Jiji Antony

Void formation during early stages of passivation: Initial oxidation of iron nanoparticles at room temperature

The examination of nanoparticles allows study of some processes and mechanisms that are not as easily observed for films or other types of studies in which sample preparation artifacts have been the cause of some uncertainties. Microstructure of iron nanoparticles passivated with iron oxide shell was studied using high-resolution transmission electron microscopy and high-angle annular dark-field imaging in aberration-corrected scanning transmission electron microscopy. Voids were readily observed on both small single-crystal α-Fe nanoparticles formed in a sputtering process and the more complex particles created by reduction of an oxide by hydrogen. Although the formation of hollow spheres of nanoparticles has been engineered for Co at higher temperatures [Y. Yin, R. M. Riou, C. K. Erdonmez, S. Hughes, G. A. Somorjari, and A. P. Alivisatos, Science 304, 711 (2004)], they occur for iron at room temperature and provide insight into the initial oxidation processes of iron. There exists a critical size of ∼8n...

Morphology and electronic structure of the oxide shell on the surface of iron nanoparticles.

An iron (Fe) nanoparticle exposed to air at room temperature will be instantly covered by an oxide shell that is typically approximately 3 nm thick. The nature of this native oxide shell, in combination with the underlying Fe(0) core, determines the physical and chemical behavior of the core-shell nanoparticle. One of the challenges of characterizing core-shell nanoparticles is determining the structure of the oxide shell, that is, whether it is FeO, Fe(3)O(4), gamma-Fe(2)O(3), alpha-Fe(2)O(3), or something else. The results of prior characterization efforts, which have mostly used X-ray diffraction and spectroscopy, electron diffraction, and transmission electron microscopic imaging, have been framed in terms of one of the known Fe-oxide structures, although it is not necessarily true that the thin layer of Fe oxide is a known Fe oxide. In this Article, we probe the structure of the oxide shell on Fe nanoparticles using electron energy loss spectroscopy (EELS) at the oxygen (O) K-edge with a spatial resolution of several nanometers (i.e., less than that of an individual particle). We studied two types of representative particles: small particles that are fully oxidized (no Fe(0) core) and larger core-shell particles that possess an Fe core. We found that O K-edge spectra collected for the oxide shell in nanoparticles show distinct differences from those of known Fe oxides. Typically, the prepeak of the spectra collected on both the core-shell and the fully oxidized particles is weaker than that collected on standard Fe(3)O(4). Given the fact that the origin of this prepeak corresponds to the transition of the O 1s electron to the unoccupied state of O 2p hybridized with Fe 3d, a weak pre-edge peak indicates a combination of the following four factors: a higher degree of occupancy of the Fe 3d orbital; a longer Fe-O bond length; a decreased covalency of the Fe-O bond; and a measure of cation vacancies. These results suggest that the coordination configuration in the oxide shell on Fe nanoparticles is defective as compared to that of their bulk counterparts. Implications of these defective structural characteristics on the properties of core-shell structured iron nanoparticles are discussed.

Morphology and oxide shell structure of iron nanoparticles grown by sputter-gas-aggregation

The crystal faceting planes and oxide coating structures of core–shell structured iron/iron-oxide nanoparticles synthesized by a sputter-gas-aggregation process were studied using transmission electron microscopy (TEM), electron diffraction and Wulff shape construction. The particles grown by this process and deposited on a support in a room temperature process have been compared with particles grown and deposited at high temperature as reported in the literature. It has been found that the Fe nanoparticles formed at RT are invariantly faceted on the {100} lattice planes and truncated by the {110} planes at different degrees. A substantial fraction of particles are confined only by the 6{100} planes (not truncated by the {110} planes); this contrasts with the Fe particles formed at high temperature (HT) for which a predominance of {110} planes has been reported. Furthermore, at RT no particle was identified to be only confined by the 12{110} planes, which is relatively common for the particles formed at HT. The Fe cubes defined by the 6{100} planes show a characteristic inward relaxation along the and directions and the reason for this behaviour is not fully understood. The oxide shell on the Fe{100} plane maintains an orientation relationship: and , which is the same as the oxide formed on a bulk Fe(001) through thermal oxidation. Orientation of the oxide that forms on the Fe{110} facets differs from that on Fe{001}: therefore, properties of core–shell structured Fe nanoparticle faceted primarily with one type of lattice plane may be fully different from that faceted with another type of lattice plane.

Room temperature ferromagnetic and ultraviolet optical properties of Co-doped ZnO nanocluster films

We prepared 2% and 5% Co-doped ZnO nanocluster films at room temperature (RT) using doped ZnO nanoclusters as building blocks. The nanoclusters are produced by a third-generation magnetron-sputtering-aggregation source. Superconducting quantum interference device (SQUID), photoluminescence (PL), x-ray diffraction (XRD), x-ray photoelectron spectrometer (XPS), and atomic force microscopy (AFM) measurements were done on the samples. The average nanocrystallite size of the nanoclusters was ∼7.5nm. The 2% Co-doped ZnO nanocluster films exhibit significant ferromagnetism and ultraviolet (UV) photoluminescence (PL) at RT. The coercivity (Hc) doubled in the 2% Co-doped samples when compared to the 5% Co-doped samples. A strong UV-PL of ∼3.33eV was observed for the 2% Co-doped ZnO nanocluster film at RT. The 5% Co-doped ZnO nanocluster film showed a ferromagnetic behavior at RT but no UV luminescence.

