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C. N. R. Rao

Publications and source records attributed to C. N. R. Rao.

At least 19 recordsLinked to original sources

Highly tunable magnetic spirals and electric polarization in Gd$_{0.5}$Dy$_{0.5}$MnO$_3$

Recent progress in the field of multiferroics led to the discovery of many new materials in which ferroelectricity is induced by cycloidal spiral orders. The direction of the electric polarization is typically constrained by spin anisotropies and magnetic field. Here, we report that the mixed rare-earth manganite, Gd$_{0.5}$Dy$_{0.5}$MnO$_3$, exhibits a spontaneous electric polarization along a general direction in the crystallographic ac-plane, which is suppressed below 10 K but re-emerges in an applied magnetic field. Neutron diffraction measurements show that the polarization direction results from a large tilt of the spiral plane with respect to the crystallographic axes and that the suppression of ferroelectricity is caused by the transformation of a cycloidal spiral into a helical one, a unique property of this rare-earth manganite. The freedom in the orientation of the spiral plane allows for a fine magnetic control of ferroelectricity, i.e. a rotation as well as a strong enhancement of the polarization depending on the magnetic field direction. We show that this unusual behavior originates from the coupling between the transition metal and rare-earth magnetic subsystems.

cond-mat.str-el↗

Weyl semimetals as catalysts

The search for highly efficient and low-cost catalysts is one of the main driving forces in catalytic chemistry. Current strategies for the catalyst design focus on increasing the number and activity of local catalytic sites, such as the edge-sites of molybdenum disulfides in the hydrogen evolution reaction (HER). Here, we propose and demonstrate a different principle that goes beyond local site optimization by utilizing topological electronic states, a global property of the material, to spur catalytic activity. For HER, we have found excellent catalysts among the transition-metal monopnictides - NbP, TaP, NbAs, and TaAs - which were recently discovered to be topological Weyl semimetals. In addition to the free energy considerations we explore the role of metallicity, carrier mobility and topological electronic states for remarkable HER performance of these materials. The combination of robust topological surface states and large room temperature carrier mobility both of which originate from bulk Dirac bands of the Weyl semimetal appears to be the recipe for good HER catalyst. Our work provides a guiding principle for the discovery of novel catalysts from the emerging field of topological materials.

cond-mat.mtrl-sci↗

A combined experimental and theoretical study of the electronic and vibrational properties of bulk and few-layer Td-WTe2

The recent discovery of non-saturating giant positive magnetoresistance in Td-WTe2 has aroused great interest in this material. We have studied the structural, electronic and vibrational properties of bulk and few-layer Td-WTe2 experimentally and theoretically. Spin-orbit coupling is found to govern the semi-metallic character of Td-WTe2. Its structural link with the metallic 1T form provides an understanding of its structural stability. We observe a metal to insulator transition and a change in the sign of the Seebeck coefficient around 373 K. Lattice vibrations in Td-WTe2 have been analyzed by first principle calculations. Out of the 33 possible zone-center Raman active modes, five distinct Raman bands are observed around 112, 118, 134, 165 and 212 cm-1 in bulk Td-WTe2. Based on symmetry analysis and the calculated Raman tensors, we assign the intense bands at 165 cm-1 and 212 cm-1 to the A_1^' and A_1^" modes respectively. We have examined the effect of temperature and the number of layers on the Raman spectrum. Most of the bands of Td-WTe2 stiffen, and the ratio of the integrated intensities of the A_1^" to A_1^' bands decreases in the few-layer sample, while all the bands soften in both bulk and few-layer samples with increasing temperature.

cond-mat.mtrl-sci↗

Interplay of 4f-3d Magnetism and Ferroelectricity in DyFeO3

DyFeO3 exhibits a weak ferromagnetism (TNFe ~ 645 K) that disappears below a spin-reorientation (Morin) transition at TSRFe ~ 50 K. It is also known that applied magnetic field induces ferroelectricity at the magnetic ordering temperature of Dy-ions (TNDy ~ 4.5 K). Here, we show that the ferroelectricity exists in the weak ferromagnetic state (TSRFe < T < TN,C) without applying magnetic field, indicating the crucial role of weak ferromagnetism in inducing ferroelectricity. 57Fe Mössbauer studies show that hyperfine field (Bhf) deviates from mean field-like behaviour that is observed in the weak ferromagnetic state and decreases below the onset of spin-reorientation transition (80 K), implying that the Bhf above TSR had additional contribution from Dy-ions due to induced magnetization by the weak ferromagnetic moment of Fe-sublattice and below TSR, this contribution decreases due to collinear ordering of Fe-sublattice. These results clearly demonstrate the presence of magnetic interactions between Dy(4f) and Fe(3d) and their correlation with ferroelectricity in the weak ferromagnetic state of DyFeO3.

cond-mat.mtrl-sci↗

Ferroelectricity at the Néel Temperature of Chromium in Rare-earth Orthochromites: Interplay of Rare-earth and Cr Magnetism

