Browsing by Author "Llewellyn, DJ"

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    Changes in metal nanoparticle shape and size induced by swift heavy-ion irradiation
    (Elsevier, 2009-03) Ridgway, MC; Kluth, P; Giulian, R; Sprouster, DJ; Araujo, LL; Schnohr, CS; Llewellyn, DJ; Byrne, AP; Foran, GJ; Cookson, DJ
    Changes in the shape and size of Co, Pt and An nanoparticles induced by swift heavy-ion irradiation (SHII) have been characterized using a combination of transmission electron microscopy, small-angle X-ray scattering and X-ray absorption near-edge Structure. Elemental nanoparticles of diameters 2-15 nm were first formed in amorphous SiO2 by ion implantation and thermal annealing and then irradiated at room temperature with 27-185 MeV Au ions as a function of fluence. Spherical nanoparticles below a minimum diameter (4-7 nm) remained spherical under SHII but progressively decreased in size as a result of dissolution into the SiO2 matrix. Spherical nanoparticles above the minimum diameter threshold were transformed to elongated rods aligned with the ion beamdirection. The nanorod width saturated at an electronic energy deposition dependent value, progressively increasing from 4-6 to 7-10nm (at 518 keV/nm, respectively) while the nanorod length exhibited a broad distribution consistent with that of the unirradiated spherical nanoparticles. The threshold diameter for spherical nanoparticle elongation was comparable to the saturation value of nanorod width. We correlate this saturation value with the diameter of the molten track induced in amorphous SiO2 by SHII. In summary, changes in nanoparticle shape and size are governed to a large extent by the ion irradiation parameters. © 2009, Elsevier Ltd.
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    Ion-irradiation-induced amorphization of Cu nanoparticles embedded in SiO2
    (American Physical Society, 2007-11) Johannessen, B; Kluth, P; Llewellyn, DJ; Foran, GJ; Cookson, DJ; Ridgway, MC
    Elemental Cu nanoparticles embedded in SiO2 were irradiated with 5 MeV Sn3+. The nanoparticle structure was studied as a function of Sn3+ fluence by extended x-ray absorption fine structure spectroscopy, small-angle x-ray scattering, and transmission electron microscopy. Prior to irradiation, Cu nanoparticles exhibited the face-centered-cubic structure. Upon irradiation at intermediate fluences (1×1013 to 1×1014 ions/cm2), the first nearest neighbor Cu-Cu coordination number decreased, while the Debye-Waller factor, bondlength, and third cumulant of the bondlength distribution increased. In particular, at a fluence of 1×1014 ions/cm2 we argue for the presence of an amorphous Cu phase, for which we deduce the structural parameters. Low temperature annealing (insufficient for nanoparticle growth) of the amorphous Cu returned the nanoparticles to the initial preirradiation structure. At significantly higher irradiation fluences (1×1015 to 1×1016 ions/cm2), the nanoparticles were dissolved in the matrix with a Cu coordination similar to that of Cu2O. © 2007, American Physical Society
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    Preferential amorphisation of Ge nanocrystals in a silica matrix
    (Australian Institute of Physics, 2005-01-31) Ridgway, MC; Azevedo, GDM; Elliman, RG; Wesch, W; Glover, CJ; Miller, R; Llewellyn, DJ; Foran, GJ; Hansen, JL; Nylandsted Larsen, A
    Relative to bulk crystalline material, Ge nanocrystals in a silica matrix exhibit subtle structural perturbations including a non-Gaussian inter-atomic distance distribution. We now demonstrate such nanocrystals are extremely sensitive to ion irradiation. Using transmission electron microscopy, Raman spectroscopy and extended x-ray absorption fine structure spectroscopy, the crystalline-to-amorphous phase transformation in -8 nm diameter nanocrystals and bulk crystalline material has been compared. Amorphisation of Ge nanocrytals in a silica matrix was achieved at an ion dose -100 times less than that required for bulk crystalline standards. This rapid amorphisation of Ge nanocrystals is attributed to the preferential nucleation of the amorphous phase at the nanocrystal/matrix interface, the pre-irradiation, higher-energy structural state of the nanocrystals themselves and an enhanced nanocrystal vacancy concentration due to the more effective trapping of irradiation-induced interstitials at the nanocrystal/matrix interface and inhibited Frenkel pair recombination when Ge interstitials are recoiled into the matrix. To demonstrate the significance of the latter, we show ion irradiation of -2 nm diameter nanocrystals yields their dissolution when the range of recoiled Ge atoms exceeds the nanocrystal bounds.
