Wurtzite Nanowires Research Articles

Unusual spin properties of InP wurtzite nanowires revealed by Zeeman splitting spectroscopy

In this study, we present a complete experimental and theoretical investigation of the fundamental exciton Zeeman splitting in wurtzite InP nanowires. We determined the exciton gyromagnetic factor, $g_{exc}$, by magneto-photoluminescence spectroscopy using magnetic fields up to 29 T. We found that $g_{exc}$ is strongly anisotropic with values differing in excess of 50\% between the magnetic field oriented parallel and perpendicular to the nanowire long axis. Furthermore, for magnetic fields oriented along the nanowire axis, $g_{exc}$ is nearly three times larger than in bulk zincblende InP and it shows a marked sublinear dependence on the magnetic field, a common feature to other non-nitride III-V wurtzite nanowires but not properly understood. Remarkably, this nonlinearity originates from only one Zeeman branch characterized by a specific type of light polarization. All the experimental findings are modeled theoretically by a robust approach combining the $k \cdot p$ method with the envelope function approximation and including the electron-hole interaction. We revealed that the nonlinear features arise due to the coupling between Landau levels pertaining to the A (heavy-hole like) and B (light-hole like) valence bands of the wurtzite crystal structure. This general behavior is particularly relevant for the understanding of the spin properties of several wurtzite nanowires that host the set for the observation of topological phases potentially at the base of quantum computing platforms.

Growth, structural and optical characterization of wurtzite GaP nanowires

Bulk gallium phosphide (GaP) crystallizes in the zinc-blende (ZB) structure and has an indirect bandgap. However, GaP nanowires (NWs) can be synthesized in the wurtzite (WZ) phase as well. The contradictory theoretical predictions and experimental reports on the band structure of WZ GaP suggest a direct or a pseudo-direct bandgap. There are only a few reports of the growth and luminescence from WZ and ZB GaP NWs. We first present a comprehensive study of the gold-catalyzed growth of GaP NWs via metalorganic vapor phase epitaxy on various crystalline and amorphous substrates. We optimized the growth parameters like temperature, pressure and reactant flow rates to grow WZ GaP NWs with minimal taper. These wires were characterized using electron microscopy, x-ray diffraction, Raman scattering and photoluminescence spectroscopy. The luminescence studies of bare GaP NWs and GaP/AlGaP core–shell heterostructures with WZ- and ZB-phase GaP cores suggest that the WZ-phase GaP has a pseudo-direct bandgap with weak near-band-edge luminescence intensity.

Simultaneous Growth of Pure Wurtzite and Zinc Blende Nanowires.

The opportunity to engineer III-V nanowires in wurtzite and zinc blende crystal structure allows for exploring properties not conventionally available in the bulk form as well as opening the opportunity for use of additional degrees of freedom in device fabrication. However, the fundamental understanding of the nature of polytypism in III-V nanowire growth is still lacking key ingredients to be able to connect the results of modeling and experiments. Here we show InP nanowires of both pure wurtzite and pure zinc blende grown simultaneously on the same InP [100]-oriented substrate. We find wurtzite nanowires to grow along [Formula: see text] and zinc blende counterparts along [Formula: see text]. Further, we discuss the nucleation, growth, and polytypism of our nanowires against the background of existing theory. Our results demonstrate, first, that the crystal growth conditions for wurtzite and zinc blende nanowire growth are not mutually exclusive and, second, that the interface energies predominantly determine the crystal structure of the nanowires.

Analysis of structural distortion in Eshelby twisted InP nanowires by scanning precession electron diffraction

Transmission electron microscopes (TEM) are widely used in nanotechnology research. However, it is still challenging to characterize nanoscale objects; their small size coupled with dynamical diffraction makes interpreting real- or reciprocal-space data difficult. Scanning precession electron diffraction ((S)PED) represents an invaluable contribution, reducing the dynamical contributions to the diffraction pattern at high spatial resolution. Here a detailed analysis of wurtzite InP nanowires (30–40 nm in diameter) containing a screw dislocation and an associated wire lattice torsion is presented. It has been possible to characterize the dislocation with great detail (Burgers and line vector, handedness). Through careful measurement of the strain field and comparison with dynamical electron diffraction simulations, this was found to be compatible with a Burgers vector modulus equal to one hexagonal lattice cell parameter despite the observed crystal rotation rate being larger (ca. 20%) than that predicted by classical elastic theory for the nominal wire diameter. These findings corroborate the importance of the (S)PED technique for characterizing nanoscale materials.

