Chandan Srivastava

Formation mechanism and composition distribution of FePt nanoparticles

Self-assembled FePt nanoparticle arrays are candidate structures for ultrahigh density magnetic storage media. One of the factors limiting their application to this technology is particle-to-particle compositional variation. This variation will affect the A1 to L10 transformation as well as the magnetic properties of the nanoparticles. In the present study, an analysis is provided for the formation mechanism of these nanoparticles when synthesized by the superhydride reduction method. Additionally, a comparison is provided of the composition distributions of nanoparticles synthesized by the thermal decomposition of Fe(CO)5 and the reduction of FeCl2 by superhydride. The latter process produced a much narrower composition distribution. A thermodynamic analysis of the mechanism is described in terms of free energy perturbation Monte Carlo simulations.

Formation of FePt nanoparticles by organometallic synthesis

Our interest in determining the mechanism of FePt nanoparticle formation has led to this study of the evolution of particle size and composition during synthesis. FePt nanoparticles were prepared by the simultaneous reduction of platinum acetylacetonate and thermal decomposition of iron pentacarbonyl. During the course of the reaction, samples were removed and the particle structure, size, and composition were determined using x-ray diffraction, transmission electron microscopy (TEM), and scanning electron microscopy–energy dispersive x-ray spectrometry. Early in the reaction the particles were Pt rich (greater than 95at.% Pt) and as the reaction proceeded the Fe content increased to the target of 50%. The particle diameter increased from 3.1to4.6nm during the reaction. Energy dispersive x-ray spectrometry measurements of individual particle compositions using a high resolution TEM showed a broad distribution of particle compositions with a standard deviation greater than 15% of the average composition.

Enhanced frequency upconversion in Ho3+/Yb3+/Li+:YMoO4 nanophosphors for photonic and security ink applications

The YMoO4 nanophosphors codoped with Ho3+/Yb3+/Li+ ions synthesized by the chemical coprecipitation method have been structurally characterized by using X-Ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), and Transmission Electron Microscopy (TEM) techniques. The TEM bright field imaging shows that the developed nanophosphors are crystalline in nature with particle size similar to 45 nm. The upconversion (UC) emission spectra upon excitation at 980 nm of the nanophosphors at low pump power ( = 900 mW) an intense broad band ranging from 400-900 nm along with a UV band has been observed. The enhancement of about similar to 104 times corresponding to the green band in the Ho3+-Yb3+-Li+ codoped nanophosphors compared to that of the Ho3+ singly doped nanophosphors has been observed. This enhancement is caused by the energy transfer from the Yb3+ to Ho3+ ions and modified the local crystal field developed around the rare earth ions. A higher value of the slope (i.e., n similar to 6.38) for broad band emission within the 944 mW-1200 mW pump power region in the Ho3+-Yb3+-Li+ codoped nanophosphors is found to be due to the involvement of the photon avalanche population process but it is not related to the black body radiation. The intense peak at similar to 564 nm and similar to 648 nm for the broad band emission is attributed to the charge transfer luminescence of codoped nanophosphors, which is related to the oxygen ion present in the MoO4 group and Yb3+ ion. The observations described in this paper may be of significant interest for developing the visible upconverters, security ink, and novel devices for displays in the low and high pump power region. Published by AIP Publishing.

Compositional evolution during the synthesis of FePt nanoparticles

A series of FePt nanoparticles was synthesized by the thermal decomposition of iron pentacarbonyl and reduction in platinum acetylacetonate in phenyl ether solvent. A range of precursor molar ratios of 2, 1.5, and 1 between iron pentacarbonyl and platinum acetylacetonate was studied. After 30 min of reflux, the synthesis method produced a wide distribution in composition and size for the nanoparticles. Given 200 min of reflux, it was observed that the particle-to-particle composition and size narrowed, and the atomic ratio of Fe to Pt, for the majority of nanoparticles, approached the initial precursor molar ratios except for the molar ratio of 1. It is speculated that the compositional variability may be a result of the slow kinetics of iron pentacarbonyl’s decomposition in the reaction.

Tailoring nucleation and growth conditions for narrow compositional distributions in colloidal synthesized FePt nanoparticles

To eliminate compositional and size variabilities between individual binary nanoparticles, it is essential to control the mechanistic steps involved in nanoparticle synthesis. A common method for synthesizing FePt nanoparticles involves the simultaneous decomposition and reduction in iron and platinum precursors, respectively. This simultaneous nucleation and growth method yields wide composition and size distributions. This paper describes and experimentally validates a methodology needed to tighten composition and size distributions for this process. By engineering the surfactant chemistry with tertiary phosphines to tightly bind the iron atoms in the iron precursor, uniform platinum rich seeds form during the initial stages of the synthesis. A thermodynamically preferred heterogeneous nucleation of iron atoms into these uniform platinum seeds in the subsequent stages produces a final dispersion with uniform particle-to-particle compositions. The paper addresses the understanding for optimizing the nucl...

FePt and Related Nanoparticles

This chapter reviews recent studies of chemically synthesized FePt and related nanoparticles. Various methods for synthesizing the nanoparticles and controlling their shape are described. Thermal effects in nanoparticles near the superparamagnetic limit are discussed. Some of the methods for reducing sintered grain growth during annealing to obtain the L10 phase are described, including the use of a hard shell, annealing in a salt matrix , and flash annealing . The effect of metal additives on the ordering temperature and on sintered grain growth is discussed. Additive Ag and Au significantly not only reduce the ordering temperature but also the grain growth temperature in close-packed 3-D arrays. Preliminary experiments that show additive Ag also reduces the ordering temperature when sintering is prevented. Easy-axis alignment of L10 FePt nanoparticles can be achieved by drying a nanoparticle dispersion in a magnetic field, and the effect of thermal fluctuations on orientation is discussed. Large particle-to-particle compositional distributions in chemically synthesized FePt nanoparticles have been measured. A method of determining the anisotropy distribution is described. Theoretical and experimental works showing the size effect on chemical ordering of FePt nanoparticles are discussed.

Depth Dependent Oxidation States in a PtRu Thin Film

The Pt-Ru alloy has received considerable attention because of its superior catalytic properties for use as the anode in automotive fuel cells. In particular, this alloy exhibits good CO tolerance. During methanol oxidation, intermediate CO is formed which binds strongly to Pt thereby blocking catalytic activity for pure Pt surfaces. When Ru is included, the Ru site catalyzes the oxidation of CO to CO2 and prevents CO poisoning of the Pt surface [1]. Thus, understanding how Ru is distributed over a Pt surface is critical. Atom probe tomography provides near atomic resolution of each element in 3-dimensions and is an ideal technique to provide this essential level of materials characterization. By being able to pin-point each atom, we can provide accurate physical descriptions of the surfaces to determine potential surface segregation effects which could enrich specific regions (free surfaces, grain boundaries, etc.) and change the catalytic response.