealed at 600-700 oC. Electrical measurements were conducted on PZT95/5 films in metal-ferroelectric-metal capacitor configuration. The PZT95/5 thin films annealed at 600-700 oC showed well-saturated hysteresis loops at an applied voltage of 20 V. At 1 kHz, the dielectric constant and dielectric loss of the films were 519 and 0.028, 677 and 0.029, 987 and 0.025, respectively for the thin films annealed at 600, 650, and 700 oC. The average remanent polarization (Pr) and the coercive electric field (Ec) obtained from the P-E hysteresis loops, were 19.1 1C/cm2 and 135.6 kV/cm, 29.31C/cm2 and 88.57 kV/cm, 45.3 1C/cm2 and 102.1 kV/cm, respectively for PZT95/5 thin films annealed at 600, 650 and 700 oC for 10 min in the oxygen atmosphere. This showed a good ferroelectricity of the prepared PZT95/5 films on Pt/Ti/SiO2/Si substrates by the simple sol-gel processing. The pyroelectric coeocient (p) of antiferroelectric PZT95/5 films was measured by a dynamic technique. At room temperature, the p values of the antiferroelectric PZT95/5 films at 1 kHz were 274, 238, and 212 1C/m2K."     

TiCl4(THF)2 impregnation on a flat SiOx/Si(1 0 0) and on polycrystalline Au foil: determination of surface species using XPS

TiCl₄(THF)₂ was impregnated by spin-coating on a Si(1 0 0) wafer covered with a thin SiO_x layer and on a polycrystalline Au foil. The nature of the surface species was determined at room temperature and after annealing, by X-ray Photoelectron Spectroscopy (XPS) and Atomic Force Microscopy (AFM). A mixed Si:O:Ti interfacial layer was formed on the silicon substrate while in the case of Au, TiOCl_x and TiO_x were the main surface species at room temperature. Annealing at 723 K leads to the total desorption of the Cl atoms, and in both cases a significant amount of Ti atoms was reduced to the Ti³⁺ state. AFM measurements revealed a homogenous distribution of nano-sized TiO_x clusters with semi-ellipsoid shape and increased contact area with the underlying silica.     

The role of the organic layer functionalization in the formation of silicon/organic layer/metal junctions with coinage metals

The design of silicon/alkyl layer/metal junctions for the formation of optimal top metal contacts requires knowledge of the mechanistic and energetic aspects of the interactions of metal atoms with the modified surface. This involves (a) the interaction of the metal with the terminal groups of the organic layer, (b) the diffusion of metal atoms through the organic layer and (c) the reactions of metal atoms with the silicon surface atoms. The diffusion through the monolayer and the metal catalyzed breakage of Si-C bonds must be avoided to obtain high quality junctions. In this work, we performed a comprehensive density functional theory investigation to identify the reaction pathways of all these processes. In the absence of a reactive terminal group, gold atoms may penetrate through a compact alkyl monolayer on Si(111) with no energy barrier. However, the presence of thiol terminal groups introduces a high energy barrier which blocks the diffusion of metals into the monolayer. The diffusion barriers increase in the order Ag < Au < Cu and correlate with the stability of metal-thiolate complexes whereas the barriers for the formation of metal silicides increase in the order Cu < Au < Ag in correlation with the increasing metallic radii. The reactivity of gold clusters with functionalized Si(111) surfaces was also investigated. Metal silicide formation can only be avoided by a compact monolayer terminated by a reactive functional group. The mechanistic and energetic picture obtained in this work contributes to understanding of the factors that influence the quality of top metal contacts during the formation of silicon/organic layer/metal junctions.     

Interfacial bonding mechanism and bonding strength of AlTiCrN coating by cathodic arc ion plating

AlTiCrN coating was prepared on the surface of YT14 tungsten carbide cutting tools by cathodic arc ion plating with Ti, Al and Cr as targets. The surface morphologies, interface energy spectrum, phase and elements' binding energy of the coatings were observed with SEM, EDS, XRD and XPS, respectively, and bonding strength of the coating interface was measured with scratch tester. The results show that the phases of AlTiCrN coating are mainly composed of AlN, CrN and TiN, the crystal plane of (111) has a strong preferred orientation. The concentrations of Al, Ti, Cr, N in the coating are higher than those in the substrate, showing the gradient diffusion distribution at the bonding interface, while C atoms of the substrate have diffused into the lattices of TiN, AlN and CrN to form an obvious interdiffusion layer, and the average bonding strength of coating interface is 57.65 N. Copyright © 2014 John Wiley & Sons, Ltd.     

