Vikash Mishra

Observation of large dielectric permittivity and dielectric relaxation phenomenon in Mn-doped lanthanum gallate

Polycrystalline LaGa1−xMnxO3 (x = 0, 0.05, 0.1, 0.15, 0.2 and 0.3) samples were prepared via the solid-state reaction method. These samples were characterized using synchrotron-based X-ray diffraction (XRD) and the X-ray absorption near edge structure (XANES). XRD studies confirm the orthorhombic structure for the prepared samples whereas XANES analysis reveals the co-existence of Mn3+ and Mn4+ in all Mn-doped samples. Dielectric relaxation is observed for all Mn-doped samples whereas a large dielectric constant (e′) is perceived in samples with higher Mn doping (x = 0.2 and x = 0.3). Occurrence of a large e′ is attributed to the huge decrease in impedance with increasing Mn doping which is governed by the hopping charge transport and extrinsic interface effects, whereas at high frequencies, this effect is observed possibly due to dipolar effects associated with the possible off-centrosymmetry of the MnO6 octahedron which is indicated by the pre-edge feature (Mn K-edge) in XANES and validated through P–E measurements. The appearance of dielectric relaxation was credited to the dipolar effects associated with the flipping of the Mn3+/Mn4+ dipole i.e., with the hopping of charge carriers between Mn3+ and Mn4+ under an external electric field. The value of activation energy (Ea = 0.36 eV), extracted from temperature-dependent dielectric data, reveals the polaron hopping mechanism.

Room temperature magnetodielectric studies on Mn-doped LaGaO3

Polycrystalline samples of LaGa1−xMnxO3 (0 ≤ x ≤ 0.3) were prepared by the solid-state reaction route. The phase purity of these samples was confirmed by powder x-ray diffraction experiments carried out on BL-12 at the Indus-2 synchrotron radiation source. The sample with x = 0.2 shows significant change in the value of capacitance with the application of a magnetic field. The observed results were understood by systematically analyzing magnetocapacitance (MC), magnetoresistance (MR), and dielectric loss as a function of frequency. Our results and analysis suggest that the observed magnetodielectric (MD) coupling may be due to the MR effect of the Maxwell–Wagner type and/or field-induced dipolar relaxation. Further, it is observed that oxygen stoichiometry plays a very crucial role in the observed MD coupling.

Electronic and optical properties of BaTiO3 across tetragonal to cubic phase transition: An experimental and theoretical investigation

Temperature dependent diffuse reflectance spectroscopy measurements were carried out on polycrystalline samples of BaTiO3 across the tetragonal to cubic structural phase transition temperature (TP). The values of various optical parameters such as band gap (Eg), Urbach energy (Eu), and Urbach focus (E0) were estimated in the temperature range of 300 K to 480 K. It was observed that with increasing temperature, Eg decreases and shows a sharp anomaly at TP. First principle studies were employed in order to understand the observed change in Eg due to the structural phase transition. Near TP, there exist two values of E0, suggesting the presence of electronic heterogeneity. Further, near TP, Eu shows metastability, i.e., the value of Eu at temperature T is not constant but is a function of time (t). Interestingly, it is observed that the ratio of Eu (t=0)/Eu (t = tm), almost remains constant at 300 K (pure tetragonal phase) and at 450 K (pure cubic phase), whereas this ratio decreases close to the transition temperature, which confirms the presence of electronic metastability in the pure BaTiO3. The time dependence of Eu, which also shows an influence of the observed metastability can be fitted with the stretched exponential function, suggesting the presence of a dynamic heterogeneous electronic disorder in the sample across TP. First principle studies suggest that the observed phase coexistence may be due to a very small difference between the total cohesive energy of the tetragonal and the cubic structure of BaTiO3. The present work implies that the optical studies may be a sensitive probe of disorder/heterogeneity in the sample.

Fe doped LaGaO3: good white light emitters

A polycrystalline sample of LaGa1−xFexO3 has been prepared by solid state reaction. The structural, optical and electronic structure of Fe doped LaGaO3 have been investigated. It is observed that with Fe doping the lattice parameter of the prepared samples systematically increases whereas the optical band gap decreases. First-principles density functional theory (DFT) calculations were carried out to understand the effect of Fe doping on the electronic structure and to understand the origin of systematic decrease in optical band gap. DFT studies suggests that there exists an indirect band gap to direct band gap transition with Fe doping which is further confirmed using photoluminescence measurements. Photoluminescence studies suggest that Fe doped LaGaO3 are potential candidates as white light emitting materials.

