Large-scale growth of Cu2ZnSnSe4 and Cu2ZnSnSe4/Cu2ZnSnS4 core/shell nanowires

We present a fast and simple protocol for large-scale preparation of quaternary Cu(2)ZnSnSe(4) (CZTSe), as well as CZTSe/Cu(2)ZnSnS(4) (CZTS) core/shell nanowires using CuSe nanowire bundles as self-sacrificial templates. CuSe nanowire bundles were synthesized by reacting Cu(2 - x)Se nanowire bundles with sodium citrate solution. CZTSe nanowires were prepared by reacting CuSe nanowire bundles with Zn(CH(3)COO)(2) and SnCl(2) in triethylene glycol. X-ray diffraction (XRD) and selected area electron diffraction studies show that stannite CZTSe is formed. The formed CZTSe nanowire bundles have diameters of 200-400 nm and lengths of up to hundreds of micrometers. CZTSe/CZTS nanocable bundles with similar morphologies were grown by the addition of some elemental sulfur to the reaction system for growth of CZTSe bundles. The stannite CZTSe/kesterite CZTS core/shell structure of the grown nanocables was confirmed by XRD and high-resolution transmission electron microscope investigation. The influence of S/Se molar ratio in the reaction system on the crystallographic structures and optical properties of CZTSe/CZTS nanocables was studied. The obtained CZTSe/CZTS core/shell nanocable bundles show broad and enhanced optical absorption over the visible and near-infrared region, which is promising for use in photovoltaic applications.     

Characterization of ordered Cu2O nanowire arrays prepared by heat treated Cu/PAM composite

Cu nanowire arrays were synthesized via a porous alumina membrane (PAM) template with a high aspect ratio, uniform pore size (120–140 nm), and ordered pore arrangement. The Cu₂O nanowire arrays were prepared from the oxidization of Cu metal nanowire arrays. The electrochemical deposition potential of Cu metal nanowires (?180 mV vs. SCE) was determined from X-ray diffraction (XRD) patterns. The microstructure and chemical composition of Cu nanowire arrays were characterized using field emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HR-TEM), and X-ray diffraction (XRD). Results indicate that the Cu/Cu₂O nanowire arrays assembled into the nanochannel of the porous alumina template with diameters of 120–140 nm. The valence of copper was controlled by the porous alumina template during the annealing process. Copper nanowires transformed to the Cu₂O phase with the space limitation of the PAM template. Single-crystal Cu₂O nanowire arrays were also obtained under the template embedded.     

Electron excitation in the interaction of slow ions and electrons with metals and monolayer graphite on Ni(111) surfaces

We report on the experimental energy distributions of electrons emitted in the interaction of slow ions and electrons with aluminium and with monolayer graphite deposited on a Ni(111) surface. Measurements on the Al surface clarify the role of plasmon decay in secondary electron emission. In contrast with theoretical calculations, our experiments indicate that the electron collision cascade inside the solid produced by electrons excited by plasmon decay does not contribute significantly to electron emission.The energy distribution of electrons emitted in the interaction of He⁺ ions with monolayer graphite reveal a high-energy feature that can be attributed to the autoionization decay of excitonic states populated by electron promotion in close He-C encounters.     

Electronic structure of surface-supported bis(phthalocyaninato) terbium(III) single molecular magnets

The electronic structure of isolated bis(phthalocyaninato) terbium(III) molecules, a novel single-molecular-magnet (SMM), supported on the Cu(111) surface has been characterized by density functional theory and scanning tunneling spectroscopy. These studies reveal that the interaction with the metal surface preserves both the molecular structure and the large spin magnetic moment of the metal center. The 4f electron states are not perturbed by the adsorption while a strong molecular/metal interaction can induce the suppression of the minor spin contribution delocalized over the molecular ligands. The calculations show that the inherent spin magnetic moment of the molecule is only weakly affected by the interaction with the surface and suggest that the SMM character might be preserved.     

