Fabrication and electrical study of large area free-standing membrane with embedded GaP NWs for flexible devices.

Flexible optoelectronic structures are required in a wide range of applications. Large scale modified silicone-embedded n-GaP nanowire arrays of a record 6 µm thin membranes were studied. A homogeneous silicone encapsulation was enabled by G-coating using a heavy-load centrifuge. The synthesized graft-copolymers of polydimethylsiloxane (PDMS) and polystyrene demonstrated two times lower adhesion to Si compared to standard PDMS, allowing 3 square inch area high quality silicone/nanowire membrane mechanical release, preserving the growth Si substrate for a further re-use after chemical cleaning. The 90% transparent single-walled carbon nanotubes electrical contacts to the embedded n-GaP nanowires demonstrated mechanical and electrical stability. The presented methods can be used for the fabrication of large scale flexible inorganic optoelectronic devices.

Ascending Si diffusion into growing GaN nanowires from the SiC/Si substrate: up to the solubility limit and beyond.

We report a novel mechanism that allows the incorporation of Si into GaN nanowires up to and beyond the solubility limit. This mechanism is documented during the growth on vicinal (misoriented) SiC/Si hybrid substrates having the step bunches. Nanowires that are grown at these locations become heavily Si doped. Such high Si concentrations were verified by secondary-ion mass spectrometry. Photoluminescence data also point to very high carrier concentrations. Moreover, Raman spectroscopy together with quantum chemical modelling shows the build up of Si into Ga sites and indicates even the possibility of the formation of a Ga(Si)N solid solution. The microscopic mechanism responsible for heavy doping and even alloying is diffusion driven by the mechano-chemical effect, which allows for the extremely efficient injection of Si atoms into the nanowires from the step bunches at the vicinal SiC/Si substrates.

Hydrogen passivation of the n-GaN nanowire/p-Si heterointerface.

The influence of hydrogen plasma treatment on the electrical and optical properties of vertical GaN nanowire (NW)/Si heterostructures synthesized via plasma assisted molecular beam epitaxy is studied. The effect of the treatment is thoroughly studied via variation of the passivation duration. Photoluminescence investigation demonstrates that the passivation affects the doping of the GaN NWs. The samples were processed as photodiodes with a top transparent electrode to obtain detailed information about the n-GaN NWs/p-Si heterointerface under illumination. The electron beam induced current measurements demonstrated the absence of potential barriers between the active parts of the diode and the contacts, indicating ohmic behavior of the latter. I-V characteristics obtained in the dark and under illumination show that hydrogen can effectively passivate the recombination centers at the GaN NWs/Si heterointerface. The optimum passivation duration, providing improved electrical properties, is found to be 10 min within the studied passivation regimes. It is demonstrated that longer treatment causes degradation of the electrical properties. The discovered phenomenon is discussed in detail.

Effects of the surface preparation and buffer layer on the morphology, electronic and optical properties of the GaN nanowires on Si.

The role of Si (111) substrate surface preparation and buffer layer composition in the growth, electronic and optical properties of the GaN nanowires (NWs) synthesized via plasma-assisted molecular beam epitaxy is studied. A comparison study of GaN NWs growth on the bare Si (111) substrate, silicon nitride interlayer, predeposited AlN and GaO x buffer layers, monolayer thick Ga wetting layer and GaN seeding layer prepared by the droplet epitaxy is performed. It is demonstrated that the homogeneity and the morphology of the NW arrays drastically depend on the chosen buffer layer and surface preparation technique. An effect of the buffer and seeding layers on the nucleation and desorption is also discussed. The lowest NWs surface density of 14 µm-2 is obtained on AlN buffer layer and the highest density exceeding the latter value by more than an order of magnitude corresponds to the growth on the 0.3 ML thick Ga wetting layer. It is shown, that the highest NWs mean elongation rate is obtained with AlN buffer layer, while the lowest elongation rate corresponds to the bare Si (111) surface and it is twice as lower as the first case. It is found, that use of AlN buffer layer corresponds to the most homogeneous NWs array with the smallest length dispersion while the least homogeneous array corresponds to the bare Si substrate. Vertically aligned GaN NWs array on the wide bandgap GaO x semiconductor buffer layer grown by plasma-enhanced chemical vapor deposition demonstrates its potential for electronic applications. Photoluminescence (PL) study of the synthesized samples is characterized by an intense optical response related to the excitons bound to neutral donors. The highest PL intensity is obtained in the sample with AlN buffer layer.

