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C. W. A. Paschoal

Publications and source records attributed to C. W. A. Paschoal.

14 recordsLinked to original sources

Coordination-Induced Tuning of Ligand-Centered Red Emission in a cis-[Cd(Tz)2(py)2] Complex for Light-Emitting Diodes

Organic--inorganic complexes are promising materials for light-emitting applications. Here, we report a new organometallic complex, cis-[Cd(Tz)$_2$(py)$_2$], featuring a distorted octahedral Cd(II) coordination environment. IR and Raman spectroscopy reveal pronounced coordination-induced changes, particularly in the Raman response of the triazene moiety, indicating electronic and structural perturbation upon Cd(II) complexation. Hirshfeld surface analysis shows that the crystal packing is mainly governed by H$\cdots$H, O$\cdots$H/H$\cdots$O, and C$\cdots$H/H$\cdots$C contacts, whereas $π$--$π$ stacking interactions contribute modestly. Solid-state UV--Vis spectroscopy reveals broad absorption from $\sim$700 to 200 nm and a direct optical band gap of 1.83 eV, indicating semiconductor-like behavior. Photoluminescence measurements show a broad emission band at 500--850 nm with enhanced red contribution upon coordination. The emission is mainly assigned to ligand-centered transitions ($π\rightarrow π^*$ and $n \rightarrow π^*$), consistent with the $d^{10}$ configuration of Cd(II), which suppresses metal-centered and charge-transfer processes. The CIE chromaticity coordinates confirm warm emission, highlighting the potential of cis-[Cd(Tz)$_2$(py)$_2$] for red-emitting optoelectronic applications.

cond-mat.mtrl-sci↗

Electron-Phonon Coupling Mediated by Fröhlich Interaction in Rb2SnBr6 Perovskite

Due to their well-suited optoelectronic properties, metal halide perovskites are emerging semiconductor materials with potential applications in solar cells, detectors, and light-emitting diodes. Beyond the traditional 3D perovskites, low-dimensional counterparts have more attractive effects such as excitonic emissions and quantum confinements that are enhanced by the reduced dimensionality, which involve the Electron-Phonon Coupling (EPC). Such phenomenon, which comprehends the interaction between charge carriers and lattice vibrations, usually strongly impacts the photoluminescence (PL) response in low-dimensional frameworks. In this paper, we investigated the intrinsic EPC onto low-temperature PL of the zero-dimensional (0D) Rb2SnBr6 perovskite. Temperature-dependent PL measurements, complemented by various characterization techniques and theoretical calculations, revealed broadband emission with a significant Stokes shift attributed to self-trapped excitons (STEs). The Fröhlich mechanism, mediated by interactions between excitonic charge carriers and longitudinal optical (LO) phonons, primarily accounts for the emission broadening through phonon-assisted radiative recombination. The EPC strength was evaluated through the Huang-Rhys factor S=34, confirming strong correlations between electronic and vibrational properties and supporting the STE emission assumption. The possible mechanism of STE formation was evaluated by the Fröhlich parameter α of 1.94 for electrons and 4.73 for holes, which points out a major contribution of the hole-polaron quasi-particle on exciton trapping. Our findings give insights regarding the influence of EPC in 0D perovskites and STE formation, which leads to the assessment of Rb2SnBr6 for light-harvesting applications.

cond-mat.mtrl-sci↗

About the Strain-Coupled Molecular Dynamics in the Ferroelastic Phase Transition of TMACd(N$_3$)$_3$

