Analysis of vapor-liquid-solid mechanism in Au-assisted GaAs nanowire growth

Harmand, J. C.; Patriarche, G.; Péré‐Laperne, Nicolas; Mérat-Combes, M. N.; Travers, Laurent; Glas, Frank

doi:10.1063/1.2128487

Cited by 254 publications

(221 citation statements)

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“…Probably the most surprising feature of these NWs is that, in contrast to their bulk counterparts, they often adopt the hexagonal wurtzite (WZ) structure. This was observed for most ZB III-V materials and growth techniques [1,3,4,10,11]. However, although often dominantly of WZ structure, the NWs usually contain stacking faults (SFs) and sequences of ZB structure.…”

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Why Does Wurtzite Form in Nanowires of III-V Zinc Blende Semiconductors?

2007

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We develop a nucleation-based model to explain the formation of the wurtzite (WZ) phase during the vapor-liquid-solid growth of free-standing nanowires of zinc-blende (ZB) semiconductors. Nucleation occurs preferentially at the edge of the solid/liquid interface, which entails major differences between ZB and WZ nuclei. Depending on the pertinent interface energies, WZ nucleation is favored at high liquid supersaturation. This explains our systematic observation of ZB during early growth.PACS numbers: 68.65. La,64.60.Qb,81.05.Ea,81.15.Kk,64.70.Nd Free-standing wires with diameters ranging from hundreds down to a few nanometers are nowadays commonly fabricated from a large range of semiconductor materials [1,2,3,4,5]. These nanowires (NWs) have remarkable physical properties and many potential applications. The present work deals with the epitaxial growth of NWs of III-V semiconductors on a hot substrate. Metal catalyst nanoparticles deposited on the substrate before growth define the wire diameter. According to the vapor-liquidsolid (VLS) growth mechanism, the atoms are fed from the vapor phase to the solid wire through this particle (or droplet), which remains liquid during growth [6].We consider III-V compounds which, under bulk form, adopt the cubic zinc-blende (ZB) crystal structure [7] (although some non-ZB high-pressure phases [8] may be metastable at atmospheric pressure [9]), leaving aside nitrogen-based NWs. We discuss the usual case of NWs grown on a [111]B (As-terminated) face of the ZB substrate. Probably the most surprising feature of these NWs is that, in contrast to their bulk counterparts, they often adopt the hexagonal wurtzite (WZ) structure. This was observed for most ZB III-V materials and growth techniques [1,3,4,10,11]. However, although often dominantly of WZ structure, the NWs usually contain stacking faults (SFs) and sequences of ZB structure. The coexistence of two phases is clearly a problem for basic studies as well as applications, so that phase purity control is one of the main challenges of III-V NW fabrication.The surprising prevalence of the WZ structure in III-V NWs has not been explained satisfactorily so far. Here, based on new experimental observations, we propose an explanation of the occurrence of the WZ structure and develop a model predicting quantitatively in which growth conditions it should form. We consider the specific case of gold-catalyzed GaAs NWs grown by molecular beam epitaxy (MBE) on a GaAs substrate but we expect our model and our conclusions to remain valid for any ZB III-V compound and any growth method.Let us start with briefly reviewing previously proposed explanations. Calculations give the difference δw in cohesive energy between ZB and WZ bulk GaAs as about 24 meV per III-V pair at zero pressure [7]. It has been argued that this favoring of the ZB form might be offset in NWs of small diameter by the large relative contribution to the total energy of either the lateral facets [12] or the vertical edges separating the latter [13] (provided the specifi...

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“…Free-standing wires with diameters ranging from hundreds down to a few nanometers are nowadays commonly fabricated from a large range of semiconductor materials [1,2,3,4,5]. These nanowires (NWs) have remarkable physical properties and many potential applications.…”

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Why Does Wurtzite Form in Nanowires of III-V Zinc Blende Semiconductors?

2007

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“…The most common epitaxial approaches involve metal-organic vapor phase epitaxy 6,7 and molecular beam epitaxy ͑MBE͒. 8,9 The most widely reported mechanism for NW assembly is the so called vapor-liquid-solid ͑VLS͒ mechanism. [10][11][12] During VLS growth, gas-phase adatoms impinge on, or diffuse toward, liquid-phase metal nanoparticles ͓typically Au, but also Ga ͑Ref.…”

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Structural and optical analysis of GaAsP/GaP core-shell nanowires

Mohseni

Rodrigues

Galzerani

et al. 2009

Journal of Applied Physics

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Influence of cross-section geometry and wire orientation on the phonon shifts in ultra-scaled Si nanowires J. Appl. Phys. 110, 094308 (2011) Study on the structural and physical properties of ZnO nanowire arrays grown via electrochemical and hydrothermal depositions J. Appl. Phys. 110, 094310 (2011) Growth of single-crystalline cobalt silicide nanowires with excellent physical properties J. Appl. Phys. 110, 074302 (2011) General hypothesis for nanowire synthesis. I. Extended principles and evidential (experimental and theoretical) demonstration J. Appl. Phys. 110, 054311 (2011) Thermoelectric properties for single crystal bismuth nanowires using a mean free path limitation model J. Appl. Phys. 110, 053702 (2011) Additional information on J. Appl. Phys. The structural and optical properties of GaAsP/GaP core-shell nanowires grown by gas source molecular beam epitaxy were investigated by transmission electron microscopy, Raman spectroscopy, photoluminescence ͑PL͒, and magneto-PL. The effects of surface depletion and compositional variations in the ternary alloy manifested as a redshift in GaAsP PL upon surface passivation, and a decrease in redshift in PL in the presence of a magnetic field due to spatial confinement of carriers.

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“…It should be noted that, after growth termination and during cooling, Ga may be released from the catalyst particles and reacts with ambient As vapor species to form GaAs. 12,15 In the case of InAs NWs ͑cooled under As vapor species͒, In was found inside the Au catalysts. 16 Even in the case of InGaAs NWs ͑cooled under As vapor species͒, Ga was released and only In was detected in the Au catalysts after the cooling .…”

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