Properties of an Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Si interface

The phase chemical composition of an Al₂O₃/Si interface formed upon molecular deposition of a 100-nm-thick Al₂O₃ layer on the Si(100) (c-Si) surface is investigated by depth-resolved ultrasoft x-ray emission spectroscopy. Analysis is performed using Al and Si L_{2, 3} emission bands. It is found that the thickness of the interface separating the c-Si substrate and the Al₂O₃ layer is approximately equal to 60 nm and the interface has a complex structure. The upper layer of the interface contains Al₂O₃ molecules and Al atoms, whose coordination is characteristic of metallic aluminum (most likely, these atoms form sufficiently large-sized Al clusters). The shape of the Si bands indicates that the interface layer (no more than 10-nm thick) adjacent to the substrate involves Si atoms in an unusual chemical state. This state is not typical of amorphous Si, c-Si, SiO₂, or SiO_x (it is assumed that these Si atoms form small-sized Si clusters). It is revealed that SiO₂ is contained in the vicinity of the substrate. The properties of thicker coatings are similar to those of the 100-nm-thick Al₂O₃ layer and differ significantly from the properties of the interfaces of Al₂O₃ thin layers.     

Optical properties of multilayer structures

The possibility of using the ellipsometry method for investigation of the optical properties of multilayer films and structures is shown. The optical properties of structures HfO₂/SiO₂/Si, HfO₂/Si, ZrO₂/Si, Ta₂O₅/Si, and Al₂O₃/Si are studied. It is found that a layer of hafnium silicate is formed at the interface between the HfO₂ film and Si. Annealing of the structures in oxygen shows that oxides studied are oxygen-permeable and that the thickness of SiO₂ at the film-substrate interface increases. The growth rate of SiO₂ layers depends on the chemical nature of an oxide. Al₂O₃ films are impermeable for oxygen diffusion. The production of layers of alloys (Al₂O₃) _x (HfO₂)_{1 ? x} is optimized, which allows one to obtain layers with a homogeneous distribution of elements over the thickness.     

X-ray spectral analysis of the interface of a thin Al<Subscript>2</Subscript>O<Subscript>3</Subscript> film prepared on silicon by atomic layer deposition

The extent and phase chemical composition of the interface forming under atomic layer deposition (ALD) of a 6-nm-thick Al₂O₃ film on the surface of crystalline silicon (c-Si) has been studied by depthresolved, ultrasoft x-ray emission spectroscopy. ALD is shown to produce a layer of mixed Al₂O₃ and SiO₂ oxides about 6–8 nm thick, in which silicon dioxide is present even on the sample surface and its concentration increases as one approaches the interface with the substrate. It is assumed that such a complex structure of the layer is the result of interdiffusion of oxygen into the layer and of silicon from the substrate to the surface over grain boundaries of polycrystalline Al₂O₃, followed by silicon oxidation. Neither the formation of clusters of metallic aluminum near the boundary with c-Si nor aluminum diffusion into the substrate was revealed. It was established that ALD-deposited Al₂O₃ layers with a thickness up to 60 nm have similar structure.     

氧化铝与Al(100)基体间界面原子结构研究

本文介绍了用MeV离子散射和沟道效应研究单晶铝表面无定型氧化层与基体之间界面原子结构的方法。报道了Al₂O₃/Al(100)界面原子结构的实验结果。实验表明,在纯氧气氛围中400℃下生成的氧化铝膜,铝和氧原子浓度比例严格为2与3之比;Al₂O₃膜和Al(100)基体之间的界面极其陡峭,氧化铝膜下Al(100)基体表面的再构层不大于一个原子层。由实验测量与用Monte Carlo方法计算结果比较,得到再构层原子离开原来晶 关键词：     

Al2O3/SiO2 films prepared by electron-beam evaporation as UV antireflection coatings on 4H-SiC

Al₂O₃/SiO₂ films have been deposited as UV antireflection coatings on 4H-SiC by electron-beam evaporation and characterized by reflection spectrum, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The reflectance of the Al₂O₃/SiO₂ films is 0.33% and 10 times lower than that of a thermally grown SiO₂ single layer at 276 nm. The films are amorphous in microstructure and characterize good adhesion to 4H-SiC substrate. XPS results indicate an abrupt interface between evaporated SiO₂ and 4H-SiC substrate free of Si-suboxides. These results make the possibility for 4H-SiC based high performance UV optoelectronic devices with Al₂O₃/SiO₂ films as antireflection coatings.     

