Initialization of Nanowire or Cluster Growth Critically Controlled by the Effective V/III Ratio at the Early Nucleation Stage.

For self-catalyzed nanowires (NWs), reports on how the catalytic droplet initiates successful NW growth are still lacking, making it difficult to control the yield and often accompanying a high density of clusters. Here, we have performed a systematic study on this issue, which reveals that the effective V/III ratio at the initial growth stage is a critical factor that governs the NW growth yield. To initiate NW growth, the ratio should be high enough to allow the nucleation to extend to the entire contact area between the droplet and substrate, which can elevate the droplet off of the substrate, but it should not be too high in order to keep the droplet. This study also reveals that the cluster growth between NWs is also initiated from large droplets. This study provides a new angle from the growth condition to explain the cluster formation mechanism, which can guide high-yield NW growth.

Low threading dislocation density and antiphase boundary free GaAs epitaxially grown on on-axis Si (001) substrates.

Epitaxial growth of III-V materials on a CMOS-compatible Si (001) substrate enables the feasibility of mass production of low-cost and high-yield Si-based III-V optoelectronic devices. However, the material dissimilarities between III-V and group-IV materials induce several types of defects, especially threading dislocations (TDs) and antiphase boundaries (APBs). The presence of these defects is detrimental to the optoelectronic device performance and thus needs to be eliminated. In this paper, the mechanism of APB annihilation during the growth of GaAs on on-axis Si (001) is clarified, along with a detailed investigation of the interaction between TDs and the periodic {110} APBs. A significant reduction in the TD density ascribed to the presence of periodic APBs is discussed. This new observation opens the possibility of reducing both APBs and TDs simultaneously by utilising optimised GaAs growth methods in the future. Hence, a thin APB-free GaAs/Si (001) platform with a low TD density (TDD) was obtained. Based on this platform, a high-performance high-yield III-V optoelectronic device grown on CMOS-compatible Si (001) substrates with an overall thickness below the cracking threshold is feasible, enabling the mass production of Si-based photonic integrated circuits (PICs).

Thermally-driven formation method for growing (quantum) dots on sidewalls of self-catalysed thin nanowires.

Embedding quantum dots (QDs) on nanowire (NW) sidewalls allows the integration of multi-layers of QDs into the active region of radial p-i-n junctions to greatly enhance light emission/absorption. However, the surface curvature makes the growth much more challenging compared with growths on thin-films, particularly on NWs with small diameters (Ø < 100 nm). Moreover, the {110} sidewall facets of self-catalyzed NWs favor two-dimensional growth, with the realization of three-dimensional Stranski-Krastanow growth becoming extremely challenging. Here, we have developed a novel thermally-driven QD growth method. The QD formation is driven by the system energy minimization when the pseudomorphic shell layer (made of QD material) is annealed under high-temperature, and thus without any restriction on the NW diameter or the participation of elastic strain. It has demonstrated that the lattice-matched Ge dots can be grown defect-freely in a controllable way on the sidewall facets of the thin (∼50 nm) self-catalyzed GaAs NWs without using any surfactant or surface treatment. This method opens a new avenue to integrate QDs on NWs, and can allow the formation of QDs in a wider range of materials systems where the growth by traditional mechanisms is not possible, with benefits for novel NWQD-based optoelectronic devices.

Self-Catalyzed AlGaAs Nanowires and AlGaAs/GaAs Nanowire-Quantum Dots on Si Substrates.

Self-catalyzed AlGaAs nanowires (NWs) and NWs with a GaAs quantum dot (QD) were monolithically grown on Si(111) substrates via solid-source molecular beam epitaxy. This growth technique is advantageous in comparison to the previously employed Au-catalyzed approach, as it removes Au contamination issues and renders the structures compatible with complementary metal-oxide-semiconductor (CMOS) technology applications. Structural studies reveal the self-formation of an Al-rich AlGaAs shell, thicker at the NW base and thinning towards the tip, with the opposite behavior observed for the NW core. Wide alloy fluctuations in the shell region are also noticed. AlGaAs NW structures with nominal Al contents of 10, 20, and 30% have strong room temperature photoluminescence, with emission in the range of 1.50-1.72 eV. Individual NWs with an embedded 4.9 nm-thick GaAs region exhibit clear QD behavior, with spatially localized emission, both exciton and biexciton recombination lines, and an exciton line width of 490 µeV at low temperature. Our results demonstrate the properties and behavior of the AlGaAs NWs and AlGaAs/GaAs NWQDs grown via the self-catalyzed approach for the first time and exhibit their potential for a range of novel applications, including nanolasers and single-photon sources.

