Taper-free and vertically oriented Ge nanowires on Ge/Si substrates grown by a two-temperature process

Taper-free and vertically oriented Ge nanowires were grown on Si (111) substrates by chemical vapor deposition with Au nanoparticle catalysts. To achieve vertical nanowire growth on the highly lattice mismatched Si substrate, a thin Ge buffer layer was first deposited, and to achieve taper-free nanowire growth, a two-temperature process was employed. The two-temperature process consisted of a brief initial base growth step at high temperature followed by prolonged growth at lower temperature. Taper-free and defect-free Ge nanowires grew successfully even at 270 °C, which is 90 °C lower than the bulk eutectic temperature. The yield of vertical and taper-free nanowires is over 90%, comparable to that of vertical but tapered nanowires grown by the conventional one-temperature process. This method is of practical importance and can be reliably used to develop novel nanowire-based devices on relatively cheap Si substrates. Additionally, we observed that the activation energy of Ge nanowire growth by the two-temperature process is dependent on Au nanoparticle size. The low activation energy (∼5 kcal/mol) for 30 and 50 nm diameter Au nanoparticles suggests that the decomposition of gaseous species on the catalytic Au surface is a rate-limiting step. A higher activation energy (∼14 kcal/mol) was determined for 100 nm diameter Au nanoparticles which suggests that larger Au nanoparticles are partially solidified and that growth kinetics become the rate-limiting step. © 2011 American Chemical Society.

Phase separation induced by Au catalysts in ternary InGaAs nanowires.

We report a novel phase separation phenomenon observed in the growth of ternary In(x)Ga(1-x)As nanowires by metalorganic chemical vapor deposition. A spontaneous formation of core-shell nanowires is investigated by cross-sectional transmission electron microscopy, revealing the compositional complexity within the ternary nanowires. It has been found that for In(x)Ga(1-x)As nanowires high precursor flow rates generate ternary In(x)Ga(1-x)As cores with In-rich shells, while low precursor flow rates produce binary GaAs cores with ternary In(x)Ga(1-x)As shells. First-principle calculations combined with thermodynamic considerations suggest that this phenomenon is due to competitive alloying of different group-III elements with Au catalysts, and variations in elemental concentrations of group-III materials in the catalyst under different precursor flow rates. This study shows that precursor flow rates are critical factors for manipulating Au catalysts to produce nanowires of desired composition.

Vertically oriented epitaxial germanium nanowires on silicon substrates using thin germanium buffer layers.

We demonstrate a method to realize vertically oriented Ge nanowires on Si(111) substrates. Ge nanowires were grown by chemical vapor deposition using Au nanoparticles to seed nanowire growth via a vapor-liquid-solid growth mechanism. Rapid oxidation of Si during Au nanoparticle application inhibits the growth of vertically oriented Ge nanowires directly on Si. The present method employs thin Ge buffer layers grown at low temperature less than 600 degrees C to circumvent the oxidation problem. By using a thin Ge buffer layer with root-mean-square roughness of approximately 2 nm, the yield of vertically oriented Ge nanowires is as high as 96.3%. This yield is comparable to that of homoepitaxial Ge nanowires. Furthermore, branched Ge nanowires could be successfully grown on these vertically oriented Ge nanowires by a secondary seeding technique. Since the buffer layers are grown under moderate conditions without any high temperature processing steps, this method has a wide process window highly suitable for Si-based microelectronics.

Twin-free uniform epitaxial GaAs nanowires grown by a two-temperature process.

We demonstrate vertically aligned epitaxial GaAs nanowires of excellent crystallographic quality and optimal shape, grown by Au nanoparticle-catalyzed metalorganic chemical vapor deposition. This is achieved by a two-temperature growth procedure, consisting of a brief initial high-temperature growth step followed by prolonged growth at a lower temperature. The initial high-temperature step is essential for obtaining straight, vertically aligned epitaxial nanowires on the (111)B GaAs substrate. The lower temperature employed for subsequent growth imparts superior nanowire morphology and crystallographic quality by minimizing radial growth and eliminating twinning defects. Photoluminescence measurements confirm the excellent optical quality of these two-temperature grown nanowires. Two mechanisms are proposed to explain the success of this two-temperature growth process, one involving Au nanoparticle-GaAs interface conditions and the other involving melting-solidification temperature hysteresis of the Au-Ga nanoparticle alloy.

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.

III-V compound semiconductor nanowires for optoelectronic device applications

GaAs and InP based III-V compound semiconductor nanowires were grown epitaxially on GaAs (or Si) (111)B and InP (111)B substrates, respectively, by metalorganic chemical vapor deposition using Au nanoparticles as catalyst. In this paper, we will give an overview of nanowire research activities in our group. In particular, the effects of growth parameters on the crystal structure and optical properties of various nanowires were studied in detail. We have successfully obtained defect-free GaAs nanowires with nearly intrinsic exciton lifetime and vertical straight nanowires on Si (111)B substrates. The crystal structure of InP nanowires, i.e., WZ or ZB, can also be engineered by carefully controlling the V/III ratio and catalyst size. © 2011 World Scientific Publishing Company.

