Peculiarities of the MBE growth of nanowhiskers on GaAs(100) substrates

We have studied the formation of nanowhiskers (NWs) by molecular beam epitaxy (MBE) on GaAs(100) substrates. The MBE growth of NWs exhibits two stages (initial and developed) and leads to the formation of NWs with surface morphology of two types (nucleation and intergrowth). The stage of developed growth is characterized by the predominant formation of intergrown NWs oriented in the 〈111〉B direction, having (110) habit (including the NW tip surface) and hexagonal cross sections with a transverse size within 50–300 nm. It was found that the transverse size of a hexagonal NW may significantly differ from that of an Au-GaAs melt droplet. The ratio of longitudinal and transverse dimensions of intergrown NWs can be on the order of 150 and above. When the transverse size of NWs exceeds a certain value (about 200 nm), the crystal length exhibits a slight decrease. The existence of two types of morphology is indicative of inhomogeneous character of the NW growth on a GaAs(100) surface, which depends on the catalyst droplet size, effective thickness of the deposited GaAs layer, and the growth temperature.     

Self-directed growth of AlGaAs core-shell nanowires for visible light applications

Al0.37Ga0.63As nanowires (NWs) were grown in a molecular beam epitaxy system on GaAs(111)B substrates. Micro-photoluminescence measurements and energy dispersive X-ray spectroscopy indicated a core--shell structure and Al composition gradient along the NW axis, producing a potential minimum for carrier confinement. The core--shell structure formed during growth as a consequence of the different Al and Ga adatom diffusion lengths.     

Multiple quantum well AlGaAs nanowires

This letter reports on the growth, structure, and luminescent properties of individual multiple quantum well (MQW) AlGaAs nanowires (NWs). The composition modulations (MQWs) are obtained by alternating the elemental flux of Al and Ga during the molecular beam epitaxy growth of the AlGaAs wire on GaAs (111)B substrates. Transmission electron microscopy and energy dispersive X-ray spectroscopy performed on individual NWs are consistent with a configuration composed of conical segments stacked along the NW axis. Microphotoluminescence measurements and confocal microscopy showed enhanced light emission from the MQW NWs as compared to nonsegmented NWs due to carrier confinement and sidewall passivation.     

In(x)Ga(₁-x)As nanowires on silicon: one-dimensional heterogeneous epitaxy, bandgap engineering, and photovoltaics

We report on the one-dimensional (1D) heteroepitaxial growth of In(x)Ga(1-x)As (x = 0.2-1) nanowires (NWs) on silicon (Si) substrates over almost the entire composition range using metalorganic chemical vapor deposition (MOCVD) without catalysts or masks. The epitaxial growth takes place spontaneously producing uniform, nontapered, high aspect ratio NW arrays with a density exceeding 1 × 10(8)/cm(2). NW diameter (～30-250 nm) is inversely proportional to the lattice mismatch between In(x)Ga(1-x)As and Si (～4-11%), and can be further tuned by MOCVD growth condition. Remarkably, no dislocations have been found in all composition In(x)Ga(1-x)As NWs, even though massive stacking faults and twin planes are present. Indium rich NWs show more zinc-blende and Ga-rich NWs exhibit dominantly wurtzite polytype, as confirmed by scanning transmission electron microscopy (STEM) and photoluminescence spectra. Solar cells fabricated using an n-type In(0.3)Ga(0.7)As NW array on a p-type Si(111) substrate with a ～ 2.2% area coverage, operates at an open circuit voltage, V(oc), and a short circuit current density, J(sc), of 0.37 V and 12.9 mA/cm(2), respectively. This work represents the first systematic report on direct 1D heteroepitaxy of ternary In(x)Ga(1-x)As NWs on silicon substrate in a wide composition/bandgap range that can be used for wafer-scale monolithic heterogeneous integration for high performance photovoltaics.     

Strain accommodation in Ga-assisted GaAs nanowires grown on silicon (111)

We study the mechanism of lattice parameter accommodation and the structure of GaAs nanowires (NWs) grown on Si(111) substrates using the Ga-assisted growth mode in molecular beam epitaxy. These nanowires grow preferentially in the zincblende structure, but contain inclusions of wurtzite at the base. By means of grazing incidence x-ray diffraction and high-resolution transmission electron microscopy of the NW-substrate interface, we show that the lattice mismatch between the NW and the substrate is released immediately after the beginning of NW growth through the inclusion of misfit dislocations, and no pseudomorphic growth is obtained for NW diameters down to 10 nm. NWs with a diameter above 100 nm exhibit a rough interface towards the substrate, preventing complete plastic relaxation. Consequently, these NWs exhibit a residual compressive strain at their bottom. In contrast, NWs with a diameter of 50 nm and below are completely relaxed because the interface is smooth.     

