Effect of growth stoichiometry on the structural properties of AlN films on thermally nitrided sapphire $(11\bar 20)$

High‐quality AlN epilayers were grown via pulsed sputtering deposition on thermally nitrided sapphire $(11\bar 20)$ with precise control of the N/Al ratio. Under slightly Al‐rich growth conditions, the growth of AlN epilayers on the thermally nitrided sapphire proceeded in a two‐dimensional mode from the initial stage of growth, and their surfaces were atomically flat stepped and terraced structures. The FWHM values of the X‐ray rocking curves were as low as 87 arcsec and 339 arcsec for the 0002 and $1 \bar 102$ diffractions, respectively, at a film thickness of 400 nm. The present approach is therefore quite promising for the low‐cost fabrication of AlGaN‐based UV optical devices. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Na‐site energy of P2‐type NaxM O2 (M = Mn and Co)

P2‐type Na_xM O₂ (M = Mn and Co) is a promising cathode material for low‐cost sodium ion secondary batteries. In this structure, there are two different crystallographic Nai (i = 1 and 2) sites with different Coulomb potential $ (\varphi _i)$ provided by M^4–x and O^2–. Here, we experimentally determine a difference ${(\rm \Delta }\varepsilon \equiv \varepsilon _1 - \varepsilon _2)$ of Na‐site energies ${(}\varepsilon _i \equiv e\varphi {\kern 1pt} _i)$ based on the temperature dependence of the site occupancies. We find that ${\rm \Delta }\varepsilon \;{=}\;56\;{K}$ for Na_0.52MnO₂ is significantly smaller than 190 K for Na_0.59CoO₂. We interpret the suppressed ${\rm \Delta }\varepsilon $ in Na_0.52MnO₂ in terms of the screening effect of the Na⁺ charge. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Persistent layer‐by‐layer growth for pulsed‐laser homoepitaxy of $(000\bar 1)$ ZnO

Persistent layer‐by‐layer growth is demonstrated for pulsed‐laser homoepitaxy of ZnO thin films on $(000\bar 1)$ ZnO single crystals. Employing interval pulsed‐laser deposition (PLD), RHEED oscillations are stabilized over a film thickness of about 90 nm. For interval pulsed laser deposited films a considerably decreased root‐mean‐square surface roughness of 0.26 nm was found, in comparison to 0.74 nm for conventional PLD. A small asymmetry in the X‐ray diffraction (XRD) 2θ –ω scan reveals compressive strain in the thin film being slightly larger for interval PLD as compared to conventional PLD. The FWHM of the photoluminescence (PL) I₆ line is higher with about 500 µeV as compared to 350 µeV for the conventional PLD. Consequently, both XRD as well as PL indicate a slightly higher amount of charged defects for the interval PLD.

     

An ab initio study of CX3‐substitution (X = H,F, Cl,Br, I) effects on the static electric polarizability and hyperpolarizability of diacetylene

We report a systematic ab initio and density functional theory (DFT) study of the electric properties of the X₃C? C≡C? C≡C? H (X = H, F, Cl, Br, and I) sequence of substituted diacetylenes. We rely on finite‐field Møller–Plesset perturbation theory and coupled‐cluster calculations with large, flexible basis sets. Our best values at the second‐order Møller–Plesset perturbation theory level for the mean dipole polarizability and second hyperpolarizability are $\overline {{\alpha} } $ /e²aE = 64.46 (? CH₃), 65.59 (? CF₃), 110.11 (? CCl₃), 138.90 (? CBr₃), 184.98 (? CI₃) and $\overline {{\gamma} } $ /e⁴aE = 21020 (? CH₃), 13469 (? CF₃), 32708 (? CCl₃), 57599 (? CBr₃), and 105251 (? CI₃). For comparison, the analogous MP2 values for diacetylene [P.Karamanis and G.Maroulis, Chem. Phys. Lett. 2003 , 376, 403.] are $\overline {{\alpha} } $ /e²aE = 49.17, and $\overline {{\gamma} } $ /e⁴aE = 16227. For the mean first hyperpolarizability we report $\overline {{\beta} } $ /e³aE = ?205.8 (? CH₃), ?55.7 (? CF₃), 120.8 (? CCl₃), 443.8 (? CBr₃), and 725.4 (? CI₃). Copyright © 2010 John Wiley & Sons, Ltd.     