3D ES势垒对Cu(111)和Cu(OO1)晶面同质外延生长的影响

三维3D ES势垒直接影响着层间扩散,在Cu(111)和Cu(100)面2D ES势垒和3D ES势垒是不同的.本文主要研究了基于(1+1)维KMC模型,在这两个特殊的晶面上Cu薄膜的同质外延生长.观察两个面的生长情况,发现随着温度的增加薄膜的粗糙度逐渐减小,由于Cu(111)表面2D ES势垒较小,所以Cu(111)面粗糙度的下降的速度比Cu(100)要快,Cu(111)表面更有利于薄膜的生长.对于纳米棒的应用,在生长时间较短时两个面的生长速率逐渐减小,但是Cu(100)面的生长速度比Cu(111)面更快,随着生长时间的增加,这两个面会出现多层台阶,Cu(111)面的生长速度会逐渐增加,最终会超过了Cu(100)面.多层台阶出现后对两个面的影响是不同的.由于Cu(111)表面3D ES势垒较大,在Cu(111)表面会形成较多的多层台阶,Cu(111)面上多层台阶数有利于纳米棒的生长,然而在Cu(100)表面3D ES势垒较小,Cu(100)表面很难形成多层台阶,所以Cu(100)面上纳米棒的生长速度并没有增加.正是因为3D ES势垒的存在才会导致多层台阶的出现,较大的3D ES势垒有利于纳米棒的生长.     

Controllable electrodeposition of ordered carbon nanowalls on Cu(111) substrates

We report the growth of amorphous carbon nanowalls with molten salt electrolytes and a carbonate carbon source at 600 °C on home-made Cu(111) foil as the growth substrate (and cathode). The nanometer thick nanowalls grow preferentially along symmetric slip lines on the Cu(111) surface and their ordered arrangement appears to also be dictated by the electrosynthesis parameters. Computational chemistry suggests that nucleation of carbon growth is favored at the slip lines (atomic steps) of the Cu(111) surface. The electrodeposited carbon structures can be varied by tuning the potential on the electrodes and temperature of the molten salt. The macro, micro, and nanoscale structure of the nanowalls was studied and is reported.     

Orientation‐Dependent Strain Relaxation and Chemical Functionalization of Graphene on a Cu(111) Foil

Epitaxial graphene grown on single crystal Cu(111) foils by chemical vapor deposition is found to be free of wrinkles and under biaxial compressive strain. The compressive strain in the epitaxial regions (0.25–0.40%) is higher than regions where the graphene is not epitaxial with the underlying surface (0.20–0.25%). This orientation‐dependent strain relaxation is through the loss of local adhesion and the generation of graphene wrinkles. Density functional theory calculations suggest a large frictional force between the epitaxial graphene and the Cu(111) substrate, and this is therefore an energy barrier to the formation of wrinkles in the graphene. Enhanced chemical reactivity is found in epitaxial graphene on Cu(111) foils as compared to graphene on polycrystalline Cu foils for certain chemical reactions. A higher compressive strain possibly favors lowering the formation energy and/or the energy gap between the initial and transition states, either of which can lead to an increase in chemical reactivity.     

Initial epitaxial growth of (111) Au/(111) Cu and (111) Cu/(111) Au

The room temperature modes of growth of Au/(111) Cu and Cu/(111) Au are described. For the former growth mode initial deposits (2.4 Å) of gold on copper form smooth flat islands delineated by coincidence lattice misfit dislocations. For 6.0 Å of gold deposit, both thick and thin gold areas were observed with almost complete substrate coverage. For a 10 Å deposit, surface coverage was complete. Strain measurements and dislocation densities obtained on the (111) Au/(111) Cu films suggest the presence of two separate misfit dislocation networks at the interface. The coincidence lattice networks were large enough for transmission electron microscopy observation but contributed little to total overlayer strain. The (van der Merwe) natural lattice misfit dislocations were too closely spaced for direct observation but their presence was inferred because of the strain measurements. The initial epitaxy of Cu/(111) Au was similar to the Stranski-Krastanov model: the initial monolayer of copper (also delineated by coincidence misfit dislocations) grew smoothly on the gold; additional copper formed essentially stress-free “nuclei” on top of the initial copper layer.     

Direct evidence of advantage of Cu(111) for graphene synthesis by using Raman mapping and electron backscatter diffraction

The advantageous crystallographic orientation of Cu surface for graphene synthesis by using thermal chemical vapor deposition (CVD) is examined by Raman mapping and electron backscatter diffraction. It is found that Cu(111) predominates over (110) and (100) for single- (SLG) or few-layer graphene (FLG) growth. To confirm this result we attempt the synthesis of graphene on Cu(111) single crystal film surfaces. We confirmed the formation of high quality and high uniformity SLG or FLG over more than 97% of the substrate surface area of 10 mm × 10 mm by Raman mapping.     