Rate-limiting mechanisms in high-temperature growth of catalyst-free InAs nanowires with large thermal stability

We identify the entire growth parameter space and rate-limiting mechanisms in non-catalytic InAs nanowires (NWs) grown by molecular beam epitaxy. Surprisingly huge growth temperature ranges are found with maximum temperatures close to ~600°C upon dramatic increase of V/III ratio, exceeding by far the typical growth temperature range for catalyst-assisted InAs NWs. Based on quantitative in situ line-of-sight quadrupole mass spectrometry, we determine the rate-limiting factors in high-temperature InAs NW growth by directly monitoring the critical desorption and thermal decomposition processes of InAs NWs. Both under dynamic (growth) and static (no growth, ultra-high vacuum) conditions the (111)-oriented InAs NWs evidence excellent thermal stability at elevated temperatures even under negligible supersaturation. The rate-limiting factor for InAs NW growth is hence dominated by In desorption from the substrate surface. Closer investigation of the group-III and group-V flux dependences on growth rate reveals two apparent growth regimes, an As-rich and an In-rich regime defined by the effective As/In flux ratio, and maximum achievable growth rates of > 6 μm h(-1). The unique features of high-T growth and excellent thermal stability provide the opportunity for operation of InAs-based NW materials under caustic environment and further allow access to temperature regimes suitable for alloying non-catalytic InAs NWs with GaAs.     

A Mask Based on a Si Epitaxial Layer for the Self-Catalytic Nanowire Growth on GaAs(111)B and GaAs(100) Substrates

Technical Physics Letters - GaAs nanowires (NWs) were generated on the surface of GaAs(111)B and GaAs(100) substrates from molecular fluxes by the self-catalytic growth method. A mask for NW growth...     

Physical consequences of the equivalence of conditions for the steady-state growth of nanowires and the nucleation on triple phase line

A new theoretical model describing the steady-state growth and crystalline structure of semiconductor nanowires (NWs) is proposed and its physical consequences are considered. It is demonstrated that the Nebol’sin-Shchetinin condition (nonwetting of the NW side surface by the liquid drop) necessary for the steady-state growth of NWs according to the vapor-liquid-solid (VLS) mechanism is equivalent to the Glas condition of nucleation on the triple phase line for the monocentric NW growth. An energy criterion for the steady-state growth of NWs is formulated in the general case of faceted NW side surface. Effective surface energies are found that determine the activation barrier for nucleation at the NW top. Based on the proposed model, the issue of determining the III–V semiconductor NW crystal structure (cubic zinc blende type versus hexagonal wurtzite type) is considered. In particular, it is shown that a decrease in the surface energy of a catalyst must lead to the predominant formation of a cubic phase, which is confirmed by experimental data on the growth of GaAs nanowires according to the VLS mechanism with Au and Ga catalysts.     

Growth of SiO(x) nanowires by laser ablation

Amorphous SiO(x) nanowires (NWs) were synthesized using laser ablation of silicon-containing targets. The influence of various parameters such as target composition, substrate type, substrate temperature and carrier gas on the growth process was studied. The NWs were characterized using high resolution scanning and transmission electron microscopes (HRSEM and HRTEM) with their attachments: electron dispersive spectroscopy (EDS) and energy electron loss spectroscopy (EELS). A metal catalyst was found essential for the NW growth. A growth temperature higher than 1000?°C was necessary for the NW formation using an Ar-based carrier gas at 500?Torr. The use of Ar-5%H(2) instead of pure Ar resulted in a higher yield and longer NWs. Application of a diffusion barrier on top of the Si substrate guaranteed the availability of metal catalyst droplets on the surface, essential for the NW growth. Ni was found to be a better catalyst than Au in terms of the NW yield and length. Two alternative sequences for the evolution of the amorphous SiO(x) NWs were considered: (a)?the formation of Si NWs first and their complete oxidation afterwards, which seems to be doubtful, (b)?the direct formation of SiO(x) NWs, which is more likely to occur. The direct formation mechanism was proposed to advance in three stages: preferential adsorption of SiO(x) clusters on the catalyst surface first, a successive surface diffusion to the catalyst droplet lower hemisphere, and finally the formation and growth of the NW between the catalyst and the substrate.     

