First-principles study of the α-Al2O3(0001)/Cu(111) interface

Adhesive energetics and interfacial electronic structures have been computed from first principles for the Cu/Al₂O₃ interface. Recent transmission electron microscopy results of Cu grown by molecular beam epitaxy on Al₂O₃(0001) were helpful in modelling the interfacial atomic structure. We found that Al₂O₃(0001) relaxation effects can lower the work of adhesion W _ad by over a factor of 3. Our computed W _ad value is in reasonably good agreement with experiment, being somewhat larger, as expected from our assumption of a coherent interface. One might begin to understand this metal/ceramic adhesion as a competition between Cu and Al for oxide formation, which is easily won by Al. However this simple picture is complicated by several indications of a significant metallic/covalent component to the Cu/Al₂O₃ adhesive bond.     

基于密度泛函理论研究掺杂Pd石墨烯吸附O2及CO

基于第一性原理的密度泛函理论研究了单个O₂和CO气体分子吸附于本征石墨烯和掺杂钯(Pd)的石墨烯的体系, 通过石墨烯掺Pd前后气体分子的吸附能、电荷转移及能带和态密度的计算, 发现掺Pd后气体分子吸附能和电荷转移显著增大, 这是由于Pd的掺杂, 在本征石墨烯能带中引入了杂质能级, 增强了石墨烯和吸附气体分子间的相互作用; 氧化性气体O₂和还原性气体CO吸附对石墨烯体系能带结构和态密度的影响明显不同, 本征石墨烯吸附O₂后, 费米能级附近态密度变大, 掺Pd后在一定程度变小; 吸附还原性的CO后, 石墨烯费米能级附近态密度几乎没有改变, 表明掺杂Pd不会影响石墨烯对CO的气体灵敏度, 但由于CO对石墨烯的吸附能增大, 可以提高石墨烯对还原性气体的气敏响应速度.     

Electronic structures and mechanical properties of Al(111)/ZrB2(0001) heterojunctions from first-principles calculation

Employing first-principles density functional theory (DFT), the structures and electronic and mechanical properties of Al(111)/ZrB₂(0001) heterojunctions are investigated. It is found that both B-terminated ZrB₂(0001) and Zr-terminated ZrB₂(0001) can form heterojunction interfaces with Al(111) surface. The heterojunction with B-terminated ZrB₂(0001) is demonstrated to be most stable by comparing the surface adhesion energies of six different heterojunction models. In the stable configurations, the Al atom is found projecting to the hexagonal hollow site of neighbouring boron layer for the B-terminated ZrB₂(001), and locating at the top site of the boron atoms for Zr-terminated ZrB₂(001) interface. The mechanisms of interface interaction are investigated by density of states, charge density difference and band structure calculations. It is found that covalent bonds between surface Al atoms and B atoms are formed in the B-terminated heterojunction, whereas the Al atoms and Zr atoms are stabilised by interface metallic bonds for the Zr-terminated case. Mechanical properties of Al/ZrB₂ heterojunctions are also predicted in the current work. The values of moduli of Al/ZrB₂ heterojunctions are determined to be between those of single crystal Al and ZrB₂, which exhibit the transition of mechanical strength between two bulk phases. DFT calculations with the current models provide the mechanical properties for each heterojunction and the corresponding contributions by each type of interface in the composite materials. This work paves the way for industrial applications of Al(111)/ZrB₂(0001) heterojunctions.     

Angular dependence of surface acoustic wave characteristics in AlN thin films on a-plane sapphire substrates

AlN thin films have been grown on a-plane sapphire (Al₂O₃(112̄0)) substrates. X-ray diffraction measurements indicate the films are fully c-plane (0001) oriented with a full width at half maximum of the AlN(0002) rocking curves of 0.92. The epitaxial growth relationships have been determined by the reflection high energy electron diffraction analysis as AlN[11̄00]//Al₂O₃[0001] and AlN[112̄0]//Al₂O₃[11̄00]. Angular dependence of important surface acoustic wave (SAW) characteristics, such as the phase velocity and electromechanical coupling coefficient, has been investigated on the AlN(0001)/Al₂O₃(112̄0) structure. While the SAW is excited at all propagation angles with an angular dispersion of the phase velocity in the range of 5503–6045 m/s, a higher velocity shear-horizontal (SH) mode is observed only at 0°, 105° and 180° off the reference Al₂O₃[11̄00] over a 180° angular period. The phase velocity of the SH mode shows dispersion (6089–6132 m/s) as a function of the SAW wavelength. Temperature coefficients of frequency are also demonstrated for both modes. PACS 81.15.Hi; 77.84.-s; 77.65.Dq     