Observation of room temperature magnetodielectric effect in Mn-doped lanthanum gallate and study of its magnetic properties

Polycrystalline samples of Mn-doped LaGa1−xMnxO3 (LGMO) with 0 ≤ x ≤ 0.2 have been prepared via solid-state reaction method. The structural phase purity of all these samples was confirmed by powder X-ray diffraction experiments carried out at the BL-12 beamline of the Indus-2 synchrotron radiation source. Room-temperature (RT) dielectric measurements were performed in the absence and presence of a magnetic field. A noticeable magnetodielectric (MD) effect, i.e., a change in the value of the dielectric constant owing to the application of a low magnetic field, was observed in the LGMO sample with x = 0.2 (LG8M2O). In order to separate the intrinsic and resistive contributions present in the observed RT MD effect, magnetoresistance impedance spectroscopy (MRIS) was performed at RT. The present MRIS analysis suggests that at frequencies corresponding to the grain contribution (≥105 Hz for the present samples), the observed MD phenomenon appears to be an intrinsic property of the presently studied samples, whereas at lower probing frequencies (<105 Hz) the observed change appears to be dominated by MR (considering frequency-dependent resistance), which was possibly due to the coexistence of Mn3+ and Mn4+. The coexistence of Mn3+ and Mn4+ was revealed by XANES (Mn K-edge) spectroscopy. Moreover, RT and low-temperature magnetization–magnetic field (M–H) measurements, along with M–T measurements in FC and ZFC modes, were performed to investigate the state of magnetic ordering. The appearance of a narrow M–H loop indicates the presence of some magnetic ordering at RT. Furthermore, a ferromagnetic (FM) transition observed around 36 K and a normal M–H loop with saturated magnetization recorded at 5 K confirm FM ordering at low temperatures, whereas a bifurcation in FC-ZFC curves indicates competing FM and antiferromagnetic (AFM) interactions at low temperatures.

Possibility of spin-polarized transport in edge fluorinated armchair boron nitride nanoribbons

We predict the possibility of spin based electronic transport in edge fluorinated armchair boron nitride nanoribbons (ABNNRs). The structural stability, electronic and magnetic properties of these edge fluorinated ABNNRs have been systematically analyzed by means of first-principles calculations within the local spin-density approximation (LSDA). Regardless of their width, ABNNRs with F-passivation at only the edge-B atoms are found to be thermodynamically stable and half-metallic in nature. The spin polarized states are found to be ∼0.4 eV more stable than that of spin compensated states. Further, upto 100% spin polarization is expected in ABNNRs with F-passivation at only the edge-B atoms as indicated by the giant splitting of spin states which is observed in the corresponding band structures, DOS and transmission spectrum. The existence of half-metallicity is attributed to the localization of electronic charge at unpassivated edge-N atoms as revealed from the analysis of Bloch states and projected density of states (PDOS). Importantly, present stability analysis suggests that the possibility of experimental realization of spin polarized transport in ABNNRs is more promising via F-passivation of ribbon edges than that of H-passivation. The observed half-metallic nature and large difference in the energies (∼0.4 eV) of spin polarized and spin compensated states projects these half-metallic ABNNRs as potential candidates for inorganic spintronic applications.

Importance of frequency dependent magnetoresistance measurements in analysing the intrinsicality of magnetodielectric effect: A case study

Magnetodielectric (MD) materials have attracted considerable attention due to their intriguing physics and potential future applications. However, the intrinsicality of the MD effect is always a major concern in such materials as the MD effect may arise also due to the MR (magnetoresistance) effect. In the present case study, we report an experimental approach to analyse and separate the intrinsic and MR dominated contributions of the MD phenomenon. For this purpose, polycrystalline samples of LaGa1-xAxO3 (A = Mn/Fe) have been prepared by solid state reaction method. The purity of their structural phase (orthorhombic) has been validated by refining the X-ray diffraction data. The RTMD (room temperature MD) response has been recorded over a frequency range of 20 Hz to 10 MHz. In order to analyse the intrinsicality of the MD effect, FDMR (frequency dependent MR) by means of IS (impedance spectroscopy) and dc MR measurements in four probe geometry have been carried out at RT. A significant RTMD effect has been observed in selected Mn/Fe doped LaGaO3 (LGO) compositions. The mechanism of MR free/intrinsic MD effect, observed in Mn/Fe doped LGO, has been understood speculatively in terms of modified cell volume associated with the reorientation/retransformation of spin-coupled Mn/Fe orbitals due to the application of magnetic field. The present analysis suggests that in order to justify the intrinsic/resistive origin of the MD phenomenon, FDMR measurements are more useful than measuring only dc MR or analysing the trends of magnetic field dependent change in the dielectric constant and tanδ. On the basis of the present case study, we propose that IS (FDMR) alone can be used as an effective experimental tool to detect and analyse the resistive and intrinsic parts contributing to the MD phenomenon.Magnetodielectric (MD) materials have attracted considerable attention due to their intriguing physics and potential future applications. However, the intrinsicality of the MD effect is always a major concern in such materials as the MD effect may arise also due to the MR (magnetoresistance) effect. In the present case study, we report an experimental approach to analyse and separate the intrinsic and MR dominated contributions of the MD phenomenon. For this purpose, polycrystalline samples of LaGa1-xAxO3 (A = Mn/Fe) have been prepared by solid state reaction method. The purity of their structural phase (orthorhombic) has been validated by refining the X-ray diffraction data. The RTMD (room temperature MD) response has been recorded over a frequency range of 20 Hz to 10 MHz. In order to analyse the intrinsicality of the MD effect, FDMR (frequency dependent MR) by means of IS (impedance spectroscopy) and dc MR measurements in four probe geometry have been carried out at RT. A significant RTMD effect has be...

