Compound Semiconductor Nanowires Research Articles

Direct Evidence of Mg Incorporation Pathway in Vapor–Liquid–Solid Grown p-type Nonpolar GaN Nanowires

Doping of III–nitride based compound semiconductor nanowires is still a challenging issue to have control over the dopant distribution in precise locations of the nanowire optoelectronic devices. Knowledge of the dopant incorporation and its pathways in nanowires for such devices is limited by the growth methods. We report the direct evidence of incorporation pathway for Mg dopants in p-type nonpolar GaN nanowires grown via vapor–liquid–solid (VLS) method in a chemical vapor deposition technique for the first time. Mg incorporation is confirmed using X-ray photoelectron (XPS) and electron energy loss spectroscopic (EELS) measurements. Energy filtered transmission electron microscopic (EFTEM) studies are used for finding the Mg incorporation pathway in the GaN nanowire. Photoluminescence studies on Mg doped GaN nanowires along with the electrical characterization on heterojunction formed between nanowires and n-Si confirm the activation of Mg atoms as p-type dopants in nonpolar GaN nanowires.

Characterization and analysis of InAs/p–Si heterojunction nanowire-based solar cell

The growth of compound semiconductor nanowires on the silicon platform has opened many new perspectives in the area of electronics, optoelectronics and photovoltaics. We have grown a 1 × 1 mm2 array of InAs nanowires on p-type silicon for the fabrication of a solar cell. Even though the nanowires are spaced by a distance of 800 nm with a 3.3% filling volume, they absorb most of the incoming light resulting in an efficiency of 1.4%. Due to the unfavourable band alignment, carrier separation at the junction is poor. Photocurrent increases sharply at the surrounding edge with the silicon, where the nanowires do not absorb anymore. This is further proof of the enhanced absorption of semiconductors in nanowire form. This work brings further elements in the design of nanowire-based solar cells.

Compound Semiconductor Nanowires for Optoelectronic Device Applications

The excitement of nanowire research is due to the unique electronic and optical properties of these nanostructures. Both axial and radial heterostructure nanowires have been proposed as nano-building blocks for the next generation devices, which are expected to revolutionise our technological world. The unique properties stem from their large surface area-to-volume ratio, very high aspect ratio, and carrier and photon confinement in two dimensions. These nanowires are usually grown by the so-called vapor-liquid-solid mechanism, which relies on a metal nanoparticle to catalyze and seed the growth. An alternative technique to grow the nanowires is by selective area growth technique, where a dielectric mask is first patterned on the substrate prior to growth.In this talk, I will present an overview of compound semiconductor nanowire research activities at The Australian National University. The optical and structural properties of binary and ternary III-V nanowires including GaAs, InGaAs, InP and GaAsSb nanowires grown by metal-organic vapour phase epitaxy will be presented. Various issues such as tapering of the nanowires, compositional non-uniformity along nanowires, crystal structure, carrier lifetime and polarization effect will be discussed. I will also present our results of III-V nanowires grown on Si substrate which are of great interests for the integration of nano-optoelectronic devices on Si platforms. Our results of enhancing the quantum efficiency of nanowires by using plasmonics are promising to improve the performance of nanowire devices. Finally, the results from our nanowire lasers and solar cells will be presented.

Non-conformal decoration of semiconductor nanowire surfaces with boron nitride (BN) molecules for stability enhancement: degradation-resistant Zn3P2, ZnO and Mg2Si nanowires.

A simple and reliable strategy for stabilizing the surfaces of compound semiconductors was presented. The strategy involved decorating the surfaces of compound semiconductor nanowires non-conformally with small molecules of boron nitride (BN). More specifically, Zn3P2, ZnO and Mg2Si nanowires, highly useful in energy conversion device fabrication (e.g., photovoltaics and thermoelectrics), have been stabilized against air- and acid-assisted degradation by decorating their surfaces with small molecules of BN. It is believed that the decoration of the nanowire surfaces with BN molecules made the nanowire surfaces non-wettable to water and aqueous acid solutions, and thereby imparted them enhanced resistance against water- and acid-assisted degradation. This procedure did not alter the bandgap of the nanowires. Moreover, this procedure aided in retaining the electrical conduction between the nanowire interfaces when the nanowires are assembled into mats or pellets. This strategy solves one of the primary bottlenecks in the widespread use of nanowires in energy conversion device fabrication, namely their stability. It is believed that this strategy is applicable for stabilizing other compound semiconductor nanowires, including nitrides, sulfides, silicides and antimonides.

