Lead-free Thin Films Research Articles

Enhanced domain switching contributing to large strain response in (Bi0.5Na0.5)TiO3–SrTiO3 lead-free thin films

The acquisition of lead-free piezoelectric films with large strain is the key factor in promoting micro-actuator development. A lead-free compound, Bi0.5Na0.5TiO3, exhibits extensive potential in achieving a large strain response and a high inverse piezoelectric coefficient. In this work, (1-x)Bi0.5Na0.5TiO3-xSrTiO3 (BNT-100xST, x = 0.1, 0.2, 0.25) solid solution thin films have been prepared using the chemical solution deposition method. The dielectric nonlinearity and ferroelectric properties of BNT-ST thin films have been systematically studied to investigate the domain wall motion in the films. The most significant domain wall motion was obtained in BNT-20STST thin film, in which film a large strain of 0.89 % was obtained. In addition, the relation between structure and properties as a function of temperature was studied by the temperature-dependent dielectric properties and Raman spectra analysis.

Tailoring breakdown strength and energy-storage performance of silicon-integrated lead-free epitaxial BZT thin films through multi-element B-site substitutions

Developing high-temperature dielectric thin films with high-performance energy-storage properties for harsh environment applications has received increased attention. Herein, a multi-element co-doping strategy is proposed to enhance the breakdown strength and energy storage properties of lead-free BaTiO3-based thin films, which were deposited on silicon substrates using pulsed laser deposition. Due to the difference in ionic radii and valence states between the multi-dopants and host Ti-cations, the local lattice distortion and local charged defects are induced, which results in the reduction in the size of polar nanoregions (PNRs) and weakened coupling interactions between these PNRs, thus achieving stronger breakdown strength (EBD). Accordingly, owing to an enhanced EBD of 7.8 MV/cm and a delayed polarization saturation, a superior recoverable energy-storage density (Ur) of 140.8 J/cm3 along with an excellent energy efficiency (η) of 93.2 % were achieved at room temperature in the multi-element doped Ba(Zr0.2Ti0.2Mn0.2Nb0.2Sm0.2)O3 (BZTMNS) thin film. Moreover, the BZTMNS thin film also exhibits an excellent Ur of 102.6 J/cm3, a good η of 86.4 %, and a high EBD of 6.6 MV/cm at an operating temperature of 200 °C. Additionally, a small fluctuation of Ur (-6.1 %) and η (-11.7 %) values can also be observed in BZTMNS thin film in high cycling endurance, up to 1010 cycles, even when operated at an elevated temperature of 200 °C. These findings in the BZTMNS thin film demonstrate a feasible way to design high-temperature capacitors for modern electronic devices for hybrid vehicles and underground oil/gas explorations.

Sputter deposited silver niobate thin films: Pathway towards phase purity

The quest for environmentally sustainable alternatives to lead-based dielectric materials in dielectric capacitors has led research to the exploration of options such as silver niobate (AgNbO3), which has been found to display excellent energy storage properties. Homogeneity and phase-purity of the used thin films are vital for optimal performance of these devices. In this study, a systematic variation of oxygen partial pressure and bias voltage during reactive d.c. magnetron co-sputtering from metallic targets is employed to synthesise AgNbO3 thin films. Structural and chemical composition of the films are investigated using X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy, elastic recoil detection analysis, and Rutherford backscattering spectrometry. The findings emphasise the necessity of precise parameter control during deposition to avoid the presence of undesirable secondary phases like Ag and Ag2Nb4O11 and to ensure the formation of homogeneous and phase-pure AgNbO3 thin films. The gained insights demonstrate the potential of reactive d.c. magnetron sputtering for the deposition of lead-free AgNbO3 thin films, offering pathways for enhanced environmental compatibility of future dielectric capacitors.