Molecular Dynamics simulations of Cu/Ta and Ta/Cu thin film growth

Molecular Dynamics simulation results of evaporated Cu deposition on bcc Ta substrates are presented. Different substrate orientations, substrate temperatures, and initial surface roughnesses were investigated. We have also simulated the deposition of Ta on flat fcc Cu (111) substrates at different temperatures. Several aspects of the microstructural evolution during deposition are reported. The results are also compared with those obtained earlier for Cu deposition on β-Ta. A connection mechanism between two different crystal structures, bcc (110) and fcc (111), which is significantly different from the classical misfit dislocation scenario, is reported. Also, mixing behaviour in a thermodynamically immiscible system during atom-by-atom deposition of Ta on fcc Cu (111) is elucidated. Finally, we show results of a Density Functional Theory verification of the accuracy of the Ta-Cu emperical potential. Results and implications are discussed. This revised version was published online in June 2006 with corrections to the Cover Date.     

PTCDA on Cu(111) partially covered with NaCl

The organic molecule 3,4,9,10-perylene-tetracarboxylic dianhydride (PTCDA) was studied by means of scanning tunneling microscopy (STM) on thin insulating NaCl films grown on a Cu(111) single crystal. The deposition of approximately two monolayers (ML) of sodium chloride onto a Cu(111) substrate at a sample temperature of about 350 K causes a rather rough growth of (100)-oriented NaCl islands up to a local height of 4 ML. For submonolayer coverages (0.1 and 0.4 ML) of PTCDA on a Cu(111) surface partly covered with NaCl, two different rod structures of PTCDA were found on the copper surface, which are in contrast to previously published data for PTCDA on Cu(111) showing a herringbone-like arrangement. These findings can be explained by the formation of a Na(x)-PTCDA complex. On NaCl covered areas, single PTCDA molecules adsorb at vacancies of [010] and [001] oriented steps of the NaCl(100) islands. In this case, the electrostatic forces between the polar step edges and the PTCDA molecules are dominant. The terraces of the alkali halide surface are free of PTCDA molecules.     

Co nanoislands on Au(111) and Cu(111) surfaces studied by scanning tunneling microscopy and spectroscopy

Co nanoislands on the Au(111) and Cu(111) surfaces have been studied by scanning tunneling microscopy and spectroscopy. The experimental results showed that Co nanoislands prefer to aggregate at the step edge and dislocation sites on the reconstructed Au(111) surface and at the step edge on the Cu(111) surface, respectively. In addition, based on dZ/dV-V spectra, in both the Co/Au(111) and the Co/Cu(111) systems, Gundlach oscillation was observed. From the peak shift of dZ/dV-V spectra between Co nanoisland and substrate surface, we can quantitatively obtain that the constant energy separation is -0.13 +/- 0.01 eV for the Co/Au(111) system, and 0.41 +/- 0.02 eV for the Co/Cu(111) system, respectively. These values indicate the work function difference between Co nanoisland and these surfaces.     

Playing with dimensions: rational design for heteroepitaxial p-n junctions

A design for a heteroepitaxial junction by the way of one-dimensional wurzite on a two-dimensional spinel structure in a low-temperature solution process was introduced, and it's capability was confirmed by successful fabrication of a diode consisting of p-type cobalt oxide (Co(3)O(4)) nanoplate/n-type zinc oxide (ZnO) nanorods, showing reasonable electrical performance. During thermal decomposition, the 30° rotated lattice orientation of Co(3)O(4) nanoplates from the orientation of β-Co(OH)(2) nanoplates was directly observed using high-resolution transmission electron microscopy. The epitaxial relations and the surface stress-induced ZnO nanowire growth on Co(3)O(4) were well supported using the first-principles calculations. Over the large area, (0001) preferred oriented ZnO nanorods epitaxially grown on the (111) plane of Co(3)O(4) nanoplates were experimentally obtained. Using this epitaxial p-n junction, a diode was fabricated. The ideality factor, turn-on voltage, and rectifying ratio of the diode were measured to be 2.38, 2.5 V and 10(4), respectively.     

All-(111) surface silicon nanowires: selective functionalization for biosensing applications

We demonstrate the utilization of selective functionalization of carbon-silicon (C-Si) alkyl and alkenyl monolayers covalently linked to all-(111) surface silicon nanowire (Si-NW) biosensors. Terminal amine groups on the functional monolayer surfaces were used for conjugation of biotin n-hydroxysuccinimide ester. The selective functionalization is demonstrated by contact angle, X-ray photoelectron spectroscopy (XPS), and high-resolution scanning electron microscopy (HRSEM) of 5 nm diameter thiolated Au nanoparticles linked with streptavidin and conjugated to the biotinylated all-(111) surface Si-NWs. Electrical measurements of monolayer passivated Si-NWs show improved device behavior and performance. Furthermore, an analytical model is presented to demonstrate the improvement in detection sensitivity of the alkyl and alkenyl passivated all-(111) Si-NW biosensors compared to conventional nanowire biosensor geometries and silicon dioxide passivation layers as well as interface design and electrical biasing guidelines for depletion-mode sensors.     

