Wurtzite InP Nanowires Research Articles

InP Crystal Phase Heterojunction Transistor with a Vertical Gate-All-Around Structure.

Crystal phase transitions can form a new type of heterojunction with different atomic arrangements in the same material: crystal phase heterojunction (CPHJ). The CPHJ has an inherently strong impact on band engineering without concerns over critical thicknesses with misfit dislocations and a semiconductor-metal transition. In-plane CPHJ was recently demonstrated in two-dimensional (2D) transition-metal dichalcogenide (TMD) materials and utilized for conventional planar field-effect transistor applications. However, scalability such as gate electrostatic control, miniaturization, and multigate structure have been limited because of the geometrical issue. Here, we demonstrated a transistor using the CPHJ with a vertical gate-all-around structure by forming a CPHJ in conventional III-V semiconductors. The CPHJ, composed of wurtzite InP nanowires with zincblende InP substrates, showed an atomically flat heterojunction without dislocations and indicated a Type-II band discontinuity across the junction. The CPHJ transistor had moderate to good gate electrostatic controllability with high on-state currents and transconductance. The CPHJ offer will provide a new switching mechanism and add a new junction and device design choice to the long history of transistors.

Hole and Electron Effective Masses in Single InP Nanowires with a Wurtzite-Zincblende Homojunction.

The formation of wurtzite (WZ) phase in III-V nanowires (NWs) such as GaAs and InP is a complication hindering the growth of pure-phase NWs, but it can also be exploited to form NW homostructures consisting of alternate zincblende (ZB) and WZ segments. This leads to different forms of nanostructures, such as crystal-phase superlattices and quantum dots. Here, we investigate the electronic properties of the simplest, yet challenging, of such homostructures: InP NWs with a single homojunction between pure ZB and WZ segments. Polarization-resolved microphotoluminescence (μ-PL) measurements on single NWs provide a tool to gain insights into the interplay between NW geometry and crystal phase. We also exploit this homostructure to simultaneously measure effective masses of charge carriers and excitons in ZB and WZ InP NWs, reliably. Magneto-μ-PL measurements carried out on individual NWs up to 29 T at 77 K allow us to determine the free exciton reduced masses of the ZB and WZ crystal phases, showing the heavier character of the WZ phase, and to deduce the effective mass of electrons in ZB InP NWs (me= 0.080 m0). Finally, we obtain the reduced mass of light-hole excitons in WZ InP by probing the second optically permitted transition Γ7C ↔ Γ7uV with magneto-μ-PL measurements carried out at room temperature. This information is used to extract the experimental light-hole effective mass in WZ InP, which is found to be mlh = 0.26 m0, a value much smaller than the one of the heavy hole mass. Besides being a valuable test for band structure calculations, the knowledge of carrier masses in WZ and ZB InP is important in view of the optimization of the efficiency of solar cells, which is one of the main applications of InP NWs.

Non-resonant Raman scattering of wurtzite GaAs and InP nanowires.

It is now possible to synthesize the wurtzite crystal phase of most III-V semiconductors in the form of nanowires. This sparks interest for fundamental research and adds extra degrees of freedom for designing novel devices. However, the understanding of many properties, such as phonon dispersion, of these wurtzite semiconductors is not yet complete, despite the extensive number of studies published. The E2L and E2H phonon modes exist in the wurtzite crystal phase only (not in zinc blende) where the E2H mode has been already experimentally observed in Ga and In arsenides and phosphides, while the E2L mode has been observed in GaP, but not in GaAs or InP. In order to determine the energy of E2L in wurtzite GaAs and InP, we performed Raman scattering measurements on wurtzite GaAs and InP nanowires. We found clear evidence of the E2L phonon mode at 64 cm-1 and 54 cm-1, respectively. Polarization-dependent experiments revealed similar selection rules for both the E2L and the E2H phonon modes (as expected) where the intensity peaked with excitation and detection polarization being perpendicular to the [0001] crystallographic direction. We further find that the splitting between the E1(TO) and A1(TO) modes is around 2 cm-1 in wurtzite GaAs and below 1 cm-1 in wurtzite InP. We believe these results will be useful for a better understanding of phonons in wurtzite crystal phase of III-V semiconductors as well as for testing and improving phonon dispersion calculations.

