Coherent Growth of InP/InAsP/InP Nanowires on a Si (111) Surface by Molecular-Beam Epitaxy

Results obtained in a study of the growth of InP/InAsP/InP nanowires on the Si (111) surface are presented. Using a special procedure of substrate preparation immediately before the growth made it possible to obtain a nanowire coherency with the substrate of nearly 100%. A high-intensity emission from nanostructures of this kind was observed at a wavelength of ~1.3 μm at room temperature.     

Growth and characterization of InP nanowires with InAsP insertions

We report on the fabrication by Au-assisted molecular beam epitaxy of InP nanowires with embedded InAsP insertions. The growth temperature affects the nucleation on the nanowire lateral surface. It is therefore possible to grow the wires in two steps: to fabricate an axial heterostructure (at 420 degrees C), and then cover it by a shell (at 390 degrees C). The InAsP alloy composition could be varied between InAs0.35P0.65 and InAs0.5P0.5 by changing the As to P flux ratio. When a shell is present, the InAsP segments show strong room-temperature photoluminescence with a peak wavelength tunable from 1.2 to 1.55 mum by adjusting the As content. If the axial heterostructure has no shell, luminescence intensity is drastically reduced. Low-temperature microphotoluminescence performed on isolated single wires shows narrow peaks with a line width as small as 120 microeV.     

Growth of GaInAs/AlInAs heterostructure nanowires for long-wavelength photon emission

We investigated the growth of GaInAs/AlInAs heterostructure nanowires on InP(111)B and Si(111) substrates in a metalorganic vapor phase epitaxy reactor. Au colloids were used to deposit Au catalysts 20 and 40 nm in diameter on the substrate surfaces. We obtained vertical GaInAs and AlInAs nanowires on InP(111)B surfaces. The GaInAs nanowires capped with GaAs/AlInAs layers show room-temperature photoluminescence. The peak exhibits a blue-shift when the Ga content in the core GaInAs nanowire is increased. For the GaInAs/AlInAs heterostructure growth, it is possible to change the Ga content sharply but Al also exists in the GaInAs layer regions. We also found that the ratios of Ga and Al contents to In content tend to increase and the axial growth rate to decrease along the nanowire toward the top. We were also able to make vertical GaInAs nanowires on Si(111) surfaces after a short growth of GaP and InP.     

Native-oxide-based selective area growth of InP nanowires via metal-organic molecular beam epitaxy mediated by surface diffusion

The growth of InP nanowires on an InP(111) B substrate is reported. The substrate native oxide was not removed from the surface prior to growth. Nanowires were grown at 400 °C from gold catalysts in a selective area manner, without bulk growth. Unlike SiO(2)-based metal-organic molecular beam epitaxy selective area growth, the growth reported here is mediated by surface diffusion with a characteristic diffusion length of 4 μm, about an order of magnitude larger than values for diffusion on bare substrates. A pre-growth heating treatment at 450 °C was found to increase the yield of nanowire nucleation from the gold catalysts.     

Growth of InAs/InP core-shell nanowires with various pure crystal structures

We have studied the epitaxial growth of an InP shell on various pure InAs core nanowire crystal structures by metal-organic vapor phase epitaxy. The InP shell is grown on wurtzite (WZ), zinc-blende (ZB), and {111}- and {110}-type faceted ZB twin-plane superlattice (TSL) structures by tuning the InP shell growth parameters and controlling the shell thickness. The growth results, particularly on the WZ nanowires, show that homogeneous InP shell growth is promoted at relatively high temperatures (～500?°C), but that the InAs nanowires decompose under the applied conditions. In order to protect the InAs core nanowires from decomposition, a short protective InP segment is first grown axially at lower temperatures (420-460?°C), before commencing the radial growth at a higher temperature. Further studies revealed that the InP radial growth rate is significantly higher on the ZB and TSL nanowires compared to WZ counterparts, and shows a strong anisotropy in polar directions. As a result, thin shells were obtained during low temperature InP growth on ZB structures, while a higher temperature was used to obtain uniform thick shells. In addition, a schematic growth model is suggested to explain the basic processes occurring during the shell growth on the TSL crystal structures.     

Controlled growth of ternary alloy nanowires using metalorganic chemical vapor deposition

We report the growth and characterization of ternary AlxGa1- xAs nanowires by metalorganic chemical vapor deposition as a function of temperature and V/III ratio. Transmission electron microscopy and energy dispersive X-ray spectroscopy show that, at high temperatures and high V/III ratios, the nanowires form a core-shell structure with higher Al composition in the nanowire core than in the shell. We develop a growth model that takes into account diffusion of reactants and decomposition rates at the nanowire catalyst and stem to describe the compositional difference and the shell growth rate. Utilizing this model, we have successfully grown compositionally uniform Al0.16Ga0.84As nanowires. The ability to rationally tune the composition of ternary alloy nanowires broadens the application range of nanowires by enabling more complex nanowire heterostructures.     

