412 resultados para Relaxor ferroelectric


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Ferroelectric ceramics with perovskite structure (ABO3) are widely used in solid state memories (FeRAM’s and DRAM's) as well as multilayered capacitors, especially as a thin films. When doped with zirconium ions, BaTiO3-based materials form a solid solution known as barium zirconate titanate (BaTi1-xZrxO3). Also called BZT, this material can undergo significant changes in their electrical properties for a small variation of zirconium content in the crystal lattice. The present work is the study of the effects of deposition parameters of BaTi0,75Zr0,25O3 thin films by spin-coating method on their morphology and physical properties, through an experimental design of the Box-Behnken type. The resin used in the process has been synthesized by the polymeric precursor method (Pechini) and subsequently split into three portions each of which has its viscosity adjusted to 10, 20 and 30 mPa∙s by means of a rotary viscometer. The resins were then deposited on Pt/Ti/SiO2/Si substrates by spin-coating method on 15 different combinations of viscosity, spin speed (3000, 5500 and 8000 rpm) and the number of deposited layers (5, 8 and 11 layers) and then calcined at 800 ° C for 1 h. The phase composition of the films was analyzed by X-ray diffraction (XRD) and indexed with the JCPDS 36-0019. Surface morphology and grain size were observed by atomic force microscopy (AFM) indicating uniform films and average grain size around 40 nm. Images of the cross section of the films were obtained by scanning electron microscopy field emission (SEM-FEG), indicating very uniform thicknesses ranging from 140-700 nm between samples. Capacitance measurements were performed at room temperature using an impedance analyzer. The films presented dielectric constant values of 55-305 at 100kHz and low dielectric loss. The design indicated no significant interaction effects between the deposition parameters on the thickness of the films. The response surface methodology enabled better observes the simultaneous effect of variables.

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This work shows that the synthesis by combustion is a prominent alternative to obtain ceramic powders of higher oxides, nanostructured and of high purity, as the ferrites of formulas Co(1-x)Zn(x)Fe2O4 e Ni(1-x)Zn(x)Fe2O4 with x ranging from 0.2 mols, in a range from 0.2 ≤ x ≥ 1.0 mol, that presents magnetic properties in coexistence of ferroelectric and ferrimagnetic states, which can be used in antennas of micro tapes and selective surfaces of low frequency in a range of miniaturized microwaves, without performance loss. The obtainment occurred through the combustion process, followed by appropriate physical processes and ordered to the utilization of the substrate sinterization process, it gave us a ceramic material, of high purity degree in a nanometric scale. The Vibrating Sample Magnetometer (VSM) analysis showed that those ferritic materials presents parameters, as materials hysteresis, that have own behavior of magnetic materials of good quality, in which the magnetization states can be suddenly changed with a relatively small variation of the field intensity, having large applications on the electronics field. The X-ray Diffraction (XRD) analysis of the ceramic powders synthesized at 900 °C, characterize its structural and geometrical properties, the crystallite size and the interplanar spacing. Other analysis were developed, as Scanning Electron Microscopy (SEM), X-ray Fluorescence (XRF), electric permittivity and the tangent loss, in high frequencies, through the equipment ZVB - 14 Vector Network Analyzer 10 MHz-14 GHz, of ROHDE & SCHWART.

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We report the results of direct measurement of remanent hysteresis loops on nanochains of BiFeO3 at room temperature under zero and ∼20 kOe magnetic field. We noticed a suppression of remanent polarization by nearly ∼40% under the magnetic field. The powder neutron diffraction data reveal significant ion displacements under a magnetic field which seems to be the origin of the suppression of polarization. The isolated nanoparticles, comprising the chains, exhibit evolution of ferroelectric domains under dc electric field and complete 180 switching in switching-spectroscopy piezoresponse force microscopy. They also exhibit stronger ferromagnetism with nearly an order of magnitude higher saturation magnetization than that of the bulk sample. These results show that the nanoscale BiFeO3 exhibits coexistence of ferroelectric and ferromagnetic order and a strong magnetoelectric multiferroic coupling at room temperature comparable to what some of the type-II multiferroics show at a very low temperature.