Formation mechanisms for the dominant kinks with different angles in InP nanowires.

The morphologies and microstructures of kinked InP nanowires (NWs) prepared by solid-source chemical vapor deposition method were examined using scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). Statistical analysis and structural characterization reveal that four different kinds of kinks are dominant in the grown InP NWs with a bending angle of approximately 70°, 90°, 110°, and 170°, respectively. The formation mechanisms of these kinks are discussed. Specifically, the existence of kinks with bending angles of approximately 70° and 110° are mainly attributed to the occurrence of stacking faults and nanotwins in the NWs, which could easily form by the glide of {111} planes, while approximately 90° kinks result from the local amorphorization of InP NWs. Also, approximately 170° kinks are mainly caused by small-angle boundaries, where the insertion of extra atomic planes could make the NWs slightly bent. In addition, multiple kinks with various angles are also observed. Importantly, all these results are beneficial to understand the formation mechanisms of kinks in compound semiconductor NWs, which could guide the design of nanostructured materials, morphologies, microstructures, and/or enhanced mechanical properties.

(Invited) Novel Luminescent Materials Based on Semiconductor Nanowires

We report novel luminescent materials based on group III-V compound semiconductor nanowires. Semiconductor nanowires are essentially one-dimensional rods with length of several microns and diameter below 100 nm. Hence, nanowires exhibit interesting quantum confinement and carrier transport properties. Nanowires are grown using metal seed particles by the vapor-liquid-solid (VLS) process in a molecular beam epitaxy or metalorganic chemical vapor deposition system. By varying the material deposition during growth, axial or radial nanowire heterostructures and p-n junctions may be formed for various device applications including light emitting diodes, lasers, and photodetectors. Due to the large surface area to volume ratio of a nanowire, lattice mismatch strain may be accommodated by elastic distortion of the nanowire without detrimental misfit dislocations, which gives a much greater ability to perform bandgap engineering in nanowires as compared to thin films. Hence, unique heterostructures are possible in nanowires that would be impossible in thin films, opening up new device applications and possibilities in condensed matter physics. We will report our recent work on the photoluminescence properties of InAsP/InP nanowires. InP nanowires were grown on <111> Si substrates by the Au-assisted vapor-liquid-solid process in a gas source molecular beam epitaxy system. InAsyP1-y segments were grown in the middle of the InP nanowires, creating a multiple quantum dot structure or superlattice. The quantum dot dimensions and composition were determined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive x-ray spectroscopy (EDX). Photoluminescence (PL) from the quantum dot structure could be tuned by the InAsyP1-y composition (y), or by the size of the quantum dot via the quantum confinement effect. Cathodoluminescence (CL) measurements confirmed localized emission from the quantum dots. To reduce detrimental surface states, the nanowires were passivated with an AlInP shell, which resulted in strong PL emission.The growth mechanism of the quantum dots were inferred from the InAsP and InP segment lengths as a function of nanowire diameter. Short InAsP segment lengths were found to grow by depletion of In from the Au particle as well as by direct impingement, while longer segments of InAsP and InP grew by diffusive transport of adatoms from the nanowire sidewalls. The present study offers a manner to engineer the lengths of InAsP quantum dots embedded in InP barriers to better control the PL or CL emission. A novel group III and V gas switching sequence is presented to improve compositional control of the QD.

Compositional disorder and its effect on the thermoelectric performance of Zn3P2 nanowire–copper nanoparticle composites