Zinc blende GaAsSb nanowires grown by molecular beam epitaxy

We report the growth of GaAsSb nanowires (NWs) on GaAs(111)B substrates by Au-assisted molecular beam epitaxy. The structural characteristics of the GaAsSb NWs have been investigated in detail. Their Sb mole fraction was found to be about?25%. Their crystal structure was found to be pure zinc blende (ZB), in contrast to the wurtzite structure observed in GaAs NWs grown under similar conditions. The ZB GaAsSb NWs exhibit rotational twins around their [111]B growth axis, with twin-free segments as long as 500?nm. The total volumes of GaAsSb segments with twinned and un-twinned orientations, respectively, were found to be equal by x-ray diffraction analysis of NW ensembles.     

III-V nanowire growth mechanism: V/III ratio and temperature effects

We have studied the dependence of Au-assisted InAs nanowire (NW) growth on InAs(111)B substrates as a function of substrate temperature and input V/III precursor ratio using organometallic vapor-phase epitaxy. Temperature-dependent growth was observed within certain temperature windows that are highly dependent on input V/III ratios. This dependence was found to be a direct consequence of the drop in NW nucleation and growth rate with increasing V/III ratio at a constant growth temperature due to depletion of indium at the NW growth sites. The growth rate was found to be determined by the local V/III ratio, which is dependent on the input precursor flow rates, growth temperature, and substrate decomposition. These studies advance understanding of the key processes involved in III-V NW growth, support the general validity of the vapor-liquid-solid growth mechanism for III-V NWs, and improve rational control over their growth morphology.     

Contactless monitoring of the diameter-dependent conductivity of GaAs nanowires

Contactless monitoring with photoelectron microspectroscopy of the surface potential along individual nanostructures, created by the X-ray nanoprobe, opens exciting possibilities to examine quantitatively size- and surface-chemistry-effects on the electrical transport of semiconductor nanowires (NWs). Implementing this novel approach-which combines surface chemical microanalysis with conductivity measurements-we explored the dependence of the electrical properties of undoped GaAs NWs on the NW width, temperature and surface chemistry. By following the evolution of the Ga 3d and As 3d core level spectra, we measured the position-dependent surface potential along the GaAs NWs as a function of NW diameter, decreasing from 120 to ?20 nm, and correlated the observed decrease of the conductivity with the monotonic reduction in the NW diameter from 120 to ~20 nm. Exposure of the GaAs NWs to oxygen ambient leads to a decrease in their conductivity by up to a factor of 10, attributed to the significant decrease in the carrier density associated with the formation of an oxide shell. Open image in new window     

Control of the crystal structure of InAs nanowires by tuning contributions of adatom diffusion

The dependence of crystal structure on contributions of adatom diffusion (ADD) and precursor direct impingement (DIM) was investigated for vapor-liquid-solid growth of InAs nanowires (NWs). The ADD contributions from the sidewalls and substrate surface can be changed by using GaAs NWs of different length as the basis for growing InAs NWs. We found that pure zinc-blende structure is favored when DIM contributions dominate. Moreover, without changing the NW diameter or growth parameters (such as temperature or V/III ratio), a transition from zinc-blende to wurtzite structure can be realized by increasing the ADD contributions. A nucleation model is proposed in which ADD and DIM contributions play different roles in determining the location and phase of the nucleus.     

Performance and electron transport properties of TiO(2) nanocomposite dye-sensitized solar cells

TiO(2) nanowire (NW)/nanoparticle (NP) composite films have been fabricated by hybridizing various ratios of hydrothermal anatase NWs and TiO(2) NPs for use in dye-sensitized solar cells (DSSCs). Scanning electron microscopy (SEM) images reveal that uniform NW/NP composite films were formed on fluorine-doped tin oxide?(FTO) substrates by the dip-coating method. The NWs are randomly but neither vertically nor horizontally oriented within the composite film. The TiO(2) NP DSSC possesses superior performance to those of the NW/NP composite and the pure NW cells, and the efficiency of the NW/NP composite DSSC increases on increasing the NP/NW ratio in the composite anode. All types of DSSC possess the same dependence of performance on the anode thickness that the efficiency increases with the anode thickness to a maximum value, then it decreases when the anode is thickened further. Electrochemical impedance spectroscopy analyses reveal that the NP DSSCs possess larger effective electron diffusion coefficients (D(eff)) in the photoanodes and smaller diffusion resistances of I(3)(-) in electrolytes compared to those in the NW/NP and the NW DSSCs. D(eff) decreases when NWs are added into the photoanode. These results suggest that the vertical feature of the NWs within the anodes is crucial for achieving a high electron transport rate in the anode.     