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c-axis oriented ferroelectric bismuth titanate (Bi4Ti 3O12) thin films were grown on (001) strontium titanate (SrTiO3) substrates by an atomic vapor deposition technique. The ferroelectric properties of the thin films are greatly affected by the presence of various kinds of defects. Detailed x-ray diffraction data and transmission electron microscopy analysis demonstrated the presence of out-of-phase boundaries (OPBs). It is found that the OPB density changes appreciably with the amount of titanium injected during growth of the thin films. Piezo-responses of the thin films were measured by piezo-force microscopy. It is found that the in-plane piezoresponse is stronger than the out-of-plane response, due to the strong c-axis orientation of the films.

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The interactions between electrons and lattice vibrations are fundamental to materials behaviour. In the case of group IV-VI, V and related materials, these interactions are strong, and the materials exist near electronic and structural phase transitions. The prototypical example is PbTe whose incipient ferroelectric behaviour has been recently associated with large phonon anharmonicity and thermoelectricity. Here we show that it is primarily electron-phonon coupling involving electron states near the band edges that leads to the ferroelectric instability in PbTe. Using a combination of nonequilibrium lattice dynamics measurements and first principles calculations, we find that photoexcitation reduces the Peierls-like electronic instability and reinforces the paraelectric state. This weakens the long-range forces along the cubic direction tied to resonant bonding and low lattice thermal conductivity. Our results demonstrate how free-electron-laser-based ultrafast X-ray scattering can be utilized to shed light on the microscopic mechanisms that determine materials properties.

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‘De Vries-like’ smectic liquid crystals exhibit low layer contraction of approximately 1% on transitions from the SmA to the SmC phase. These materials have received considerable attention as potential solutions for problems affecting liquid crystal displays using surface-stabilized ferroelectric liquid crystals (SSFLC). In SSFLCs, layer contraction of 710% is normally observed during the SmA to SmC phase transition. A study by the Lemieux group has shown that liquid crystals with nanosegregating carbosilane segments exhibit enhanced ‘de Vries-like’ properties through the formation of smectic layers and by lengthening the nanosegregating carbosilane end-groups from monocarbosilane to tricarbosilane. This observed enhancement is assumed to be due to an increase in the cross-section of the free volume in the hydrocarbon sub-layer. To test this hypothesis, it is assumed that dimers with a tricarbosilane linking group have smaller cross-sections on time average. In his thesis, this hypothesis is tested through the characterization of new liquid crystalline monomers (QL39-n) and dimers (QL40-n) with 2-phenylpyrimidine cores and tricarbosilane end-groups and spacers, respectively. The thesis describes the synthesis of two homologous series of liquid crystals and their characterization using a variety of techniques, including polarized optical microscopy, differential scanning calorimetry and X-ray diffraction. The results show that the monomers QL39-n form a tilted SmC phase only, whereas the dimers QL40-n form an orthogonal SmA phase. These results are discussed in the context of our hypothesis.

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The standard “Kittel Law” for the thickness and shape of ferroelectric, ferroelastic, or ferromagnet domains assumes mechanical equilibrium. The present paper shows that such domains may be highly nonequilibrium, with unusual thicknesses and shapes. In lead germanate and multiferroic lead zirconate titanate iron tantalate domain wall instabilities resemble hydrodynamics (Richtmyer–Meshkov and Helfrich–Hurault, respectively).

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Multiferroic behaviour at room temperature is demonstrated in ε-Fe2O3. The simple composition of this new ferromagnetic ferroelectric oxide and the discovery of a robust path for its thin film growth by using suitable seed layers may boost the exploitation of ε-Fe2O3 in novel devices.