We report ferroelectricity with fairly large spontaneous polarization (P ~ 0.2 - 0.8 \muC/cm2) below the Néel temperature of chromium (TNCr) in weakly ferromagnetic rare-earth orthochromites, RCrO3 (R=rare-earth) only when the rare-earth ion is magnetic. Intriguingly, the ferroelectricity in ErCrO3 (TC = 133 K) disappears at a spin-reorientation (Morin) transition (TSR ~ 22 K) below which the weak ferromagnetism associated with the Cr-sublattice also disappears, demonstrating the crucial role of weak ferromagnetism in inducing ferroelectricity. Further, the ferroelectric polarization (P) could be reversed by reversing the spontaneous magnetization (M) by changing the polarity of magnetic field, indicating a strong magnetoelectric effect. We suggest that the ferroelectricity occurs in RCrO3, due to the combined effect of poling field that breaks the symmetry and the exchange field on R-ion from Cr-sublattice stabilizes the polar state. We propose that a similar mechanism could work in the isostructural rare-earth orthoferrites, RFeO3 as well.

cond-mat.mtrl-sci↗

Field-induced Polar Order at the Néel Temperature of Chromium in Rare-earth Orthochromites: Interplay of Rare-earth and Cr Magnetism

We report field-induced switchable polarization (P = 0.2 ~ 0.8 microC/cm2) below the Néel temperature of chromium (TN Cr) in weakly ferromagnetic rareearth orthochromites, RCrO3 (R=rareearth) but only when the rareearth ion is magnetic. Intriguingly, the polarization in ErCrO3 (TC ~ 133 K) disappears at a spin reorientation (Morin) transition (TSR ~ 22 K) below which the weak ferromagnetism associated with the Cr sublattice also disappears, demonstrating the crucial role of weak ferromagnetism in inducing the polar order. Further, the polarization (P) is strongly influenced by applied magnetic field, indicating a strong magneto electric effect. We suggest that the polar order occurs in RCrO3, due to the combined effect of poling field that breaks the symmetry and the exchange field on R ion from Cr sublattice stabilizes the polar state. We propose that a similar mechanism could work in the isostructural rareearth orthoferrites, RFeO3 as well.

cond-mat.mtrl-sci↗

Multiferroic and magnetoelectric nature of GaFeO3, AlFeO3 and related oxides

GaFeO3, AlFeO3 and related oxides are ferrimagnetic exhibiting magnetodielectric effect. There has been no evidence to date for ferroelectricity and hence multiferroicity in these oxides. We have investigated these oxides as well as oxides of the composition Al1-x-yGaxFe1+yO3 (x = 0.2, y = 0.2) for possible ferroelectricity by carrying out pyroelectric measurements. These measurements establish the occurrence of ferroelectricity at low temperatures below the Nèel temperature in these oxides. They also exhibit significant magnetoelectric effect. We have tried to understand the origin of ferroelectricity based on non-centrosymmetric magnetic ordering and disorder by carrying out first-principles calculations.

cond-mat.mtrl-sci↗

Coupled Phonons, Magnetic Excitations and Ferroelectricity in AlFeO3: Raman and First-principles Studies

We determine the nature of coupled phonons and magnetic excitations in AlFeO3 using inelastic light scattering from 5 K to 315 K covering a spectral range from 100-2200 cm-1 and complementary first-principles density functional theory-based calculations. A strong spin-phonon coupling and magnetic ordering induced phonon renormalization are evident in (a) anomalous temperature dependence of many modes with frequencies below 850 cm-1, particularly near the magnetic transition temperature Tc ~ 250 K, (b) distinct changes in band positions of high frequency Raman bands between 1100-1800 cm-1, in particular a broad mode near 1250 cm-1 appears only below Tc attributed to the two-magnon Raman scattering. We also observe weak anomalies in the mode frequencies at ~ 100 K, due to a magnetically driven ferroelectric phase transition. Understanding of these experimental observations has been possible on the basis of first-principles calculations of phonons spectrum and their coupling with spins.

cond-mat.str-el↗

XPS evidence for molecular charge-transfer doping of graphene

By employing x-ray photoelectron spectroscopy (XPS), we have been able to establish the occurrence of charge-transfer doping in few-layer graphene covered with electron acceptor (TCNE) and donor (TTF) molecules. We have performed quantitative estimates of the extent of charge transfer in these complexes and elucidated the origin of unusual shifts of their Raman G bands and explained the differences in the dependence of conductivity on n- and p-doping. The study unravels the cause of the apparent difference between the charge-transfer doping and electrochemical doping.

cond-mat.mtrl-sci↗

Graphene analogue BCN: femtosecond nonlinear optical susceptibility and hot carrier dynamics

Third-order nonlinear absorption and refraction coefficients of a few-layer boron carbon nitride (BCN) and reduced graphene oxide (RGO) suspensions have been measured at 3.2 eV in the femtosecond regime. Optical limiting behavior is exhibited by BCN as compared to saturable absorption in RGO. Nondegenerate time-resolved differential transmissions from BCN and RGO show different relaxation times. These differences in the optical nonlinearity and carrier dynamics are discussed in the light of semiconducting electronic band structure of BCN vis-à-vis the Dirac linear band structure of graphene.