Raman scattering and disorder effect in Cu2ZnSnS4

The Raman spectra of surface regions of bulk Cu₂ZnSnS₄ (CZTS) samples with different Cu and Zn cation content were obtained and the differences in the spectra are attributed to statistical disorder effects in the cation sublattice. This disorder in the Cu and Zn sublattices may initiate a change of the crystal symmetry from kesterite‐type $({I\bar 4})$ to $({I\bar 42m})$ space group. The investigated CZTS crystals grown at high temperature are characterised by the co‐existence of regions with different composition ratio of Cu/(Zn + Sn) which results in kesterite and disordered kesterite phases. The presence of a disordered phase with ${I\bar 42m}$ symmetry is reflected in the appearance of a dominant broadened A‐symmetry peak at lower frequency than the peak of the main A‐symmetry kesterite mode at 337 cm^–1. We suppose that due to a small energy barrier between these phases the transition from one phase to the other can be stimulated by optical excitation of Cu₂ZnSnS₄. The analysis of the Raman spectra measured under different excitation conditions has allowed obtaining first (to our knowledge) experimental evidence of the existence of such optically induced structural transition in CZTS. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Double resonance Raman effects in InN nanowires

We study the excitation wavelength dependence of the Raman spectra of InN nanowires. The $ E_1 ({\rm LO})$ phonon mode, which is detected in backscattering configuration because of light entering through lateral faces, exhibits an upward fre‐ quency shift that can be explained by Martin's double resonance. The $ E_1 ({\rm LO})$ /$ E_2^h $ intensity ratio increases with the excitation wavelength more rapidly than the $A_1 ({\rm LO})/E_2^h $ ratio measured in InN thin films. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Epitaxy of m ‐plane ZnO on (112) LaAlO3 substrate

Heteroepitaxial growth of non‐polar m ‐plane (10 0) ZnO has been demonstrated on (112) LaAlO₃ single crystal substrates using the pulsed laser deposition method. X‐ray diffraction, reflection high energy electron diffraction, and cross‐sectional transmission electron microscopy with selected‐area diffraction, have been used to characterize the structural properties of deposited ZnO films. The epitaxial relationship between ZnO and LAO is shown to be (10 0)_ZnO ∥ (112)_LAO, (11 0)_ZnO ∥ ( 1)_LAO and [0001]_ZnO ∥ [ 10]_LAO. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Theoretical study of the initial stage of InN growth on cubic zirconia (111) substrates

An initial stage of InN growth on cubic zirconia (111) substrates has been investigated using first‐principles calculations based on density functional theory (DFT). We have evaluated adsorption energies of indium and nitrogen atoms on cubic zirconia (111) surfaces, and have found that the differences in the adsorption energies of the indium atoms at various adsorption sites were small, indicating that the migration of the indium atoms on zirconia (111) surfaces occurs readily. On the other hand, we have found that the differences in the adsorption energies of the nitrogen atoms at various adsorption sites were large, implying that the nitrogen atoms tend to stay at the stable site with the largest adsorption energy, which was identified as the O–Zr bridge site. These results suggest that the first layer of InN films is the nitrogen layer. In addition, we have found that the energetically favorable arrangement is comprised of InN(0001)//cubic zirconia (111) and InN $ [11\bar 20] $ //cubic zirconia $ [1 \bar 10], $ which is quite consistent with previously obtained experimental data. Furthermore, the hybridization effect between N 2p and O 2p plays a crucial role in determining the interface structure for the growth of InN on cubic zirconia (111) surfaces. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structures of 3‐methyl‐2(1H)‐quinoxalinone and three substituted derivatives

3‐Methyl‐2(1H)‐quinoxalinone and three derivatives (3,7‐dimethyl‐2(1H)‐quinoxalinone, 3‐methyl‐6,7‐dichloro‐2(1H)‐quinoxalinone and 3‐methyl‐7‐nitro‐2(1H)‐quinoxalinone) have been synthesised and analysed by ¹H NMR and IR spectral spectroscopies. The crystal structures have been determined at room temperature from X‐ray single crystal diffraction data for three of them and from powder diffraction data for the nitro derivative. 3‐Methyl‐2(1H)‐quinoxalinone crystallises in the P2₁/c monoclinic system, 3,7‐dimethyl‐2(1H)‐quinoxalinone in the Pbca orthorhombic system and the two others compounds in the P$\overline {1} $ triclinic system. For the nitro derivative, C? H$\cdots $ N short contacts are established between the carbon of the methyl and the double bounded nitrogen of the ring. For the three other compounds N? H$\cdots $ O hydrogen bonds involve the atoms of the heterocyclic ring. Copyright © 2011 John Wiley & Sons, Ltd.     

