Unit cell parameters of wurtzite InP nanowires determined by x-ray diffraction

High resolution x-ray diffraction is used to study the structural properties of the wurtzite polytype of InP nanowires. Wurtzite InP nanowires are grown by metal-organic vapor phase epitaxy using S-doping. From the evaluation of the Bragg peak position we determine the lattice parameters of the wurtzite InP nanowires. The unit cell dimensions are found to differ from the ones expected from geometric conversion of the cubic bulk InP lattice constant. The atomic distances along the c direction are increased whereas the atomic spacing in the a direction is reduced in comparison to the corresponding distances in the zinc-blende phase. Using core/shell nanowires with a thin core and thick nominally intrinsic shells we are able to determine the lattice parameters of wurtzite InP with a negligible influence of the S-doping due to the much larger volume in the shell. The determined material properties will enable the ab initio calculation of electronic and optical properties of wurtzite InP nanowires.     

Formation of wurtzite InP nanowires explained by liquid-ordering

We report an in situ surface X-ray diffraction study of liquid AuIn metal alloys in contact with zinc-blende InP (111)(B) substrates at elevated temperatures. We observe strong layering of the liquid metal alloy in the first three atomic layers in contact with the substrate. The first atomic layer of the alloy has a higher indium concentration than in bulk. In addition, in this first layer we find evidence for in-plane ordering at hollow sites, which could sterically hinder nucleation of zinc-blende InP. This can explain the typical formation of the wurtzite crystal structure in InP nanowires grown from AuIn metal particles.     

Electronic and structural characteristics of zinc-blende wurtzite biphasic homostructure GaN nanowires

We report a new biphasic crystalline wurtzite/zinc-blende homostructure in gallium nitride nanowires. Cathodoluminescence was used to quantitatively measure the wurtzite and zinc-blende band gaps. High-resolution transmission electron microscopy was used to identify distinct wurtzite and zinc-blende crystalline phases within single nanowires through the use of selected area electron diffraction, electron dispersive spectroscopy, electron energy loss spectroscopy, and fast Fourier transform techniques. A mechanism for growth is identified.     

Band alignment tuning in twin-plane superlattices of semiconductor nanowires

The band alignments of twin-plane superlattices in semiconductor nanowires are systematically investigated on the basis of density functional calculations. Our calculations demonstrate that for nanowires with small diameters the quantum-confinement effect is prominent within wurtzite structure regions and the energy gap in wurtzite-structured nanowires is remarkably larger than that including zinc-blende structure. This results in the straddling band alignment, in which both electrons and holes are confined in zinc-blende structure region. The analysis using a simple tight-binding methods also clarifies that the straddling band alignments can be realized when the diameters of nanowires are less than 4-8 nm, leading to full control of band alignments by varying the nanowire diameter. Our results provide the ability of band-alignment tuning and open new possibilities for band engineering.     

Probing the wurtzite conduction band structure using state filling in highly doped InP nanowires

We have grown InP nanowires doped with hydrogen sulfide, which exhibit sulfur concentrations of up to 1.4%. The highest doped nanowires show a pure wurtzite crystal structure, in contrast to bulk InP which has the zinc blende structure. The nanowires display photoluminescence which is strongly blue shifted compared with the band gap, well into the visible range. We find evidence of a second conduction band minimum at the gamma point about 0.23 eV above the band edge, in excellent agreement with recent theoretical predictions. Electrical measurements show high conductivity and breakdown currents of 10(7) A/cm(2).     

Interplay between crystal phase purity and radial growth in InP nanowires

The interplay between crystal phase purity and radial growth in InP nanowires is investigated. By modifying the growth rate and V/III ratio, regions of high or low stacking fault density can be controllably introduced into wurtzite nanowires. It is found that regions with high stacking fault density encourage radial growth. Through careful choice of growth conditions pure wurtzite InP nanowires are then grown which exhibit narrow 4.2?K photoluminescence linewidths of 3.7?meV at 1.490?meV, and no evidence of emission related to stacking faults or zincblende insertions.     

First principles computational study of wurtzite CdTe nanowires

An ab initio computational study was performed for wurtzite [0001] CdTe nanowires enclosed by (10[`1]0)(10\bar{1}0) surface facets over a range of diameters and cross-sectional topologies. Calculations show that hexagonal nanowires are highly stable, possessing a large electronic band gap and a band structure without dispersionless states in the gap. Passivation of the dangling bonds for the largest hexagonal nanowire was found to have a minimal effect on the electronic structure, resulting in only a 0.05 eV increase in the band gap over the unpassivated nanowire.     

