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Kumar, Amit

Publications and source records attributed to Kumar, Amit.

At least 109 records · Page 6

Mutual Ferromagnetic-Ferroelectric Coupling in Multiferroic Copper-Doped ZnO

A mutual ferromagnetic and ferroelectric coupling (multiferroic behavior) in Cu-doped ZnO is demonstrated via deterministic control of Cu doping and defect engineering. The coexistence of multivalence Cu ions and oxygen vacancies is important to multiferroic behaviors in ZnO:Cu. The samples show clear ferroelectric and ferromagnetic domain patterns. These domain structures may be written reversibly via electric and magnetic bias.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Thickness dependent self limiting 1-D tin oxide nanowire arrays by nanosecond pulsed laser irradiation

Fast, sensitive and discriminating detection of hydrogen at room temperature is crucial for storage, transportation, and distribution of hydrogen as an energy source. One dimensional nanowires of SnO2 are potential candidates for improved H2 sensor performance. The single directional conducting continuous nanowires can decrease electrical noise, and their large active surface area could improve the response and recovery time of the sensor. In this work we discuss synthesis and characterization of nanowire arrays made using nanosecond ultraviolet wavelength (266 nm) laser interference processing of ultrathin SnO2 films on SiO2 substrates. The laser energy was chosen to be above the melting point of the films. The results show that the final nanowire formation is dominated by preferential evaporation as compared to thermocapillary flow. The nanowire height (and hence wire aspect ratio) increased with increasing initial film thickness ho and with increasing laser energy density Eo. Furthermore, a self-limiting effect was observed where-in the wire formation ceased at a specific final remaining thickness of SnO2 that was almost independent of ho for a given Eo. To understand these effects, finite element modeling of the nanoscale laser heating was performed. This showed that the temperature rise under laser heating was a strong non-monotonic function of film thickness. As a result, the preferential evaporation rate varies as wire formation occurs, eventually leading to a shut-off of evaporation at a characteristic thickness. This results in the stoppage of wire formation. This combination of nanosecond pulsed laser experiments and thermal modeling shows that several unique synthesis approaches can be utilized to control the nanowire characteristics.

08 HYDROGEN↗

Nanoscale Control of Phase Variants in Strain-Engineered BiFeO3

Development of magnetoelectric, electromechanical, and photovoltaic devices based on mixed-phase rhombohedral tetragonal (R-T) BiFeO3 (BFO) systems is possible only if the control of the engineered R phase variants is realized. Accordingly, we explore the mechanism of a bias induced phase transformation in this system. Single point spectroscopy demonstrates that the T->R transition is activated at lower voltages compared to T->T polarization switching. With phase field modeling, the transition is shown to be electrically driven. We further demonstrate that symmetry of formed R-phase rosettes can be broken by a proximal probe motion, allowing controlled creation of R variants with defined orientation. This approach opens a pathway to designing next-generation magnetoelectronic and data storage devices in the nanoscale.

Bismuth ferrite↗

Mapping Irreversible Electrochemical Processes on the Nanoscale: Ionic Phenomena in Li-ion Conductive Glass Ceramics

A scanning probe microscopy approach for mapping local irreversible electrochemical processes based on detection of bias-induced frequency shifts of cantilevers in contact with the electrochemically active surface is demonstrated. Using Li-ion conductive glass ceramic as a model, we demonstrate near unity transference numbers for ionic transport and establish detection limits for current-based and strain based detection. The tip-induced electrochemical process is shown to be a first order transformation and nucleation potential is close to the Li-metal reduction potential. Spatial variability of the nucleation bias is explored and linked to the local phase composition. These studies both provide insight into nanoscale ionic phenomena in practical Li-ion electrolyte, and also open pathways for probing irreversible electrochemical, bias-induced, and thermal transformations in nanoscale systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nonlinear phenomena in multiferroic nanocapacitor: Joule heating and electromechanical effects

We demonstrate an approach for probing nonlinear electromechanical responses in BiFeO3 thin film nanocapacitors using half-harmonic band excitation piezoresponse force microscopy (PFM). Nonlinear PFM images of nanocapacitor arrays show clearly visible clusters of capacitors associated with variations of local leakage current through the BiFeO3 film. Strain spectroscopy measurements and finite element modeling point to significance of the Joule heating and show that the thermal effects caused by the Joule heating can provide nontrivial contributions to the nonlinear electromechanical responses in ferroic nanostructures. This approach can be further extended to unambiguous mapping of electrostatic signal contributions to PFM and related techniques.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Real-space mapping of dynamic phenomena during hysteresis loop measurements: Dynamic Switching Spectroscopy Piezoresponse Force Microscopy

Dynamic switching spectroscopy piezoresponse force microscopy is developed to separate thermodynamic and kinetic effects in local bias-induced phase transitions. The approaches for visualization and analysis of 5D data are discussed. The spatial and voltage variability of relaxation behavior of the a-c domain lead zirconate-titanate surface suggest the interpretation in terms of surface charge dynamics. This approach is applicable to local studies of dynamic behavior in any system with reversible bias-induced phase transitions ranging from ferroelectrics and multiferroics to ionic systems such as Li-ion and oxygen-ion conductors in batteries, fuel cells, and electroresistive systems.