Recent studies indicated that nanowire format of materials is ideal for enhancing the thermoelectric performance of materials. Most of these studies were performed using individual nanowires as the test elements. It is not currently clear whether bulk assemblies of nanowires replicate this enhanced thermoelectric performance of individual nanowires. Therefore, it is imperative to understand whether enhanced thermoelectric performance exhibited by individual nanowires can be extended to bulk assemblies of nanowires. It is also imperative to know whether the addition of metal nanoparticle to semiconductor nanowires can be employed for enhancing their thermoelectric performance further. Specifically, it is important to understand the effect of microstructure and composition on the thermoelectric performance on bulk compound semiconductor nanowire–metal nanoparticle composites. In this study, bulk composites composed of mixtures of copper nanoparticles with either unfunctionalized or 1,4-benzenedithiol (BDT) functionalized Zn3P2 nanowires were fabricated and analyzed for their thermoelectric performance. The results indicated that use of BDT functionalized nanowires for the fabrication of composites leads to interface-engineered composites that have uniform composition all across their cross-section. The interface engineering allows for increasing their Seebeck coefficients and electrical conductivities, relative to the Zn3P2 nanowire pellets. In contrast, the use of unfunctionalized Zn3P2 nanowires for the fabrication of composite leads to the formation of composites that are non-uniform in composition across their cross-section. Ultimately, the composites were found to have Zn3P2 nanowires interspersed with metal alloy nanoparticles. Such non-uniform composites exhibited very high electrical conductivities, but slightly lower Seebeck coefficients, relative to Zn3P2 nanowire pellets. These composites were found to show a very high zT of 0.23 at 770 K, orders of magnitude higher than either interface-engineered composites or Zn3P2 nanowire pellets. The results indicate that microstructural composition of semiconductor nanowire–metal nanoparticle composites plays a major role in determining their thermoelectric performance, and such composites exhibit enhanced thermoelectric performance.

Perturbation of Au-assisted planar GaAs nanowire growth by p-type dopant impurities

III-V compound semiconductor nanowires (NWs), with their direct bandgaps and high mobilities, have been shown to be promising materials for many applications including solar cells, light emitting diodes, transistors, and lasers. Self-aligned, twin-plane-defect free, planar GaAs NWs can be grown by metalorganic chemical vapor deposition (MOCVD) through the Au-assisted vapor-liquid-solid mechanism. In this report, planar GaAs NW growth on GaAs (100) substrates is perturbed by introducing common p-type dopant impurities, zinc (Zn) or carbon (C), and characterized structurally and electrically. The implications of the results on planar NW growth and doping mechanism are discussed.

In Situ Real-Time TEM Reveals Growth, Transformation and Function in One-Dimensional Nanoscale Materials: From a Nanotechnology Perspective

This paper summarises recent developments in in situ TEM instrumentation and operation conditions. The focus of the discussion is on demonstrating how improved understanding of fundamental physical phenomena associated with nanowire or nanotube materials, revealed by following transformations in real time and high resolution, can assist the engineering of emerging electronic and optoelectronic devices. Special attention is given to Si, Ge, and compound semiconductor nanowires and carbon nanotubes (CNTs) as one of the most promising building blocks for devices inspired by nanotechnology.

Vapor–liquid–solid growth of serrated GaN nanowires: shape selection driven by kinetic frustration

Compound semiconducting nanowires are promising building blocks for several nanoelectronic devices yet the inability to reliably control their growth morphology is a major challenge. Here, we report the Au-catalyzed vapor–liquid–solid (VLS) growth of GaN nanowires with controlled growth direction, surface polarity and surface roughness. We develop a theoretical model that relates the growth form to the kinetic frustration induced by variations in the V(N)/III(Ga) ratio across the growing nanowire front. The model predictions are validated by the trends in the as-grown morphologies induced by systematic variations in the catalyst particle size and processing conditions. The principles of shape selection highlighted by our study pave the way for morphological control of technologically relevant compound semiconductor nanowires.

Large-scale synthesis and in situ functionalization of Zn3P2 and Zn4Sb3 nanowire powders

A simple method for the large-scale synthesis of gram quantities of compound semiconductor nanowires without the need for any external catalysts or templates is presented. This method is demonstrated using zinc phosphide (Zn3P2) and zinc antimonide (β-Zn4Sb3) nanowires as example systems. Large-scale synthesis of Zn3P2 and Zn4Sb3 nanowire powders was accomplished using a hot-walled chemical vapor deposition chamber by transporting phosphorus and antimony, respectively, via the vapor phase onto heated zinc foils. The zinc foils were rolled concentrically into coils to maximize the substrate surface area, and consequently, the nanowire yield. Using this method, 250 mg of Zn3P2 nanowires were obtained on 480 cm(2) of zinc foil in a span of 45 minutes. Furthermore, a process of exposing the synthesized nanowires to a vapor of organic functional molecules immediately after their synthesis and before their removal from the vacuum chamber was developed to obtain large quantities of surface functionalized nanowire powders. This in situ vapor-phase functionalization procedure passivated the nanowire surfaces without adversely affecting their morphology or dimensions. Our studies revealed that both 4-aminothiophenol and 3-propanedithiol functionalized Zn3P2 nanowires were stable over a 120 day duration without any agglomeration or degradation. This method of mass producing nanowires can also be extended to other binary semiconductors.