Fabrication of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Al structure by nitric acid oxidation at room temperature

A thick Al₂O₃/aluminum (Al) structure has been fabricated by oxidation of Al with 68wt% and 98wt% nitric acid (HNO₃) aqueous solutions at room temperature. Measurements of the Al₂O₃ thickness vs. the oxidation time show that reaction and diffusion are the rate-determining steps for oxidation with 68wt% and 98wt% HNO₃ solutions, respectively. Observation of transmission electron micrographs shows that the Al₂O₃ layer formed with 68wt% HNO₃ has a structure with cylindrically shaped pores vertically aligned from the Al₂O₃ surface to the Al₂O₃/Al interface. Due to the porous structure, diffusion of HNO₃ proceeds easily, resulting in the reaction-limited oxidation mechanism. In this case, the Al₂O₃/Al structure is considerably rough. The Al₂O₃ layer formed with 98wt% HNO₃ solutions, on the other hand, possesses a denser structure without pores, and the Al₂O₃/Al interface is much smoother, but the thickness of the Al₂O₃ layer formed on crystalline Al regions is much smaller than that on amorphous Al regions. Due to the relatively uniform Al₂O₃ thickness, the leakage current density flowing through the Al₂O₃ layer formed with 68wt% HNO₃ is lower than that formed with 98wt% HNO₃.     

Correlation between Al2O3 particles and interface of Al-Al2O3 coatings by cold spray

Al-Al₂O₃ composite coatings with different Al₂O₃ particle shapes were prepared on Si and Al substrate by cold spray. The powder compositions of metal (Al) and ceramic (Al₂O₃) having different sizes and agglomerations were varied into ratios of 10:1 wt% and 1:1 wt%. Al₂O₃ particles were successfully incorporated into the soft metal matrix of Al. It was found that crater formation between the coatings and substrate, which is typical characteristic signature of cold spray could be affected by initial starting Al₂O₃ particles. In addition, when the large hard particles of fused Al₂O₃ were employed, the deep and big craters were generated at the interface between coatings and hard substrates. In the case of pure soft metal coating such as Al on hard substrate, it is very hard to get proper adhesion due to lack of crater formation. Therefore, the composite coating would have certain advantages.     

Fluorination of Al2O3 blocking layer for improving the performance of metal‐oxide‐nitride‐oxide‐silicon flash memory

The characteristics of Al₂O₃ film grown by atomic‐layer deposition as blocking layer with and without fluorine plasma treatment were investigated based on a capacitor structure of Al/Al₂O₃/TaON/SiO₂/Si. The physical structure was studied by transmission electron microscopy, and the chemical composition of the blocking layer was analyzed by X‐ray photoelectron spectroscopy and secondary ion mass spectroscopy. Moreover, the surface roughness of the blocking layer was investigated by atomic force microscopy. Compared with a capacitor with Al₂O₃ blocking layer, the one with fluorinated Al₂O₃ displayed higher programming/erasing speeds, better endurance property and better charge retention characteristic because the fluorination could reduce excess oxygen and traps in the blocking layer, thus forming a larger barrier height at the interface between the charge‐trapping layer and the blocking layer. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure and mechanical properties of ceramic coatings fabricated by plasma electrolytic oxidation on aluminized steel

Ceramic coatings were formed by plasma electrolytic oxidation (PEO) on aluminized steel. Characteristics of the average anodic voltages versus treatment time were observed during the PEO process. The micrographs, compositions and mechanical properties of ceramic coatings were investigated. The results show that the anodic voltage profile for processing of aluminized steel is similar to that for processing bulk Al alloy during early PEO stages and that the thickness of ceramic coating increases approximately linearly with the Al layer consumption. Once the Al layer is completely transformed, the FeAl intermetallic layer begins to participate in the PEO process. At this point, the anodic voltage of aluminized steel descends, and the thickness of ceramic coating grows more slowly. At the same time, some micro-cracks are observed at the Al₂O₃/FeAl interface. The final ceramic coating mainly consists of γ-Al₂O₃, mullite, and α-Al₂O₃ phases. PEO ceramic coatings have excellent elastic recovery and high load supporting performance. Nanohardness of ceramic coating reaches about 19.6 GPa.     

Blocking of interfacial diffusion at Ag/Alq3 by LiF

X-ray photoelectron spectroscopy has been applied to interface studies of Ag/tris-(8-hydroxyquinoline) aluminum (Alq₃) and Ag/LiF/Alq₃. For Ag/Alq₃, diffusion of Ag atoms into the Alq₃ layer occurs immediately after the adhesion of the metal onto the organic layer and the process lasts several hours. Insertion of a monolayer-thick LiF buffer at the interface can effectively block the diffusion process. This is quite different from what is observed from Al/LiF/Alq₃, where Al penetrates into the LiF layer as deep as several nanometers. It is thus concluded that the LiF buffer may play different roles in Ag/LiF/Alq₃ and Al/LiF/Alq₃ and hence different mechanisms may dominate in the two cases for the enhanced carrier injection observed.     