Preferred growth direction of III-V nanowires on differently oriented Si substrates.

One of the nanowire (NW) characteristics is its preferred elongation direction. Here, we investigated the impact of Si substrate crystal orientation on the growth direction of GaAs NWs. We first studied the self-catalyzed GaAs NW growth on Si (111) and Si (001) substrates. SEM observations show GaAs NWs on Si (001) are grown along four <111> directions without preference on one or some of them. This non-preferential NW growth on Si (001) is morphologically in contrast to the extensively reported vertical <111> preferred GaAs NW growth on Si (111) substrates. We propose a model based on the initial condition of an ideal Ga droplet formation on Si substrates and the surface free energy calculation which takes into account the dangling bond surface density for different facets. This model provides further understanding of the different preferences in the growth of GaAs NWs along selected <111> directions depending on the Si substrate orientation. To verify the prevalence of the model, NWs were grown on Si (311) substrates. The results are in good agreement with the three-dimensional mapping of surface free energy by our model. This general model can also be applied to predictions of NW preferred growth directions by the vapor-liquid-solid growth mode on other group IV and III-V substrates.

Checked patterned elemental distribution in AlGaAs nanowire branches via vapor-liquid-solid growth.

Morphology, crystal defects and crystal phase can significantly affect the elemental distribution of ternary nanowires (NWs). Here, we report the synergic impact of the structure and crystal phase on the composition of branched self-catalyzed AlxGa1-xAs NWs. Branching events were confirmed to increase with Al incorporation rising, while twinning and polytypism were observed to extend from the trunk to the branches, confirming the epitaxial nature of the latter. The growth mechanism of these structures has been ascribed to Ga accumulation at the concave sites on the rough shell. This is in agreement with the ab initio calculations which reveal Ga atoms tend to segregate at the trunk/branch interface. Notably, uncommon, intricate compositional variations are exposed in these branched NWs, where Ga-rich stripes parallel to the growth direction of the branches intersect with another set of periodic arrangements of Ga-rich stripes which are perpendicular to them, leading to the realization of an elemental checked pattern. The periodic variations perpendicular to the growth direction of the branches are caused by the constant rotation of the sample during growth whilst Ga-rich stripes along the growth direction of the branches are understood to be driven by the different nucleation energies and polarities on facets of different crystal phase at the interface between the catalyst droplets and the branched NW tip. These results lead to further comprehension of phase segregation and could assist in the compositional engineering in ternary NWs via harnessing this interesting phenomenon.

Growth and Fabrication of High-Quality Single Nanowire Devices with Radial p-i-n Junctions.

Nanowires (NWs) with radial p-i-n junction have advantages, such as large junction area and small influence from the surface states, which can lead to highly efficient material use and good device quantum efficiency. However, it is difficult to make high-quality core-shell NW devices, especially single NW devices. Here, the key factors during the growth and fabrication process that influence the quality of single core-shell p-i-n NW devices are studied using GaAs(P) NW photovoltaics as an example. By p-doping and annealing, good ohmic contact is achieved on NWs with a diameter as small as 50-60 nm. Single NW photovoltaics are subsequently developed and a record fill factor of 80.5% is shown. These results bring valuable information for making single NW devices, which can further benefit the development of high-density integration circuits.

Hybrid III-V/IV Nanowires: High-Quality Ge Shell Epitaxy on GaAs Cores.