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Epitaxial heterostructures combining ferroelectric (FE) and ferromagnetic (FiM) oxides are a possible route to explore coupling mechanisms between the two independent order parameters, polarization and magnetization of the component phases. We report on the fabrication and properties of arrays of hybrid epitaxial nanostructures of FiM NiFe(2)O(4) (NFO) and FE PbZr(0.52)Ti(0.48)O(3) or PbZr(0.2)Ti(0.8)O(3), with large range order and lateral dimensions from 200 nm to 1 micron. METHODS: The structures were fabricated by pulsed-laser deposition. High resolution transmission electron microscopy and high angle annular dark-field scanning transmission electron microscopy were employed to investigate the microstructure and the epitaxial growth of the structures. Room temperature ferroelectric and ferrimagnetic domains of the heterostructures were imaged by piezoresponse force microscopy (PFM) and magnetic force microscopy (MFM), respectively. RESULTS: PFM and MFM investigations proved that the hybrid epitaxial nanostructures show ferroelectric and magnetic order at room temperature. Dielectric effects occurring after repeated switching of the polarization in large planar capacitors, comprising ferrimagnetic NiFe2O4 dots embedded in ferroelectric PbZr0.52Ti0.48O3 matrix, were studied. CONCLUSION: These hybrid multiferroic structures with clean and well defined epitaxial interfaces hold promise for reliable investigations of magnetoelectric coupling between the ferrimagnetic / magnetostrictive and ferroelectric / piezoelectric phases.

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As we reach the physical limit of Moore’s law and silicon based electronics, alternative schemes for memory and sensor devices are being proposed on
a regular basis. The properties of ferroelectric materials on the nanoscale are key to developing device applications of this intriguing material class, and nanostructuring has been readily pursued in recent times. Focused ion beam (FIB) microscopy is one of the most signi cant techniques for achieving
this. When applied in tandem with the imaging and nanoscale manipulation afforded by proximal scanning force microscopy tools, FIB-driven nanoscale characterization has demonstrated the power and ability which simply may not be possible by other fabrication techniques in the search for innovative and novel ferroic phenomena. At the same time the process is not without pitfalls; it is time-consuming and success is not always guaranteed thus often being the bane in progress. This balanced review explores a brief history of the relationship between the FIB and ferroelectrics, the fascinating properties it has unveiled, the challenges associated with FIB that have led to alterna- tive nanostructuring techniques and nally new ideas that should be explored using this exciting technique.

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Nonlinear optics is a broad field of research and technology that encompasses subject matter in the field of Physics, Chemistry, and Engineering. It is the branch of Optics that describes the behavior of light in nonlinear media, that is, media in which the dielectric polarization P responds nonlinearly to the electric field E of the light. This nonlinearity is typically only observed at very high light intensities. This area has applications in all optical and electro optical devices used for communication, optical storage and optical computing. Many nonlinear optical effects have proved to be versatile probes for understanding basic and applied problems. Nonlinear optical devices use nonlinear dependence of refractive index or absorption coefficient on the applied field. These nonlinear optical devices are passive devices and are referred to as intelligent or smart materials owing to the fact that the sensing, processing and activating functions required for optical processes are inherent to them which are otherwise separate in dynamic devices.The large interest in nonlinear optical crystalline materials has been motivated by their potential use in the fabrication of all-optical photonic devices. Transparent crystalline materials can exhibit different kinds of optical nonlinearities which are associated with a nonlinear polarization. The choice of the most suitable crystal material for a given application is often far from trivial; it should involve the consideration of many aspects. A high nonlinearity for frequency conversion of ultra-short pulses does not help if the interaction length is strongly limited by a large group velocity mismatch and the low damage threshold limits the applicable optical intensities. Also, it can be highly desirable to use a crystal material which can be critically phasematched at room temperature. Among the different types of nonlinear crystals, metal halides and tartrates have attracted due to their importance in photonics. Metal halides like lead halides have drawn attention because they exhibit interesting features from the stand point of the electron-lattice interaction .These materials are important for their luminescent properties. Tartrate single crystals show many interesting physical properties such as ferroelectric, piezoelectric, dielectric and optical characteristics. They are used for nonlinear optical devices based on their optical transmission characteristics. Among the several tartrate compounds, Strontium tartrate, Calcium tartrate and Cadmium tartrate have received greater attention on account of their ferroelectric, nonlinear optical and spectral characteristics. The present thesis reports the linear and nonlinear aspects of these crystals and their potential applications in the field of photonics.

