Gallium Phosphide Nanowires Research Articles

Highly-doped MBE-grown GaP nanowires: Synthesis, electrical study and modeling

Efficient doping of semiconductor nanowires remains a major challenge towards the commercialization of nanowire-based devices. In this work we investigate the growth regimes and electrical properties of MBE-grown p- and n-type gallium phosphide nanowires doped with Be and Si, respectively. Electrical conductivity of individual nanowires is quantitatively studied via atomic force microscopy supported with numerical analysis. Based on conductivity measurements, we provide growth strategies for achieving the doping level up to ND=5⋅1018 cm-3 and NA=2⋅1019 cm-3 for GaP:Si and GaP:Be nanowires respectively, which is high enough for technological applications.

Hybrid Photonic Structures: Gallium Phosphide Nanowires Decorated with Carbon Dots for Enhanced Broadband Emission

AbstractCarbon dots (CDs) are promising nanostructures in the field of photonics owing to the ease of fabrication, tunable and efficient emission. Gallium phosphide (GaP) nanowires are known for high surface area, optical density, waveguiding, resonant optical properties but lacking the luminescence due to the indirect bandgap. Here, hybrid photonic structures – GaP nanowires decorated with the CDs are fabricated and studied. Feasible drop‐casting deposition technique allows fabrication of dense vertical structures exhibiting efficient photoluminescence. Deposition of the CDs over the nanowires does not affect their luminescent properties demonstrating tolerance of the approach toward the surface aggregation. Tuning of the emission spectrum is obtained via variation of the excitation wavelength and CDs’ synthesis protocol. The structures emitting throughout the visible range are obtained. Analysis of the photoluminescence of an individual structure demonstrates the most intense and fast recombination processes at the ends of a nanowire. It is shown that the luminescence of the CDs’ covering a nanowire acting as a Fabry–Perot cavity is enhanced up to a factor of 3 governed by the Purcell effect. The obtained results unveil a path for fabrication of novel photonic devices via decoration of optically dense nanowires with CDs for enhanced and directed broadband emission.

Pulmonary toxicity and translocation of gallium phosphide nanowires to secondary organs following pulmonary exposure in mice

BackgroundIII-V semiconductor nanowires are envisioned as being integrated in optoelectronic devices in the near future. However, the perspective of mass production of these nanowires raises concern for human safety due to their asbestos- and carbon nanotube-like properties, including their high aspect ratio shape. Indeed, III-V nanowires have similar dimensions as Mitsui-7 multi-walled carbon nanotubes, which induce lung cancer by inhalation in rats. It is therefore urgent to investigate the toxicological effects following lung exposure to III-V nanowires prior to their use in industrial production, which entails risk of human exposure. Here, female C57BL/6J mice were exposed to 2, 6, and 18 µg (0.12, 0.35 and 1.1 mg/kg bw) of gallium phosphide (III-V) nanowires (99 nm diameter, 3.7 μm length) by intratracheal instillation and the toxicity was investigated 1, 3, 28 days and 3 months after exposure. Mitsui-7 multi-walled carbon nanotubes and carbon black Printex 90 nanoparticles were used as benchmark nanomaterials.ResultsGallium phosphide nanowires induced genotoxicity in bronchoalveolar lavage cells and acute inflammation with eosinophilia observable both in bronchoalveolar lavage and lung tissue (1 and 3 days post-exposure). The inflammatory response was comparable to the response following exposure to Mitsui-7 multi-walled carbon nanotubes at similar dose levels. The nanowires underwent partial dissolution in the lung resulting in thinner nanowires, with an estimated in vivo half-life of 3 months. Despite the partial dissolution, nanowires were detected in lung, liver, spleen, kidney, uterus and brain 3 months after exposure.ConclusionPulmonary exposure to gallium phosphide nanowires caused similar toxicological effects as the multi-walled carbon nanotube Mitsui-7.Graphical