Tetramethylammonium (TMA) cadmium azide, is a new perovskite-like compound which undergoes a series of first-order phase transitions, including a ferroelastic transition above room temperature. Understanding the order-disorder structural phase transition (SPT) mechanism in hybrid organic--inorganic perovskites (HOIPs) is crucial for designing new compounds with enhanced barocaloric efficiency, as well as unlocking other multifunctional properties. In this paper, we employed the energy fluctuation (EF) model to investigate the experimental linewidth of Raman modes in TMACd(N$_3$)$_3$ near the critical phase transition temperature ($T_C = {322}{K}$), aiming to gain insights into the molecular dynamics around the SPT. The temperature dependence of the strain, used as an order parameter, was obtained using the appropriate thermodynamic potential for the first-order phase transition in TMACd(N$_3$)$_3$, expressed through a Landau expansion, which can be successfully employed to model first-order ferroelastic phase transitions. We show that the EF model suitably captures the behavior of the Raman linewidths in the vicinity of the structural phase transition in TMACd(N$_3$)$_3$. The activation energies obtained for TMACd(N$_3$)$_3$ are comparable to those of DMACd(N$_3$)$_3$, as well as to $k_B T_C$. Additionally, the temperature dependence of the relaxation reveals that the torsional and librational modes require longer to renormalize after the phase transition in TMACd(N$_3$)$_3$ when compared with DMACd(N$_3$)$_3$. The discussion based on these new parameters provides a new perspective for understanding molecular dynamics in systems undergoing order-disorder phase transitions, particularly in ferroelastic transitions, where order-disorder mechanisms are coupled to symmetry-breaking lattice distortions.

cond-mat.mtrl-sci↗

Resonant Raman Scattering and Optical Absorption Studies of Zn(II) Impurities in L-Alanine Single Crystal

We present a study of low-concentration Zn (II) impurities in L-Alanine Single Crystal (ZNLA) employing resonant Raman scattering and optical absorption spectroscopy. By analyzing the relative integrated intensity of the selective vibrational modes, we observe a resonant enhancement of Raman-active modes near the UV absorption band, associated with vibrations of the amino and carboxyl groups in ZNLA. These findings suggest that zinc cations occupy an interstitial position coordinated by amino and carboxyl groups. Also, ZNLA single crystal shows a strong antiresonance behavior for some modes associated with amino and carboxyl groups. The antiresonance model in the cross-section allowed the estimation of the bandgap to be 3.8 eV, which perfectly agrees with the direct bandgap obtained from the absorption spectrum (3.75 eV). Finally, our approach proves to be useful for detecting interactions between transition metal ion impurities and intramolecular structures in other transition metal-doped organic amino acid systems.

cond-mat.mtrl-sci↗

Tuning Electric Polarization via Exchange Striction Interaction in CaMn$_7$O$_{12}$ by Sr-Doping

Magnetoelectric (ME) materials displaying strong magnetically induced polarization have attracted considerable interest due to their potential applications in spintronics and various fast electrically controlled magnetic devices. CaMn$_7$O$_{12}$ (CMO) stands out for its giant spin-induced ferroelectric polarization. However, the origin of the induced electric polarization in CMO remains highly controversial and continues to be a subject of ongoing debate. In this paper, through room temperature X-ray powder diffraction (XRPD), temperature-dependent magnetic susceptibility, and thermally stimulated depolarizing current (TSDC) measurements, we provide experimental evidence for a route to tune the magnetically induced polarization by modifying the exchange-striction in CMO via Sr-doping. Our findings demonstrate that the large and broad current peaks observed near the first magnetic phase transition ($T_N1 \sim 90$ K) indicate contributions to the TSDC density from both extrinsic thermally stimulated depolarization processes and intrinsic pyroelectric current arising from magnetically induced polarization changes. We suggest that this reduction in induced electric polarization in CMO originates from the increase in the Mn$^{3+}$ -- O -- Mn$^{4+}$ bond angle due to Sr$^{2+}$ doping, weakening the exchange-striction interaction. Meanwhile, the Dzyaloshinskii-Moriya (DM) effect determines the direction of the induced electric polarization. Our result sheds light on understanding the intriguing giant-induced polarization in CMO and similar compounds with complex magnetic structures.