Metalorganic vapor phase epitaxy of wurtzite InP nanowires on GaN

The metalorganic vapor phase epitaxy of wurtzite InP nanowires on GaN (0001) is demonstrated. The InP nanowires exhibit the same wurtzite structure as the underlying wurtzite GaN. The photoluminescence studies indicate that the InP nanowires are single-phase wurtzite with high crystalline quality which is supported by transmission and scanning electron microscopy images. The position of the second valence band or valence band splitting energy is also deduced from the photoluminescence data to be ΔAB=30 meV at room temperature. The InP/GaN heterojunction can enable exotic optoelectronic and spintronic experiments and applications. In addition, these results can enable traditional III–V growth on III-N materials for heterojunction devices.

Wavelength-tunable InAsP quantum dots in InP nanowires

There is considerable interest in quantum dots incorporated in nanowires for nanolasers and quantum emitters. In this letter, we demonstrate single InAsP quantum dots embedded in InP nanowires grown by metalorganic vapor-phase epitaxy. Despite the abrupt change of growth conditions at the interface, InAsP quantum dots can be grown in pure wurtzite InP nanowires. We develop a model and analyze the effects of the thickness of InAsP quantum dots and the composition of As on the formation of dislocations. Furthermore, the InAsP/InP quantum dot nanowires show bright photoluminescence up to room temperature without any surface passivation. The emission from the quantum dots could be well tuned by adjusting the dot size either vertically or laterally. The study demonstrates the potential of this material system for optoelectronic applications.

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.

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.

Determination of the spin orbit coupling and crystal field splitting in wurtzite InP by polarization resolved photoluminescence

Excitation photoluminescence spectroscopy is usually used to extract the crystal field splitting (ΔCR) and spin orbit coupling (ΔSO) parameters of wurtzite (Wz) InP nanowires (NWs). However, the equations expressing the valence band splitting are symmetric with respect to these two parameters, and a choice ΔCR > ΔSO or ΔCR < ΔSO has to be taken into account in order to assign the numerical values. To solve this issue, polarization resolved micro-photoluminescence was performed on vertically aligned and untapered Wz InP NWs grown on silicon. The experimental results combined with a theoretical model and finite difference time domain calculations allow us to conclude that ΔCR > ΔSO in Wz InP.

Electronic properties of wurtzite-phase InP nanowires determined by optical and magneto-optical spectroscopy

Thanks to their peculiar shape and dimensions, semiconductor nanowires (NWs) are emerging as building components of novel devices. The presence of wurtzite (WZ) phase in the lattice structure of non-nitride III-V NWs is one of the most surprising findings in these nanostructures: this phase, indeed, cannot be found in the same materials in the bulk form, where the zincblende (ZB) structure is ubiquitous, and therefore the WZ properties are poorly known. This review focuses on WZ InP NWs, because growth techniques have reached a high degree of control on the structural properties of this material, and optical studies performed on high-quality samples have allowed determining the most useful electronic properties, which are reviewed here. After an introduction summarizing the reasons for the interest in WZ InP nanowires (Sec. I), we give an overview on growth process and structural and optical properties of WZ InP NWs (Sec. II). In Sec. III, a complete picture of the energy and symmetry of the lowest-energy...