Influence of nanowire density on the shape and optical properties of ternary InGaAs nanowires

We have synthesized ternary InGaAs nanowires on (111)B GaAs surfaces by metal-organic chemical vapor deposition. Au colloidal nanoparticles were employed to catalyze nanowire growth. We observed the strong influence of nanowire density on nanowire height, tapering, and base shape specific to the nanowires with high In composition. This dependency was attributed to the large difference of diffusion length on (111)B surfaces between In and Ga reaction species, with In being the more mobile species. Energy dispersive X-ray spectroscopy analysis together with high-resolution electron microscopy study of individual InGaAs nanowires shows large In/Ga compositional variation along the nanowire supporting the present diffusion model. Photoluminescence spectra exhibit a red shift with decreasing nanowire density due to the higher degree of In incorporation in more sparsely distributed InGaAs nanowires.     

<Emphasis Type="Italic">In situ</Emphasis> etching for total control over axial and radial nanowire growth

We report a method using in situ etching to decouple the axial from the radial nanowire growth pathway, independent of other growth parameters. Thereby a wide range of growth parameters can be explored to improve the nanowire properties without concern of tapering or excess structural defects formed during radial growth. We demonstrate the method using etching by HCl during InP nanowire growth. The improved crystal quality of etched nanowires is indicated by strongly enhanced photoluminescence as compared to reference nanowires obtained without etching.      

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

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

Diameter-dependent or independent: toward a mechanistic understanding of the vapor-liquid-solid si nanowire growth rate

Si nanowires have received continued increased attention because they keep the promise of monolithic integration of high-performance semiconductors with new functionality into existing silicon technology. Most Si nanowires are grown by vapor-liquid-solid mechanism, and despite many years of study, this growth mechanism remains under lively debate. For instance, contradictory results have been reported on the effect of diameter size on nanowire growth rate. Here, we developed a universal kinetic model of Si nanowire growth based on surface diffusion which takes into account adatom diffusion from the sidewall and substrate surface into the liquid droplet as well as the Gibbs-Thomson effect. Our analysis shows that the diameter independence for Si nanowires is affected by the interplay between the Gibbs-Thomson effect and the surface diffusion, whereas the diameter dependence is mainly influenced by the Gibbs-Thomson effect. The results based on the proposed model are in good agreement with experimental data.     

Remote p-doping of InAs nanowires

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

The effects of Au surface diffusion to formation of Au droplets/clusters and nanowire growth on GaAs substrate using VLS method

Using VLS method with the separated 220 nm thick Au catalyst circles/stripes configurations sputtered onto GaAs substrate surface, this paper investigated the effects of the Au droplets/clusters formation as well as the nanowires growth process inside and outside the Au circles/stripes configurations. The Au surface outward diffusion from the Au layer edge up to several tens of micrometers has strongly dominated. The effects of Au surface diffusion to formation of Au droplets/cluster and to the nanowires growth on GaAs semiconductor substrate in the region outside the Au layers have been shown. The mechanism of the droplets/clusters formation outside the Au layer could explained by the surface cluster diffusion, meanwhile the nanowires have grown simultaneously during the Au outward diffusion. The growth could explain by the diffusion of Ga and As atoms into the diffusing Au droplets/clusters via dissociative mechanism to form nanowire seeds inside for nanowires growth. The Au droplets/clusters formation and nanowires growth on GaAs substrate outside Au layer could be applied for making nanodevices blocks outside the Au layer. Unfortunately if this Au surface diffusion phenomenon is occurring on the GaAs semiconductor containing the Au stripes interconnections in micro/nanocircuits this could also cause the short-circuits phenomenon, even at thin Au layer.     

Catalytic role of gold nanoparticle in GaAs nanowire growth: a density functional theory study

The energetics of Ga, As, and GaAs species on the Au(111) surface (employed as a model for Au nanoparticles) is investigated by means of density functional calculations. Apart from formation of the compound Au(7)Ga(2), Ga is found to form a surface alloy with gold with comparable ΔH ~ -0.5 eV for both processes. Dissociative adsorption of As(2) is found to be exothermic by more than 2 eV on both clean Au(111) and AuGa surface alloys. The As-Ga species formed by reaction of As with the surface alloy is sufficiently stable to cover the surface of an Au particle in vacuo in contact with a GaAs substrate. The results of the calculations are interpreted in the context of Au-catalyzed growth of GaAs nanowires. We argue that arsenic is supplied to the growth zone of the nanowire mainly by impingement of molecules on the gold particle and identify a regime of temperatures and As(2) partial pressures suitable for Au-catalyzed nanowire growth in molecular beam epitaxy.     