cond-mat.mtrl-sci↗

Strong Electron-Phonon Coupling and Lattice Dynamics in One-Dimensional [(CH3)2NH2]PbI3 Hybrid Perovskite

Hybrid halide perovskites (HHPs) have attracted significant attention due to their remarkable optoelectronic properties that combine the advantages of low cost-effective fabrication methods of organic-inorganic materials. Notably, low-dimensional hybrid halide perovskites including two-dimensional (2D) layers and one-dimensional (1D) chains, are recognized for their superior stability and moisture resistance, making them highly appealing for practical applications. Particularly, DMAPbI3 has attracted attention due to other interesting behaviors and properties, such as thermally induced order-disorder processes, dielectric transition, and cooperative electric ordering of DMA dipole moments. In this paper, we investigated the interplay between low-temperature SPT undergone by the low-dimensional (1D) hybrid halide perovskite-like material DMAPbI3 and its optoelectronic properties. Our approach combines synchrotron X-ray powder diffraction, Raman spectroscopy, thermo-microscopy, differential scanning calorimetry (DSC), and photoluminescence (PL) techniques. Temperature-dependent Synchrotron powder diffraction and Raman Spectroscopy reveal that the modes associated with I-Pb-I and DMA+ ion play a crucial role in the order-disorder SPT in DMAPbI3. The reversible SPT modifies its optoelectronic properties, notably affecting its thermochromic behavior and PL emission. The origin of the PL phenomenon is associated to self-trapped excitons (STEs), which are allowed due to a strong electron-phonon coupling quantified by the Huang-Rhys factor (S = 97+-1). Notably, we identify the longitudinal optical (LO) phonon mode at 84 cm-1 which plays a significant role in electron-phonon interaction. Our results show these STEs not only intensify the PL spectra at lower temperatures but also induce a shift in the color emission, transforming it from a light orange-red to an intense bright strong red.

cond-mat.mtrl-sci↗

Short-range antiferromagnetic interaction and spin-phonon coupling in La2CoMnO6 double perovskite

Weak antiferromagnetic (AF) interaction in the ferromagnetic (FM) partially ordered La2CoMnO6 (LCMO) was detected by Raman spectroscopy by monitoring spin-phonon coupling. Because of the sensibility to probe short-range disorder and lattice modifications, the Raman spectroscopy showed to be an useful tool to indicate less remarkable magnetic transitions in LCMO compound. Apart from the expected spin-phonon coupling due to the long-range FM superexchange (Tc~230 K), phonons parameters pointed out an additional spin-phonon coupling related to the short-range AF interaction at Tc~135 K, which was not detected from the magnetic bulk response. These results reinforce the Raman spectroscopy as a powerful technique to detect antisite disorder into A2B'B"O6 magnetic double perovskites, whose magnetic properties are driven by superexchange interactions.

cond-mat.mtrl-sci↗

High-temperature structural phase transition and infrared dielectric features of La2CoMnO6

Temperature-dependent FAR-infrared reflectivity spectra of partially ordered magnetodielectric La2CoMnO6 is presented, from room temperature up to 675 K. A clear first-ordered structural phase transition (SPT) from a monoclinic structure with P2_1/n symmetry to a rhombohedral phase with R-3 symmetry was evidenced from the behaviour of polar phonon modes at TC~590 K. The temperature dependences of the transversal and longitudinal phonon branches, dielectric strengths, and damping of the strongest dielectric modes confirm the significant contribution of the phonon modes on the SPT, and revealed an important lattice anharmonicity, particularly for the low frequency modes. In addition, these investigations showed that structural ordering does not inhibit the SPT, and provided valuable information towards the polar phonons, their implications on intrinsic dielectric constant in double perovskites and in related compounds.

cond-mat.mtrl-sci↗

Boosting Room-Temperature Li$^+$ Conductivity via strain in solid electrolytes for Lithium-ion Batteries