Branched-gallium phosphide nanowires seeded by palladium nanoparticles

Palladium nanoparticles were produced by a chemical reagent-free and versatile method called spark ablation with control over particle size and density. These nanoparticles were used as catalytic seed particles for gallium phosphide nanowire growth by metalorganic vapour-phase epitaxy. Controlled growth of GaP nanowires using significantly small Pd nanoparticles between 10 and 40 nm diameter was achieved by varying several growth parameters. Low V/III ratios below 2.0 promote higher Ga incorporation into the Pd nanoparticles. Moderate growth temperatures under 600 °C avoid kinking and undesirable GaP surface growth. In addition, a second batch of palladium nanoparticles of concentration up to 1000 particles μm−2 was deposited onto the GaP nanowires. Subsequently, three-dimensional nanostructures evolved, with branches growing along the surface of the GaP nanowires. The GaP nanowires revealed a zinc blende structure with multiple twinning and a PdGa phase at the tip of the nanowires and branches.

Elastic Gallium Phosphide Nanowire Optical Waveguides-Versatile Subwavelength Platform for Integrated Photonics.

Emerging technologies for integrated optical circuits demand novel approaches and materials. This includes a search for nanoscale waveguides that should satisfy criteria of high optical density, small cross-section, technological feasibility and structural perfection. All these criteria are met with self-assembled gallium phosphide (GaP) epitaxial nanowires. In this work, the effects of the nanowire geometry on their waveguiding properties are studied both experimentally and numerically. Cut-off wavelength dependence on the nanowire diameter is analyzed to demonstrate the pathways for fabrication of low-loss and subwavelength cross-section waveguides for visible and near-infrared (IR) ranges. Probing the waveguides with a supercontinuum laser unveils the filtering properties of the nanowires due to their resonant action. The nanowires exhibit perfect elasticity allowing fabrication of curved waveguides. It is demonstrated that for the nanowire diameters exceeding the cut-off value, the bending does not sufficiently reduce the field confinement promoting applicability of the approach for the development of nanoscale waveguides with a preassigned geometry. Optical X-coupler made of two GaP nanowires allowing for spectral separation of the signal is fabricated. The results of this work open new ways for the utilization of GaP nanowires as elements of advanced photonic logic circuits and nanoscale interferometers.

Direct Observation of Liquid–Solid Two‐Phase Seed Particle‐Assisted Kinking in GaP Nanowire Growth

In the last decades, the metal‐assisted growth approach of semiconductor nanowires (NWs) has shown its potential in controlling crystal properties, such as crystal structure, composition, and morphology. Recently, literature reports have shown successful semiconductor NW growth with multiphase seed particles under growth conditions. Exploring alternative metal seeds and the mechanisms for growing semiconductor NWs is an exciting research field aiming to improve the control over the crystal growth process. Herein, the gallium phosphide (GaP) NW growth using Cu as seed particles inside an environmental transmission electron microscope is studied. In particular, the transformations of the Cu‐rich seed particles during the nucleation and growth of GaP NWs are observed. The supply of a relatively high amount of Ga atoms by the precursor mixture led to a solid Cu‐rich seed particle core covered by a liquid phase. Different growth dynamics within the two‐phase seed particle resulted in local competition in NW growth. As a result, the GaP NW kinked into another growth direction by forming a new interface at the NW growth front. The generated results enable insights into fundamental processes occurring in the seed particle during growth, creating leverage points for controlling the NW morphology.

Self-assembled photonic structure: a Ga optical antenna on GaP nanowires.

Semiconductor nanowires are the perfect platform for nanophotonic applications owing to their resonant, waveguiding optical properties and technological capabilities providing control over their crystalline and chemical compositions. The vapor-liquid-solid growth mechanism allows the formation of hybrid metal-dielectric nanostructures promoting sub-wavelength light manipulation. In this work, we explore both experimentally and numerically the plasmonic effects promoted by a gallium (Ga) nanoparticle optical antenna decorating the facet of gallium phosphide (GaP) nanowires. Raman, photoluminescence and near-field mapping techniques are used to study the effects. We demonstrate several phenomena including field enhancement, antenna effect and increase in internal reflection. We show that the observed effects have to be considered when nanowires with a plasmonic particle are used in nanophotonic circuits and discuss the ways for utilization of these effects for efficient coupling of light into nanowire waveguide and field tailoring. The results open up promising pathways for the development of both passive and active nanophotonic elements, light harvesting and sensorics.

