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.     

Unit cell structure of crystal polytypes in InAs and InSb nanowires

The atomic distances in hexagonal polytypes of III-V compound semiconductors differ from the values expected from simply a change of the stacking sequence of (111) lattice planes. While these changes were difficult to quantify so far, we accurately determine the lattice parameters of zinc blende, wurtzite, and 4H polytypes for InAs and InSb nanowires, using X-ray diffraction and transmission electron microscopy. The results are compared to density functional theory calculations. Experiment and theory show that the occurrence of hexagonal bilayers tends to stretch the distances of atomic layers parallel to the c axis and to reduce the in-plane distances compared to those in zinc blende. The change of the lattice parameters scales linearly with the hexagonality of the polytype, defined as the fraction of bilayers with hexagonal character within one unit cell.     

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.     

Crystal structure transfer in core/shell nanowires

Structure engineering is an emerging tool to control opto-electronic properties of semiconductors. Recently, control of crystal structure and the formation of a twinning superlattice have been shown for III-V nanowires. This level of control has not been obtained for Si nanowires, the most relevant material for the semiconductor industry. Here, we present an approach, in which a designed twinning superlattice with the zinc blende crystal structure or the wurtzite crystal structure is transferred from a gallium phosphide core wire to an epitaxially grown silicon shell. These materials have a difference in lattice constants of only 0.4%, which allows for structure transfer without introducing extra defects. The twinning superlattices, periodicity, and shell thickness can be tuned with great precision. Arrays of free-standing Si nanotubes are obtained by a selective wet-chemical etch of the core wire.     

First-principles study of the electronic properties of wurtzite, zinc-blende, and twinned InP nanowires

The electronic properties of zinc-blende, wurtzite, and rotationally twinned InP nanowires were studied using first-principles calculations. The results show that all the simulated nanowires exhibit a semiconducting character, and the band gap decreases with increasing the nanowire size. The band gap difference between the zinc-blende, wurtzite, and twinned InP nanowires and bulk InP can be described by ΔE(g)(wire) = 0.88/D(1.23), ΔE(g)(wire) = 0.79/D(1.22) and ΔE(g)(twin) = 1.3/D(1.19), respectively, where D is the diameter of the nanowires. The valence band maximum (VBM) and conduction band minimum (CBM) originate mainly from the p-orbitals of the P atoms and s-orbitals of the In atoms at the core regions of the nanowires, respectively. The hexagonal (2H) stacking inside the cubic (3C) stacking has no effect on the electronic properties of thin InP nanowires.     

Kinetic effects in InP nanowire growth and stacking fault formation: the role of interface roughening

InP nanowire polytypic growth was thoroughly studied using electron microscopy techniques as a function of the In precursor flow. The dominant InP crystal structure is wurtzite, and growth parameters determine the density of stacking faults (SF) and zinc blende segments along the nanowires (NWs). Our results show that SF formation in InP NWs cannot be univocally attributed to the droplet supersaturation, if we assume this variable to be proportional to the ex situ In atomic concentration at the catalyst particle. An imbalance between this concentration and the axial growth rate was detected for growth conditions associated with larger SF densities along the NWs, suggesting a different route of precursor incorporation at the triple phase line in that case. The formation of SFs can be further enhanced by varying the In supply during growth and is suppressed for small diameter NWs grown under the same conditions. We attribute the observed behaviors to kinetically driven roughening of the semiconductor/metal interface. The consequent deformation of the triple phase line increases the probability of a phase change at the growth interface in an effort to reach local minima of system interface and surface energy.     

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.     

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.     

Zinc blende and wurtzite crystal phase mixing and transition in indium phosphide nanowires

Indium phosphide (InP) nanowires, which have crystal phase mixing and transition from zinc blende (ZB) to wurtzite (WZ), are grown in intermediate growth conditions between ZB and WZ by using selective-area metalorganic vapor phase epitaxy (SA-MOVPE). The shape of InP nanowires is tapered unlike ZB or WZ nanowires. A growth model has been developed for the tapered nanowires, which is simply described as the relationship between tapered angle and the ratio of ZB and WZ segments. In addition, the peak energy shift in photoluminescence measurement was attributed to the quantum confinement effect of the quantum well of the ZB region located in the polytypic structure of ZB and WZ in nanowires.     

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.     