Orientation of ethyl mercaptan on Cu(111) surface

X-Ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS) studies have been performed on ethyl mercaptan adsorbed on a clean Cu(111) surface at 85 K. At submonolayer coverage (0.36 ML), two different states of sulfur (thiolate) are identified with the aid of XPS investigations. Polarization dependence of S K-edge NEXAFS of the submonolayer phase indicates that the S---C bond for the two thiolate phases are tilted 33±7° and 30±7° from the surface.     

Decoupling co-existing surface plasmon polariton (SPP) modes in a nanowire plasmonic waveguide for quantitative mode analysis

Knowledge of surface plasmon polariton (SPP) modes in one-dimensional (1D) metallic nanostructures is essential for the development of subwavelength optical devices such as photonic circuits,integrated light sources,and photodetectors.Despite many efforts to characterize the propagation parameters of these subwavelength 1D plasmonic waveguides,such as Ag nanowires,large discrepancies exist among available reports owing to their sensitivity to the relative weights of co-existing SPP modes and the lack of a method of decoupling these modes and analyzing them separately.In this work,we develop an interference method to distinguish different SPP modes that are simultaneously excited in a Ag nanowire waveguide and measure their propagation parameters separately.By extracting information from the propagation-distancedependent intensity oscillations of the scattered light from the nanowire tip,the effective refractive indices,propagation lengths,and relative mode weights of co-existing SPP modes supported by the nanowire are derived from a mode interference model.These parameters depend strongly on the nanowire diameter and excitation wavelength.In particular,we demonstrate the possibility of selective excitation of different SPP modes by varying the nanowire diameter.This new mode analysis technique provides unique insights into the development and optimization of SPP-based applications.     

Single and double layer growth mechanisms induced by quantum size effects in Pb films deposited on Cu(111)

The specular intensity of nearly mono-energetic helium atom beams (E_i= 7–20 meV) has been measured during epitaxial deposition of Pb films on a clean and well annealed Cu(111) surface. A complicated modulated structure was found indicating an alternation between single and double layer growth mechanisms. This is also supported by kinematic studies and step height determinations performed at various points in the growth curve. A quantum size effect in the overlayer electronic states is shown to influence the growth mechanism. The frequency of alternation between single and double layer growth, with increasing thicknesses, corresponds to that frequency predicted by the fit or misfit of Pb Fermi-energy standing waves in the overlayers.     

Probing quantized image-potential states at supported carbon nanotubes

Discrete image-potential states (ISs) are revealed at double-walled carbon nanotubes by means of scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) in the distance-voltage z(V) spectroscopy mode. The nanotubes are supported by flat Au(111) substrates. Due to the high sensitivity of the hot IS electrons to local variations of the surface potential, they can be considered as a sensitive probe to investigate interactions with the supporting substrate and impurities or defects at the nanotube surface. ISs provide information on the local electronic structure as well as on the electron dynamics at supported nanotubes.     

Controlling silicon nanowire growth direction via surface chemistry

We report on the first in situ chemical investigation of vapor-liquid-solid semiconductor nanowire growth and reveal the important, and previously unrecognized, role of transient surface chemistry near the triple-phase line. Real-time infrared spectroscopy measurements coupled with postgrowth electron microscopy demonstrate that covalently bonded hydrogen atoms are responsible for the (left angle bracket 111 right angle bracket) to (left angle bracket 112 right angle bracket) growth orientation transition commonly observed during Si nanowire growth. Our findings provide insight into the root cause of this well-known nanowire growth phenomenon and open a new route to rationally engineer the crystal structure of these nanoscale semi-conductors.     

分子动力学模拟Gd原子在Cu低密勒表面的扩散过程

为了分析Gd吸附原子在Cu（001）、Cu（110）和Cu（111）表面的扩散机制，本文用分子动力学对该扩散过程进行模拟。模拟结果表明在Cu（001）和Cu（111）表面，Gd原子通过跳跃机制扩散；在Cu（110）表面，在[110]方向Gd原子通过跳跃机制扩散，而且多步跳跃频率很高，而在[001]方向则通过交换机制扩散。通过对扩散频率的拟合，发现在各种扩散机制都符合Arrhenius公式，从而确定了在Cu（001）和Cu（111）表面扩散势垒分别为0．19eV和0．013eV，在Cu（110）表面，沿[110]方向跳跃扩散势垒和沿[001]方向交换扩散势垒分别为0．097eV和0．33eV。