Growth of pure wurtzite InAs nanowires over a wide diameter range

We demonstrate pure wurtzite InAs nanowires over a wide diameter range. The nanowires are grown on an InP (1 1 1)B substrate by Au-catalyzed metal organic chemical vapor deposition. The crystal structure of nanowires strongly depends on the growth temperature and V/III ratio. Under optimized growth condition, pure wurtzite phase is obtained over the full length of the tens-of-micrometer-long nanowire, covering a broad diameter range of 70–420 nm. The broad diameter range of wurtzite phase is attributed to a high actual V/III ratio due to a reduction of In amount because of the InP substrate. The pure wurtzite nanowires exhibit much higher electron mobility than those with dense stacking faults, showing great potential in high-speed electronic and optoelectronic devices.

Spin-orbit coupling effects in zinc-blende InSb and wurtzite InAs nanowires: Realistic calculations with multiband k·p method

A systematic numerical investigation of spin-orbit fields in the conduction bands of III-V semiconductor nanowires is performed. Zinc-blende InSb nanowires are considered along [001], [011], and [111] directions, while wurtzite InAs nanowires are studied along [0001] and [10$\overline{1}$0] or [11$\overline{2}$0] directions. Realistic multiband $\vec{k} \cdot \vec{p}\,$ Hamiltonians are solved by using plane-wave expansions of real-space parameters. In all cases the linear and cubic spin-orbit coupling parameters are extracted for nanowire widths from 30 to 100 nm. Typical spin-orbit energies are on the $\mu$eV scale, except for InAs wurtzite nanowires grown along [10$\overline{1}$0] or [11$\overline{2}$0], in which the spin-orbit energy is about meV, largely independent of the wire diameter. Significant spin-orbit coupling is obtained by applying a transverse electric field, causing the Rashba effect. For an electric field of about 4 mV/nm the obtained spin-orbit energies are about 1 meV for both materials in all investigated growth directions. The most favorable system, in which the spin-orbit effects are maximal, are InAs WZ nanowires grown along [1010] or [11$\overline{2}$0], since here spin-orbit energies are giant (meV) already in the absence of electric field. The least favorable are InAs WZ nanowires grown along [0001], since here even the electric field does not increase the spin-orbit energies beyond 0.1 meV. The presented results should be useful for investigations of optical orientation, spin transport, weak localization, and superconducting proximity effects in semiconductor nanowires.

Optical properties of Cs adsorbed wurtzite GaAs nanowires by first-principles study

In order to research the optical properties of negative electron affinity (NEA) GaAs nanowire photocathodes, (10-10) surface models of clean wurtzite GaAs nanowire and nanowires adsorbed by one Cs, two Cs, three Cs and four Cs atoms are established. Band structures, density of states, dielectric function, absorption spectrum, reflectivity spectrum, complex refractive index and loss function for different Cs adsorption models are investigated utilizing first-principles. Results show that with increasing surface Cs coverage, the band gap of GaAs nanowires gradually disappear and surfaces exhibit semi-metal characteristic. The average values of reflectivity spectrum for Cs atoms adsorbed GaAs nanowire models are all less than that of clean surface, which makes the incident photons come across the Cs-adsorbed surfaces easier and excite more photoelectrons. During the energy range from 0 eV to 2.2 eV, the absorption coefficients for different Cs adsorption models are all larger than that of the clean one, indicating that Cs atoms can enhance the optical absorption properties of wurtzite GaAs nanowires material. All calculations in this study can give a theoretical guidance for the preparation of NEA GaAs nanowire photocathodes.

Realization of Wurtzite GaSb Using InAs Nanowire Templates

AbstractThe crystal structure of a material has a large impact on the electronic and material properties such as band alignment, bandgap energy, and surface energies. Au‐seeded III–V nanowires are promising structures for exploring these effects, since for most III–V materials they readily grow in either wurtzite or zinc blende crystal structure. In III–Sb nanowires however, wurtzite crystal structure growth has proven difficult. Therefore, other methods must be developed to achieve wurtzite antimonides. For GaSb, theoretical predictions of the band structure diverge significantly, but the absence of wurtzite GaSb material has prevented any experimental verification of the properties. Having access to this material is a critical step toward clearing the uncertainty in the electronic properties, improving the theoretical band structure models and potentially opening doors toward application of this material. This work demonstrates the use of InAs wurtzite nanowires as templates for realizing GaSb wurtzite shell layers with varying thicknesses. The properties of the axial and radial heterointerfaces are studied at the atomic scale by means of aberration‐corrected scanning transmission electron microscopy, revealing their sharpness and structural quality. The transport characterizations point toward a positive offset in the valence bandedge of wurtzite compared to zinc blende.