Cover Picture: Contrib. Plasma Phys. 2/2012

Density fluctuations δn_e($ \bar r $ ) at the surface. Figure 3a of the paper by T. Raitza, I. Broda, H. Reinholz, and G. Röpke (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

DFT study and NBO analysis of the mutual interconversion of cumulene compounds

The B3LYP/6‐31G* method was used to investigate the configurational properties of allene (1,2‐propadiene) ( 1 ), 1,2,3‐butatriene ( 2 ), 1,2,3,4‐pentateriene ( 3 ), 1,2,3,4,5‐hexapentaene ( 4 ), 1,2,3,4,5,6‐heptahexaene ( 5 ), 1,2,3,4,5,6,7‐octaheptaene ( 6 ), 1,2,3,4,5,6,7,8‐nonaoctaene ( 7 ), and 1,2,3,4,5,6,7,8,9‐decanonaene ( 9 ). The calculations at the B3LYP/6‐31G* level of theory showed that the mutual interconversion energy barrier in compounds 1 – 8 are: 209.73, 131.77, 120.34, 85.00, 80.91, 62.19, 55.56, and 46.83 kJ mol^?1, respectively. The results showed that the difference between the average C?C double bond lengths ( ) values in cumulene compounds 1 and 2 , is larger than those between 7 and 8 , which suggest that with large n (number of carbon atoms in cumulene chain), the values approach a limiting value. Accordingly, based on the plotted data, the extrapolation to n = ∞, gives nearly the same limiting (i. e., ). Also, NBO results revealed that the sum of π‐bond occupancies, , decrease from 1 to 8 , and inversely, the sum of π‐antibonding orbital occupancies, , increase from compound 1 to compound 8 . The decrease of values for compounds 1 – 8 , is found to follow the same trend as the barrier heights of mutual interconversion in compounds 1 – 8 , while the decrease of the barrier height of mutual interconversion in compounds 1 – 8 is found to follow the opposite trend as the increase in the number of carbon atom. Accordingly, besides the previously reported allylic resonant stabilization effect in the transition state structures, the results reveal that the values, , Δ(E_HOMO ? E_LUMO), and the C atom number could be considered as significant criteria for the mutual interconversion in cumulene compounds 1 – 8 . This work reports also useful predictive linear relationships between mutual interconversion energy barriers ( ) in cumulene compounds and the following four parameters: , , Δ(E_HOMO ? E_LUMO), and C_Number. Copyright © 2007 John Wiley & Sons, Ltd.     

Room‐temperature epitaxial growth of high‐quality m ‐plane InGaN films on ZnO substrates

The authors have grown high‐quality m ‐plane In_0.36Ga_0.64N (1 00) films on ZnO (1 00) substrates at room temperature (RT) by pulsed laser deposition (PLD) and have investigated their structural properties. m ‐plane InGaN films grown on ZnO substrates at RT possess atomically flat surfaces with stepped and terraced structures, indicating that the film growth proceeds in a two‐dimensional mode. X‐ray diffraction measurements have revealed that the m ‐plane InGaN films grow without phase separation reactions at RT. The full‐width at half‐maximum values of the 1 00 X‐ray rocking curves of films with X‐ray incident azimuths perpendicular to the c ‐ and a‐axis are 88 arcsec and 78 arcsec, respectively. Reciprocal space‐mapping has revealed that a 50 nm thick m ‐plane In_0.36Ga_0.64N film grows coherently on the ZnO substrate, which can probably explain the low defect density that is observed in the film. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Hierarchy of the non‐covalent interactions in the alanine‐based secondary structures. DFT study of the frequency shifts and electron‐density features

The alanine (Ala)‐based cluster models of C5, C7, and C10 H‐bonds are studied at the DFT/B3LYP level. CPMD/BLYP simulations of the infinite polyalanine α‐helix (C13 H‐bond) and the two‐stranded β‐sheets are performed. Combined use of frequency shifts and electron‐density features enable us to detect and describe quantitatively the non‐covalent interactions (H‐bonds) defining the intrinsic properties of Ala‐based secondary structures. The energies of the primary N? H O H‐bonds are decreasing in the following way: C13 > C5 ≥ C7 > C10. The energies of the secondary N? H O, N?H N, and H H interactions are comparable to those of the primary H‐bonds (～4.5 kcal/mol). Side chain–backbone C? H O interaction is found to be the weakest non‐covalent interaction in the considered species. Its energy is ～0.5 kcal/mol in the infinite polyalanine α‐helix. Quantum‐topological electron‐density analysis is found to be a powerful tool for the detection of secondary non‐covalent interactions (C?O H? C and H H) and bifurcated H‐bonds, while the frequency shift study is useful for the identification and characterization of primary or secondary H‐bonds of the N? H O type. Copyright © 2008 John Wiley & Sons, Ltd.     