30 DIRECT ENERGY CONVERSION↗

Composition dependence of local piezoelectric nonlinearity in (0.3)Pb(Ni0.33Nb0.67)O-3-(0.7)Pb(ZrxTi1-x)O-3 films

The composition dependence of dielectric and piezoelectric nonlinearities were characterized in epitaxially grown (0.3)Pb(Ni0.33Nb0.67)O3-(0.7)Pb(ZrxTi1 x)O3 thin films deposited on SrTiO3. Tetragonal, morphotropic phase boundary (MPB) and rhombohedral films were prepared by changing the Zr/Ti ratio. The relative dielectric permittivity r and the converse piezoelectric coefficient d33,f were found to follow the Rayleigh law. The local piezoelectric nonlinearity map showed the formation of micron-sized clusters of higher nonlinear activity for the MPB and rhombohedral compositions. The ratios of the irreversible to the reversible Rayleigh constants / init and the spatially averaged d/d33,init ratio were larger for the rhombohedral and MPB compositions compared to the tetragonal composition. The larger dielectric and piezoelectric nonlinearities observed for the rhombohedral sample are interpreted in terms of a higher domain wall mobility due to a smaller ferroelectric distortion and superior crystal quality.

Griggio, Flavio↗

Ferroelectric and electrical characterization of multiferroic BiFeO3 at the single nanoparticle level

Ferroelectric BiFeO3 (BFO) nanoparticles deposited on epitaxial substrates of SrRuO3 (SRO) and La1xSrxMnO3 (LSMO) were studied using band excitation piezoresponse spectroscopy (BEPS), piezoresponse force microscopy (PFM), and ferromagnetic resonance (FMR). BEPS confirms that the nanoparticles are ferroelectric in nature. Switching behavior of nanoparticle clusters were studied and showed evidence for inhomogeneous switching. The dimensionality of domains within nanoparticles was found to be fractal in nature, with a dimensionality constant of 1.4, on par with ferroelectric BFO thin-films under 100 nm in thickness. Ferromagnetic resonance studies indicate BFO nanoparticles only weakly affect the magnetic response of LSMO.

Ferroelectric↗

Mapping piezoelectric nonlinearity in the Rayleigh regime using band excitation piezoresponse force microscopy

Band excitation piezoresponse force microscopy enables local investigation of the nonlinear piezoelectric behavior of ferroelectric thin films. However, the presence of additional nonlinearity associated with the dynamic resonant response of the tip-surface junction can complicate the study of a material s nonlinearity. Here, the relative importance of the two non-linearity sources was examined as a function of the excitation function. It was found that in order to minimize the effects of nonlinear tip-surface interactions but achieve good signal to noise level, an optimal excitation function must be used.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

ESM of Ionic and Electrochemical Phenomena on the Nanoscale

Operation of energy storage and conversion devices is ultimately controlled by series of intertwined ionic and electronic transport processes and electrochemical reactions at surfaces and interfaces, strongly mediated by strain and mechanical processes [1-4]. In a typical fuel cell, these include chemical species transport in porous cathode and anode materials, gas-solid electrochemical reactions at grains and triple-phase boundaries (TPBs), ionic and electronic flows in multicomponent electrodes, and chemical and electronic potential drops at internal interfaces in electrodes and electrolytes. All these phenomena are sensitively affected by the microstructure of materials from device level to the atomic scales as illustrated in Fig. 1. Similar spectrum of length scales and phenomena underpin operation of other energy systems including primary and secondary batteries, as well as hybrid systems such flow and metal-air/water batteries.

25 ENERGY STORAGE↗

Spatially Resolved Mapping of Disorder Type and Distribution in Random Systems using Artificial Neural Network Recognition

The spatial variability of the polarization dynamics in thin film ferroelectric capacitors was probed by recognition analysis of spatially-resolved spectroscopic data. Switching spectroscopy piezoresponse force microscopy was used to measure local hysteresis loops and map them on a 2D random-bond, random-field Ising model. A neural-network based recognition approach was utilized to analyze the hysteresis loops and their spatial variability. Strong variability is observed in the polarization dynamics around macroscopic cracks due to the modified local elastic and electric boundary conditions, with most pronounced effect on the length scale of ~100 nm away from the crack.