The effects of oxygen on the surface passivation of InP nanowires

The effects of surface passivation on the electronic and structural properties of InP nanowires have been investigated by first-principles calculations. We compare the properties of nanowires whose surfaces have been passivated in several ways, always by H atoms and OH radicals. Taking as the initial reference nanowires that are fully passivated by H atoms, we find that the exchange of these atoms at the surface by OH radicals is always energetically favorable. A nanowire fully passivated by OH radicals is about 2.5?eV per passivated dangling bond more stable than a nanowire fully passivated by H atoms. However, the energetically most stable passivated surface is predicted to have all In atoms bonded to OH radicals and all P atoms bonded to H atoms. This mixed passivation is 2.66?eV per passivated dangling bond more stable than a nanowire fully passivated by H atoms. Our results show that, in comparison with the fully H-saturated nanowire, the fully OH-saturated nanowire has a smaller energy band gap and localized states near the energy band edges. Also, more interestingly, concerning optical applications, the most stable H+OH passivated nanowire has a well-defined energy band gap, only 10% smaller than the H-saturated nanowire energy gap, and few localized states always close to the valence band maximum.     

Growth of InAs/InP core-shell nanowires with various pure crystal structures

We have studied the epitaxial growth of an InP shell on various pure InAs core nanowire crystal structures by metal-organic vapor phase epitaxy. The InP shell is grown on wurtzite (WZ), zinc-blende (ZB), and {111}- and {110}-type faceted ZB twin-plane superlattice (TSL) structures by tuning the InP shell growth parameters and controlling the shell thickness. The growth results, particularly on the WZ nanowires, show that homogeneous InP shell growth is promoted at relatively high temperatures (～500?°C), but that the InAs nanowires decompose under the applied conditions. In order to protect the InAs core nanowires from decomposition, a short protective InP segment is first grown axially at lower temperatures (420-460?°C), before commencing the radial growth at a higher temperature. Further studies revealed that the InP radial growth rate is significantly higher on the ZB and TSL nanowires compared to WZ counterparts, and shows a strong anisotropy in polar directions. As a result, thin shells were obtained during low temperature InP growth on ZB structures, while a higher temperature was used to obtain uniform thick shells. In addition, a schematic growth model is suggested to explain the basic processes occurring during the shell growth on the TSL crystal structures.     

VLS growth of alternating InAsP/InP heterostructure nanowires for multiple-quantum-dot structures

We investigated the Au-assisted growth of alternating InAsP/InP heterostructures in wurtzite InP nanowires on InP(111)B substrates for constructing multiple-quantum-dot structures. Vertical InP nanowires without stacking faults were obtained at a high PH(3)/TMIn mole flow ratio of 300-1000. We found that the growth rate changed largely when approximately 40 min passed. Ten InAsP layers were inserted in the InP nanowire, and it was found that both the InP growth rate and the background As level increased after the As supply. We also grew the same structure using TBAs/TBP and could reduce the As level in the InP segments. A simulation using a finite-difference time-domain method suggests that the nanowire growth was dominated by the diffusion of the reaction species with long residence time on the surface. For TBAs/TBP, when the source gases were changed, the formed surface species showed a short diffusion length so as to reduce the As background after the InAsP growth.     

Optical properties of rotationally twinned InP nanowire heterostructures

We have developed a technique so that both transmission electron microscopy and microphotoluminescence can be performed on the same semiconductor nanowire over a large range of optical power, thus allowing us to directly correlate structural and optical properties of rotationally twinned zinc blende InP nanowires. We have constructed the energy band diagram of the resulting multiquantum well heterostructure and have performed detailed quantum mechanical calculations of the electron and hole wave functions. The excitation power dependent blue-shift of the photoluminescence can be explained in terms of the predicted staggered band alignment of the rotationally twinned zinc blende/wurzite InP heterostructure and of the concomitant diagonal transitions between localized electron and hole states responsible for radiative recombination. The ability of rotational twinning to introduce a heterostructure in a chemically homogeneous nanowire material and alter in a major way its optical properties opens new possibilities for band-structure engineering.     

