skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Formation of Ge–GeS core–shell nanostructures via solid-state sulfurization of Ge nanowires
Germanium nanowires (NWs) have attractive properties for a variety of applications, including micro- and optoelectronics, memory devices, solar energy conversion, and energy storage, among others. For applications that involve exposure to air, the poor chemical stability and electronic surface passivation of native oxides have remained a long-standing concern. Termination by sulfur-rich surface layers has emerged as a promising strategy for passivation of planar Ge surfaces. Here we discuss experiments on solid-state sulfurization of Ge nanowires in sulfur vapor at near-ambient pressures and at different temperatures. Combined transmission electron microscopy imaging and chemical mapping establishes that Ge NWs remain intact during vapor-phase reaction with S at elevated temperatures, and show the formation of sulfur-rich shells with T-dependent morphology and thickness on the Ge NW surface. Photoluminescence of ensembles of such core–shell nanowires is dominated by strong emission at ∼1.85 eV, consistent with luminescence of GeS. Cathodoluminescence spectroscopy on individual NWs establishes that this luminescence originates in thin GeS shells formed by sulfurization of the NWs. Our work establishes direct sulfurization as a viable approach for forming stable, wide-bandgap surface terminations on Ge NWs.  more » « less
Award ID(s):
1607795
PAR ID:
10155315
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
CrystEngComm
Volume:
20
Issue:
15
ISSN:
1466-8033
Page Range / eLocation ID:
2193 to 2200
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Reactions of Ge with S vapor, of interest as a potential approach for forming thin passivation layers on Ge surfaces, have been studied by photoelectron spectroscopy and Raman spectroscopy. Exposure of Ge(100) and Ge(111) to S drives the formation of Ge sulfide near-surface layers. At low temperatures, the reaction products comprise a thin GeS interlayer terminated by near-surface GeS 2 . Above 400 °C, exposure to sulfur gives rise to single-phase GeS 2 layers whose thickness increases with temperature. Arrhenius analysis of the GeS 2 thickness yields an activation energy (0.63 ± 0.08) eV, close to the barrier that controls Ge oxidation by O radicals. XPS measurements after extended ambient exposure show a stable, ultrathin near-surface GeS 2 without significant oxidation, indicating that Ge–sulfides may provide an effective surface passivation for Ge surfaces. 
    more » « less
  2. Abstract This work evaluates the passivation efficacy of thermal atomic layer deposited (ALD) Al 2 O 3 dielectric layer on self-catalyzed GaAs 1- x Sb x nanowires (NWs) grown using molecular beam epitaxy. A detailed assessment of surface chemical composition and optical properties of Al 2 O 3 passivated NWs with and without prior sulfur treatment were studied and compared to as-grown samples using x-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and low-temperature photoluminescence (PL) spectroscopy. The XPS measurements reveal that prior sulfur treatment followed by Al 2 O 3 ALD deposition abates III–V native oxides from the NW surface. However, the degradation in 4K-PL intensity by an order of magnitude observed for NWs with Al 2 O 3 shell layer compared to the as-grown NWs, irrespective of prior sulfur treatment, suggests the formation of defect states at the NW/dielectric interface contributing to non-radiative recombination centers. This is corroborated by the Raman spectral broadening of LO and TO Raman modes, increased background scattering, and redshift observed for Al 2 O 3 deposited NWs relative to the as-grown. Thus, our work seems to indicate the unsuitability of ALD deposited Al 2 O 3 as a passivation layer for GaAsSb NWs. 
    more » « less
  3. Core–shell Ge/GeSn nanowires provide a route to dislocation-free single crystal germanium-tin alloys with desirable light emission properties because the Ge core acts as an elastically compliant substrate during misfitting GeSn shell growth. However, the uniformity of tin incorporation during reduced pressure chemical vapor deposition may be limited by the kinetics of mass transfer to the shell during GeSn growth. The balance between Sn precursor flux and available surfaces for GeSn nucleation and growth determines whether defects are formed and their type. On the one hand, when the Sn precursor delivery is insufficient, local variations in Sn arrival rate at the nanowire surfaces during GeSn growth produce asymmetries in shell growth that induce wire bending. This inhomogeneous elastic dilatation due to the varying composition occurs via deposition of Sn-poor regions on some of the {112} sidewall facets of the nanowires. On the other hand, when the available nanowire surface area is insufficient to accommodate the arriving Sn precursor flux, Sn-rich precipitate formation results. Between these two extremes, there exists a regime of growth conditions and nanowire densities that permits defect-free GeSn shell growth. 
    more » « less
  4. A cobalt oxide (Co3O4)-decorated silicon carbide (SiC) nano-tree array (denoted as Co3O4/SiC NTA) electrode is synthesized, and it is investigated for use in micro-supercapacitor applications. Firstly, the well-standing SiC nanowires (NWs) are prepared by nickel (Ni)-catalyzed chemical vapor deposition (CVD) method, and then the thin layer of Co3O4 and the hierarchical Co3O4 nano-flower-clusters are, respectively, fabricated on the side-walls and the top side of the SiC NWs via electrodeposition. The deposition of Co3O4 on the SiC NWs benefits the charge transfer at the electrode/aqueous electrolyte interface due to its extremely hydrophilic surface characteristic after Co3O4 decoration. Furthermore, the Co3O4/SiC NTA electrode provides a directional charge transport route along the length of SiC nanowires owing to their well-standing architecture. By using the Co3O4/SiC NTA electrode for micro-supercapacitor application, the areal capacitance obtained from cyclic voltammetry measurement reaches 845 mF cm−2 at a 10 mV s−1 scan rate. Finally, the capacitance durability is also evaluated by the cycling test of cyclic voltammetry at a high scan rate of 150 mV s−1 for 2000 cycles, exhibiting excellent stability. 
    more » « less
  5. ABSTRACT Chemical vapor deposition (CVD) growth of two-dimensional molybdenum disulfide (MoS 2 ) using molybdenum trioxide (MoO 3 ) and sulfur (S) powder often results in intermediate molybdenum oxy-sulfide (MoOS 2 ) species along with MoS 2 due to a lack of control over the vapor pressure required for the clean growth. Much effort has been devoted in understanding and controlling of these intermediate MoOS 2 specifies. Here, we show that with a second step sulfurization at moderate temperatures, these MoOS 2 crystals can be transformed to monolayer MoS 2 crystals. Scanning electron microscopy, Raman and photoluminescence spectroscopy and atomic force microscopy characterization carried out before and after re-sulfurization confirm the monolayer MoS 2 growth via this route. This study shows that MoOS 2 formed at the intermediate state can be successfully recycled to MoS 2 . 
    more » « less