Disappearance of dielectric anomaly in spite of presence of structural phase transition in reduced BaTiO3: Effect of defect states within the bandgap

We report the structural, optical, ferroelectric, and dielectric properties of reduced BaTiO3 samples. For this purpose, oxygen vacancies in BaTiO3 are created by heating these samples with a Ti metal in a vacuum environment at different temperatures. It is observed that with an increase in oxygen deficiencies, the c/a ratio decreases as compared to that of the oxygen treated sample. The ferroelectric properties of the oxygen deficient samples are visibly different as compared to those of the oxygen treated sample. The disappearance of the P-E loop and the anomaly in the temperature variation of the dielectric constant have been observed; however, the structural phase transition corresponding to ferroelectric phase transitions still persists. Thus, it appears that the anomaly in dielectric data and the presence of the P-E loop are getting masked possibly by the Maxwell-Wagner effect. The presence of Ti+3 states in the prepared samples has been confirmed by X-ray absorption near edge structure measurements. The Kubelka-Munk optical absorption shows the presence of extra states below fundamental transition, indicating the emergence of new electronic states within the bandgap, which might be due to Ti+3 states. These new states appear at different energy positions, and with different intensities for different samples, which are reduced in the presence of Ti. These new states within the bandgap appear to modify the electronic structure, thereby reducing the overall bandgap, and hence, they seem to modify the ferroelectric and dielectric properties of the samples. Our results may be treated as experimental evidence for theoretically proposed defect states in oxygen deficient or reduced BaTiO3.We report the structural, optical, ferroelectric, and dielectric properties of reduced BaTiO3 samples. For this purpose, oxygen vacancies in BaTiO3 are created by heating these samples with a Ti metal in a vacuum environment at different temperatures. It is observed that with an increase in oxygen deficiencies, the c/a ratio decreases as compared to that of the oxygen treated sample. The ferroelectric properties of the oxygen deficient samples are visibly different as compared to those of the oxygen treated sample. The disappearance of the P-E loop and the anomaly in the temperature variation of the dielectric constant have been observed; however, the structural phase transition corresponding to ferroelectric phase transitions still persists. Thus, it appears that the anomaly in dielectric data and the presence of the P-E loop are getting masked possibly by the Maxwell-Wagner effect. The presence of Ti+3 states in the prepared samples has been confirmed by X-ray absorption near edge structure measurements...

Effect of Mn doping on dielectric response and optical band gap of LaGaO3

Abstract In order to realize the effect of Mn doping on dielectric behavior and optical band gap (Eg) of Lanthanum Gallate; pure and Mn doped LaGaO3 samples were prepared. The phase purity of these samples was confirmed by x-ray diffraction experiments. It was found that all samples possess orthorhombic structure. Room temperature (RT) dielectric response and Eg of LaGa1−xMnxO3 (LGMO) with, x = 0.0 to 0.9, has been recorded using impedance analyzer (LCR meter) and diffuse reflectance spectroscopy respectively. It has been observed that at RT, pure LaGaO3 exhibits moderate dielectric constant (ε′ ≈ 25) with very low dielectric loss (tan δ). Interestingly, the value of RT ε′ significantly increases with Mn doping whereas tan δ remains relatively low upto x = 0.4 and increases abruptly x > 0.4. The observed increase in ε′ and tan δ with Mn doping has been understood in terms of structural coherency and systematic decrease in Eg. A shift in ε′-anomaly (tan δ-peak) with increasing Mn percentage and low frequency large ε′ were also observed in Mn doped LGO. Both of these effects have been understood in terms of coexisting Mn3+ and Mn4+ ions. The LGMO samples (x ≤ 0.4) showing high value of ε′ and very low tan δ can be suitable candidates for capacitive applications.

Intrinsic Half-metallicity in Edge Fluorinated Armchair Boron Nitride Nanoribbons

We predict intrinsic half-metallicity in armchair boron nitride nanoribbons (ABNNRs) via edge fluorination. The stability, electronic and magnetic properties of bare and edge fluorinated ABNNRs have been systematically analyzed by means of first-principles calculations within the local spin-density approximation (LSDA). The ribbons whose only edge-B atoms passivated with F atoms (i.e., edge-N atoms are un-passivated), regardless of width, are found half-metallic with a half-metal gap of 0.3 eV. A 100 \% spin polarized charge transport across the Fermi level is expected for such ribbons as the spin polarized states are