Remote p-doping of InAs nanowires

We report on remote p-type doping of InAs nanowires by a p-doped InP shell grown epitaxially on the core nanowire. This approach addresses the challenge of obtaining quantitative control of doping levels in nanowires grown by the vapor-liquid-solid (VLS) mechanism. Remote doping of III-V nanowires is demonstrated here with the InAs/InP system. It is especially challenging to make p-type InAs wires because of Fermi level pinning around 0.1 eV above the conduction band. We demonstrate that shielding with a p-doped InP shell compensates for the built-in potential and donates free holes to the InAs core. Moreover, the off-current in field-effect devices can be reduced up to 6 orders of magnitude. The effect of shielding critically depends on the thickness of the InP capping layer and the dopant concentration in the shell.     

Electrical and optical properties of InP nanowire ensemble p⁺-i-n⁺ photodetectors

We report on a comprehensive study of electrical and optical properties of efficient near-infrared p?-i-n? photodetectors based on large ensembles of self-assembled, vertically aligned i-n? InP nanowires monolithically grown on a common p? InP substrate without any buffer layer. The nanowires have a polytype modulated crystal structure of wurtzite and zinc blende. The electrical data display excellent rectifying behavior with an ideality factor of about 2.5 at 300 K. The ideality factor scales with 1/T, which possibly reflects deviations from classical transport models due to the mixed crystal phase of the nanowires. The observed dark leakage current is of the order of merely ～100 fA/nanowire at 1 V reverse bias. The detectors display a linear increase of the photocurrent with reverse bias up to about 10 pA/nanowire at 5 V. From spectrally resolved measurements, we conclude that the photocurrent is primarily generated by funneling photogenerated carriers from the substrate into the NWs. Contributions from direct excitation of the NWs become increasingly important at low temperatures. The photocurrent decreases with temperature with an activation energy of about 50 meV, which we discuss in terms of a temperature-dependent diffusion length in the substrate and perturbed transport through the mixed-phase nanowires.     

Superior Functionality by Design: Selective Ozone Sensing Realized by Rationally Constructed High‐Index ZnO Surfaces

A new technique is reported for the transformation of smooth nonpolar ZnO nanowire surfaces to zigzagged high‐index polar surfaces using polycrystalline ZnO thin films deposited by atomic layer deposition (ALD). The c‐axis‐oriented ZnO nanowires with smooth nonpolar surfaces are fabricated using vapor deposition method and subsequently coated by ALD with a ZnO particulate thin film. The synthesized ZnO–ZnO core–shell nanostructures are annealed at 800 °C to transform the smooth ZnO nanowires to zigzagged nanowires with high‐index polar surfaces. Ozone sensing response is compared for all three types of fabricated nanowire morphologies, namely nanowires with smooth surfaces, ZnO–ZnO core–shell nanowires, and zigzagged ZnO nanowires to determine the role of crystallographic surface planes on gas response. While the smooth and core–shell nanowires are largely non‐responsive to varying O₃ concentrations in the experiments, zigzagged nanowires show a significantly higher sensitivity (ppb level) owing to inherent defect‐rich high‐index polar surfaces.     

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.     

InAs/InP radial nanowire heterostructures as high electron mobility devices

Radial core/shell nanowires (NWs) represent an important class of one-dimensional (1D) systems with substantial potential for exploring fundamental materials electronic and photonic properties. Here, we report the rational design and synthesis of InAs/InP core/shell NW heterostructures with quantum-confined, high-mobility electron carriers. Transmission electron microscopy studies revealed single-crystal InAs cores with epitaxial InP shells 2-3 nm in thickness, and energy-dispersive X-ray spectroscopy analysis further confirmed the composition of the designed heterostructure. Room-temperature electrical measurements on InAs/InP NW field-effect transistors (NWFETs) showed significant improvement in the on-current and transconductance compared to InAs NWFETs fabricated in parallel, with a room-temperature electron mobility, 11,500 cm(2)/Vs, substantially higher than other synthesized 1D nanostructures. In addition, NWFET devices configured with integral high dielectric constant gate oxide and top-gate structure yielded scaled on-currents up to 3.2 mA/microm, which are larger than values reported for other n-channel FETs. The design and realization of high electron mobility InAs/InP NWs extends our toolbox of nanoscale building blocks and opens up opportunities for fundamental and applied studies of quantum coherent transport and high-speed, low-power nanoelectronic circuits.     