Spontaneous and piezo‐phototronics effect on geometrical shape of III‐Nitride wurtzite nanowires for high efficiency photovoltaic applications

In this study, the influence of spontaneous and piezo-phototronic effect on the performance of hexagonal and triangular III-Nitride nanowire (NW) photovoltaic devices are investigated. The effect of stress/strain distribution on band structure of GaN/InxGa1-xN/GaN core/shell/shell NW solar cell with hexagonal and triangular geometrical shape are also intensively investigated by numerical calculations. It is observed that NW solar cells possess a non-uniform pattern of polarisation charges (PCs) due to complex distribution of strain and stress parameters depending upon growth orientations of NWs. Effect of PCs, especially due to piezo-phototronic effect on the polar, semi-polar and non-polar planes of NW having Miller–Bravais indices of {000-1}, {1-101} and {1-100} are discussed in detail, respectively. This numerical study not only provides the basic theoretical understanding about the spontaneous and piezo-phototronic effect on III-Nitride solar cell but also assists to obtain most optimised geometrical design to achieve high performance NW solar cell.

Growth of InAs Wurtzite Nanocrosses from Hexagonal and Cubic Basis.

Epitaxially connected nanowires allow for the design of electron transport experiments and applications beyond the standard two terminal device geometries. In this Letter, we present growth methods of three distinct types of wurtzite structured InAs nanocrosses via the vapor-liquid-solid mechanism. Two methods use conventional wurtzite nanowire arrays as a 6-fold hexagonal basis for growing single crystal wurtzite nanocrosses. A third method uses the 2-fold cubic symmetry of (100) substrates to form well-defined coherent inclusions of zinc blende in the center of the nanocrosses. We show that all three types of nanocrosses can be transferred undamaged to arbitrary substrates, which allows for structural, compositional, and electrical characterization. We further demonstrate the potential for synthesis of as-grown nanowire networks and for using nanowires as shadow masks for in situ fabricated junctions in radial nanowire heterostructures.

Effect of seed layers (Al, Ti) on optical and morphology of Fe-doped ZnO thin film nanowires grown on Si substrate via electron beam evaporation

The effects of Al and Ti seed layers were studied for undoped and Fe-doped ZnO thin films deposited on n-type Si substrates by electron beam (e-beam) evaporation. The films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The films grown on seed layers showed wurtzite hexagonal crystal nanorod and nanowire structures. A higher angle phase shift was observed in the doped thin films compared to the pristine ZnO films. Microstructural studies confirmed the growth of nanorods and nanowires with average widths of ~32nm and ~8–29nm, respectively. The nanostructures were denser and more crystalline on the Al seed layer than on the Ti seed layer for the doped thin films. However, in the undoped thin films, a more crystalline nature was observed on the Ti seeded layer than the Al seeded layer.

Critical Temperature for the Conversion from Wurtzite to Zincblende of the Optical Emission of InAs Nanowires

One hour annealing at 300 °C changes the optical emission characteristics of InAs nanowires (NWs) from the wurtzite (WZ) phase into that of zincblende (ZB). These results are accounted for by the conversion of a small fraction of the NW WZ metastable structure into the stable ZB structure. Several paths toward the polytype transformation in the configuration space are also demonstrated using first-principles calculations. For lower annealing temperatures, emission which is likely related to WZ polytypes is observed at energies that agree with theoretical predictions. These results demonstrate severe constraints on thermal processes to which devices made from InAs WZ NWs can be exposed.

Wurtzite ZnTe Nanotrees and Nanowires on Fluorine-Doped Tin Oxide Glass Substrates.

ZnTe nanotrees and nanowires were grown on fluorine-doped tin oxide glass by physical vapor transport. Sn from a fluorine-doped tin oxide layer catalyzed the growth at a growth temperature of 320 °C. Both the stem and branch nanowires grew along ⟨0001⟩ in the rarely observed wurtzite structure. SnTe nanostructures were formed in the liquid catalyst and simultaneously ZnTe nanowire grew under Te-limited conditions, which made the formation of the wurtzite structure energetically favorable. Through polarization-dependent and power-dependent microphotoluminescence measurements from individual wurtzite nanowires at room temperature, we could determine the so far unknown fundamental bandgap of wurtzite ZnTe, which was 2.297 eV and thus 37 meV higher than that of zinc-blend ZnTe. From the analysis of doublet photoluminescence spectra, the valence band splitting energy between heavy hole and light hole bands is estimated to be 69 meV.