Ab initio study of heterojunction discontinuities in the ZnO/Cu2O system

Solar cells based on transparent conductive oxides such as ZnO/Cu₂O constitute a very advanced way to build high-performance cells. In this work, we are interested in the characterization of the interface through nanoscale modeling based on ab initio approaches (density functional theory, local density approximation, and pseudopotential). This work aims to build a supercell containing a heterojunction ZnO/Cu₂O and study the structural properties and the discontinuity of the valence band (band offset) from a semiconducting to another phase. We build a zinc oxide in the wurtzite structure along [0001] on which we place the copper oxide in the hexagonal (CdI₂-type) structure. We choose the method of Van de Walle and Martin to calculate the energy offset. This approach fits well the density functional theory. Our calculation of the band offset gives a value that corresponds to other experimental and theoretical values.     

Electronic structure of bismuth ferrite and hematite single crystals: X-ray photoelectron study and calculation

The X-ray photoelectron spectra of the inner levels and valence bands of the surfaces of BiFeO₃ and Fe₂O₃ single crystals have been measured using X-ray photoelectron spectroscopy on an ESCALAB 250 X-ray photoelectron microprobe with monochromatization of X-ray radiation of the AlK _α line. The ab initio calculations have been performed by the full-potential pseudopotential method in terms of the density functional theory (Quantum-Espresso program package). The band structure and the total and partial densities of states have been calculated for the BiFeO₃ and Fe₂O₃ systems. A comparison of the theoretical and experimental results has demonstrated good agreement between theory and experiment.     

Si掺杂β-Ga2O3的第一性原理计算与实验研究

采用基于密度泛函理论(DFT)的第一性原理平面波超软赝势(USPP)法, 在广义梯度近似(GGA)下计算了本征β-Ga₂O₃和Si掺杂β-Ga₂O₃的能带结构、电子态密度、差分电荷密度和光学特性. 在蓝宝石衬底(0001)晶面上用脉冲激光沉积(PLD)法制备了本征β-Ga₂O₃和Si掺杂β-Ga₂O₃薄膜, 测量了其吸收光谱和反射光 关键词： 第一性原理 超软赝势 密度泛函理论 2O₃')" href="#">Si掺杂β-Ga₂O₃     

Substrate effects on V2O3 thin films

We apply density functional theory and the augmented spherical wave method to analyze the electronic structure of V₂O₃ in the vicinity of an interface to Al₂O₃. The interface is modeled by a heterostructure setup of alternating vanadate and aluminate slabs. We focus on the possible modifications of the V₂O₃ electronic states in this geometry, induced by the presence of the aluminate layers. In particular, we find that the tendency of the V 3d states to localize is enhanced and may even cause a metal-insulator transition.     

Theoretical study on the catalytic properties of single-atom catalyst stabilised on silicon-doped graphene sheets

ABSTRACT

The stable configurations, electronic structures and catalytic activities of single-atom metal catalyst anchored silicon-doped graphene sheets (3Si-graphene-M, M?=?Ni and Pd) are investigated by using density functional theory calculations. Firstly, the adsorption stability and electronic property of different gas reactants (O₂, CO, 2CO, CO/O₂) on 3Si-graphene-M substrates are comparably analysed. It is found that the coadsorption of O₂/CO or 2CO molecules is more stable than that of the isolated O₂ or CO molecule. Meanwhile, the adsorbed species on 3Si-graphene-Ni sheet are more stable than those on the 3Si-graphene-Pd sheet. Secondly, the possible CO oxidation reactions on the 3Si-graphene-M are investigated through Eley–Rideal (ER), Langmuir–Hinshelwood (LH) and new termolecular Eley–Rideal (TER) mechanisms. Compared with the LH and TER mechanisms, the interaction between 2CO and O₂ molecules (O₂?+?CO → CO₃, CO₃?+?CO → 2CO₂) through ER reactions (< 0.2?eV) are an energetically more favourable. These results provide important reference for understanding the catalytic mechanism for CO oxidation on graphene-based catalyst.     