Numerical Study of GaP Nanowires: Individual and Coupled Optical Waveguides and Resonant Phenomena.

The development of novel nanophotonic devices and circuits necessitates studies of optical phenomena in nanoscale structures. Catalyzed semiconductor nanowires are known for their unique properties including high crystallinity and silicon compatibility making them the perfect platform for optoelectronics and nanophotonics. In this work, we explore numerically optical properties of gallium phosphide nanowires governed by their dimensions and study waveguiding, coupling between the two wires and resonant field confinement to unveil nanoscale phenomena paving the way for the fabrication of the integrated optical circuits. Photonic coupling between the two adjacent nanowires is studied in detail to demonstrate good tolerance of the coupling to the distance between the two aligned wires providing losses not exceeding 30% for the gap of 100 nm. The dependence of this coupling is investigated with the wires placed nearby varying their relative position. It is found that due to the resonant properties of a nanowire acting as a Fabry-Perot cavity, two coupled wires represent an attractive system for control over the optical signal processing governed by the signal interference. We explore size-dependent plasmonic behaviors of the metallic Ga nanoparticle enabling GaP nanowire as an antenna-waveguide hybrid system. We demonstrate numerically that variation of the structure dimensions allows the nearfield tailoring. As such, we explore GaP NWs as a versatile platform for integrated photonic circuits.

Nanoscale Electric Field Probing in a Single Nanowire with Raman Spectroscopy and Elastic Strain.

In this work we investigate the Raman response of extremely strained gallium phosphide nanowires. We analyze new strain-induced spectral phenomena such as 2-fold and 3-fold phonon peak splitting which arise due to nontrivial internal electric field distribution coupled with inhomogeneous strain. We show that high bending strain acts as a probe allowing us to define the electric field distribution with deep subwavelength resolution using the corresponding changes of the Raman spectra. We investigate the nature of the localization with respect to nanowire diameter, excitation spot position, and light polarization, supporting the experiment with 3D numerical modeling. Based on our findings we propose a research tool allowing to precisely localize the electric field in a certain subwavelength region of the nanophotonic resonator.

Characterization of optical and nonlinear properties of individual GaP nanowires using optical tweezers

Semiconductor nanowires (NWs) offer multiple advantages for designing novel optoelectronic devices, such as small footprint, high quantum efficiency, high nonlinear susceptibility. Gallium phosphide (GaP) is one of the attractive materials owing to its low optical absorption and high nonlinear susceptibility. However NWs should be transferred to planar substrates for optical studies, which do not allow efficient signal outcoupling. We demonstrate efficient second harmonic generation in individual GaP nanowires trapped using optical tweezers. Such vertically arranged configuration of NW allows to both efficiently generate second harmonic and to probe linear optical response using broadband light source. Such experiment allows to examine interplay between harmonic generation efficiency and NW dimensions.

Vapor–liquid–solid growth of highly stoichiometric gallium phosphide nanowires on silicon: restoration of chemical balance, congruent sublimation and maximization of band-edge emission

Vapor–liquid–solid growth of highly stoichiometric gallium phosphide nanowires on silicon: restoration of chemical balance, congruent sublimation and maximization of band-edge emission

Single GaP nanowire nonlinear characterization with the aid of an optical trap.

Semiconductor nanowires exhibit numerous capabilities to advance the development of future optoelectronic devices. Among the III-V material family, gallium phosphide (GaP) is an attractive platform with low optical absorption and high nonlinear susceptibility, making it especially promising for nanophotonic applications. However, investigation of single nanostructures and their waveguiding properties remains challenging owing to typically planar experimental arrangements. Here we study the linear and nonlinear waveguiding optical properties of a single GaP nanowire in a special experimental layout, where an optically trapped structure is aligned along its major axis. We demonstrate efficient second harmonic generation in individual nanowires and unravel phase matching conditions, linking between linear guiding properties of the structure and its nonlinear tensorial susceptibility. The capability to pick up single nanowires, sort them with the aid of optomechanical manipulation and accurately position pre-tested structures opens a new avenue for the generation of optoelectronic origami-type devices.