Improvement of morphology, structure, and optical properties of GaAs nanowires grown on Si substrates

We investigate vertical and defect-free growth of GaAs nanowires on Si (111) substrates via a vapor-liquid-solid (VLS) growth mechanism with Au catalysts by metal-organic chemical vapor deposition (MOCVD). By using annealed thin GaAs buffer layers on the surface of Si substrates, most nanowires are grown on the substrates straight, following (111) direction; by using two temperature growth, the nanowires were grown free from structural defects, such as twin defects and stacking faults. Systematic experiments about buffer layers indicate that V/III ratio of precursor and growth temperature can affect the morphology and quality of the buffer layers. Especially, heterostructural buffer layers grown with different V/III ratios and temperatures and in-situ post-annealing step are very helpful to grow well arranged, vertical GaAs nanowires on Si substrates. The initial nanowires having some structural defects can be defect-free by two-temperature growth mode with improved optical property, which shows us positive possibility for optoelectronic device application. ©2010 IEEE.

Au-catalyzed InP nanowires: The influence of growth temperature and V/III ratio

Growth of Au-catalyzed InP nanowires (NWs) by metalorganic chemical vapor deposition (MOCVD) has been studied in the temperature range of 400-510 °C and V/III ratio of 44-700. We demonstrate that minimal tapering of InP NWs can be achieved at 400 °C and V/III ratio of 350. Zinc-blende (ZB) or wurtzite (WZ) NWs is obtained depending on the growth conditions. 4K microphotoluminescence (μ-PL) studies show that emission energy is blue-shifted as growth temperature increases. By changing these growth parameters, one can tune the emission wavelength of InP NWs which is attractive for applications in developing novel optoelectronic devices. © 2010 IEEE.

Nanowires for optoelectronic device applications

GaAs and InP based nanowires were grown epitaxially on GaAs or InP (111)B substrates by metalorganic chemical vapor deposition using Au nanoparticles as catalyst. In this paper, we will give an overview of nanowire research activities in our group. In particular, the effects of growth parameters for GaAs and InP nanowires on the crystal quality were studied in detail. We demonstrated the ability to obtain defect-free GaAs nanowires via either two-temperature procedure, or by controlling V/III ratio or growth rate. The crystal structure of InP nanowires, ie, WZ or ZB, can also be engineered by just controlling the V/III ratio. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.

III-V compound semiconductor nanowires

GaAs and InP based nanowires were grown epitaxially on GaAs or InP (111)B substrates by metalorganic chemical vapor deposition using Au nanoparticles as catalyst. In this talk, I will give an overview of nanowire research activities in our group. Especially, the effects of growth parameters for GaAs and InP nanowires on the crystal quality have been studied in detail. We demonstrated the ability to obtain defect-free GaAs nanowires and control the crystal structure of InP nanowires, ie, WZ or ZB, by choosing a combination of growth parameters, such as temperature, V/III ratio and nanowire diameter. © 2009 IEEE.

Understanding the kink formation in GaAs/InAs heterostructural nanowires

The kinks formation in heterostructural nanowires was observed to be dominant when InAs nanowires were grown on GaAs nanowires. Nanowires were grown through vapor-liquid-solid (VLS) mechanism in an MOCVD (metalorganic chemical vapor deposition) reactor. GaAs nanowires were grown in [1 1 1 ]B direction on a GaAs (1 1 1 )B substrate. When InAs nanowires grown on the GaAs nanowires, most of the InAs nanowires changed their growth directions from [1 1 1 ]B to other 〈111〉B directions. The kinks formation is ascribed to the large compressive misfit strain at the GaAs/InAs interface (7.2% lattice mismatch between GaAs and InAs) and the high mobility of indium species during MOCVD growth. The in-depth analysis of the kinks formation was done by growing InAs for short times on the GaAs nanowires and characterizing the samples. The hindrance to compressively strain InAs to form coherent layers with GaAs pushed the InAs/Au interfaces to the sides of the GaAs nanowires growth ends. New InAs/Au interfaces have generated at the sides of GaAs nanowires, due to lateral growth of InAs on GaAs nanowires. These new interfaces led the InAs nanowires growth in other 〈111〉B directions. The morphological and structural features of these heterostructural kinked nanowires were characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. © 2006 IEEE.

Growth of GaAs/InAs vertical nanowires on GaAs (111)B by metalorganic chemical vapor deposition

The growth mechanism and properties of GaAs/InAs nanowires prepared by metalorganic chemical vapor deposition are investigated. Vertical InAs nanowires on GaAs (111)B substrates are successfully grown despite the large lattice mismatch (-7.2%). The crystallographic perfection of InAs nanowires is confirmed by hexagonal or triangular cross section. An interesting L-shaping of GaAs/InAs heterostructure nanowire which could be useful for novel device application is observed. © 2005 IEEE.