Growth of Polycrystalline Indium Phosphide Nanowires on Copper

ABSTRACTOur nation discards more than 50% of the total input energy as waste heat in various industrial processes such as metal refining, heat engines, and cooling. If we could harness a small fraction of the waste heat through the use of thermoelectric (TE) devices while satisfying the economic demands of cost versus performance, then TE power generation could bring substantial positive impacts to our society in the forms of reduced carbon emissions and additional energy. To increase the unit-less figure of merit, ZT, single-crystal semiconductor nanowires have been extensively studied as a building block for advanced TE devices because of their predicted large reduction in thermal conductivity and large increase in power factor. In contrast, polycrystalline bulk semiconductors also indicate their potential in improving overall efficiency of thermal-to-electric conversion despite their large number of grain boundaries. To further our goal of developing practical and economical TE devices, we designed a material platform that combines nanowires and polycrystalline semiconductors which are integrated on a metallic surface. We will assess the potential of polycrystalline group III-V compound semiconductor nanowires grown on low-cost copper sheets that have ideal electrical/thermal properties for TE devices. We chose indium phosphide (InP) from group III-V compound semiconductors because of its inherent characteristics of having low surface states density in comparison to others, which is expected to be important for polycrystalline nanowires that contain numerous grain boundaries. Using metal organic chemical vapor deposition (MOCVD) polycrystalline InP nanowires were grown in three-dimensional networks in which electrical charges and heat travel under the influence of their characteristic scattering mechanisms over a distance much longer than the mean length of the constituent nanowires. We studied the growth mechanisms of polycrystalline InP nanowires on copper surfaces by analyzing their chemical, optical, and structural properties in comparison to those of single-crystal InP nanowires formed on single-crystal surfaces. We also assessed the potential of polycrystalline InP nanowires on copper surfaces as a TE material by modeling based on finite-element analysis to obtain physical insights of three-dimensional networks made of polycrystalline InP nanowires. Our discussion will focus on the synthesis of polycrystalline InP nanowires on copper surfaces and structural properties of the nanowires analyzed by transmission electron microscopy that provides insight into possible nucleation mechanisms, growth mechanisms, and the nature of grain boundaries of the nanowires.

Manipulated Growth of GaAs Nanowires: Controllable Crystal Quality and Growth Orientations via a Supersaturation-Controlled Engineering Process

Controlling the crystal quality and growth orientation of high performance III–V compound semiconductor nanowires (NWs) in a large-scale synthesis is still challenging, which could restrict the implementation of nanowires for practical applications. Here we present a facile approach to control the crystal structure, defects, orientation, growth rate and density of GaAs NWs via a supersaturation-controlled engineering process by tailoring the chemical composition and dimension of starting AuxGay catalysts. For the high Ga supersaturation (catalyst diameter < 40 nm), NWs can be manipulated to grow unidirectionally along ⟨111⟩ with the pure zinc blende phase with a high growth rate, density and minimal amount of defect concentration utilizing the low-melting-point catalytic alloys (AuGa, Au2Ga, and Au7Ga3 with Ga atomic concentration > 30%), whereas for the low Ga supersaturation (catalyst diameter > 40 nm), NWs are grown inevitably with a mixed crystal orientation and high concentration of defects from high-melting-point alloys (Au7Ga2 with Ga atomic concentration < 30%). In addition to the complicated control of processing parameters, the ability to tune the composition of catalytic alloys by tailoring the starting Au film thickness demonstrates a versatile approach to control the crystal quality and orientation for the uniform NW growth.

Using seed particle composition to control structural and optical properties of GaN nanowires

The morphology, structure, and optical properties of gallium nitride (GaN) nanowires grown using metal–organic chemical vapor deposition (MOCVD) on r-plane sapphire using gold and nickel seed particles were investigated. We found that different seed particles result in different growth rates and densities of structural defects in MOCVD-grown GaN nanowires. Ni-seeded GaN nanowires grow faster than Au-seeded ones, and they do not contain the basal plane stacking faults that are observed in Au-seeded GaN nanowires. We propose that stacking fault formation is related to the supersaturation and surface energies in different types of seed particles. Room temperature photoluminescence studies revealed a blue-shifted peak in Au-seeded GaN nanowires compared to the GaN near-bandgap emission. The blue-shifted peak evolves as a function of the growth time and originates from the nanowire base, likely due to strain and Al diffusion from the substrate. Our results demonstrate that seed particle composition has a direct impact on the growth, structure, and optical properties of GaN nanowires and reveal some general requirements for seed particle selection for the growth of compound semiconductor nanowires.

