Browsing by Author "Giulian, R"

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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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    Fcc-hcp phase transformation in Co nanoparticles induced by swift heavy-ion irradiation
    (American Physical Society, 2009-09) Sprouster, DJ; Giulian, R; Schnohr, CS; Araujo, LL; Kluth, P; Byrne, AP; Foran, GJ; Johannessen, B; Ridgway, MC
    We demonstrate a face-centered cubic (fcc) to hexagonally close-packed (hcp) phase transformation in spherical Co nanoparticles achieved via swift heavy-ion irradiation. Co nanoparticles of mean diameter 13.2 nm and fcc phase were first formed in amorphous SiO2 by ion implantation and thermal annealing and then irradiated at room temperature with 9-185 MeV Au ions. The crystallographic phase was identified with x-ray absorption spectroscopy and electron diffraction and quantified, as functions of the irradiation energy and fluence, with the former. The transformation was complete at low fluence prior to any change in nanoparticle shape or size and was governed by electronic stopping. A direct-impact mechanism was identified with the transformation interaction cross-section correlated with that of a molten ion track in amorphous SiO2. We suggest the shear stress resulting from the rapid thermal expansion about an ion track in amorphous SiO2 was sufficient to initiate the fcc-to-hcp phase transformation in the Co nanoparticles. © 2009, American Physical Society
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    Influence of annealing conditions on the growth and structure of embedded Pt nanocrystals
    (American Institute of Physics, 2009-02-15) Giulian, R; Araujo, LL; Kluth, P; Sprouster, DJ; Schnohr, CS; Johannessen, B; Foran, GJ; Ridgway, MC
    The growth and structure of Pt nanocrystals (NCs) formed by ion implantation in a-SiO2 has been investigated as a function of the annealing conditions. Transmission electron microscopy and small-angle x-ray scattering measurements demonstrate that the annealing ambient has a significant influence on NC size. Samples annealed in either Ar, O-2, or forming gas (95% N-2: 5% H-2) at temperatures ranging from 500 degrees C-1300 degrees C form spherical NCs with mean diameters ranging from 1-14 nm. For a given temperature, annealing in Ar yields the smallest NCs. O-2 and forming gas ambients produce NCs of comparable size though the latter induces H chemisorption at 1100 degrees C and above, as verified with x-ray absorption spectroscopy. This H intake is accompanied by a bond-length expansion and increased structural disorder in NCs of diameter >3 nm. © 2009, American Institute of Physics
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    Ion irradiation effects on metallic nanocrystals
    (Taylor & Francis, 2007-07) Kluth, P; Johannessen, B; Giulian, R; Schnohr, CS; Foran, GJ; Cookson, DJ; Byrne, AP; Ridgway, MC
    We have investigated structural and morphological properties of metallic nanocrystals ( NCs) exposed to ion irradiation. NCs were characterized by transmission electron microscopy in combination with advanced synchrotron-based analytical techniques, in particular X-ray absorption spectroscopy and small-angle X-ray scattering. A number of different effects were observed depending on the irradiation conditions. At energies where nuclear stopping is predominant, structural disorder/amorphization followed by inverse Ostwald ripening/dissolution due to ion beam mixing was observed for Au and Cu NCs embedded in SiO2. The ion-irradiation-induced crystalline to amorphous transition in the NCs, which cannot be achieved in the corresponding bulk metals, was attributed to their initially higher structural energy as compared to bulk material and possibly preferential nucleation of the amorphous phase at the NC/SiO2 interface. At very high irradiation energies (swift heavy ion irradiation), where the energy loss is nearly entirely due to electronic stopping, a size-dependent shape transformation of the NCs from spheres to rod like shapes was apparent in Au NCs. Our preliminary results are in good agreement with considerations on melting of the NCs in the ion track as one mechanism involved in the shape transformation. © 2007, Taylor & Francis Ltd.
