Recent advances of lead-free metal halide perovskite single crystals and nanocrystals: synthesis,crystal structure,optical properties,and their diverse applications

Lead halide hybrid perovskites have received massive research attention because of their unique inherent photophysical properties that driven them for potential application in the fields of photovoltaics, light-emitting devices, lasing, X-ray detector, and so on. Perovskite single crystals and nanocrystals are generally synthesized via various low-cost solution-processed techniques. The emergence of simple growth approaches of perovskite structures enable to fabricate low-cost and highly efficient devices. However, toxicity of Pb atoms and instability of perovskite structures obstruct further commercialization of these technologies. Recent efforts have been shifted to discover novel, eco-friendly, and stable lead-free metal halide perovskite (LFHP) materials and exploring their different growth processes for various device applications. This review aims to provide an up-to-date analysis of recent progress report on LFHPs and will mainly focus on their growth processes in the single crystalline and nanocrystalline forms. This review also tries to understand how the perovskite crystal structure impacts on their fundamental properties. In addition, we discuss the current progress in various field of applications and their future aspects.     

Lead-free ferroelectric BaTiO3 doped-(Na0.5Bi0.5)TiO3 thin films processed by pulsed laser deposition technique

The difficulties in synthesizing phase pure BaTiO₃ doped-(Na_0.5Bi_0.5)TiO₃ are known. In this work, we reporting the optimized pulsed laser deposition (PLD) conditions for obtaining pure phase 0.92(Na_0.5Bi_0.5)TiO₃-0.08BaTiO₃, (BNT-BT_0.08), thin films. Dielectric, ferroelectric and piezoelectric properties of BNT-BT_0.08, thin films deposited by PLD on Pt/TiO₂/SiO₂/Si substrates are investigated in this paper. Perovskite structure of BNT-BT_0.08 thin films with random orientation of nanocrystallites has been obtained by deposition at 600 °C. The relative dielectric constant and loss tangent at 100 kHz, of BNT-BT_0.08 thin film with 530 nm thickness, were 820 and 0.13, respectively. Ferroelectric hysteresis measurements indicated a remnant polarization value of 22 μC/cm² and a coercive field of 120 kV/cm. The piezoresponse force microscopy (PFM) data showed that most of the grains seem to be constituted of single ferroelectric domain. The as-deposited BNT-BT_0.08 thin film is ferroelectric at the nanoscale level and piezoelectric.     

Oxidation kinetics of thin copper films and wetting behaviour of copper and Organic Solderability Preservatives (OSP) with lead-free solder

The oxide formation on thin copper films deposited on Si wafer was studied by XPS, SEM and Sequential Electrochemical Reduction Analysis SERA. The surfaces were oxidized in air with a reflow oven as used in electronic assembly at temperatures of 100 °C, 155 °C, 200 °C, 230 °C and 260 °C. The SERA analyses detected only the formation of Cu₂O but the XPS analysis done for the calibration of the SERA equipment proved also the presence of a CuO layer smaller than 2 nm above the Cu₂O oxide. The oxide growth follows a power-law dependence on time within this temperature range and an activation energy of 33.1 kJ/mol was obtained. The wettability of these surfaces was also determined by measuring the contact angle between solder and copper substrate after the soldering process. A correlation between oxide thickness and wetting angle was established. It was found that the wetting is acceptable only when the oxide thickness is smaller than 16 nm. An activation energy of 27 kJ/mol was acquired for the spreading of lead free solder on oxidized copper surfaces.From wetting tests on copper surfaces protected by Organic Solderability Preservatives (OSP), it was possible to calculate the activation energy for the thermal decomposition of these protective layers.     

Generalized layerwise mechanics for the static and modal response of delaminated composite beams with active piezoelectric sensors

A coupled linear layerwise laminate theory and a beam FE are formulated for analyzing delaminated composite beams with piezoactuators and sensors. The model assumes zig-zag fields for the axial displacements and the electric potential and it treats the discontinuities in the displacement fields due to the delaminations as additional degrees of freedom. The formulation naturally includes the excitation of piezoelectric actuators, their interactions with the composite laminate, and the effect of delamination on the predicted sensory voltage. The quasistatic and modal response of laminated composite Gr/Epoxy beams with active or sensory layers having various delamination sizes is predicted. The numerical results illustrate the strong effect of delamination on the sensor voltage, on through the thickness displacement and on the stress fields. Finally, the effect of delamination on modal frequencies and shapes are predicted and compared with previously obtained experimental results.     