Transport modulation in Ge/Si core/shell nanowires through controlled synthesis of doped Si shells

Appropriately controlling the properties of the Si shell in Ge/Si core/shell nanowires permits not only passivation of the Ge surface states, but also introduces new interface phenomena, thereby enabling novel nanoelectronics concepts. Here, we report a rational synthesis of Ge/Si core/shell nanowires with doped Si shells. We demonstrate that the morphology and thickness of Si shells can be controlled for different dopant types by tuning the growth parameters during synthesis. We also present distinctly different electrical characteristics that arise from nanowire field-effect transistors fabricated using the synthesized Ge/Si core/shell nanowires with different shell morphologies. Furthermore, a clear transition in the modification of device characteristics is observed for crystalline shell nanowires following removal of the shell using a unique trimming process of successive native oxide formation/etching. Our results demonstrate that the preferred transport path through the nanowire structure can be modulated by appropriately tuning the growth conditions.     

Observation of Self‐Assembled Core–Shell Structures in Epitaxially Embedded TbErAs Nanoparticles

Self‐assembled core–shell structured rare‐earth nanoparticles (TbErAs) are observed in a III–V semiconductor host matrix (In_0.53Ga_0.47As) nominally lattice‐matched to InP, grown via molecular beam epitaxy. Atom probe tomography demonstrates that the TbErAs nanoparticles have a core–shell structure, as seen both in the tomographic atom‐by‐atom reconstruction and concentration profiles. A simple thermodynamic model is created to determine when it is energetically favorable to have core–shell structures; the results strongly agree with the observations.     

Elastic and Piezoelectric Properties of Zincblende and Wurtzite Crystalline Nanowire Heterostructures

The elastic and piezoelectric properties of zincblende and wurtzite crystalline InAs/InP nanowire heterostructures have been studied using electro‐elastically coupled continuum elasticity theory. A comprehensive comparison of strains, piezoelectric potentials and piezoelectric fields in the two crystal types of nanowire heterostructures is presented. For each crystal type, three different forms of heterostructures—core‐shell, axial superlattice, and quantum dot nanowire heterostructures—are considered. In the studied nanowire heterostructures, the principal strains are found to be insensitive to the change in the crystal structure. However, the shear strains in the zincblende and wurtzite nanowire heterostructures can be very different. All the studied nanowire heterostructures are found to exhibit a piezoelectric field along the nanowire axis. The piezoelectric field is in general much stronger in a wurtzite nanowire heterostructure than in its corresponding zincblende heterostructure. Our results are expected to be particularly important for analyzing and understanding the properties of epitaxially grown nanowire heterostructures and for applications in nanowire electronics, optoelectronics, and biochemical sensing.     

3D Atomic‐Scale Insights into Anisotropic Core–Shell‐Structured InGaAs Nanowires Grown by Metal–Organic Chemical Vapor Deposition

III–V ternary InGaAs nanowires have great potential for electronic and optoelectronic device applications; however, the 3D structure and chemistry at the atomic‐scale inside the nanowires remain unclear, which hinders tailoring the nanowires for specific applications. Here, atom probe tomography is used in conjunction with a first‐principles simulation to investigate the 3D structure and chemistry of InGaAs nanowires, and reveals i) the nanowires form a spontaneous core–shell structure with a Ga‐enriched core and an In‐enriched shell, due to different growth mechanisms in the axial and lateral directions; ii) the shape of the core evolves from hexagon into Reuleaux triangle and grows larger, which results from In outward and Ga inward interdiffusion occurring at the core–shell interface; and iii) the irregular hexagonal shell manifests an anisotropic growth rate on {112}A and {112}B facets. Accordingly, a model in terms of the core–shell shape and chemistry evolution is proposed, which provides fresh insights into the growth of these nanowires.     

Homoepitaxial n-core: p-shell gallium nitride nanowires: HVPE overgrowth on MBE nanowires

We present the homoepitaxial growth of p-type, magnesium doped gallium nitride shells by use of halide vapor phase epitaxy (HVPE) on n-type gallium nitride nanowires grown by plasma-assisted molecular beam epitaxy (MBE). Scanning electron microscopy shows clear dopant contrast between the core and shell of the nanowire. The growth of magnesium doped nanowire shells shows little or no effect on the lattice parameters of the underlying nanowires, as measured by x-ray diffraction (XRD). Photoluminescence measurements of the nanowires show the appearance of sub-bandgap features in the blue and the ultraviolet, indicating the presence of acceptors. Finally, electrical measurements confirm the presence of electrically active holes in the nanowires.