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    Shape transformation of Pt nanoparticles induced by swift heavy-ion irradiation
    (American Physical Society, 2008-09) Giulian, R; Kluth, P; Araujo, LL; Sprouster, DJ; Byrne, AP; Cookson, DJ; Ridgway, MC
    Pt nanoparticles (NPs) formed by ion-beam synthesis in amorphous SiO2 were irradiated with Au ions in the energy range of 27-185 MeV. Small-angle x-ray scattering (SAXS) and transmission electron microscopy were used to characterize an irradiation-induced shape transformation within the NPs. A simple yet effective way of analyzing the SAXS data to determine both NP dimensions is presented. A transformation from spherical to rodlike shape with increasing irradiation fluence was observed for NPs larger than an energy-dependent threshold diameter, which varied from 4.0 to 6.5 nm over 27-185 MeV. NPs smaller than this threshold diameter remained spherical upon irradiation but decreased in size as a result of dissolution. The latter was more pronounced for the smallest particles. The minor dimension of the transformed NPs saturated at an energy-dependent value comparable to the threshold diameter for elongation. The saturated minor dimension was less than the diameter of the irradiation-induced molten track within the matrix. We demonstrate that Pt NPs of diameter 13 nm reach saturation of the minor dimension beyond a total-energy deposition into the matrix of 20 keV/nm(3). © 2008, American Physical Society
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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 and vibrational properties of co nanoparticles formed by ion implantation
    (American Institute of Physics, 2010-01-01) Sprouster, DJ; Giulian, R; Araujo, LL; Kluth, P; Johannessen, B; Cookson, DJ; Foran, GJ; Ridgway, MC
    We report on the structural and vibrational properties of Co nanoparticles formed by ion implantation and thermal annealing in amorphous silica. The evolution of the nanoparticle size, phase, and structural parameters were determined as a function of the formation conditions using transmission electron microscopy, small-angle x-ray scattering, and x-ray absorption spectroscopy. The implantation fluence and annealing temperature governed the spherical nanoparticle size and phase. To determine the latter, x-ray absorption near-edge structure analysis was used to quantify the hexagonal close packed, face-centered cubic and oxide fractions. The structural properties were characterized by extended x-ray absorption fine structure spectroscopy (EXAFS) and finite-size effects were readily apparent. With a decrease in nanoparticle size, an increase in structural disorder and a decrease in both coordination number and bondlength were observed as consistent with the non-negligible surface-area-to-volume ratio characteristic of nanoparticles. The surface tension of Co nanoparticles calculated using a liquid drop model was more than twice that of bulk material. The size-dependent vibrational properties were probed with temperature-dependent EXAFS measurements. Using a correlated anharmonic Einstein model and thermodynamic perturbation theory, Einstein temperatures for both nanoparticles and bulk material were determined. Compared to bulk Co, the mean vibrational frequency of the smallest nanoparticles was reduced as attributed to a greater influence of loosely bonded, undercoordinated surface atoms relative to the effect of capillary pressure generated by surface curvature. © 2010, American Institute of Physics
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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.
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    Temperature-dependent EXAFS analysis of embedded Pt nanocrystals
    (Institute of Physics, 2009-04-15) Giulian, R; Araujo, LL; Kluth, P; Sprouster, DJ; Schnohr, CS; Foran, GJ; Ridgway, MC
    The vibrational and thermal properties of embedded Pt nanocrystals (NCs) have been investigated with temperature-dependent extended x-ray absorption fine structure (EXAFS) spectroscopy. NCs of diameter 1.8-7.4 nm produced by ion implantation in amorphous SiO2 were analysed over the temperature range 20-295 K. An increase in Einstein temperature (similar to 194 K) relative to that of a Pt standard (similar to 179 K) was evident for the smallest NCs while those larger than similar to 2.0 nm exhibited values comparable to bulk material. Similarly, the thermal expansion of interatomic distances was lowest for small NCs. While the amorphous SiO2 matrix restricted the thermal expansion of interatomic distances, it did not have a significant influence on the mean vibrational frequency of embedded Pt NCs. Instead, the latter was governed by finite-size effects or, specifically, capillary pressure. © 2009, Institute of Physics