Direct atomic scale imaging of III-V nanowire surfaces

We have succeeded in direct atomic scale imaging of the exterior surfaces of III-V nanowires by scanning tunneling microscopy (STM). By using atomic hydrogen, we expose the crystalline surfaces of InAs nanowires with regular InP segments in vacuum while retaining the wire morphology. We show images with atomic resolution of the two major types of InAs wurtzite nanowire surface facets and scanning tunneling spectroscopy (STS) data. Ab initio calculations of the lowest energy surface structures and simulated STM images, agree very well with experiments.     

Internal structure of multiphase zinc-blende wurtzite gallium nitride nanowires

In this paper, the internal structure of novel multiphase gallium nitride nanowires in which multiple zinc-blende and wurtzite crystalline domains grow simultaneously along the entire length of the nanowire is investigated. Orientation relationships within the multiphase nanowires are identified using high-resolution transmission electron microscopy of nanowire cross-sections fabricated with a focused ion beam system. A coherent interface between the zinc-blende and wurtzite phases is identified. A mechanism for catalyst-free vapor-solid multiphase nanowire nucleation and growth is proposed.     

Wurtzite InP/InAs/InP core-shell nanowires emitting at telecommunication wavelengths on Si substrate

Optical properties of wurtzite InP/InAs/InP core-shell nanowires grown on silicon substrates by solid source molecular beam epitaxy are studied by means of photoluminescence and microphotoluminescence. The growth conditions were optimized to obtain purely wurtzite radial quantum wells emitting in the telecom bands with a radiative lifetime in the 5-7 ns range at 14 K. Optical studies on single nanowires reveal that the polarization is mainly parallel to the growth direction. A 20-fold reduction of the photoluminescence intensity is observed between 14 and 300 K confirming the very good quality of the nanowires.     

Twinned Growth of Metal‐Free,Triazine‐Based Photocatalyst Films as Mixed‐Dimensional (2D/3D) van der Waals Heterostructures

Design and synthesis of ordered, metal‐free layered materials is intrinsically difficult due to the limitations of vapor deposition processes that are used in their making. Mixed‐dimensional (2D/3D) metal‐free van der Waals (vdW) heterostructures based on triazine (C₃N₃) linkers grow as large area, transparent yellow‐orange membranes on copper surfaces from solution. The membranes have an indirect band gap (E _g,opt = 1.91 eV, E _g,elec = 1.84 eV) and are moderately porous (124 m² g^?1). The material consists of a crystalline 2D phase that is fully sp² hybridized and provides structural stability, and an amorphous, porous phase with mixed sp²–sp hybridization. Interestingly, this 2D/3D vdW heterostructure grows in a twinned mechanism from a one‐pot reaction mixture: unprecedented for metal‐free frameworks and a direct consequence of on‐catalyst synthesis. Thanks to the efficient type I heterojunction, electron transfer processes are fundamentally improved and hence, the material is capable of metal‐free, light‐induced hydrogen evolution from water without the need for a noble metal cocatalyst (34 µmol h^?1 g^?1 without Pt). The results highlight that twinned growth mechanisms are observed in the realm of “wet” chemistry, and that they can be used to fabricate otherwise challenging 2D/3D vdW heterostructures with composite properties.     

Growth and characterization of indium phosphide nanowires on transparent conductive ZnO:Al films

The epitaxial growth of indium phosphide nanowires (InP NWs) on transparent conductive aluminum-doped zinc oxide (ZnO:Al) thin films is proposed and demonstrated. ZnO:Al thin films were prepared on quartz substrates by radio frequency magnetron sputtering, then InP NWs were grown on them by plasma enhanced metal organic chemical vapor deposition with gold catalyst. Microstructure and optical properties of InP nanowires on ZnO:Al thin films were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectric spectroscopy (XPS), photoluminescence and Raman spectroscopy at room temperature. SEM shows that randomly oriented and intersecting InP nanowires were grown to form a network on ZnO:Al thin films. Both wurtzite (WZ) and zincblende (ZB) structures coexist in the random orientation InP NWs on ZnO:Al thin film had been proved by XRD analysis. XPS result indicates Zn diffusion exists in the InP NWs on ZnO:Al. The photoluminescence spectra of InP nanowires with Zn diffusion present an emission at 915 nm. Zn diffusion also bring effect on Raman spectra of InP NWs, leading to more Raman-shift and larger relative intensity ratio of TO/LO.     