Silicon surface passivation by aluminium oxide studied with electron energy loss spectroscopy

The origin behind crystalline silicon surface passivation by Al₂O₃ films is studied in detail by means of spatially‐resolved electron energy loss spectroscopy. The bonding configurations of Al and O are studied in as‐deposited and annealed Al₂O₃ films grown on c‐Si substrates by plasma‐assisted and thermal atomic layer deposition. The results confirm the presence of an interfacial SiO₂‐like film and demonstrate changes in the ratio between tetrahedrally and octahedrally coordinated Al in the films after annealing. These observations reveal the underlying origin of c‐Si surface passivation by Al₂O₃. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation of Ceramic-Like Coatings Formed on Aluminum Composites by Microarc Oxidation

Ceramic-like coatings with a thickness of up to 40 μm are formed on aluminum composites without additives and with copper additives (1 and 4.5%) in a silicate-alkaline electrolyte by microarc oxidation. The composites are prepared by powder metallurgy (cold pressing and sintering in forevacuum). An increase in the copper concentration in the composites to 4.5% leads to the retardation of anode voltage growth on the initial stage of oxidation corresponding to the formation of a barrier layer. The coatings are studied by scanning electron microscopy, X-ray microanalysis, X-ray photoelectron spectroscopy, and X-ray diffraction. The morphology of their surface corresponds to the morphology of the surface of coatings on compact aluminum alloys. According to X-ray photoelectron spectroscopy, a thin 1-μm layer forms on the surface. It consists predominantly of electrolyte components. X-ray diffraction analysis shows that the coatings mainly consist of γ-Al₂O₃ oxide as well as the η-Al₂O₃ phase, the peaks of which are broadened. This broadening is characteristic of the amorphous component and may be due to the presence of nanocrystalline regions in the coating structure. In the coatings on the composite Al + 4.5% Cu, mullite Al₂SiO₅ and copper oxide CuO are also found. The excess aluminum content may be associated with residual unoxidized aluminum inclusions in the structure of the coatings.     

The diffusion of silicon atoms in stack structures of La2O3 and Al2O3

The interfacial reactions and electrical characteristics of stack structures of La₂O₃ and Al₂O₃ were investigated as a function of the annealing temperature. In the case of Al₂O₃/La₂O₃/Si (ALO structure), the La₂O₃ in contact with the Si substrate was readily transformed into La-silicate by the diffusion of Si atoms, while in the case of La₂O₃/Al₂O₃/Si (LAO structure), interfacial reactions between the Al₂O₃ layer and the Si substrate were suppressed. After an annealing treatment at 700 °C, the Al₂O₃ in the ALO structure can play an effective role in blocking the hydration of La₂O₃, resulting in an unchanged interfacial layer. However, the Al₂O₃ layer in the LAO structure was unable to suppress the diffusion of Si atoms into the La₂O₃ film. When the annealing temperature reached 900 °C, both structures showed a similar depth distribution with a high content of Si atoms diffused into the films. The change in the elemental distributions via the diffusion and reaction of Si atoms affected the electrical characteristics at the interface between ALO/LAO structure and Si substrate, specifically the trap charge density (D_it) and band gap (E_g) values.     

Atomic layer deposition of nanolaminate oxide films on Si

Among the methods for depositing thin films, atomic layer deposition is unique for its capability of growing conformal thin films of compounds with a control of composition and thickness at the atomic level. The conformal growth of thin films can be of particular interest for covering nanostructures since it assures the homogeneous growth of the ALD film in all directions, independent of the position of the sample with respect to the incoming precursor flow. Here we describe the technique for growing the HfO₂/Al₂O₃ bilayer on Si substrate and our in situ approach for its investigation by means of synchrotron radiation photoemission. In particular, we study the interface interactions between the two oxides for various thickness compositions ranging from 0.4 to 2.7 nm. We find that the ALD of HfO₂ on Si induces the increase of the interfacial SiO₂ layer, and a change in the band bending of Si. On the contrary, the ALD of Al₂O₃ on HfO₂ shows negligible interaction between layers as the binding energies of Hf4f, Si2p, and O1s core level peaks and the valence band maximum of HfO₂ do not change and the interfacial SiO₂ does not increase.     

Interface characteristics and mechanical properties of short carbon fibers/Al composites with different coatings

Three kinds of coatings, Ni, Cu and Al₂O₃, were obtained on the surface of short carbon fibers (SCFs). The interface characteristics and mechanical properties of SCFs/Al composites with the various coatings were systematically studied in this paper. The results showed that, compared to non-coating, Ni or Cu coating improved the wettability of SCFs and Al melt. However, the harmful phases Al₃Ni or CuAl₂ generated in interface zone and Al matrix result in the lower mechanical properties. Al₂O₃ coating protected the SCFs and prevented the harmful reaction of Al and SCFs. The interface of Al/Al₂O₃/SCF without any other phase was clean and well bonded, and the Al₂O₃-coated SCFs/Al composite had the highest mechanical properties. The interfacial indentation and fracture mechanism of all the composites were analyzed in detail.     