Electronic structure of (In,Mn)As quantum dots buried in GaAs investigated by soft-x-ray ARPES.

Electronic structure of a molecular beam epitaxy-grown system of (In,Mn)As quantum dots (QDs) buried in GaAs is explored with soft-x-ray angle-resolved photoelectron spectroscopy (ARPES) using photon energies around 1 keV. This technique, ideally suited for buried systems, extends the momentum-resolving capabilities of conventional ARPES with enhanced probing depth as well as elemental and chemical state specificity achieved with resonant photoexcitation. The experimental results resolve the dispersive energy bands of the GaAs substrate buried in ∼2 nm below the surface, and the impurity states (ISs) derived from the substitutional Mn atoms in the (In,Mn)As QDs and oxidized Mn atoms distributed near the surface. An energy shift of the Mn ISs in the QDs compared to (In,Mn)As DMS is attributed to the band offset and proximity effect at the interface with the surrounding GaAs. The absence of any ISs in the vicinity of the VBM relates the electron transport in (In,Mn)As QDs to the prototype (In,Mn)As diluted magnetic semiconductor. The SX-ARPES results are supported by measurements of the shallow core levels under variation of probing depth through photon energy. X-ray absorption measurements identify significant diffusion of interstitial Mn atoms out of the QDs towards the surface, and the role of magnetic circular dichroism is to block the ferromagnetic response of the (In,Mn)As QDs. Possible routes are drawn to tune the growth procedure aiming at practical applications of the (In,Mn)As based systems.

Photovoltaic properties of GaAsP core-shell nanowires on Si(001) substrate.

We report on the growth and electro-optical studies of photovoltaic properties of GaAsP nanowires. Low density GaAsP nanowires were grown by Au assisted MOVPE on Si(001) substrates using a two step procedure to form a radial p-n junction. The STEM analyses show that the nanowires have cubic structure with the alloy composition GaAs0.88P0.12 in the nanowire core and GaAs0.76P0.24 in the shell. The nanowire ensembles were processed in the form of sub-millimeter size mesas. The photovoltaic properties were characterized by optical beam induced current (OBIC) and electronic beam induced current (EBIC) maps. Both OBIC and EBIC maps show that the photovoltage is generated by the nanowires; however, a strong signal variation from wire to wire is observed. Only one out of six connected nanowires produce a measurable signal. These strong fluctuations can be tentatively explained by the variation of the resistance of the nanowire-to-substrate connection, which is highly sensitive to the quality of the Si-GaAsP interface. This study demonstrates the importance of the spatially resolved charge collection microscopy techniques for the diagnosis of failures in nanowire photovoltaic devices.

New mode of vapor-liquid-solid nanowire growth.

We report on the new mode of the vapor-liquid-solid nanowire growth with a droplet wetting the sidewalls and surrounding the nanowire rather than resting on its top. It is shown theoretically that such an unusual configuration happens when the growth is catalyzed by a lower surface energy metal. A model of a nonspherical elongated droplet shape in the wetting case is developed. Theoretical predictions are compared to the experimental data on the Ga-catalyzed growth of GaAs nanowires by molecular beam epitaxy. In particular, it is demonstrated that the experimentally observed droplet shape is indeed nonspherical. The new VLS mode has a major impact on the crystal structure of GaAs nanowires, helping to avoid the uncontrolled zinc blende-wurtzite polytylism under optimized growth conditions. Since the triple phase line nucleation is suppressed on surface energetic grounds, all nanowires acquire pure zinc blende phase along the entire length, as demonstrated by the structural studies of our GaAs nanowires.

Photoluminescence properties of InAs nanowires grown on GaAs and Si substrates.

We report the first photoluminescence (PL) characterization of InAs nanowires (NWs). The InAs NWs were grown on GaAs(111) B and Si(111) substrates using the Au-assisted molecular beam epitaxy (MBE) growth technique or metal-organic chemical vapor deposition (MOCVD). We compared the PL response of four samples grown under different conditions using MBE or MOCVD. High-resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) patterns were utilized to determine the crystal structure and growth directions of the NWs to relate PL features to NW structural parameters. We observed mainly three PL peaks which were below, near and above InAs bandgaps, respectively. Temperature and excitation intensity dependence PL measurements were also performed to help elucidate the origins of the PL peaks of NWs. Of particular interest was a band-edge emission peak that was blue-shifted due to quantization effects of the InAs NWs, as confirmed by our calculation.

