Bruna Silva

Multiferroic BaTiO₃ (BTO, piezoelectric)/CoFe₂O₄ (CFO, magnetostrictive) bilayer thin films were prepared by laser ablation on conductive Nb-doped SrTiO₃ (100) substrates to investigate the influence of BTO layer thickness on their structural, microstructural, dielectric, and electrical (DC and AC) properties. X-ray diffraction confirmed the coexistence of the cubic spinel CoFe₂O₄ phase and the tetragonal ferroelectric BaTiO₃ phase. The films exhibit preferred orientation, with CFO showing the [400] direction along the growth axis and BTO displaying (100)/(001) planes stacked parallel to it. The CFO unit cell is compressed along the growth direction, while BTO presents the ferroelectric distortion with a tetragonality ratio (c/a) slightly below, but close to, the bulk value. Second harmonic generation studies further verified the non-centrosymmetric ferroelectric nature of BTO at room temperature. The temperature-dependent dielectric permittivity was modeled using the Havriliak–Negami function with an additional conductivity term to extract relaxation dynamics, DC conductivity, Curie temperature (Tc), and activation energies. The Curie temperature increases with BTO thickness, approaching the bulk value for thicker layers. DC conductivity activation energies exhibit a change at Tc, from below 0.5 eV for T < Tc to above 0.5 eV for T > Tc, consistent with small-polaron tunneling. The AC conductivity follows a Jonscher-type frequency dependence with two power-law contributions reflecting the behavior of both layers. Temperature-dependent analysis of the power-law exponents reveals that small-polaron tunneling dominates conduction in BTO, while ion hopping between octahedral sites governs conduction in CFO. Underoxidation leads to a more complex transport regime in BTO, showing a transition from quantum-mechanical tunneling below Tc to correlated barrier hopping above it. By revealing how transport processes operate within multiferroic oriented bilayer systems, these findings advance our understanding of material interactions and pave the way for the design of innovative multifunctional platforms optimized for spintronic technologies.

Laser ablation was used to successfully fabricate multiferroic bilayer thin films, composed of BaTiO₃ (BTO) and CoFe₂O₄ (CFO), on highly doped (100) Si substrates. This study investigates the influence of BaTiO₃ layer thickness (50–220 nm) on the films’ structural, magnetic, and dielectric properties. The dense, polycrystalline films exhibited a tetragonal BaTiO₃ phase and a cubic spinel CoFe₂O₄ layer. Structural analysis revealed compression of the CoFe₂O₄ unit cell along the growth direction, while the BaTiO₃ layer showed a tetragonal distortion, more pronounced in thinner BTO layers. These strain effects, attributed to the mechanical interaction between both layers, induced strain-dependent wasp-waisted behavior in the films’ magnetic hysteresis cycles. The strain effects gradually relaxed with increasing BaTiO₃ thickness. Raman spectroscopy and second harmonic generation studies confirmed BTO’s non-centrosymmetric ferroelectric structure at room temperature. The displayed dielectric permittivity dispersion was modeled using the Havriliak–Negami function combined with a conductivity term. This analysis yielded relaxation times, DC conductivities, and activation energies. The observed BTO relaxation time behavior, indicative of small-polaron transport, changed significantly at the BTO ferroelectric Curie temperature (Tc), presenting activation energies E_τ in the 0.1–0.3 eV range for T < Tc and E_τ > 0.3 eV for T > Tc. The BTO thickness-dependent Tc behavior exhibited critical exponents ν ~ 0.82 consistent with the 3D random Ising universality class, suggesting local disorder and inhomogeneities in the films. This was attributed to the composite structure of BTO grains, comprising an inner bulk-like structure, a gradient strained layer, and a disordered surface layer. DC conductivity analysis indicated that CoFe₂O₄ conduction primarily occurred through hopping in octahedral sites. These findings provide crucial insights into the dynamic dielectric behavior of multiferroic bilayer thin films at the nanoscale, enhancing their potential for application in emerging Si electronics-compatible magneto-electric technologies.

This study describes the synthesis and characterization of the lead-free organic ferroelectric perovskite N-methyl-N’-diazabicyclo [2.2.2]octonium)-ammonium trichloride (MDABCO-NH₄Cl₃). The electrospinning technique was employed to obtain nanofibers embedded with this perovskite in a PVC polymer for hybrid fiber production. The dielectric, piezoelectric, and pyroelectric properties of these fibers were carefully examined. Based on measurements of the dielectric permittivity temperature and frequency dependence, together with the pyroelectric results, a transition from a high temperature paraelectric to a ferroelectric phase that persisted at room temperature was found to occur at 438 K. The measured pyroelectric coefficient yielded values as high as 290 μC K⁻¹ m⁻², which is in between the values reported for MDABCO-NH₄I₃ and the semiorganic ferroelectric triglycine sulfate (TGS)_. The hybrid nanofibers exhibited good morphological characteristics and demonstrated very good piezoelectric properties. Specifically, a piezoelectric coefficient of 42 pC/N was obtained when applying a periodical force of 3 N and a piezoelectric voltage coefficient of g_eff = 0.65 V mN⁻¹. The performance of these fibers is on par with that of materials discussed in the existing literature for the fabrication of nano energy-harvesting generators. Importantly, the perovskite nanocrystals within the fibers are protected from degradation by the surrounding polymer, making them a promising environmentally friendly platform for flexible mechanical energy harvesting.