Time evolution of the microstructures of LaAlO3 thin films grown on Si substrates

The structure and stability of amorphous LaAlO₃ thin films deposited on Si substrates were investigated by an X-ray reflectivity technique. The results show that the film/substrate interface contains a La_xAl_yO_zSi layer and a SiO_x layer. X-ray reflectivity profiles showed a continuous change after the films were exposed to ambient air for six months at room temperature. The X-ray reflectivity simulations suggest a diffusion of La and Al (mostly La) from the LaAlO₃ layer to the La_xAl_yO_zSi layer. This process stopped after about six months, and then the films reached a relative equilibrium state. Moreover, post-air-exposure annealing at 300 °C in air atmosphere could not change the final distributions of La and Al along the normal to the film’s substrate. On the other hand, the leakage-current density slightly decreases after annealing at 300 °C, which might be caused by the decrease of oxygen vacancies in the films. PACS 61.10.Kw; 77.55.+f; 68.60.Dv     

Nb-Al合金高温氧化机理

通过自编软件建立了铝氧化膜与基体铌界面的原子集团模型,用递归法计算了合金的原子埋置能、原子结合能等电子参数,从电子层面分析铌合金高温氧化机理.研究表明:铝通过晶界扩散偏聚在合金表面,并与氧结合生成致密的Al2O3氧化膜,阻挡氧向铌基体扩散.晶界和稀土元素能提高氧化膜与基体间的原子结合能,增加其界面的结合强度,加强氧化膜与基体铌间的黏附性.因此,通过在合金中添加稀土元素或细化合金晶粒均能提高铌合金的抗高温氧化性能.     

Preparation and characterization of ferroelectric SrBi2Ta2O9 thin films on Si using Al2O3 buffer layers

SrBi₂Ta₂O₉ (SBT) thin films were prepared on p-type Si(100) substrates with Al₂O₃ buffer layers. Both the SBT films and the Al₂O₃ buffer layers were deposited by a pulsed laser deposition technique using a KrF excimer laser. An Al prelayer was used to prevent Si surface oxidization in the initial growth stage. It is shown that Al₂O₃ buffer layers effectively prevented interdiffusion between SBT and Si substrates. Furthermore, the capacitance–voltage (C-V) characteristics of the SBT/Al₂O₃/Si heterostructures show a hysteresis loop with a clockwise trace, demonstrating the ferroelectric switching properties of SBT films and showing a memory window of 1.6 V at 1 MHz. Received: 17 July 2000 / Accepted: 16 August 2000 / Published online: 30 November 2000     

Physical and mechanical properties of silicon near the SiO2/Si interface

The influence of an oxide coating on the strength characteristics of single-crystal silicon surface layers is investigated by the microindentation method. It is shown experimentally that a strengthened layer with a thickness of 0.2–0.4 μm and a microhardness of 20–35 GPa, which is two or three times as much as the microhardness of bulk single-crystal silicon, is present near the SiO₂/Si interface. The thickness and microhardness of this layer depends on the growth conditions of the oxide. The formation of this layer is most probably caused by interstitial silicon atoms formed near the SiO₂/Si interface during silicon oxidation.     

Fe-Cr-Al合金氧化膜形成机理电子理论研究

通过自编软件建立了Fe-Cr-Al合金表面、氧化膜/基体界面模型,采用递归法计算了合金元素在Fe-Cr-Al合金表面、氧化膜/基体界面的环境敏感镶嵌能、亲和能、结合能、态密度等电子结构参数.从电子层次系统研究了Fe-Cr-Al合金氧化膜的形成机理、稀土元素和杂质硫对氧化膜形成过程及黏附性的影响机理.研究表明Fe-Cr-Al合金中Al的偏聚驱动力远大于Y,Cr.氧化初期氧从合金表面向合金内部扩散,合金内部Al向合金表面扩散,使合金形成富铝、氧表面层;氧与Al间的亲和力较大（亲和能低）,氧原子容易与Al结合生成Al₂O₃保护膜;合金中加入Y后,Y在合金表面偏聚,抑制Al向合金表面扩散,氧化膜的横向生长得到有效控制,从而避免氧化膜皱褶形貌的发生,提高氧化膜的黏附性;合金内部的S通过扩散汇集在基体/氧化膜界面,S使界面区原子的总能增高,总态密度降低,减小了界面的稳定性,进而削弱氧化膜与合金基体的结合力. 关键词： 电子结构 高温氧化 Fe-Cr-Al合金