Laser–MBE growth of high-quality ZnO thin films on Al2O3(0001) and SiO2/Si(100) using the third harmonics of a Nd:YAG laser

High-quality ZnO thin films were grown on single-crystalline Al₂O₃(0001) and amorphous SiO₂/Si(100) substrates at 400–640 °C using laser molecular beam epitaxy. For film growth, the third harmonics of a pulsed Nd:YAG laser were illuminated on a ZnO target. The ZnO films were epitaxially grown on Al₂O₃(0001) with the narrow X-ray diffraction full width at half maximum (FWHM) of 0.04° and the films on SiO₂/Si(100) exhibited a preferred c-axis orientation. Furthermore, the films exhibited excellent optical properties in photoluminescence (PL) measurements with very sharp excitonic and weak deep-level emission peaks. At 15 K, PL FWHM values of the films grown on Al₂O₃(0001) and SiO₂/Si(100) were 3 and 18 meV, respectively. Received: 8 May 2001 / Accepted: 18 September 2001 / Published online: 20 December 2001     

Interface traps contribution to capacitance of Al2O3/(GaN)AlGaN/GaN heterostructures at low frequencies

Influence of interface traps at Al₂O₃/(GaN)/AlGaN interface on low and high frequency capacitance of Al₂O₃/(GaN)/AlGaN/GaN heterostructure capacitor was studied. New features were observed in the capacitance curves. Obtained experimental results were modeled and simulated and accordance with the experiment has been obtained. For lower frequencies a new capacitance peak in the depletion and increase of the capacitance in a plateau region were measured. The capacitance peak in the depletion region was successfully explained by a capacitance response of the interface traps with U-shape density distribution. On the other hand the increase of the capacitance plateau was modeled by the homogeneous interface trap distribution. We assume that the traps located near the band edges having the highest density are able to respond to the low frequency measuring.     

Photoluminescence behavior of pulsed laser deposited ZnGa<Subscript>2</Subscript>O<Subscript>4</Subscript> thin-film phosphors grown on various substrates

ZnGa₂O₄ thin-film phosphors have been grown on Si(100), Al₂O₃(0001) and MgO(100) substrates using pulsed laser deposition. The structural characterization was carried out on a series of ZnGa₂O₄ films grown on various substrates under various substrate temperatures and oxygen pressures. The films grown on these substrates not only have different crystallinity and surface morphology, but also different Zn/Ga composition ratio. The crystallinity and photoluminescence (PL) of the ZnGa₂O₄ films are highly dependent on the deposition conditions, in particular the stoichiometry ratio of Zn/Ga and the kind of substrate. The variation of Zn/Ga in the films also depends on not only the oxygen pressure but also the substrate temperature during deposition. The PL properties of pulsed laser deposited ZnGa₂O₄ thin films have indicated that Al₂O₃(0001) and MgO(100) are promising substrates for the growth of high-quality ZnGa₂O₄ thin films and that the luminescence brightness depends on the substrate. The luminescence spectra show a broad band extending from 350 to 600 nm and peaking at 460 nm. Received: 11 July 2002 / Accepted: 31 July 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +82-51-6206356, E-mail: jhjeong@pknu.ac.kr     

Crystalline-phase-dependent red emission behaviors of Gd2O3:Eu3+ thin-film phosphors

Gd₂O₃:Eu³⁺ luminescent thin films have been grown on Al₂O₃(0001) substrates using pulsed-laser deposition. The films grown at different deposition conditions showed different crystalline phases, surface morphologies and luminescent characteristics. Both cubic and monoclinic crystalline phases were observed for the Gd₂O₃:Eu³⁺ films, and the crystalline structure and the surface morphology of the films were highly dependent on the oxygen pressure and substrate temperature. The cubic system showed a higher luminescence than the monoclinic system. The luminescence characteristics were strongly influenced by not only the crystalline structure but also the surface morphology of the films. The photoluminescencebrightness data obtained from Gd₂O₃:Eu³⁺ films indicate that Al₂O₃(0001) is a promising substrate for growth of high-quality Gd₂O₃:Eu³⁺ thin-film red phosphor. In particular, the Gd₂O₃:Eu³⁺ films showed a much better photoluminescence behavior than a Y₂O₃:Eu³⁺ films with the same thickness. PACS 78.20.-e; 78.55.-m; 78.66.-w     

A route to transparent bulk metals

Hypothetical compounds based on a sapphire host are investigated with respect to their structural as well as electronic features. The results are obtained by electronic structure calculations within density functional theory and the generalized gradient approximation. A quarter of the Al atoms in Al₂O₃ is replaced by a 4d transition metal M ion, with d⁰ to d⁹ electronic configuration. We perform structure optimizations for all the compounds and analyze the electronic states. Due to the sizeable band gap of the Al₂O₃ host, we can identify promising candidates for transparent bulk metals. We explain the mechanisms leading to this combination of materials properties. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Band gap opening and optical absorption enhancement in graphene using ZnO nanocluster

Electronic, optical and transport properties of the graphene/ZnO heterostructure have been explored using first-principles density functional theory. The results show that Zn₁₂O₁₂ can open a band gap of 14.5 meV in graphene, increase its optical absorption by 1.67 times covering the visible spectrum which extends to the infra-red (IR) range, and exhibits a slight non-linear I–V characteristic depending on the applied bias. These findings envisage that a graphene/Zn₁₂O₁₂ heterostructure can be appropriate for energy harvesting, photodetection, and photochemical devices.     