The integration of optically active III-V and electronic-suitable IV materials on the same nanowire could provide a great potential for the combination of photonics and electronics in the nanoscale. In this Letter, we demonstrate the growth of GaAs/Ge core-shell nanowires on Si substrates by molecular beam epitaxy and investigate the radial and axial Ge epitaxy on GaAs nanowires in detail. High-quality core-shell nanowires with smooth side facets and dislocation-free, sharp interfaces are achieved. It is found that the low shell growth temperature leads to smoother side facets, while higher shell growth temperatures lead to more relaxed structures with significantly faceted sidewalls. The possibility of forming a III-V/IV heterostructure nanowire with a Ge section development in the axial direction of a GaAs nanowire using a Ga droplet is also revealed. These nanowires provide an ideal platform for nanoscale III-V/IV combination, which is promising for highly integrated photonic and electronic hybrid devices on a single chip.

Near Full-Composition-Range High-Quality GaAs1-xSbx Nanowires Grown by Molecular-Beam Epitaxy.

Here we report on the Ga self-catalyzed growth of near full-composition-range energy-gap-tunable GaAs1-xSbx nanowires by molecular-beam epitaxy. GaAs1-xSbx nanowires with different Sb content are systematically grown by tuning the Sb and As fluxes, and the As background. We find that GaAs1-xSbx nanowires with low Sb content can be grown directly on Si(111) substrates (0 ≤ x ≤ 0.60) and GaAs nanowire stems (0 ≤ x ≤ 0.50) by tuning the Sb and As fluxes. To obtain GaAs1-xSbx nanowires with x ranging from 0.60 to 0.93, we grow the GaAs1-xSbx nanowires on GaAs nanowire stems by tuning the As background. Photoluminescence measurements confirm that the emission wavelength of the GaAs1-xSbx nanowires is tunable from 844 nm (GaAs) to 1760 nm (GaAs0.07Sb0.93). High-resolution transmission electron microscopy images show that the grown GaAs1-xSbx nanowires have pure zinc-blende crystal structure. Room-temperature Raman spectra reveal a redshift of the optical phonons in the GaAs1-xSbx nanowires with x increasing from 0 to 0.93. Field-effect transistors based on individual GaAs1-xSbx nanowires are fabricated, and rectifying behavior is observed in devices with low Sb content, which disappears in devices with high Sb content. The successful growth of high-quality GaAs1-xSbx nanowires with near full-range bandgap tuning may speed up the development of high-performance nanowire devices based on such ternaries.

Two-step fabrication of self-catalyzed Ga-based semiconductor nanowires on Si by molecular-beam epitaxy.

For the epitaxial growth of Ga-based III-V semiconductor nanowires (NWs) on Si, Ga droplets could provide a clean and compatible solution in contrast to the common Au catalyst. However, the use of Ga droplets is rather limited except for that in Ga-catalyzed GaAs NW studies in a relatively narrow growth temperature (Ts) window around 620 °C on Si. In this paper, we have investigated the two-step growth of Ga-catalyzed III-V NWs on Si (111) substrates by molecular-beam epitaxy. First, by optimizing the surface oxide, vertically aligned GaAs NWs with a high yield are obtained at Ts = 620 °C. Then a two-temperature procedure is adopted to preserve Ga droplets at lower Ts, which leads to an extension of Ts down to 500 °C for GaAs NWs. Based on this procedure, systematic morphological and structural studies for Ga-catalyzed GaAs NWs in the largest Ts range could be presented. Then within the same growth scheme, for the first time, we demonstrate Ga-catalyzed GaAs/GaSb heterostructure NWs. These GaSb NWs are axially grown on the GaAs NW sections and are pure zinc-blende single crystals. Compositional measurements confirm that the catalyst particles indeed mainly consist of Ga and GaSb sections are of high purity but with a minor composition of As. In the end, we present GaAsSb NW growth with a tunable Sb composition. Our results provide useful information for the controllable synthesis of multi-compositional Ga-catalyzed III-V semiconductor NWs on Si for heterogeneous integration.

Robust Manipulation of Magnetism in Dilute Magnetic Semiconductor (Ga,Mn)As by Organic Molecules.

Surface adsorption of organic molecules provides a new method for the robust manipulation of ferromagnetism in (Ga,Mn)As. Electron acceptor and donor molecules yield significant enhancement and suppression, respectively, of ferromagnetism with modulation of the Curie temperature spanning 36 K. Dip-pen nanolithography is employed to directly pattern monolayers on (Ga,Mn)As, which is presented as a novel pathway toward producing magnetic nanostructures.