Polarized Raman spectroscopy of GaP nanowires under 5% elastic strain

Optical porperties of highly-strained gallium phosphide nanowires were investigated via polarized Raman spectroscopy. 5% elastic strain was created in individual nanowire lying on nickel substrate by the means of atomic force microscopy. Micro-Raman mapping along the nanowire cross section in parallel and perpendicular polarization was carried out. Strain-induced effects on transverse optical mode position and shape were analyzed. The pronounced splitting of the mode due to high level of strain was observed. It was found that in parallel polarization the mode shape is sensitive to the position of the pumping spot which can be attributed to enhanced light-nanowire coupling effects.

Work function of polytypic gallium phosphide nanowires

In this work we investigate the work function of gallium phosphide nanowires by the means of frequency-modulated Kelvin probe force microscopy. Polytypic wurtzite/zinc blende nanowires were synthesized via self-catalytic molecular beam epitaxy. Mixed crystal phase was achieved by controlling the catalytic droplet contact angle and confirmed via transmission electron microscopy and Raman spectroscopy. Kelvin probe study showed a contrast between the work function of (110) zinc blende and (1120) wurtzite gallium phosphide: ϕZB = 4.28 eV and ϕWZ = 4.2 eV. Also, it was shown that sub-monolayer arsenic shell increases the work function up to 4.75 eV. Thus, two mechanisms for work function adjustment in the range 4.2-4.75 eV are shown. The results are important for optimization of Schottky barriers in nanowire-based devices.

Tailoring Morphology and Vertical Yield of Self-Catalyzed GaP Nanowires on Template-Free Si Substrates.

Tailorable synthesis of III-V semiconductor heterostructures in nanowires (NWs) enables new approaches with respect to designing photonic and electronic devices at the nanoscale. We present a comprehensive study of highly controllable self-catalyzed growth of gallium phosphide (GaP) NWs on template-free silicon (111) substrates by molecular beam epitaxy. We report the approach to form the silicon oxide layer, which reproducibly provides a high yield of vertical GaP NWs and control over the NW surface density without a pre-patterned growth mask. Above that, we present the strategy for controlling both GaP NW length and diameter independently in single- or two-staged self-catalyzed growth. The proposed approach can be extended to other III-V NWs.

Effect of crystal structure on the Young’s modulus of GaP nanowires

Young’s modulus of tapered mixed composition (zinc-blende with a high density of twins and wurtzite with a high density of stacking faults) gallium phosphide (GaP) nanowires (NWs) was investigated by atomic force microscopy. Experimental measurements were performed by obtaining bending profiles of as-grown inclined GaP NWs deformed by applying a constant force to a series of NW surface locations at various distances from the NW/substrate interface. Numerical modeling of experimental data on bending profiles was done by applying Euler–Bernoulli beam theory. Measurements of the nano-local stiffness at different distances from the NW/substrate interface revealed NWs with a non-ideal mechanical fixation at the NW/substrate interface. Analysis of the NWs with ideally fixed base resulted in experimentally measured Young’s modulus of 155 ± 20 GPa for ZB NWs, and 157 ± 20 GPa for WZ NWs, respectively, which are in consistence with a theoretically predicted bulk value of 167 GPa. Thus, impacts of the crystal structure (WZ/ZB) and crystal defects on Young’s modulus of GaP NWs were found to be negligible.

Fluorescence Signal Enhancement in Antibody Microarrays Using Lightguiding Nanowires.