Different shape of GaAs quantum structures under various growth conditions

We report the influences of growth parameters on the characteristics of GaAs quantum rings (QRs) and quantum dots (QDs) formed on AlGaAs/GaAs by the droplet epitaxy (DE) method. After forming Ga droplets on the AlGaAs/GaAs surface, varying amounts of arsenic (As) flux were introduced to fabricate the GaAs quantum structures. By decreasing the As flux from 8 × 10^− 5 to 3 × 10^− 5 Torr, the shape of the GaAs quantum structures was changed from QDs to elongated QRs. With further decreasing As flux, the shape of the elongated QRs became symmetric. The formation characteristics of the GaAs QRs from the QDs with the amount of As flux were discussed in terms of migration behaviors of the gallium (Ga) atoms on the GaAs(001)-c(4 × 4) surface. The effects of the amount of Ga supply and the growth temperature for the deposition of Ga droplets on the formation of the GaAs quantum structures were also considered.     

Growth and characterization of GaAs nanowires on carbon nanotube composite films: toward flexible nanodevices

Poly(ethylene imine) functionalized carbon nanotube thin films, prepared using the vacuum filtration method, were decorated with Au nanoparticles by in situ reduction of HAuCl4 under mild conditions. These Au nanoparticles were subsequently employed for the growth of GaAs nanowires (NWs) by the vapor-liquid-solid process in a gas source molecular beam epitaxy system. The process resulted in the dense growth of GaAs NWs across the entire surface of the single-walled nanotube (SWNT) films. The NWs, which were orientated in a variety of angles with respect to the SWNT films, ranged in diameter between 20 to 200 nm, with heights up to 2.5 microm. Transmission electron microscopy analysis of the NW-SWNT interface indicated that NW growth was initiated upon the surface of the nanotube composite films. Photoluminescence characterization of a single NW specimen showed high optical quality. Rectifying asymmetric current-voltage behavior was observed from contacted NW ensembles and attributed to the core-shell pn-junction within the NWs. Potential applications of such novel hybrid architectures include flexible solar cells, displays, and sensors.     

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.     

Composition and local strain mapping in Au-catalyzed axial Si/Ge nanowires

For most applications, heterostructures in nanowires (NWs) with lattice mismatched materials are required and promise certain advantages thanks to lateral strain relaxation. The formation of Si/Ge axial heterojunctions is a challenging task to obtain straight, defect free and extended NWs. And the control of the interface will determine the future device properties. This paper reports the growth and analysis of NWs consisting of an axial Si/Ge heterostructure grown by a vapor-liquid-solid process. The composition gradient and the strain distribution at the heterointerface were measured by advanced quantitative electron microscopy methods with a resolution at the nanometer scale. The transition from pure Ge to pure Si shows an exponential slope with a transition width of 21?nm for a NW diameter of 31?nm. Although diffuse, the heterointerface makes possible strain engineering along the axis of the NW. The interface is dislocation-free and a tensile out-of-plane strain is noticeable in the Ge section of the NW, indicating a lattice accommodation. Experimental results were compared to finite element calculations.     

Growth of high-density titanium silicide nanowires in a single direction on a silicon surface

Understanding the growth mechanisms of nanowires is essential for their successful implementation in advanced devices applications. In situ ultrahigh-vacuum transmission electron microscopy has been applied to elucidate the interaction mechanisms of titanium disilicide nanowires (TiSi2 NWs) on Si(111) substrate. Two phenomena were observed: merging of the two NWs in the same direction, and collapse of one NW on a competing NW in a different direction when they meet at the ends. On the other hand, as one NW encounters the midsection of the other NW in a different direction, it recedes in favor of bulging of the other NW at the midsection. Since crystallographically the nanowires are favored to grow on Si(110) only in the [1 -1 0] direction, this crucial information has been fruitfully exploited to focus on the growth of a high density of long and high-aspect-ratio Ti silicide NWs parallel to the surface on Si(110) in a single direction. The achievement in growth of high-density NWs in a single direction represents a significant advance in realizing the vast potential for applications of silicide NWs in nanoelectronics devices.     

Growth mode transitions induced by hydrogen-assisted MBE on vicinal GaAs(110)

The homoepitaxial growth of GaAs by hydrogen-assisted molecular beam epitaxy (H-MBE) on (110) substrates vicinal to (111)A has been studied by reflection high energy electron diffraction (RHEED) and atomic force microscopy (AFM) for different kinetic regimes. When the GaAs growth rate is limited by the kinetics of adatom incorporation to steps, the presence of chemisorbed H on the surface after oxide removal promotes the incorporation of adatoms to steps from the lower terraces, leading to the formation of multiatomic step arrays or ridge patterns by a combination of step propagation and two-dimensional layer-by-layer growth. Supply of atomic H during epitaxy favours three-dimensional growth, leading to Ga-induced surface roughening or mound formation. At high temperatures, the Ga–As interactions at step edges are faster and stable growth of GaAs occurs by step propagation, leading to a faceted surface when H is used both during oxide removal and/or MBE growth.