36 MATERIALS SCIENCE↗

Measuring oxygen reduction/evolution reactions on the nanoscale

The efficiency of fuel cells and metal-air batteries is significantly limited by the activation of oxygen reduction and evolution reactions (ORR/OER). Despite the well-recognized role of oxygen reaction kinetics on the viability of energy technologies, the governing mechanisms remain elusive and until now addressable only by macroscopic studies. This lack of nanoscale understanding precludes optimization of material architecture. Here we report direct measurements of oxygen reduction/evolution reactions and oxygen vacancy diffusion on oxygen-ion conductive solid surfaces with sub-10 nanometer resolution. In electrochemical strain microscopy (ESM), the biased scanning probe microscopy tip acts as a moving, electrocatalytically active probe exploring local electrochemical activity. The probe concentrates an electric field in a nanometer-scale volume of material, and bias-induced, picometer-level surface displacements provide information on local electrochemical processes. Systematic mapping of oxygen activity on bare and Pt-functionalized yttria-stabilized zirconia (YSZ) surfaces is demonstrated. This approach allows directly visualization of ORR/OER activation process at the triple-phase boundary, and can be extended to broad spectrum of oxygen-conductive and electrocatalytic materials.

30 DIRECT ENERGY CONVERSION↗

First-Order Reversal Curve Probing of Spatially Resolved Polarization Dynamics in Ferroelectric Nanocapacitors

Spatially resolved polarization switching in ferroelectric nanocapacitors was studied on the sub-25 nm scale using the first-order reversal curve (FORC) method. The chosen capacitor geometry allows both a high-veracity observation of the ferroelastic domain structure and the mapping of polarization switching in a uniform field, synergistically combining microstructural observations and probing of uniform-field polarization responses as relevant to device operation. A classical Kolmogorov-Avrami-Ishibashi model has been adapted to the voltage domain and the individual switching dynamics of the FORC response curves are well approximated by the adapted model. The comparison with microstructures suggests a strong spatial variability of the switching dynamics inside the nanocapacitors.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Probing Li-ion Dynamics and Reactivity on the Nanoscale

Progress in development and optimization of energy storage and conversion materials necessitates understanding their ionic and electrochemical functionality on the nanometer scale level of single grain cluster, grain, or extended defect. Classical electrochemical strategies based on Faradaic current detection are fundamentally limited on the nanoscale. Here, we review principles and recent applications of Electrochemical Strain Microscopy (ESM), a scanning probe microscopy (SPM) technique utilizing intrinsic coupling between ionic pehnomena and molar volumes. ESM imaging, as well as time and voltage spectroscopies, are illustrated for several Li-ion cathode and anode materials. Perspectives for future ESM development and applications to other ionic systems are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

ESM of ionic and electrochemical phenomena on the nanoscale

Operation of energy storage and conversion devices is ultimately controlled by series of intertwined ionic and electronic transport processes and electrochemical reactions at surfaces and interfaces, strongly mediated by strain and mechanical processes. In a typical fuel cell, these include chemical species transport in porous cathode and anode materials, gas-solid electrochemical reactions at grains and triple-phase boundaries (TPBs), ionic and electronic flows in multicomponent electrodes, and chemical and electronic potential drops at internal interfaces in electrodes and electrolytes. Furthermore, all these phenomena are sensitively affected by the microstructure of materials from device level to the atomic scales. Similar spectrum of length scales and phenomena underpin operation of other energy systems including primary and secondary batteries, as well as hybrid systems such flow and metal-air/water batteries.

36 MATERIALS SCIENCE↗

Study Of Nature Of Structural Defects In A Prussian Blue Type Cu{sub 0.73}Mn{sub 0.77}[Fe(CN){sub 6}]{center_dot}zH{sub 2}O Molecular Magnet

We have determined crystal structure and nature of structural defects in the Cu{sub 0.73}Mn{sub 0.77}[Fe(CN){sub 6}]{center_dot}zH{sub 2}O molecular magnetic compound by employing the Rietveld refinement and reverse Monte Carlo (RMC) simulation techniques on the neutron scattering data. It crystallizes in a face centred cubic structure (Space group: Fm3m). The analysis of the pair-correlation functions for the oxygen atoms of the coordinated and non-coordinated water molecules reveals a correlated local ordering of water molecules at and around the empty Fe(CN){sub 6} sites in this compound.

36 MATERIALS SCIENCE↗