Bidirectional growth of indium phosphide nanowires

We present a bidirectional growth mode of InP nanowires grown by selective-area metalorganic vapor-phase epitaxy (SA-MOVPE). We studied the effect of the supply ratio of DEZn ([DEZn]) on InP grown structure morphology and crystal structures during the SA-MOVPE. Two growth regimes were observed in the investigated range of the [DEZn] on an InP(111)B substrate. At low [DEZn], grown structures formed tripod structures featuring three nanowires branched toward the [111]A directions. At high [DEZn], we obtained hexagonal pillar-type structures vertically grown on the (111)B substrate. These results show that the growth direction changes from [111]A to [111]B as [DEZn] is increased. We propose a growth mechanism based on the correlation between the incident facet of rotational twins and the shapes of the grown structures. Our results bring us one step closer to controlling the direction of nanowires on a Si substrate that has a nonpolar nature. They can also be applied to the development of InP nanowire devices.     

Ultra-fast microwave-assisted hydrothermal synthesis of long vertically aligned ZnO nanowires for dye-sensitized solar cell application

Long vertically aligned ZnO nanowire arrays were synthesized using an ultra-fast microwave-assisted hydrothermal process. Using this method, we were able to grow ZnO nanowire arrays at an average growth rate as high as 200?nm?min(-1) for maximum microwave power level. This method does not suffer from the growth stoppage problem at long growth times that, according to our investigations, a normal microwave-assisted hydrothermal method suffers from. Longitudinal growth of the nanowire arrays was investigated as a function of microwave power level and growth time using cross-sectional FESEM images of the grown arrays. Effect of seed layer on the alignment of nanowires was also studied. X-ray diffraction analysis confirmed c-axis orientation and single-phase wurtzite structure of the nanowires. J-V curves of the fabricated ZnO nanowire-based mercurochrome-sensitized solar cells indicated that the short-circuit current density is increased with increasing the length of the nanowire array. According to the UV-vis spectra of the dyes detached from the cells, these increments were mainly attributed to the enlarged internal surface area and therefore dye loading enhancement in the lengthened nanowire arrays.     

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.     

Dynamics of strongly degenerate electron-hole plasmas and excitons in single InP nanowires

Low-temperature time-resolved photoluminescence spectroscopy is used to probe the dynamics of photoexcited carriers in single InP nanowires. At early times after pulsed excitation, the photoluminescence line shape displays a characteristic broadening, consistent with emission from a degenerate, high-density electron-hole plasma. As the electron-hole plasma cools and the carrier density decreases, the emission rapidly converges toward a relatively narrow band consistent with free exciton emission from the InP nanowire. The free excitons in these single InP nanowires exhibit recombination lifetimes closely approaching that measured in a high-quality epilayer, suggesting that in these InP nanowires, electrons and holes are relatively insensitive to surface states. This results in higher quantum efficiencies than other single-nanowire systems as well as significant state-filling and band gap renormalization, which is observed at high electron-hole carrier densities.     

The catalyst-free synthesis of large-area tungsten oxide nanowire arrays on ITO substrate and field emission properties

Tungsten oxide nanowire arrays have been grown on indium tin oxide coated glass substrate using tungsten trioxide powders as source by thermal evaporation approach without any catalysts. When the O₂/Ar flow rate ratio was 1/100, large-scale, high-density and uniformly distributed tungsten oxide nanowire arrays were obtained. The morphology and structure properties of the tungsten oxide nanowires were characterized by scanning electron microscopy, X-ray diffraction, and transmission electron microscopy. The influences of the oxygen concentration on the growth, density, shape and structure of the nanowires were investigated. The possible growth mechanism which governs the various types of nanowire arrays as the O₂/Ar flow rate ratios changed is also discussed. Field emission properties of tungsten oxide nanowire arrays were studied at a poor vacuum condition. The remarkable performance reveals that the tungsten oxide nanowire arrays can be served as a good candidate for commercial application as electron emitters.     

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

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

Direct atomic scale imaging of III-V nanowire surfaces

We have succeeded in direct atomic scale imaging of the exterior surfaces of III-V nanowires by scanning tunneling microscopy (STM). By using atomic hydrogen, we expose the crystalline surfaces of InAs nanowires with regular InP segments in vacuum while retaining the wire morphology. We show images with atomic resolution of the two major types of InAs wurtzite nanowire surface facets and scanning tunneling spectroscopy (STS) data. Ab initio calculations of the lowest energy surface structures and simulated STM images, agree very well with experiments.