Controlled Synthesis of Kinked Ultrathin ZnS Nanorods/Nanowires Triggered by Chloride Ions: A Case Study

Colloidal synthesis of kinked ultrathin ZnS nanorods/nanowires with mixed phases using tiny Ag₂S nanocrystals as catalysts is reported. It is found that chloride ions can induce the controlled morphology transition from straight to kinking. The synthetic parameters modulating the growth of kinked ZnS nanorods/nanowires are systematically investigated. Chloride ions introduced in the reaction can generate more proportion of wurtzite phase by slowing the nucleation and growth rates during the growth of one‐dimensional (1D) ZnS nanorods/nanowires. The formation of kinked morphology is responsible for the increased domains of mixed stacking and twinning in single 1D nanostructures. The present recipe on controlled synthesis of 1D kinked nanorods/nanowires provides a model of crystal growth control, and these unique 1D nanostructures may also offer new opportunities to fabricate nanodevices with special functions.     

Atomic and electronic properties of realizable size single-crystal GaN nanotubes by first principles

We studied the diameter and wall thickness dependent atomic and electronic properties of practical size single-crystal GaN nanotubes using first principle calculations. Single-crystal GaN nanotubes are similar to the hexagonal GaN nanowires, grown in the [0001] direction with [10-10] facets, except there is an axial hexagonal void in them. We first demonstrated that the atomic and electronic properties of these tubes are mainly determined by the thickness of their wurtzite walls; and their diameters have negligible effects. Then, considering the individual walls of GaN nanotubes in two-dimensional slab calculations we examine the bond distances, formation energy, band gap, effective electron mass and the evolution of electronic density of the states as a function of thickness for unsaturated and hydrogen-saturated slabs of GaN. Calculations revealed that the unsaturated dangling bonds at the surfaces induce defect states in the band gap region of unsaturated tubes. Therefore, regardless of diameter and wall thickness, their band gaps are always smaller than that of the bulk GaN. However, the band gaps of the hydrogen-saturated tubes are found to be amplified with respect to bulk GaN. The amplification in the band gaps as a function of wall thickness in the range of 5.6-16.9 A and 16.9-28.1 A scales with a factor of 1/d(0.9281) and 1/d(1.769), respectively. Our results show that, regardless of diameter, hydrogen saturated single-crystal GaN tubes with the wall thickness as small as 28.1 A would be stable and they would have a noticeably larger band gap with respect to the band gap of bulk GaN.     

Photomodulated rayleigh scattering of single semiconductor nanowires: probing electronic band structure

The internal electronic structures of single semiconductor nanowires can be resolved using photomodulated Rayleigh scattering spectroscopy. The Rayleigh scattering from semiconductor nanowires is strongly polarization sensitive which allows a nearly background-free method for detecting only the light that is scattered from a single nanowire. While the Rayleigh scattering efficiency from a semiconductor nanowire depends on the dielectric contrast, it is relatively featureless as a function of energy. However, if the nanowire is photomodulated using a second pump laser beam, the internal electronic structure can be resolved with extremely high signal-to-noise and spectral resolution. The photomodulated Rayleigh scattering spectra can be understood theoretically as a first derivative of the scattering efficiency that results from a modulation of the band gap and depends sensitively on the nanowire diameter. Fits to spectral lineshapes provide both the band structure and the diameter of individual GaAs and InP nanowires under investigation.     

Stable zinc-blende ZnO thin films: formation and physical properties

The development of technologically important material zinc-blende ZnO has been hindered due to the difficulties inherent in obtaining a stable zinc-blende phase. In this paper, we fabricate the stable zinc-blende ZnO on Pt/Ti/SiO₂/Si substrate through phase transformation from the originally wurtzite to the zinc-blende phase. X-ray diffraction data in combination with high-resolution TEM measurements provide the direct evidence on the formation of the well-defined zinc-blende structure with predominated (202) orientation. According to the experimental results and first principles calculations, the incorporation of titanium dopants into ZnO system favors the formation of the zinc-blende structure. The platinum (Pt) surface stabilizes the ZnO zinc-blende structure at the interface (thin film) due to its low ZnO/Pt interface energy, preventing the decomposition in ZnO wurtzite and Zn₂TiO₄. Additionally, magnetic and optical properties of the ZnO zinc-blende thin films are investigated. Unexpectedly, the film is found to exhibit magnetization of ~75 emu/cm³, while its ZnO wurtzite counterpart is non-ferromagnetic.