This study describes the synthesis, and characterization of lead-free organic ferroelectric perovskite N-methyl-N’-diazabicyclo[2.2.2]octonium)-ammonium trichloride (MDABCO-NH4Cl3). The electrospinning technique was employed to obtain nanofibers embedded with this perovskite into PVC polymer for hybrid fiber production. The dielectric, piezoelectric and pyroelectric properties of these fibers were carefully examined. From measurements of the dielectric permittivity temperature and frequency dependence, together with the pyroelectric results, a transition from a high temperature paraelectric to a ferroelectric phase that remained down to room temperature, was found to occur at 438 K. A pyroelectric coefficient as high as 290 C K-1 m-2value obtained is within the same order of magnitude as that reported for MDABCO-NH4I3 and the semiorganic ferroelectric triglycine sulfate (TGS). The hybrid nanofibers exhibited good morphological characteristics and demonstrated very good piezoelectric properties. Specifically, a piezoelectric coefficient of 42 pC/N was obtained when a periodical force of 3 N was applied. The performance of these fibers is on par with materials discussed in the existing literature for fabrication of nano energy harvesting generators. Importantly, the perovskite nanocrystals within the fibers not harmed by oxidation, making them a promising environmentally friendly platform for flexible energy harvesting.

Hybrid biomaterials were engineered using the electrospinning technique, incorporating the dipeptide Boc–L-phenylalanyl–L-isoleucine into microfibers composed of biocompatible polymers. The examination by scanning electron microscopy affirmed the morphology of the microfibers, exhibiting diameters ranging between 0.9 and 1.8 µm. The dipeptide self-assembles into spheres with a hydrodynamic size between 0.18 and 1.26 µm. The dielectric properties of these microfibers were characterized through impedance spectroscopy where variations in both temperature and frequency were systematically studied. The investigation revealed a noteworthy rise in the dielectric constant and AC electric conductivity with increasing temperature, attributable to augmented charge mobility within the material. The successful integration of the dipeptide was substantiated through the observation of Maxwell–Wagner interfacial polarization, affirming the uniform dispersion within the microfibers. In-depth insights into electric permittivity and activation energies were garnered using the Havriliak–Negami model and the AC conductivity behavior. Very importantly, these engineered fibers exhibited pronounced pyroelectric and piezoelectric responses, with Boc–Phe–Ile@PLLA microfibers standing out with the highest piezoelectric coefficient, calculated to be 56 pC/N. These discoveries help us understand how dipeptide nanostructures embedded into electrospun nano/microfibers can greatly affect their pyroelectric and piezoelectric properties. They also point out that polymer fibers could be used as highly efficient piezoelectric energy harvesters, with promising applications in portable and wearable devices.

Hybrid biomaterials were engineered using the electrospinning technique, incorporating the dipeptide Boc-L-phenylalanyl-L-Isoleucine into microfibers composed of biocompatible polymers. The examination by scanning electron microscopy affirmed the morphology of the microfibers, exhibiting diameters ranging between 0.9 to 1.8 µm. The dipeptide self-assemblies into spheres with a hydrodynamic size between 0.18 to 1.26 µm. The dielectric properties of these microfibers were characterized through impedance spectroscopy, where variations in both temperature and frequency were systematically studied. The investigation revealed a noteworthy rise in the dielectric constant and AC electric conductivity with increasing temperature, attributable to augmented charge mobility within the material. The successful integration of the dipeptide was substantiated through the observation of Maxwell-Wagner interfacial polarization, affirming the uniform dispersion within the microfibers. In-depth insights into electric permittivity and activation energies were garnered using the Havriliak-Negami model and the AC conductivity behavior. Very importantly, these engineered fibers exhibited pronounced pyroelectric and piezoelectric responses, with Boc-Phe-Ile@PLLA microfibers standing out with the highest piezoelectric coefficient, calculated to be 56 pC/N. These discoveries help us understand how dipeptide nanostructures embedded into electrospun nano/microfibers can greatly affect their pyroelectric and piezoelectric properties. They also point out that polymer fibers could be used as highly efficient piezoelectric energy harvesters, with promising applications in portable and wearable devices.

The crystal structure of a polymorph of Glycyl-L-alanine HI.H2O was synthesized from chiral cyclic Glycyl-L-alanine dipeptide, known to show molecular flexibility in different environments. The space group is polar (P21) and therefore pyroelectricity and optical second harmonic generation properties are allowed by symmetry. We report a pyroelectric coefficient as high as 45 µC/m2K occurring at 345 K, one order of magnitude smaller than the semi-organic ferroelectric Triglycine Sulphate (TGS) crystal. Furthermore, the polymorph displays a nonlinear optical effective coefficient of 0.14 pm/V, around 14 times smaller than the value from a phase-matched inorganic Barium Borate (BBO) single crystal.