Controlled synthesis of phase-pure InAs nanowires on Si(111) by diminishing the diameter to 10 nm.

Here we report the growth of phase-pure InAs nanowires on Si (111) substrates by molecular-beam epitaxy using Ag catalysts. A conventional one-step catalyst annealing process is found to give rise to InAs nanowires with diameters ranging from 4.5 to 81 nm due to the varying sizes of the Ag droplets, which reveal strong diameter dependence of the crystal structure. In contrast, a novel two-step catalyst annealing procedure yields vertical growth of highly uniform InAs nanowires ∼10 nm in diameter. Significantly, these ultrathin nanowires exhibit a perfect wurtzite crystal structure, free of stacking faults and twin defects. Using these high-quality ultrathin InAs nanowires as the channel material of metal-oxide-semiconductor field-effect transistor, we have obtained a high ION/IOFF ratio of ∼10(6), which shows great potential for application in future nanodevices with low power dissipation.

All zinc-blende GaAs/(Ga,Mn)As core-shell nanowires with ferromagnetic ordering.

Combining self-catalyzed vapor-liquid-solid growth of GaAs nanowires and low-temperature molecular-beam epitaxy of (Ga,Mn)As, we successfully synthesized all zinc-blende (ZB) GaAs/(Ga,Mn)As core-shell nanowires on Si(111) substrates. The ZB GaAs nanowire cores are first fabricated at high temperature by utilizing the Ga droplets as the catalyst and controlling the triple phase line nucleation, then the (Ga,Mn)As shells are epitaxially grown on the side facets of the GaAs core at low temperature. The growth window for the pure phase GaAs/(Ga,Mn)As core-shell nanowires is found to be very narrow. Both high-resolution transmission electron microscopy and scanning electron microscopy observations confirm that all-ZB GaAs/(Ga,Mn)As core-shell nanowires with smooth side surface are obtained when the Mn concentration is not more than 2% and the growth temperature is 245 °C or below. Magnetic measurements with different applied field directions provide strong evidence for ferromagnetic ordering in the all-ZB GaAs/(Ga,Mn)As nanowires. The hybrid nanowires offer an attractive platform to explore spin transport and device concepts in fully epitaxial all-semiconductor nanospintronic structures.

Evidence for structural phase transitions induced by the triple phase line shift in self-catalyzed GaAs nanowires.

Self-catalyzed growth of GaAs nanowires are widely ascribed to the vapor-liquid-solid (VLS) mechanism due to the presence of Ga particles at the nanowire tips. Here we report synthesis of self-catalyzed GaAs nanowires by molecular-beam epitaxy covering a large growth parameter space. By carefully controlling the Ga flux and its ratio with the As flux, GaAs nanowires without Ga particles and exhibiting a flat growth front are produced. Using scanning electron microscopy and high-resolution transmission electron microscopy, we compare the growth rate and structure, especially near the growth front, of the nanowires with and without Ga droplets. We find that regardless of whether Ga droplets are present on top, the nanowires have a short wurtzite section following the zinc-blende bulk structure. The nanowires without Ga droplets are terminated by a thin zinc-blende cap, while the nanowires with Ga droplets do not have such a cap. The bulk zinc-blende phase is attributed to the Ga droplet wetting the sidewall during growth, pinning the triple phase line on the sidewall. The zinc-blend/wurtzite/(zinc-blende) phase transitions at the end of growth are fully consistent with the triple phase line shifting up to the growth front due to the progressive consumption of the Ga in the droplet by crystallization with As. The results imply an identical VLS growth mechanism for both types of GaAs NWs, and their intricate structures provide detailed comparison with and specific experimental verification of the recently proposed growth mechanism for self-catalyzed III-V semiconductor nanowires ( Phy. Rev. Lett. 2011 , 106 , 125505 ). Using this mechanism as a guideline, we successfully demonstrated controllable fabrication of two distinct types of axial superlattice GaAs NWs consisting of zinc-blende/defect-section and wurtzite/defect-section units.