Uniaxial strain-modulated electronic structures of CdX (X = S, Se, Te) from first-principles calculations: A comparison between bulk and nanowires**Project supported by the National Natural Science Foundation of China (Grant Nos. 11204296 and 61427901) and the National Basic Research Program of China (Grant Nos. 2014CB643902 and 2013CB933304).

Using first-principles calculations based on density functional theory, we systematically study the structural deformation and electronic properties of wurtzite CdX (X = S, Se, Te) bulk and nanowires (NWs) under uniaxial [0001] strain. Due to the intrinsic shrinking strain induced by surface contraction, large NWs with {100} facets have heavy hole (HH)-like valence band maximum (VBM) states, while NWs with {110} facets have crystal hole (CH)-like VBM states. The external uniaxial strain induces an HH–CH band crossing at a critical strain for both bulk and NWs, resulting in nonlinear variations in band gap and hole effective mass at VBM. Unlike the bulk phase, the critical strain of NWs highly depends on the character of the VBM state in the unstrained case, which is closely related to the size and facet of NWs. The critical strain of bulk is at compressive range, while the critical strain of NWs with HH-like and CH-like VBM appears at compressive and tensile strain, respectively. Due to the HH–CH band crossing, the charge distribution of the VBM state in NWs can also be tuned by the external uniaxial strain. Despite the complication of the VBM state, the electron effective mass at conduction band minimum (CBM) of NWs shows a linear relation with the CBM–HH energy difference, the same as the bulk material.

Modeling the electronic properties of GaAs polytype nanostructures: Impact of strain on the conduction band character

We study the electronic properties of GaAs nanowires composed of both the zincblende and wurtzite modifications using a ten-band k.p model. In the wurtzite phase, two energetically close conduction bands are of importance for the confinement and the energy levels of the electron ground state. These bands form two intersecting potential landscapes for electrons in zincblende/wurtzite nanostructures. The energy difference between the two bands depends sensitively on strain, such that even small strains can reverse the energy ordering of the two bands. This reversal may already be induced by the non-negligible lattice mismatch between the two crystal phases in polytype GaAs nanostructures, a fact that was ignored in previous studies of these structures. We present a systematic study of the influence of intrinsic and extrinsic strain on the electron ground state for both purely zincblende and wurtzite nanowires as well as for polytype superlattices. The coexistence of the two conduction bands and their opposite strain dependence results in complex electronic and optical properties of GaAs polytype nanostructures. In particular, both the energy and the polarization of the lowest intersubband transition depends on the relative fraction of the two crystal phases in the nanowire.

The electronic structures of AlN and InN wurtzite nanowires

We derive the relations between the analogous seven Luttinger-Kohn parameters and six Rashba-Sheka-Pikus parameters for wurtzite semiconductors, which can be used to investigate the electronic structures of some wurtzite semiconductors such as AlN and InN materials, including their low-dimensional structures. As an example, the electronic structures of AlN and InN nanowires are calculated by using the derived relations and six-band effective-mass k·p theory. Interestingly, it is found that the ground hole state of AlN nanowires is always a pure S state whether the radius R is small (1 nm) or large (6 nm), and the ground hole state only contains |Z〉 Bloch orbital component. Therefore, AlN nanowires is the ideal low-dimensional material for the production of purely linearly polarized π light, unlike ZnO nanowires, which emits plane-polarized σ light. However, the ground hole state of InN nanowires can be tuned from a pure S state to a mixed P state when the radius R is larger than 2.6 nm, which will make the polarized properties of the lowest optical transition changes from linearly polarized π light to plane-polarized σ light. Meanwhile, the valence band structures of InN nanowires will present strong band-crossings when the radius R increases to 6 nm, and through the detail analysis of possible transitions of InN nanowires at the Γ point, we find some of the neighbor optical transitions are almost degenerate, because the spin-orbit splitting energy of InN material is only 0.001 eV. Therefore, it is concluded that the electronic structures and optical properties of InN nanowires present great differences with that of AlN nanowires.

First-principles calculations for mechanical and electronic features of strained GaP nanowires

The mechanical and electronic properties of GaP nanowires are investigated by computing the Young’s modulus, Poisson’s ratio, energy band gap and effective carrier masses using first-principles calculations based on density functional theory. The wurtzite structural nanowires with diameters upper limited to [Formula: see text][Formula: see text]Å are strained by uniaxial strains in the range of [Formula: see text]–[Formula: see text]. The Young’s moduli of nanowires are found to be decreased with increase of the size in the direction of the Young’s modulus of the bulk GaP. The Poisson’s effect is determined to be stronger in GaP nanowires than in the bulk. The energy band gaps of the unstrained and strained nanowires are obtained to be enlarged with decrease of the size due to the quantum size effect. The confinement effect is found larger in the compressed nanowires than in the stretched ones. All the unstrained nanowires except the largest one are indirect band gap materials. Indirect to direct band gap transition is determined to be size and strain dependent. The effective carrier masses in all unstrained nanowires are found small compared to the ones in the bulk GaP. The effective electron and hole masses are obtained to be modulated in nanowires of this work by the compressive and both compressive/tensile strains, respectively.