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Thesis (Ph.D.)--University of Washington, 2016-08

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In this thesis the critical dynamics of several magnetoelectric compounds at their phase transition were examined. Mostly measurements of the dielectric properties in the frequency range of below 1 Hz up to 5 GHz were employed to evaluate the critical exponents for both magnetic field and temperature-dependent measurements. Most of the materials that are part of this work show anomalous behavior, especially at very low temperatures where quantum fluctuations are of the order of or even dominate those induced thermally. This anomalous behavior manifests in different forms. In Dy2Ti2O7 we demonstrate the existence of electric dipoles on magnetic monopoles. Here the dynamics at the critical endpoint located at 0.36K and in a magnetic field of 1T parallel to the [111] direction are of special interest. At this critical endpoint the expected critical slowing down of the dynamics could not only not be observed but instead the opposite, critical speeding-up by several orders of magnitude, could be demonstrated. Furthermore, we show that the phase diagram of Dy2Ti2O7 in this field direction can be reproduced solely from the dynamical properties, for example the resonance frequency of the observed relaxation that is connected to the monopole movement. Away from this point of the phase diagram the dynamics are slowing-down with reduction of temperature as one would expect. Additional measurements on Y2Ti2O7, a structurally identical but non-magnetic material, show only slowing down with reduction of temperature and no additional features. A possible explanation for the observed critical speeding-up is a coherent movement of magnetic monopoles close to the critical field that increases the resonance frequency by reducing the damping of the process. LiCuVO4 on the other hand behaves normally at its phase transition as long as the temperature is higher than 0.4 K. In this temperature regime the dynamics show critical slowing-down analogous to classical ferroelectric materials. This analogy extends also towards higher frequencies where the permittivity displays a ‘dispersion’ minimum that is temperature-dependent but of the order of 2 GHz. Below 0.4K the observed behavior changes drastically. Here we found no longer relaxational behavior but instead an excitation with very low energy. This low energy excitation was predicted by theory and is caused by nearly gapless soliton excitations within the 1D Cu2+ chains of LiCuVO4. Finally, in TbMnO3 the dynamics of the phase transition into the multiferroic phase was observed at roughly 27 K, a much higher temperature compared to the other materials. Here the expected critical slowing-down was observed, even though in low-frequency measurements this transition into the ferroelectric phase is overshadowed by the so-called c-axis relaxation. Therefore, only frequencies above 1MHz could be used to determine the critical exponents for both temperatureand magnetic-field-dependent measurements. This was done for both the peak frequency as well as the relaxation strength. In TbMnO3 an electromagnetic soft-mode with small optical weight causes the observed fluctuations, similar to the case of multiferroic MnWO4.

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In this thesis, the magnetic properties of four transition-metal oxides are presented. Their multiferroic and magnetoelectric phases have been investigated by means of different neutron scattering techniques. The materials TbMnO3 and MnWO4 belong to the group of spin-induced multiferroics. Their ferroelectric polarization can be explained by the inverse DzyaloshinskiiMoriya interaction. Another common feature of both materials is the presence of subsequent magnetic transitions from a spin-density wave to a spin spiral. The features of the phase transitions have been studied in both materials and it could be shown that diffuse magnetic scattering from the spin spiral is present even in the ordered spin-density wave phase. The excitation spectrum in the multiferroic phase of TbMnO3 was investigated in detail and a comprehensive dataset was obtained using time-of-flight spectroscopy. A spin-wave model could be obtained which can quantitatively describe the full dispersion. Furthermore, the polarization of the zone-center excitations could be derived which fit well to data from inelastic neutron spectroscopy and infrared spectroscopy. With the combination of spherical neutron polarimetry and a poling of the sample by an electric field, it was possible to observe the chiral magnetic component of the magnetic excitations in TbMnO3 and MnWO4. The spin-wave model for TbMnO3 obtained in this thesis is able to correctly describe the dispersion of this component. The double tungstate NaFe(WO4)2 is isostructural to the multiferroic MnWO4 and develops a complex magnetic phase diagram. By the use of neutron diffraction techniques, the zero-field structure and high-field structures in magnetic field applied along the b-axis could be determined. The data reveal a direct transition into an incommensurate spin-spiral structure. The value of the incommensurability is driven by anharmonic modulations and shows strong hysteresis effects. The static and dynamic properties in the magnetoelectric spin-glass phase of Ni0.42Mn0.58TiO3 were studied in detail. The spin-glass phase is composed of short-ranged MnTiO3 and NiTiO3-type order. The antiferromagnetic domains could be controlled by crossed magnetic and electric fields, which was visualized using spherical neutron polarimetry. A comprehensive dataset of the magnetic excitations in the spin-glass phase was collected. The dataset revealed correlations in the hexagonal plane which are only weakly coupled along the c-axis. The excitation spectra could be simulated by taking into account the MnTiO3-type order.