cond-mat.mes-hall↗

Graphene produced by radiation-induced reduction of graphene oxide

Effect of irradiation on graphene oxide by sunlight, UV light and KrF excimer laser has been investigated in detail. Both sunlight and ultraviolet light reduce graphene oxide well after prolonged irradiation, but laser irradiation produces graphene with negligible oxygen functionalities within a short time. Laser irradiation is also useful for one-step synthesis of metal particle decorated graphene. Laser irradiation of graphene oxide appears to be an efficient procedure for large-scale synthesis of graphene.

cond-mat.mes-hall↗

Quenching of fluorescence of aromatic molecules by graphene due to electron transfer

Investigations on the fluorescence quenching of graphene have been carried out with two organic donor molecules, pyrene butanaoic acid succinimidyl ester (PyBS, I) and oligo(p-phenylenevinylene) methyl ester (OPV-ester, II). Absorption and photoluminescence spectra of I and II recorded in mixture with increasing the concentrations of graphene showed no change in the former, but remarkable quenching of fluorescence. The property of graphene to quench fluorescence of these aromatic molecules is shown to be associated with photo-induced electron transfer, on the basis of fluorescence decay and time-resolved transient absorption spectroscopic measurements.

cond-mat.mtrl-sci↗

Temperature-Dependent Infrared Reflectivity Studies of Multiferroic TbMnO_{3}: Evidence for Spin-Phonon Coupling

We have measured near normal incidence far infrared (FIR) reflectivity spectra of a single crystal of TbMnO3 from 10K to 300K in the spectral range of 50 cm$^{-1}$ to 700 cm$^{-1}$. Fifteen transverse optic (TO) and longitudinal optic (LO) modes are identified in the imaginary part of the dielectric function $ε_2$($ω$) and energy loss function Im(-1/$ε$($ω$)), respectively. Some of the observed phonon modes show anomalous softening below the magnetic transition temperature T$_N$ (~ 46K). We attribute this anomalous softening to the spin-phonon coupling caused by phonon modulation of the super-exchange integral between the Mn$^{3+}$ spins. The effective charge of oxygen (Z$_O$) calculated using the measured LO-TO splitting increases below T$_N$.

cond-mat.mtrl-sci↗

Raman evidence for Orbiton-Mediated Multiphonon Scattering in Multiferroic TbMnO$_3$

Temperature-dependent Raman spectra of TbMnO$_3$ from 5 K to 300 K in the spectral range of 200 to 1525 cm$^{-1}$ show five first-order Raman allowed modes and two high frequency modes. The intensity ratio of the high frequency Raman band to the corresponding first order Raman mode is nearly constant and high ($\sim$ 0.6) at all temperatures, suggesting a orbiton-phonon mixed nature of the high frequency mode. One of the first order phonon modes shows anomalous softening below T$_N$ ($\sim$ 46 K), suggesting a strong spin-phonon coupling.

cond-mat.str-el↗

Femtosecond carrier dynamics and saturable absorption in graphene suspensions

Nonlinear optical properties and carrier relaxation dynamics in graphene, suspended in three different solvents, are investigated using femtosecond (80 fs pulses) Z-scan and degenerate pumpprobe spectroscopy at 790 nm. The results demonstrate saturable absorption property of graphene with a nonlinear absorption coefficient, $beta$, of ~2 to 9x10^-8 cm/W. Two distinct time scales associated with the relaxation of photoexcited carriers, a fast one in the range of 130-330 fs (related to carrier-carrier scattering) followed by a slower one in 3.5-4.9 ps range (associated with carrier-phonon scattering) are observed.

cond-mat.mtrl-sci↗

NO2 and Humidity Sensing Characteristics of Few-layer Graphene

Sensing characteristics of few-layer graphenes for NO2 and humidity have been investigated with graphene samples prepared by the thermal exfoliation of graphitic oxide (EG), conversion of nanodiamond (DG) and arc-discharge of graphite in hydrogen (HG). The sensitivity for NO2 is found to be highest with DG. Nitrogen-doped HG (n-type) shows increased sensitivity for NO2 compared to pure HG. The highest sensitivity for humidity is observed with HG. The sensing characteristics of graphene have been examined for different aliphatic alcohols and the sensitivity is found to vary with the chain length and branching.

physics.chem-ph↗

Implications and consequences of ferromagnetism universally exhibited by inorganic nanoparticles

Occurrence of surface ferromagnetism in inorganic nanoprticles as a universal property not only explains many of the unusual magnetic features of oxidic thin films, but also suggests its possible use in creating new materials, as exemplified by multiferroic BaTiO3 nanoparticles. While the use of Mn-doped ZnO and such materials in spintronics appears doubtful, it is possible to have materials exhibiting coexistence of (bulk) superconductivity with (surface) ferromagnetism.

cond-mat.mtrl-sci↗