Different growth regimes in InP nanowire growth mediated by Ag nanoparticles

We report on the existence of two different regimes in one-step Ag-seeded InP nanowire growth. The vapor–liquid–solid-mechanism is present at larger In precursor flows and temperatures, ∼500 °C, yielding high aspect ratio and pure wurtzite InP nanowires with a semi-spherical metal particle at the thin apex. Periodic diameter oscillations can be achieved under extreme In supersaturations at this temperature range, showing the presence of a liquid catalyst. However, under lower temperatures and In precursor flows, large diameter InP nanowires with mixed wurtzite/zincblende segments are obtained, similarly to In-assisted growth. Chemical composition analysis suggest that In-rich droplet formation is catalyzed at the substrate surface via Ag nanoparticles; this process might be facilitated by the sulfur contamination detected in these nanoparticles. Furthermore, part of the original Ag nanoparticle remains solid and is embedded inside the actual catalyst, providing an in situ method to switch growth mechanisms upon changing In precursor flow. Nevertheless, our Ag-seeded InP nanowires exhibit overall optical emission spectra consistent with the observed structural properties and similar to Au-catalyzed InP nanowires. We thus show that Ag nanoparticles may be a suitable replacement for Au in InP nanowire growth.

Effective Surface Passivation of InP Nanowires by Atomic-Layer-Deposited Al2O3 with POx Interlayer.

III/V semiconductor nanostructures have significant potential in device applications, but effective surface passivation is critical due to their large surface-to-volume ratio. For InP such passivation has proven particularly difficult, with substantial depassivation generally observed following dielectric deposition on InP surfaces. We present a novel approach based on passivation with a phosphorus-rich interfacial oxide deposited using a low-temperature process, which is critical to avoid P-desorption. For this purpose we have chosen a POx layer deposited in a plasma-assisted atomic layer deposition (ALD) system at room temperature. Since POx is known to be hygroscopic and therefore unstable in atmosphere, we encapsulate this layer with a thin ALD Al2O3 capping layer to form a POx/Al2O3 stack. This passivation scheme is capable of improving the photoluminescence (PL) efficiency of our state-of-the-art wurtzite (WZ) InP nanowires by a factor of ∼20 at low excitation. If we apply the rate equation analysis advocated by some authors, we derive a PL internal quantum efficiency (IQE) of 75% for our passivated wires at high excitation. Our results indicate that it is more reliable to calculate the IQE as the ratio of the integrated PL intensity at room temperature to that at 10 K. By this means we derive an IQE of 27% for the passivated wires at high excitation (>10 kW cm–2), which constitutes an unprecedented level of performance for undoped InP nanowires. This conclusion is supported by time-resolved PL decay lifetimes, which are also shown to be significantly higher than previously reported for similar wires. The passivation scheme displays excellent long-term stability (>7 months) and is additionally shown to substantially improve the thermal stability of InP surfaces (>300 °C), significantly expanding the temperature window for device processing. Such effective surface passivation is a key enabling technology for InP nanowire devices such as nanolasers and solar cells.

Young's Modulus of Wurtzite and Zinc Blende InP Nanowires.

The Young's modulus of thin conical InP nanowires with either wurtzite or mixed "zinc blende/wurtzite" structures was measured. It has been shown that the value of Young's modulus obtained for wurtzite InP nanowires (E[0001] = 130 ± 30 GPa) was similar to the theoretically predicted value for the wurtzite InP material (E[0001] = 120 ± 10 GPa). The Young's modulus of mixed "zinc blende/wurtzite" InP nanowires (E[111] = 65 ± 10 GPa) appeared to be 40% less than the theoretically predicted value for the zinc blende InP material (E[111] = 110 GPa). An advanced method for measuring the Young's modulus of thin and flexible nanostructures is proposed. It consists of measuring the flexibility (the inverse of stiffness) profiles 1/k(x) by the scanning probe microscopy with precise control of loading force in nanonewton range followed by simulations.