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Alkali tantalates and niobates, including K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, are a very promising ferroic family of lead-free compounds with perovskite-like structures. Their versatile properties make them potentially interesting for current and future application in microelectronics, photocatalysis, energy and biomedics. Among them potassium tantalate, KTaO3 (KTO), has been raising interest as an alternative for the well-known strontium titanate, SrTiO3 (STO). KTO is a perovskite oxide with a quantum paraelectric behaviour when electrically stimulated and a highly polarizable lattice, giving opportunity to tailor its properties via external or internal stimuli. However problems related with the fabrication of either bulk or 2D nanostructures makes KTO not yet a viable alternative to STO. Within this context and to contribute scientifically to the leverage tantalate based compounds applications, the main goals of this thesis are: i) to produce and characterise thin films of alkali tantalates by chemical solution deposition on rigid Si based substrates, at reduced temperatures to be compatible with Si technology, ii) to fulfil scientific knowledge gaps in these relevant functional materials related to their energetics and ii) to exploit alternative applications for alkali tantalates, as photocatalysis. In what concerns the synthesis attention was given to the understanding of the phase formation in potassium tantalate synthesized via distinct routes, to control the crystallization of desired perovskite structure and to avoid low temperature pyrochlore or K-deficient phases. The phase formation process in alkali tantalates is far from being deeply analysed, as in the case of Pb-containing perovskites, therefore the work was initially focused on the process-phase relationship to identify the driving forces responsible to regulate the synthesis. Comparison of phase formation paths in conventional solid-state reaction and sol-gel method was conducted. The structural analyses revealed that intermediate pyrochlore K2Ta2O6 structure is not formed at any stage of the reaction using conventional solid-state reaction. On the other hand in the solution based processes, as alkoxide-based route, the crystallization of the perovskite occurs through the intermediate pyrochlore phase; at low temperatures pyrochlore is dominant and it is transformed to perovskite at >800 °C. The kinetic analysis carried out by using Johnson-MehlAvrami-Kolmogorow model and quantitative X-ray diffraction (XRD) demonstrated that in sol-gel derived powders the crystallization occurs in two stages: i) at early stage of the reaction dominated by primary nucleation, the mechanism is phase-boundary controlled, and ii) at the second stage the low value of Avrami exponent, n ~ 0.3, does not follow any reported category, thus not permitting an easy identification of the mechanism. Then, in collaboration with Prof. Alexandra Navrotsky group from the University of California at Davis (USA), thermodynamic studies were conducted, using high temperature oxide melt solution calorimetry. The enthalpies of formation of three structures: pyrochlore, perovskite and tetragonal tungsten bronze K6Ta10.8O30 (TTB) were calculated. The enthalpies of formation from corresponding oxides, ∆Hfox, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -203.63 ± 2.84 kJ/mol, - 358.02 ± 3.74 kJ/mol, and -1252.34 ± 10.10 kJ/mol, respectively, whereas from elements, ∆Hfel, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol, and -13393.04 ± 31.15 kJ/mol, respectively. The possible decomposition reactions of K-deficient KTa2.2O6 pyrochlore to KTaO3 perovskite and Ta2O5 (reaction 1) or to TTB K6Ta10.8O30 and Ta2O5 (reaction 2) were proposed, and the enthalpies were calculated to be 308.79 ± 4.41 kJ/mol and 895.79 ± 8.64 kJ/mol for reaction 1 and reaction 2, respectively. The reactions are strongly endothermic, indicating that these decompositions are energetically unfavourable, since it is unlikely that any entropy term could override such a large positive enthalpy. The energetic studies prove that pyrochlore is energetically more stable phase than perovskite at low temperature. Thus, the local order of the amorphous precipitates drives the crystallization into the most favourable structure that is the pyrochlore