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    Preferential amorphisation of Ge nanocrystals in a silica matrix
    (Elsevier, 2004-09-05) Ridgway, MC; Azevedo, GDM; Elliman, RG; Wesch, W; Glover, CJ; Miller, R; Llewellyn, DJ; Foran, GJ; Hansen, JL; Nylandsted Larsen, A
    Extended X-ray absorption fine structure and Raman spectroscopies have been used to compare the crystalline-to-amorphous phase transformation in nanocrystalline and polycrystalline Ge. We demonstrate Ge nanocrystals are extremely sensitive to ion irradiation and are rendered amorphous at an ion dose ∼40 times less than that required to amorphise bulk, crystalline standards. This rapid amorphisation is attributed to the higher-energy nanocrystalline structural state prior to irradiation, inhibited Frenkel pair recombination when Ge interstitials are recoiled into the matrix and preferential nucleation of the amorphous phase at the nanocrystal/matrix interface. © 2005 Elsevier B.V
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    Size-dependent characterization of embedded Ge nanocrystals: structural and thermal properties
    (American Physical Society, 2008-09) Araujo, LL; Giulian, R; Sprouster, DJ; Schnohr, CS; Llewellyn, DJ; Kluth, P; Cookson, DJ; Foran, GJ; Ridgway, MC
    A combination of conventional and synchrotron-based techniques has been used to characterize the size-dependent structural and thermal properties of Ge nanocrystals (NCs) embedded in a silica (a-SiO2) matrix. Ge NC size distributions with four different diameters ranging from 4.0 to 9.0 nm were produced by ion implantation and thermal annealing as characterized with small-angle x-ray scattering and transmission electron microscopy. The NCs were well represented by the superposition of bulklike crystalline and amorphous environments, suggesting the formation of an amorphous layer separating the crystalline NC core and the a-SiO2 matrix. The amorphous fraction was quantified with x-ray-absorption near-edge spectroscopy and increased as the NC diameter decreased, consistent with the increase in surface-to-volume ratio. The structural parameters of the first three nearest-neighbor shells were determined with extended x-ray-absorption fine-structure (EXAFS) spectroscopy and evolved linearly with inverse NC diameter. Specifically, increases in total disorder, interatomic distance, and the asymmetry in the distribution of distances were observed as the NC size decreased, demonstrating that finite-size effects govern the structural properties of embedded Ge NCs. Temperature-dependent EXAFS measurements in the range of 15-300 K were employed to probe the mean vibrational frequency and the variation of the interatomic distance distribution (mean value, variance, and asymmetry) with temperature for all NC distributions. A clear trend of increased stiffness (higher vibrational frequency) and decreased thermal expansion with decreasing NC size was evident, confirming the close relationship between the variation of structural and thermal/vibrational properties with size for embedded Ge NCs. The increase in surface-to-volume ratio and the presence of an amorphous Ge layer separating the matrix and crystalline NC core are identified as the main factors responsible for the observed behavior, with the surrounding a-SiO2 matrix also contributing to a lesser extent. Such results are compared to previous reports and discussed in terms of the influence of the surface-to-volume ratio in objects of nanometer dimensions. © 2008, American Physical Society
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    Structural characterization of Ge nanocrystals in silica amorphised by ion irradiation
    (Elsevier, 2008-06) Araujo, LL; Giulian, R; Johannessen, B; Llewellyn, DJ; Kluth, P; Azevedo, GDM; Cookson, DJ; Ridgway, MC
    Ge nanocrystals (NCs) grown by ion implantation in amorphous silica matrices were irradiated with 5 MeV Si ions over a different fluence range (2 x 10(11)-2 x 10(13) cm(-2)) than previously reported. Size and depth distributions as well as structural disorder in the NCs were measured by RBS, TEM, SAXS and EXAFS. The EXAFS results show that the embedded Ge NCs are rendered amorphous at fluences similar to 40 times lower than bulk crystalline Ge (c-Ge). No significant changes in the size or depth distribution of the NCs are observed for all irradiation fluences. Compared to c-Ge, the higher-energy structural state of the NCs prior to irradiation and the presence of the nanocrystal/matrix interface are considered the main causes for the peculiar amorphisation behavior of embedded Ge NCs. © 2008, Elsevier Ltd.