Silver: a novel growth catalyst for Ge nanoislands on Si(113)

The impact of silver pre‐adsorption on germanium growth on Si(113) was investigated using in‐situ low‐energy electron microscopy (LEEM) as well as low‐energy electron diffraction (LEED). The adsorption of silver leads to the formation of a regular pattern of nanofacets along the [1 0] direction. The periodicity of this pattern in [33 ] direction was determined to (44 ± 4) nm. From LEED series at different energies the facets were identified to be of (111) and (115) orientation. While the (111) facets show a (√3 × √3)‐R30° reconstruction, the (115) facets exhibit a (2 × n) superstructure. The subsequent growth of Ge results in the formation of nanoislands that are aligned along the facets. These Ge islands have an anisotropic shape with typical sizes of about 100 nm in [33 ] direction and 400 nm in [1 0] direction. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Substituent effect on the UV spectra of p‐disubstituted compounds XPh(CHCHPh)nY (n = 0, 1, 2)

Three parameters, , and , are developed to express the substituent effect and the effect of the parent molecular structure of p‐disubstituted compounds XPh(CH?CHPh)_nY (n = 0, 1, 2). The investigated result shows a good correlation between the UV absorption wavenumbers (υ_max) and the three parameters for a diverse set of title compounds, and the correlation equation can be used to predict the UV absorption energy of compounds with the mentioned structure. This approach provides a new insight for the quantitative structure‐property relationship (QSPR) correlation of the UV absorption energy of p‐disubstituted homologues. Copyright © 2010 John Wiley & Sons, Ltd.     

Influence of Ga coverage on the sizes of GaAs quantum dash pairs grown by high temperature droplet epitaxy

We investigate the formation of GaAs quantum dash pairs with different coverages by droplet epitaxy. The GaAs quantum dash pairs of various sizes are fabricated by high temperature droplet epitaxy. Dual‐sized quantum dash pairs are observed along $[01\bar 1]$ orientation. Depending on the Ga cov‐ erage, the width of the quantum dash pairs can be tuned from ～100 nm to ～300 nm while keeping the height in the range of 4 nm to 10 nm. The coverage dependence of quantum dash pairs is also confirmed with photoluminescence measurement. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Epitaxial phase‐change materials

Epitaxial $ {\rm Ge}_{2} {\rm Sb}_{2} {\rm Te}_{5} $ thin layers were successfully grown in the metastable cubic phase on both slightly lattice‐mismatched (GaSb) and highly lattice‐mismatched (Si) templates. The higher quality of the films grown on (111)‐oriented substrates is attributed to the tendency to form layered structures in the stable bulk phase as well as to the nature of distortion in the metastable cubic phase. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Semipolar (11\bar 2\bar 2) ZnO thin films grown on LaAlO3‐buffered LSAT (112) single crystals by pulsed laser deposition

Semipolar (11\bar 2 \bar 2) ZnO was successfully grown on (112) LaAlO₃/(LaAlO₃)_0.29(Sr₂AlTaO₆)_0.35 substrate by pulsed laser deposition. The epitaxial relationship is [11\bar 23]_{\rm ZnO} // [11\bar 1]_{\rm LAO/LSAT} with the polar axis of [000\bar 1]_{\rm ZnO} pointing to the surface. For ZnO films with thickness of 1.6 μm, the threading dislocation density is ～1 × 10⁹ cm^–2, and the density of basal stacking faults is below 1 × 10⁴ cm^–1. The (11\bar 2 \bar 2) ZnO exhibits strong D⁰X emissions with a FWHM of 9 meV and very few green–yellow emissions in the low‐temperature (10 K) and room‐temperature photoluminescence spectra, respectively.

     

From RHIC to LHC: a relativistic diffusion approach

We investigate the energy dependence of stopping and hadron production in high‐energy heavy‐ion collisions based on a three‐sources Relativistic Diffusion Model. The transport coefficients are extrapolated from Au + Au and Cu + Cu at RHIC energies ( = 19.6–200 GeV) to Pb + Pb at LHC energies = 5.52 TeV. Rapidity distributions for net protons, and pseudorapidity spectra for produced charged particles in central collisions are compared to data at RHIC energies, and discussed for several extrapolations to LHC energies.     

Orientations of ZnO grown on GaN

On semipolar epitaxial ZnO grown by chemical vapor deposition consists of two distinct orientations as evidenced by transmission electron microscopy and X‐ray diffraction. The initially grown ZnO on GaN follows the GaN lattice with the epitaxial relationship of // and The other oriented ZnO domains then grow on faceted with and with good coherency with the ‐oriented grains. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)