one with similar local organization; the distance between nearest neighbours in the amorphous or short-range ordered phase is very close to that in pyrochlore. Taking into account the stoichiometric deviation in KTO system, the selection of the most appropriate fabrication / deposition technique in thin films technology is a key issue, especially concerning complex ferroelectric oxides. Chemical solution deposition has been widely reported as a processing method to growth KTO thin films, but classical alkoxide route allows to crystallize perovskite phase at temperatures >800 °C, while the temperature endurance of platinized Si wafers is ~700 °C. Therefore, alternative diol-based routes, with distinct potassium carboxylate precursors, was developed aiming to stabilize the precursor solution, to avoid using toxic solvents and to decrease the crystallization temperature of the perovskite phase. Studies on powders revealed that in the case of KTOac (solution based on potassium acetate), a mixture of perovskite and pyrochlore phases is detected at temperature as low as 450 °C, and gradual transformation into monophasic perovskite structure occurs as temperature increases up to 750 °C, however the desired monophasic KTaO3 perovskite phase is not achieved. In the case of KTOacac (solution with potassium acetylacetonate), a broad peak is detected at temperatures <650 °C, characteristic of amorphous structures, while at higher temperatures diffraction lines from pyrochlore and perovskite phases are visible and a monophasic perovskite KTaO3 is formed at >700 °C. Infrared analysis indicated that the differences are due to a strong deformation of the carbonate-based structures upon heating. A series of thin films of alkali tantalates were spin-coated onto Si-based substrates using diol-based routes. Interestingly, monophasic perovskite KTaO3 films deposited using KTOacac solution were obtained at temperature as low as 650 °C; films were annealed in rapid thermal furnace in oxygen atmosphere for 5 min with heating rate 30 °C/sec. Other compositions of the tantalum based system as LiTaO3 (LTO) and NaTaO3 (NTO), were successfully derived as well, onto Si substrates at 650 °C as well. The ferroelectric character of LTO at room temperature was proved. Some of dielectric properties of KTO could not be measured in parallel capacitor configuration due to either substrate-film or filmelectrode interfaces. Thus, further studies have to be conducted to overcome this issue. Application-oriented studies have also been conducted; two case studies: i) photocatalytic activity of alkali tantalates and niobates for decomposition of pollutant, and ii) bioactivity of alkali tantalate ferroelectric films as functional coatings for bone regeneration. Much attention has been recently paid to develop new type of photocatalytic materials, and tantalum and niobium oxide based compositions have demonstrated to be active photocatalysts for water splitting due to high potential of the conduction bands. Thus, various powders of alkali tantalates and niobates families were tested as catalysts for methylene blue degradation. Results showed promising activities for some of the tested compounds, and KNbO3 is the most active among them, reaching over 50 % degradation of the dye after 7 h under UVA exposure. However further modifications of powders can improve the performance. In the context of bone regeneration, it is important to have platforms that with appropriate stimuli can support the attachment and direct the growth, proliferation and differentiation of the cells. In lieu of this here we exploited an alternative strategy for bone implants or repairs, based on charged mediating signals for bone regeneration. This strategy includes coating metallic 316L-type stainless steel (316L-SST) substrates with charged, functionalized via electrical charging or UV-light irradiation, ferroelectric LiTaO3 layers. It was demonstrated that the formation of surface calcium phosphates and protein adsorption is considerably enhanced for 316L-SST functionalized ferroelectric coatings. Our approach can be viewed as a set of guidelines for the development of platforms electrically functionalized that can stimulate tissue regeneration promoting direct integration of the implant in the host tissue by bone ingrowth and, hence contributing ultimately to reduce implant failure.