ZnO nanoclusters: Synthesis and photoluminescence

ZnO nanoclusters were prepared and deposited at room temperature using a newly developed cluster source. The nanoclusters act as a building block for the cluster films deposited on various substrates. The cluster films were characterized by transmission electron microscopy, x-ray photoelectron spectroscopy, x-ray diffraction, and photoluminescence. We prepared monodispersed crystalline ZnO nanoclusters of ∼7nm diameter. These clusters have a significant blueshift of ∼125meV (compared to the results published so far) within the ultraviolet region at room temperature. No PL in our samples was observed in the visible region, which implies negligible defect formation in ZnO nanocluster films.

Synthesis of core-shell nanoclusters with high magnetic moment for biomedical applications

Biocompatible magnetic nanoparticles have been found to be promising in several biomedical applications for tagging, imaging, sensing, and separation in recent years. Most magnetic particles or beads currently used in biomedical applications are based on ferromagnetic iron oxides with very low specific magnetic moments of about 20-30 emu/g. Here, we report a new approach to synthesize monodispersive core-shell nanostructured clusters with high specific magnetic moments above 200 emu/g. The Fe nanoclusters, ranging in size from 2 to 100 nm, are produced from a newly developed cluster source and go to a deposition chamber, where a chemical reaction starts, and the nanoclusters are coated with Fe oxides. High-resolution transmission electron microscopy images show the coatings are very uniform. The core-shell nanoclusters are superparamagnetic at room temperature for sizes less than 12 nm, and have the coercivity of about 1.5 kOe at low temperature (5 K).

Size-dependent specific surface area of nanoporous film assembled by core-shell iron nanoclusters

Nanoporous films of core-shell iron nanoclusters have improved possibilities for remediation, chemical reactivity rate, and environmentally favorable reaction pathways. Conventional methods often have difficulties to yield stable monodispersed core-shell nanoparticles. We produced core-shell nanoclusters by a cluster source that utilizes combination of Fe target sputtering along with gas aggregations in an inert atmosphere at 7°C. Sizes of core-shell iron-iron oxide nanoclusters are observed with transmission electron microscopy (TEM). The specific surface areas of the porous films obtained from Brunauer-Emmett-Teller (BET) process are size-dependent and compared with the calculated data.

Synthesis and characterization of stable iron-iron oxide core-shell nanoclusters for environmental applications.

The uniformity and reproducibility of the photoresist nanopatterns fabricated using near-field scanning optical nanolithography (NSOL) are investigated. The nanopatterns could be used as nanomasks for pattern transfer on a silicon wafer. In the NSOL process, uniform patterning with high reproducibility is essential for reliable transfer of the mask patterns on a silicon substrate. Using an aperture type cantilever nanoprobe operated at contact mode and a positive photoresist, various nanopatterns are produced on thin photoresist layer coated on the silicon substrate. The size and shape variations of thereby produced patterns are investigated using atomic force microscope to determine their uniformity and reproducibility. It is demonstrated that the NSOL-produced photo-resist nanomasks can be successfully applied for silicon pattern transfer by fabricating a silicon nanochannel array.

The effect of particle size distribution on the usage of the ac susceptibility in biosensors

Magnetic nanoparticles in a liquid have two relaxation times, Neel relaxation τN and Brownian relaxation τB. For particle size larger than 25nm, τN quickly becomes much larger than τB and can be ignored. τB has a relaxation period from 10−1to10−5s, and related to the particle’s hydrodynamic volume, which includes coatings and biomolecules attached to the magnetic nanoparticle cores. This causes the imaginary part of the ac magnetic susceptibility to display a maximum at a frequency f=1∕2πτB, and can be used to create a sensor capable of detecting biomolecules. Because this is based on particle size, a size distribution will broaden the curve and reduce the sensitivity. Although the magnetic nanoparticles may have a narrow size distribution, this may not be true once coatings have been added and biomolecules have bonded to the magnetic cores. Our group has examined the effects of normal and lognormal size distributions on the ac magnetic susceptibility using several theoretical measurements, and we have fo...

Ferromagnetic semiconductor nanoclusters: Co-doped Cu2O

5% Co-doped cuprous oxide dilute magnetic semiconducting cluster film composed of two different sizes of crystalline nanoclusters, prepared using sputtering-aggregation technique is found to be ferromagnetic at 400K. With the increase in average crystallite size from 4.2to8nm, the coercivity increased. Magnetic field up to 2T is applied and saturation magnetization is achieved at 3kOe field in both cases. Cu2O phase is observed from cluster film deposited on Si wafer when analyzed using x-ray diffraction. Co in Cu2O host reveals a +2 oxidation state via x-ray photoelectron spectroscopy. Positive magnetoresistance from samples exhibits a temperature dependent decrease.