Fluorescence-based detection assays play an essential role in the life sciences and medicine. To offer better detection sensitivity and lower limits of detection (LOD), there is a growing need for novel platforms with an improved readout capacity. In this context, substrates containing semiconductor nanowires may offer significant advantages, due to their proven light-emission enhancing, waveguiding properties, and increased surface area. To demonstrate and evaluate the potential of such nanowires in the context of diagnostic assays, we have in this work adopted a well-established single-chain fragment antibody-based assay, based on a protocol previously designed for biomarker detection using planar microarrays, to freestanding, SiO2-coated gallium phosphide nanowires. The assay was used for the detection of protein biomarkers in highly complex human serum at high dilution. The signal quality was quantified and compared with results obtained on conventional flat silicon and plastic substrates used in the established microarray applications. Our results show that using the nanowire-sensor platform in combination with conventional readout methods, improves the signal intensity, contrast, and signal-to-noise by more than one order of magnitude compared to flat surfaces. The results confirm the potential of lightguiding nanowires for signal enhancement and their capacity to improve the LOD of standard diagnostic assays.

Genetic Algorithm Optimization of Core-Shell Nanowire Betavoltaic Generators

Numerical optimization has been used to determine the optimum junction design for core–shell nanowires used in betavoltaic generators. A genetic algorithm has been used to calculate the relative thickness, height, and doping of each segment within silicon, gallium arsenide, and gallium phosphide nanowires. Using the simulated spectra and energy deposition of nickel-63, nickel citrate, tritium, and tritiated butyl, devices with power output and overall efficiency up to 8 µW.cm−2 and 12%, respectively, have been predicted. Compared to previously investigated axial nanowires, the core–shell structures simulated here have realized drastic improvements by reducing surface recombination for longer nanowires. In addition, core–shell nanowires are shown to be capable of nearly matching the ideal performance predicted for this device structure. A new approach for calculating the practical upper limit of betavoltaic performance is presented and additional methods for improvement are discussed.

Perovskite-Gallium Phosphide Platform for Reconfigurable Visible-Light Nanophotonic Chip.

Reduction of the wavelength in on-chip light circuitry is critically important not only for the sake of keeping up with Moore's law for photonics but also for reaching toward the spectral ranges of operation of emerging materials, such as atomically thin semiconductors, vacancy-based single-photon emitters, and quantum dots. This requires efficient and tunable light sources as well as compatible waveguide networks. For the first challenge, halide perovskites are prospective materials that enable cost-efficient fabrication of micro- and nanolasers. On the other hand, III-V semiconductor nanowires are optimal for guiding of visible light as they exhibit a high refractive index as well as excellent shape and crystalline quality beneficial for strong light confinement and long-range waveguiding. Here, we develop an integrated platform for visible light that comprises gallium phosphide (GaP) nanowires directly embedded into compact CsPbBr3-based light sources. In our devices, perovskite microcrystals support stable room-temperature lasing and broadband chemical tuning of the emission wavelength in the range of 530-680 nm, whereas GaP nanowaveguides support efficient outcoupling of light, its subwavelength (<200 nm) confinement, and long-range guiding over distances more than 20 μm. As a highlight of our approach, we demonstrate sequential transfer and conversion of light using an intermediate perovskite nanoparticle in a chain of GaP nanowaveguides.

Optical Absorption Exhibits Pseudo-Direct Band Gap of Wurtzite Gallium Phosphide

Definitive evidence for the direct band gap predicted for Wurtzite Gallium Phosphide (WZ GaP) nanowires has remained elusive due to the lack of strong band-to-band luminescence in these materials. In order to circumvent this problem, we successfully obtained large volume WZ GaP structures grown by nanoparticle-crawling assisted Vapor-Liquid-Solid method. With these structures, we were able to observe bound exciton recombination at 2.14 eV with FHWM of approximately 1 meV. In addition, we have measured the optical absorption edges using photoluminescence excitation spectroscopy. Our results show a 10 K band gap at 2.19 eV and indicate a weak oscillator strength for the lowest energy band-to-band absorption edge, which is a characteristic feature of a pseudo-direct band gap semiconductor. Furthermore, the valence band splitting energies are estimated as 110 meV and 30 meV for the three highest bands. Electronic band structure calculations using the HSE06 hybrid density functional agree qualitatively with the valence band splitting energies.