Anisotropic electrical properties of Bi0.5(Na0.75K0.25)0.5TiO3 ceramics fabricated by reactive templated grain growth (RTGG)

We have fabricated lead-free Bi_0.5(Na_0.75K_0.25)_0.5TiO₃ (BNKT) ceramics by a conventional process (CP) and reactive templated grain growth (RTGG) methods. The effect of grain orientation on structure, dielectric, complex impedance and electrical properties was investigated. The phase formation and grain morphology of BNKT ceramics were examined by X-ray diffraction (XRD) and scanning electron microscope (SEM), respectively. High dielectric constant and low dielectric loss was observed for grain oriented (textured) BNKT ceramics. Complex impedance, temperature dependent ac and dc conductivity were performed to explore the conduction behavior of the prepared BNKT ceramics.     

Fabrication of textured KNNT ceramics by reactive template grain growth using NN templates

Lead-free non-stoichiometric (K_0.470Na_0.545)(Nb_0.55Ta_0.45)O₃ (KNNT) textured ceramics were prepared by a reactive templated grain growth method using NaNbO₃ (NN) templates. The Plate-like NaNbO₃ (NN) templates were synthesized from bismuth layer-structured Bi_2.5Na_3.5Nb₅O₁₈ (BNN) particles by a topochemical microcrystal conversion (TMC) method. Using 5 wt% of NN templates, textured KNNT ceramics were fabricated, and their crystal structure, microstructure, dielectric and piezoelectric properties were compared with non-textured KNNT ceramics prepared by a conventional solid state reaction method. The textured KNNT ceramics exhibited high grain orientation and high dielectric constant. In addition, piezoelectric properties of textured KNNT ceramics were improved, giving a high piezoelectric coefficient d₃₃ = 390 pC/N and piezoelectric coupling coefficient k_p = 0.60.     

Structural and electrical properties of lanthanum-substituted lead titanate ceramics

The effect of lanthanum substitution on the structural, dielectric and piezoelectric properties of lead calcium titanate (PCT) ceramics is studied. Samples with compositional formula Pb_{0.76? x} La _x Ca_0.24Ti_0.98Mn_0.02O₃ (PLCT) (x?=?0–0.08, in steps of 0.02) were prepared by the conventional dry ceramic technique. Phase and structural analysis was carried out using XRD and SEM respectively. X-ray analysis confirmed the formation of single-phase compound with tetragonal crystal structure. Dielectric properties were studied in detail as a function of frequency and temperature. The Curie temperature (T _C) and tetragonality (c/a) was found to decrease with increase in lanthanum content. The Curie temperature was also confirmed from the thermal-expansion behaviour of the sintered samples. Piezoelectric coefficients (d ₃₃, d ₃₁, g ₃₃, g ₃₁, g _h, d _h, k _t and k _p) were measured at room temperature. From this study it is found that La³⁺ substitution helps in the improvement of electro-mechanical anisotropy.     

Preliminary results on sol-gel processing of 〈100〉 oriented Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript> thin films using diol-based solutions

A novel sol-gel method is used here for the synthesis of air-stable and precipitate-free diol-based sols of 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ (PMN-PT). Sols containing a 15 mol% lead excess have been used for the preparation of PMN-PT thin films. The films were deposited onto (111)Pt/TiO₂/SiO₂/(100)Si substrates, and crystallised in oxygen by Rapid Thermal Processing (RTP), using different temperatures and soaking times. Single perovskite films are obtained when treated at temperatures between 600 and 700°C for 6 s. Those crystallised at other temperatures contain a secondary pyrochlore phase. This phase also appears in the films treated at 650°C with soaking times longer than 6 s. PMN-PT films with a 〈100〉 preferred orientation were prepared by using a PbTiO₃ seeding layer onto the substrate. These PMN-PT films present relaxor-type electrical properties. Dielectric permittivity, , shows significant dispersion. Its temperature dependence presents a broad maximum at 110–130°C, which position shifts towards higher temperatures with frequency. Ferroelectric hysteresis loops show high values of saturation polarisation but very low remanence. The piezoelectric activity of the films has been tested by the measurement of their local piezoelectric hysteresis loops.     

Lead-free KNLNT piezoelectric ceramics for high-frequency ultrasonic transducer application

This paper presents the latest development of a lead-free piezoelectric ceramic and its application to transducers suitable for high-frequency ultrasonic imaging. A lead-free piezoelectric ceramic with formula of (K_0.5Na_0.5)_0.97Li_0.03(Nb_0.9 Ta_0.1)O₃ (abbreviated as KNLNT-0.03/0.10) was fabricated and characterized. The material was found to have a clamped dielectric constant ε₃₃^S/ε₀ = 890, piezoelectric coefficient d₃₃ = 245 pC/N, electromechanical coupling factor k_t = 0.42 and Curie temperature T_c > 300 °C. High-frequency (40 MHz) ultrasound transducers were successfully fabricated with the lead-free material. A representative lead-free transducer had a bandwidth of 45%, two-way insertion loss of -18 dB. This performance is comparable to reported performances of popular lead-based transducers. The comparison results suggest that the lead-free piezoelectric material may serve as an alternative to lead-based piezoelectric materials for high-frequency ultrasonic transducer applications.