3D ToF-SIMS view of interfacial diffusion between Cr2AlC coating and zircaloy substrate

A diffused interface between a ceramic coating and a metallic substrate is expected to signify a more solid bonding. In addition to depth profiling, a novel 3D view and imaging approach based on ToF-SIMS analysis was developed to investigate the diffused species around the interface. The diffusion of Al species in a Cr₂AlC ceramic coating and Zircaloy substrate system was investigated in both the as-deposited and postannealed states. In terms of the 3D view and imaging of CsAl⁺ after Gaussian convolution, Al species visibly diffused into the substrate after annealing at 800°C for only 5 minutes compared with that in the as-deposited sample.     

The interface effect on the lithiation of silicon/graphene composites: The first principles study

To reveal the interaction mechanism between lithium (Li) and silicon/graphene (Si/Gra) interface at the atomic scale, it was calculated that the energy band structure, density of states, charge transfer, radial distribution function and Li diffusion coefficient based on the first principles. The results indicated that the volume expansion of Si was effectively limited by the Si/Gra interface during Li insertion. There appeared the interface effect of Si/Gra on the combination of Li and Si atoms, according to the longer Li-C (2.9 Å) and the larger electron cloud near the Li atom at the Si/Gra interface. The better diffusion channel for Li atoms was constructed at the Si/Gra interface, due to the lower diffusion energy barrier (0.42–0.44 eV) and higher diffusion coefficient (D_Li = 0.784 × 10⁻⁴ cm²/s) for Li⁺ diffusion.     

Chemical solution-deposited PbZr 0.53 Ti 0.47 O3 on La 0.5 Sr 0.5 Co O3. SIMS investigation of the effect of different precursor additives on the layer structure

Chemical solution-deposited thin films of PbZr(0.53)Ti(0.47)O(3)/La(0.5)Sr(0.5)CoO(3) on Pt/TiO(2)/SiO(2)/Si substrates have been investigated by dynamic SIMS. The PbZr(0.53)Ti(0.47)O(3) (PZT) is intended to serve as a ferroelectric layer for microelectronic or microelectromechanical applications; conducting La(0.5)Sr(0.5)CoO(3) (LSCO) is a buffer layer intended to eliminate fatigue effects which usually occur at the Pt/PZT interface. Depth profiles of the main components were obtained and revealed that significant diffusion occurred during the deposition and crystallisation processes. Two types of sample, with different thickness of PZT and different types of poly(vinyl alcohol) (PVA) added to the LSCO precursor, were investigated.     

Change in the interfacial reaction of Hf-silicate film as a function of thickness and stoichiometry

Medium energy ion scattering and high-resolution transmission electron microscopy are used to investigate the depth of the interfacial reaction of Hf-silicate film. The interfacial reaction is critically affected by the film thickness and the mole fraction of HfO(2) in silicate film. The interfacial compressive strain generated at the surface of the Si substrate is dependent on the film thickness during the postannealing process in film with a thickness of approximately 4 nm. Finally, the phase separation phenomenon demonstrates critically different behaviors at different film thicknesses and stoichiometries because the diffusion of Si from interface to surface is dependent on these factors. Moreover, the oxidation by oxygen impurity in the inert ambient causes SiO(2) top formation.     

Radiation induced defects on Si-SiO2 interface

The density of surface states at Si?SiO₂ interface is examined for dry and wet oxidization process on 〈111〉 silicon substrate. The trivalent silicon centers are probably responsible for thermal and radiation generated surface states at the Si?SiO₂ interface. The dependence of the radiation induced surface state density is compared for various oxide thicknesses and oxidization methods used.     

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.