Dynamic properties of III–V polytypes from density-functional theory

The recently discovered hexagonal wurtzite phase of several III–V nanowires opens up strong opportunity to engineer optoelectronic and transport properties of III–V materials. Herein, we explore the dynamical and dielectric properties of cubic (3C) and wurtzite (2H) III–V compounds (AlP, AlAs, AlSb, GaP, GaAs, GaSb, InP, InAs, and InSb). For cubic III–V compounds, our calculated phonon frequencies agree well with neutron diffraction and Raman-scattering measurements. In the case of 2H III–V materials, our calculated phonon modes at the zone-center Γ point are in distinguished agreement with available Raman-spectroscopy measurements of wurtzite GaAs, InP, GaP, and InAs nanowires. Particularly, the “fingerprint” of the wurtzite phase, which is our predicted E2(high) phonon mode, at 261 cm−1(GaAs), 308 cm−1(InP), 358 cm−1(GaP), and 214 cm−1(InAs) matches perfectly the respective Raman values of 258 cm−1, 306.4 cm−1, 353 cm−1, and 213.7 cm−1 for GaAs, InP, GaP, and InAs. Moreover, the dynamic charges and high-frequency dielectric constants are predicted for III–V materials in both cubic (3C) and hexagonal (2H) crystal polytypes. It is found that the dielectric properties of InAs and InSb contrast markedly from those of other 2H III–V compounds. Furthermore, InAs and InSb evidence relative strong anisotropy in their dielectric constants and Born effective charges, whereas GaP evinces the higher Born effective charge anisotropy of 2H III–V compounds.

Overcoming power broadening of the quantum dot emission in a pure wurtzite nanowire

One of the key challenges in developing quantum networks is to generate single photons with high brightness, purity, and long temporal coherence. Semiconductor quantum dots potentially satisfy these requirements; however, due to imperfections in the surrounding material, the coherence generally degrades with increasing excitation power yielding a broader emission spectrum. Here we overcome this power broadening regime and demonstrate the longest coherence at exciton saturation where the detection count rates are highest. We detect single-photon count rates of 460,000 counts per second under pulsed laser excitation while maintaining a single-photon purity of greater than 99%. Importantly, the enhanced coherence is attained with quantum dots in ultraclean wurtzite InP nanowires, where the surrounding charge traps are filled by exciting above the wurtzite InP nanowire bandgap. By raising the excitation intensity, the number of possible charge configurations in the quantum dot environment is reduced, resulting in a narrower emission spectrum. Via Monte Carlo simulations we explain the observed narrowing of the emission spectrum with increasing power. Cooling down the sample to 300 mK, we further enhance the single-photon coherence two-fold as compared to operation at 4.5 K, resulting in a homogeneous coherence time, T2, of 1.2 ns.

Spatially Resolved Doping Concentration and Nonradiative Lifetime Profiles in Single Si-Doped InP Nanowires Using Photoluminescence Mapping.

We report an analysis method that combines microphotoluminescence mapping and lifetime mapping data of single semiconductor nanowires to extract the doping concentration, nonradiative lifetime, and internal quantum efficiency along the length of the nanowires. Using this method, the doping concentration of single Si-doped wurtzite InP nanowires are mapped out and confirmed by the electrical measurements of single nanowire devices. Our method has important implication for single nanowire detectors and LEDs and nanowire solar cells applications.

Polarized light absorption in wurtzite InP nanowire ensembles.

We investigate the absorption properties of ensembles of wurtzite (WZ) InP nanowires (NWs) by high-resolution polarization-resolved photoluminescence excitation (PLE) spectroscopy at T = 10 K. The degree of linear polarization of absorbed light, ρ(abs), resulting from the PLE spectra is governed by a competition between the dielectric mismatch effect and the WZ selection rules acting differently on different optical transitions. These two contributions are deconvoluted with the help of finite-difference time-domain simulations, thus providing information about the symmetry of the three highest valence bands (A, B, and C) of WZ InP and the extent of the spin-orbit interaction on these states. Moreover, ρ(abs) shows two characteristic dips corresponding to the two sharp A and B exciton resonances in the PLE spectra. A model developed for the dip in A provides the first experimental evidence of an enhancement in the dielectric mismatch effect originating from the Coulomb interaction between electron and hole.