Value and Anisotropy of the Electron and Hole Mass in Pure Wurtzite InP Nanowires.

The effective mass of electrons and holes in semiconductors is pivotal in determining the dynamics of carriers and their confinement energy in nanostructured materials. Surprisingly, this quantity is still unknown in wurtzite (WZ) nanowires (NWs) made of III-V compounds (e.g., GaAs, InAs, GaP, InP), where the WZ phase has no bulk counterpart. Here, we investigate the magneto-optical properties of InP WZ NWs grown by selective-area epitaxy that provides perfectly ordered NWs featuring high-crystalline quality. The combined analysis of the energy of free exciton states and impurity levels under magnetic field (B up to 29 T) allows us to disentangle the dynamics of oppositely charged carriers from the Coulomb interaction and thus to determine the values of the electron and hole effective mass. By application of B⃗ along different crystallographic directions, we also assess the dependence of the transport properties with respect to the NW growth axis (namely, the WZ ĉ axis). The effective mass of electrons along ĉ is me∥ = (0.078 ± 0.002) m0 (m0 is the electron mass in vacuum) and perpendicular to ĉ is me⊥ = (0.093 ± 0.001) m0, resulting in a 20% mass anisotropy. Holes exhibit a much larger (∼320%) and opposite mass anisotropy with their effective mass along and perpendicular to ĉ equal to mh∥ = (0.81 ± 0.18) m0 and mh⊥ = (0.250 ± 0.016) m0, respectively. While no full consensus is found with current theoretical results on WZ InP, our findings show trends remarkably similar to the experimental data available in WZ bulk materials, such as InN, GaN, and ZnO.

First-principles study of size-, surface- and mechanical strain-dependent electronic properties of wurtzite and zinc-blende InSb nanowires

Using first-principle calculations with density functional theory, we investigated the modification of electronic properties in zinc-blende (ZB) and wurtzite (WZ) InSb nanowires (NWs) grown along the [111] and [0001] directions for different size, different surface coverage and different mechanical strain. The results show that before the surface passivation, ZBNWs and WZNWs exhibit the metallic character and the semiconductor character, respectively. WZNWs show a crossover from a direct to an indirect as diameter decreases. After the surface passivation, both ZBNWs and WZNWs are found to be direct-gap character. The electronic band structure shows a significant response to changes in surface passivation with pseudo hydrogen and halogen. The band structure with mechanical strain is strongly dependent on the crystal orientation and the NW diameter. In ZBNWs, compressive strain induces the indirect band gap character, whereas tensile strain can not form it. WZNWs have various strain dependence in that both compressive and tensile strain make InSb show a direct band gap character. A brief analysis of these results is given.

Band structures and spatial carrier confinement in GaAs/GaP core-shell nanowires: Core/shell composition and size effects

The core/shell composition and size effects on band structures and spatial confinement of carriers in zinc-blende and wurtzite GaAs/GaP core-shell nanowires are investigated by using first-principles calculations. Our results demonstrate that surface GaP shell layer in the core-shell nanowires suppresses surface states of GaAs core, resulting in an intrinsic semiconductor characteristic. The results of electronic structures suggest that band gap, band-structure characteristic, and spatial carrier confinement of core-shell nanowires strongly depend on their size, core/shell composition, and crystal phase. Unlike the direct band gap in wurtzite core-shell nanowires, there is an indirect-to-direct band-gap transition in zinc-blende core-shell nanowires with increasing composition x. The direct band-gap characteristic in zinc-blende core-shell nanowires can be maintained in a larger composition range (0.12 < x ≤ 1). The spatial charge-density distribution of band-edge states indicate that the smaller-sized GaAs/GaP core-shell nanowires (d < 5 nm) have a pseudo-type I band alignment that creates a stronger confinement for hole carriers but there is a type-I band alignment in larger-sized nanowires where both electrons and holes are localized in the GaAs core. The findings provide a theoretical guidance for engineering electronic structures of GaAs/GaP nanowires and their applications in electronic and optoelectronic devices.