Transmission electron microscopy studies on structure and defects in crystalline yttria and lanthanum oxide thin films grown on single crystal sapphire by molecular beam synthesis

The Molecular beam synthesis and characterization are reported for Y₂O₃ thin films grown on Al₂O₃ (0001) substrate. The Y₂O₃ layer was highly oriented in the [111] direction with predominant orientation relations (111) Y₂O₃ ‖ (0001) Al₂O₃ and [110] Y₂O₃ ‖ [2110] Al₂O₃, corresponding to a lattice mismatch of ～20% at the interface. No significant interfacial layers were found at the Y₂O₃/Al₂O₃ interface and the large lattice misfit was accommodated by formation of stacking faults, dislocations and secondary orientation in the Y₂O₃ layer. A La₂O₃ interlayer improved the quality of the Y₂O₃ films. Full width at half maximum (FWHM) of the Y₂O₃ (222) peak decreased from 3.12° to 1.43° and the defect density in the Y₂O₃ layer was significantly reduced. These results may be relevant in the broader context of designing oxide heterolayers with controlled microstructures.     

Ion synthesis and optical properties of gold nanoparticles in an Al2O3 matrix

Single-crystal Al₂O₃(0001) and Al₂O₃(1120) substrates are implanted by 160-keV Au⁺ ions with doses from 10¹⁵ to 10¹⁷ cm^?2. Some of the implanted samples are air-annealed at 800–1200°C. The properties of the synthesized composite layers are studied by Rutherford backscattering and linear optical reflection measurements, and their nonlinear optical characteristics are examined by RZ-scanning using a picosecond Nd: YAG laser operating at a wavelength of 1064 nm. The Rutherford backscattering spectra indicate that the implanted impurity concentrates near the surface of the Al₂O₃. The formation of gold nanoparticles in the Al₂O₃ can be judged from the characteristic optical plasmon resonance band in the reflectance spectra of the samples irradiated to a dose higher than 6.0 × 10¹⁶ cm^?2. The synthesized particles are shown to be responsible for nonlinear optical refraction in the samples. The nonlinear refractive index, n ₂, and the real part of the third-order susceptibility, Rex⁽³⁾, of the composite layers are determined.     

Ni与Co掺杂Fe2O3（0001）表面增强析氧反应活性

Fe based oxides are considered as a promising catalyst for the oxygen evolution reaction (OER) due to their low cost and high stability. Here, based on density functional theory calculations, the electrocatalytic behaviors of pure and metal (Ni, Co) doped Fe-terminated Fe₂O₃(0001) are investigated. The potential-limiting step for OER is determined as the formation of O^* by dehydrogenating surface hydroxyl and it is suggested that the doping enhances the catalytic activity of Fe₂O₃(0001) by reducing the free energy change of rate limiting step on doped Ni or Co atom. Especially, the calculated over-potential of Co-doped Fe₂O₃ (0001) surface is about 0.63 eV on Co site, which is comparable with the theoretical over-potential of 0.56 eV for RuO₂.     

Investigation of 4H—SiC metal—insulation—semiconductor structure with Al2O3/SiO2 stacked dielectric

Atomic layer deposited (ALD) Al₂O₃/dry-oxidized ultrathin SiO₂ films as high-k gate dielectric grown on the 8° off-axis 4H-SiC (0001) epitaxial wafers are investigated in this paper. The metal-insulation-semiconductor (MIS) capacitors, respectively with different gate dielectric stacks (Al₂O₃/SiO₂, Al₂O₃, and SiO₂) are fabricated and compared with each other. The I-V measurements show that the Al₂O₃/SiO₂ stack has a high breakdown field ( ≥ 12 MV/cm) comparable to SiO₂, and a relatively low gate leakage current of 1× 10^-7 A/cm² at electric field of 4 MV/cm comparable to Al₂O₃. The 1-MHz high frequency C-V measurements exhibit that the Al₂O₃/SiO₂ stack has a smaller positive flat-band voltage shift and hysteresis voltage, indicating less effective charge and slow-trap density near the interface.     

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.