(Invited) Passivation of III-V Nanowires for Optoelectronics

Surface passivation of III-V compound semiconductor nanowires is presented. InAs and GaAs nanowire cores were grown using gas source molecular beam epitaxy followed by a passivating shell of InAl(As,P). Improvements in electrical and optical (luminescence) properties of the nanowires were observed upon passivation due to removal of detrimental surface states. Passivation of InP nanowires by polysulfide solution is also demonstrated to improve luminescence.

Position-Controlled III–V Compound Semiconductor Nanowire Solar Cells by Selective-Area Metal–Organic Vapor Phase Epitaxy

We demonstrate position-controlled III-V semiconductor nanowires (NWs) by using selective-area metal-organic vapor phase epitaxy and their application to solar cells. Efficiency of 4.23% is achieved for InP core-shell NW solar cells. We form a 'flexible NW array' without a substrate, which has the advantage of saving natural resources over conventional thin film photovoltaic devices. Four junction NW solar cells with over 50% efficiency are proposed and discussed.

Tunable Catalytic Alloying Eliminates Stacking Faults in Compound Semiconductor Nanowires

Planar defects in compound (III-V and II-VI) semiconductor nanowires (NWs), such as twin and stacking faults, are universally formed during the catalytic NW growth, and they detrimentally act as static disorders against coherent electron transport and light emissions. Here we report a simple synthetic route for planar-defect free II-VI NWs by tunable alloying, i.e. Cd(1-x)Zn(x)Te NWs (0 ≤ x ≤ 1). It is discovered that the eutectic alloying of Cd and Zn in Au catalysts immediately alleviates interfacial instability during the catalytic growth by the surface energy minimization and forms homogeneous zinc blende crystals as opposed to unwanted zinc blende/wurtzite mixtures. As a direct consequence of the tunable alloying, we demonstrated that intrinsic energy band gap modulation in Cd(1-x)Zn(x)Te NWs can exploit the tunable spectral and temporal responses in light detection and emission in the full visible range.

Anisotropic photonic properties of III–V nanowires in the zinc-blende and wurtzite phase

Some critical aspects of the anisotropic absorption and emission properties of quasi one-dimensional structures are reviewed in the context of III-V compound semiconductor nanowires. The unique optical and electronic properties of III-V nanowires stem from the combination of dielectric effects due to their large aspect ratio, and their specific crystallographic structure which can differ significantly from the bulk case. The growth conditions leading to single-crystal nanowires with either zinc blende or wurtzite phase are first presented. Dipole selection rules for interband transitions in common III-V compounds are then summarized for the two different phases, and corroborated by ab initio Density Functional Theory calculations of the oscillator strength. The optical anisotropy is discussed considering both the effect of refractive index mismatch between the nanowire and its surroundings and the polarization of the emitting dipoles set by the nanowire crystallographic structure and orientation. Finite Difference Time Domain simulations are finally employed to illustrate the influence of the emitting dipole orientation and the nanowire diameter on the distribution of radiation in the far-field. The importance of the correlation between structural and optoelectronic properties is highlighted in view of potential applications in future nanowire photonics.

In(Ga)N Nanowire Heterostructures and Optoelectronic Device Applications

Significant developments have been made in III-nitride compound semiconductor nanowire heterostructures. This paper provides an overview on the recent progress of III-nitride nanowire heterostructures and their emerging device applications. The growth mechanisms of III-nitride nanowires are first described, followed by a review of the structural, electrical, and optical properties of In(Ga)N nanowires. The use of III-nitride nanowires to realize functional photonic devices, including light emitting diodes, lasers, solar cells, and sensors are also briefly described, with special attention paid to the emerging nanowire LEDs for applications in solid state lighting.

In(Ga)N Nanowire Heterostructures and Optoelectronic Device Applications

Significant developments have been made in III-nitride compound semiconductor nanowire heterostructures. This paper provides an overview on the recent progress of III-nitride nanowire heterostructures and their emerging device applications. The growth mechanisms of III-nitride nanowires are first described, followed by a review of the structural, electrical, and optical properties of In(Ga)N nanowires. The use of III-nitride nanowires to realize functional photonic devices, including light emitting diodes, lasers, solar cells, and sensors are also briefly described, with special attention paid to the emerging nanowire LEDs for applications in solid state lighting.