Shape modification of III-V nanowires: the role of nucleation on sidewalls.

The effect of sidewall nucleation on nanowire morphology is studied theoretically. The model provides a semiquantitative description of nanowire radius as a function of its length and the distance from the surface. It is demonstrated that the wire shape critically depends on the diffusion flux of adatoms from the substrate and on the rate of direct impingement to the sidewalls. At high diffusion flux the wire shape is cylindrical. A decrease of diffusion from the surface leads to the onset of nucleation on the sidewalls resulting in the lateral extension and in the reduction of wire length. The wire shape changes from cylindrical to conical, because the supersaturation of adatoms driving the nucleation is higher at the wire foot than at the top. It is shown that the shape modification becomes pronounced at low growth temperatures. Theoretical results are used to model the experimentally observed shapes of GaAs and GaP wires, grown by Au-assisted molecular beam epitaxy at different temperatures.

Theoretical analysis of the vapor-liquid-solid mechanism of nanowire growth during molecular beam epitaxy.

A theoretical model of nanowire formation by the vapor-liquid-solid mechanism during molecular beam epitaxy and related growth techniques is presented. The model unifies the conventional adsorption-induced model, the diffusion-induced model, and the model of nucleation-mediated growth on the liquid-solid interface. The concentration of deposit atoms in the liquid alloy, the nanowire diameter, and all other characteristics of the growth process are treated dynamically as functions of the growth time. The model provides theoretical length-diameter dependences of nanowires and the dependence of the nanowire length on the technologically controlled growth conditions, such as the surface temperature and the deposition thickness. In particular, it is shown that the length-diameter curves of nanowires might convert from decreasing to increasing at a certain critical diameter and that the nanowires taper when their length becomes comparable with the adatom diffusion length on the sidewalls. The theoretical dependence of the nanowire morphology on its lateral size and length and on the surface temperature are compared to the available experimental data obtained recently for Si and nanowires.

Growth of Inclined GaAs Nanowires by Molecular Beam Epitaxy: Theory and Experiment.

The growth of inclined GaAs nanowires (NWs) during molecular beam epitaxy (MBE) on the rotating substrates is studied. The growth model provides explicitly the NW length as a function of radius, supersaturations, diffusion lengths and the tilt angle. Growth experiments are carried out on the GaAs(211)A and GaAs(111)B substrates. It is found that 20° inclined NWs are two times longer in average, which is explained by a larger impingement rate on their sidewalls. We find that the effective diffusion length at 550°C amounts to 12 nm for the surface adatoms and is more than 5,000 nm for the sidewall adatoms. Supersaturations of surface and sidewall adatoms are also estimated. The obtained results show the importance of sidewall adatoms in the MBE growth of NWs, neglected in a number of earlier studies.

Facet and in-plane crystallographic orientations of GaN nanowires grown on Si(111).

We have determined the in-plane orientation of GaN nanowires relative to the Si (111) substrate on which they were grown. We used x-ray diffraction pole figure measurements to evidence two types of crystallographic orientation, all the nanowires having [Formula: see text] lateral facets. The proportion of these two orientations was determined and shown to be influenced by the pre-deposition of Al(Ga)N intermediate layers. In the main orientation, the GaN basal [Formula: see text] directions are aligned with the [Formula: see text] directions. This orientation corresponds to an in-plane coincidence of GaN and Si lattices.

Temperature conditions for GaAs nanowire formation by Au-assisted molecular beam epitaxy.

Molecular beam epitaxial growth of GaAs nanowires using Au particles as a catalyst was investigated. Prior to the growth during annealing, Au alloyed with Ga coming from the GaAs substrate, and melted. Phase transitions of the resulting particles were observed in situ by reflection high-energy electron diffraction (RHEED). The temperature domain in which GaAs nanowire growth is possible was determined. The lower limit of this domain (320 °C) is close to the observed catalyst solidification temperature. Below this temperature, the catalyst is buried by GaAs growth. Above the higher limit (620 °C), the catalyst segregates on the surface with no significant nanowire formation. Inside this domain, the influence of growth temperature on the nanowire morphology and crystalline structure was investigated in detail by scanning electron microscopy and transmission electron microscopy. The correlation of the nanowire morphology with the RHEED patterns observed during the growth was established. Wurtzite GaAs was found to be the dominant crystal structure of the wires.