Room-temperature (RT) conductivity of most candidates for solid electrolytes of miniaturized lithium-ion batteries is still 1-2 orders of magnitude below commercial requirements, therefore several approaches are being pursued aiming the enhancement of such values. In this letter, we report for the first time direct theoretical evidence that epitaxial strain can be an efficient tool to reach this goal.

cond-mat.mtrl-sci↗

Intrinsic dielectric properties of magnetodielectric La$_2$CoMnO$_6$

Manganites with double perovskite structure are being attractive because of their interesting magnetoelectric and dielectric responses. Particularly, colossal dielectric constant (CDC) behavior has been observed in La$_2$CoMnO$_6$ (LCMO), at radio frequencies and room temperature. In this paper, we employed infrared-reflectivity spectroscopy onto a LCMO ceramic obtained through a modified Pechini's method to determine the phonon contribution to the intrinsic dielectric response of the system and to investigate the CDC origin. The analysis of the main polar modes and of the obtained phonon parameters show that CDC effect of LCMO is of pure extrinsic origin. In addition, we have estimated the dielectric constant and quality factor of the material in microwave region, $e'_s \sim 16$ and $Q_u \times f \sim 124$ THz, which shows that LCMO is appropriate for applications into microwave devices and circuitry.

cond-mat.mtrl-sci↗

Spin-phonon and magnetostriction phenomena in CaMn7O12 helimagnet probed by Raman spectroscopy

In this letter we investigated the temperature-dependent Raman spectra of CaMn7O12 helimagnet from room temperature down to 10 K. The temperature dependence of the Raman mode parameters show remarkable anomalies for both antiferromagnetic and incommensurate transitions that this compound undergoes at low temperatures. The anomalies observed at the magnetic ordering transition indicate a spin-phonon coupling at higher-temperature magnetic transition in this material, while a magnetostrinction effect at the lower-temperature magnetic transition.

cond-mat.mtrl-sci↗

Role of rare-earth ionic radii on the spin-phonon coupling in multiferroic ordered double perovskites

In this paper we investigated the influence of the rare-earth ionic radii on the spin-phonon coupling in RE2NiMnO6 double perovskites by Raman spectroscopy. Spin-phonon in dense Nd2NiMnO6 and Gd2NiMnO6 ceramics were investigated by Raman spectroscopy at low temperatures. The magnitude of the coupling observed in comparison with other isostructural compounds shows that it is not influenced by the rare-earth ionic radius, as well as the deviation of the position of the stretching phonon in the ferromagnetic phase with relation to the anharmonic contributions follows a power law.

cond-mat.mtrl-sci↗

Spin-phonon coupling in Gd(Co1/2Mn1/2)O3 perovskite

We have investigated the temperature-dependent Raman-active phonons and the magnetic properties of Gd(Co1/2Mn1/2)O3 perovskite ceramics in the temperature range from 40 K to 300 K. The samples crystallized in an orthorhombic distorted simple perovskite, whose symmetry belongs to the Pnma space group. The data reveals spin-phonon coupling near the ferromagnetic transition occurring at around 120 K. The correlation of the Raman and magnetization data suggests that the structural order influences the magnitude of the spin-phonon coupling.

cond-mat.mtrl-sci↗

Low Temperature Phase Transition in Sr(0.66)Ba(0.34)Nb2O6 single Crystal Fibers

The structural changes in Sr(0.66)Ba(0.34)Nb2O6 single crystal fibers when the temperature decreases from 295 to 10 K is investigated by dielectric constant measurements and Raman spectroscopy. The anomaly observed in the plot of e is associated to the variation in the intensity and frequency of some Raman modes. We observe that the intensity of some low energy modes has a very singular behavior for the y(xz)y scattering geometry. In the high energy region (> 850 cm-1), a band at ~ 880 cm-1 disappears when the temperature is cooled down to 10K for the y(xz)y geometry and shifts to higher energy values for the y(zz)y geometry.

cond-mat.mtrl-sci↗