Controllable growth and optical properties of InP and InP/InAs nanostructures on the sidewalls of GaAs nanowires

The growth and optical properties of InP and InP/InAs nanostructures on GaAs nanowires are investigated. InP quantum well and quantum dots (QDs) are formed on the sidewalls of GaAs nanowires successively with increasing the deposition time of InP. The GaAs/InP nanowire heterostructure exhibits a type-II band alignment. The wavelength of the InP quantum well is in the range of 857–892 nm at 77 K, which means that the quantum well is nearly fully strained. The InP quantum dot, which has a bow-shaped cross section, exhibits dislocation-free pure zinc blende structure. Stranski-Krastanow InAs quantum dots are subsequently formed on the GaAs/InP nanowire core-shell structure. The InAs quantum dots are distributed over the middle part of the nanowire, indicating that the In atoms contributing to the quantum dots mainly come from the vapor rather than the substrate. The longest emission wavelength obtained from the InAs QDs is 1039 nm at 77 K. The linewidth is as narrow as 46.3 meV, which is much narrower than those on planar InP substrates and wurtzite InP nanowires, suggesting high-crystal-quality, phase-purity, and size-uniformity of quantum dots.

Carrier Thermalization Dynamics in Single Zincblende and Wurtzite InP Nanowires

Using transient Rayleigh scattering (TRS) measurements, we obtain photoexcited carrier thermalization dynamics for both zincblende (ZB) and wurtzite (WZ) InP single nanowires (NW) with picosecond resolution. A phenomenological fitting model based on direct band-to-band transition theory is developed to extract the electron-hole-plasma density and temperature as a function of time from TRS measurements of single nanowires, which have complex valence band structures. We find that the thermalization dynamics of hot carriers depends strongly on material (GaAs NW vs InP NW) and less strongly on crystal structure (ZB vs WZ). The thermalization dynamics of ZB and WZ InP NWs are similar. But a comparison of the thermalization dynamics in ZB and WZ InP NWs with ZB GaAs NWs reveals more than an order of magnitude slower relaxation for the InP NWs. We interpret these results as reflecting their distinctive phonon band structures that lead to different hot phonon effects. Knowledge of hot carrier thermalization dynamics is an essential component for effective incorporation of nanowire materials into electronic devices.

Tunable absorption resonances in the ultraviolet for InP nanowire arrays.

The ability to tune the photon absorptance spectrum is an attracting way of tailoring the response of devices like photodetectors and solar cells. Here, we measure the reflectance spectra of InP substrates patterned with arrays of vertically standing InP nanowires. Using the reflectance spectra, we calculate and analyze the corresponding absorptance spectra of the nanowires. We show that we can tune absorption resonances for the nanowire arrays into the ultraviolet by decreasing the diameter of the nanowires. When we compare our measurements with electromagnetic modeling, we generally find good agreement. Interestingly, the remaining differences between modeled and measured spectra are attributed to a crystal-phase dependence in the refractive index of InP. Specifically, we find indication of significant differences in the refractive index between the modeled zinc-blende InP nanowires and the measured wurtzite InP nanowires in the ultraviolet. We believe that such crystal-phase dependent differences in the refractive index affect the possibility to excite optical resonances in the large wavelength range of 345 < λ < 390 nm. To support this claim, we investigated how resonances in nanostructures can be shifted in wavelength by geometrical tuning. We find that dispersion in the refractive index can dominate over geometrical tuning and stop the possibility for such shifting. Our results open the door for using crystal-phase engineering to optimize the absorption in InP nanowire-based solar cells and photodetectors.

Far field emission profile of pure wurtzite InP nanowires

We report on the far field emission profile of pure wurtzite InP nanowires in comparison to InP nanowires with predominantly zincblende crystal structure. The emission profile is measured on individual nanowires using Fourier microscopy. The most intense photoluminescence of wurtzite nanowires is collected at small angles with respect to the nanowire growth axis. In contrast, zincblende nanowires present a minimum of the collected light intensity in the direction of the nanowire growth. Results are explained by the orientation of electric dipoles responsible for the photoluminescence, which is different from wurtzite to zincblende. Wurtzite nanowires have dipoles oriented perpendicular to the nanowire growth direction, whereas zincblende nanowires have dipoles oriented along the nanowire axis. This interpretation is confirmed by both numerical simulations and polarization dependent photoluminescence spectroscopy. Knowledge of the dipole orientation in nanostructures is crucial for developing a wide range of photonic devices such as light-emitting diodes, photodetectors, and solar cells.