Excellent Energy Storage and Photovoltaic Performances in Bi0.45Na0.45Ba0.1TiO3-Based Lead-Free Ferroelectricity Thin Film

Excellent Energy Storage and Photovoltaic Performances in Bi0.45Na0.45Ba0.1TiO3-Based Lead-Free Ferroelectricity Thin Film

Lead-free methyl ammonium tin iodide perovskite thin film growth in single step via plasma enhanced chemical vapour deposition technique and its optoelectronic properties

In the present work, lead free methyl ammonium tin iodide (CH3NH3SnI3 or MASnI3) perovskite thin films have been deposited via single step plasma enhanced chemical vapour deposition (PECVD) technique. In our earlier work, we reported lead based methyl ammonium lead iodide (CH3NH3PbI3 or MAPbI3) perovskite thin film deposition in 2-step, using sputtering technique for the PbI2 thin films and PECVD technique for CH3NH3I (MAI) thin films. Similarly, CH3NH3SnI3 perovskite thin films are deposited in this work using PECVD technique in single step. Lead is substituted with tin due to its toxic behaviour, environmental and health related issues. CH3NH3SnI3 perovskite is doped n-type via changing the molar ratio of SnI2 and CH3NH3I. SnI2/CH3NH3I ratio is changed from 0.33 to 2 to study the n-type doping of CH3NH3SnI3 perovskite. Deposited CH3NH3SnI3 perovskite thin films are deposited over p-type silicon wafer to make n-type doped n-CH3NH3SnI3/p-Si heterojunction photodiode.

Engineering multi-ion doping by entropy for high energy storage density with high efficiency in amorphous thin film

In the field of stored energy materials, lead-free amorphous thin films have the advantages of high breakdown strength, excellent stability, environmental protection and pollution-free, and are a very competitive energy storage material. However, the difficulty of simultaneous optimization of polarization and breakdown strength has always been a difficulty in improving the energy storage properties of amorphous thin films. Entropy can be used to design multi-ion doping to improve the energy storage performance of amorphous film. Amorphous films with different entropy are prepared by sol-gel method doped with 50 % Zr4+ and 5 %, 10 %, 15 %, 20 % Bi(Mn0·5Ti0.5)O3. The Bi0·1Ba0·85Sr0·05Mn0·05Ti0·45Zr0·5O3 amorphous thin film prepared at medium entropy (S = 1.37) has a recoverable energy storage density of 107.4 J cm−3 at 8.42 MV cm−1, and the energy storage efficiency is 93.9 %. Under the interaction of multiple elements, entropy design can give full play to the advantages of composite effects, improve breakdown field strength and energy storage efficiency, and is a new method to enhance energy storage performance.

Effects of annealing temperature and ion doping on energy storage performance of Na0.5Bi0.5TiO3-Based thin films

Lead-free ferroelectric thin film capacitors offering superb power density and fast charge-discharge rates are ideal for energy storage applications. However, the trade-off relationship between polarization strength and breakdown strength significantly hinders the improvement of energy storage performance. In this work, relaxor-ferroelectric Na0.5Bi0.5TiO3 (NBT) thin films have been deposited on Pt/Ti/SiO2/Si substrate via sol-gel method. First, the energy storage performance of the films is optimized by adjusting the annealing temperature. It is found that the NBT film annealed at 650 °C has both excellent breakdown strength and polarization strength. Then the influence of ion doping on the energy storage performance of NBT films has been studied. An excellent energy storage density of 42.1 J/cm3 and efficiency of 55.8 % are simultaneously achieved in the 2 % Mn-NBT thin film. Additionally, the energy storage performance remains stable within the temperature range of 25–180 °C and frequency range of 500–5000 Hz. The energy storage performance of 2 % Mn-NBT thin film did not decrease significantly after 107 electrical cycles. It is predicted that this work will advance the utilization of Na0.5Bi0.5TiO3-based film capacitors in energy storage systems.

Strain-driven high energy storage in BaTiO3-based lead-free epitaxial thin films

In this work, the epitaxial 0.85BaTiO3-0.15Bi(Mg1/2Ti1/2)O3 (BT-BMT) films with large compressive strain were fabricated on SrTiO3 (001). The expansion of the unit cell volume and out-of-plane lattice parameter and the large built-in electric field (Ebi) in BT-BMT films indicate the existence of defect dipoles. It was found that the polarization and the breakdown strength can be optimized by the strain and the defects, respectively. Ultimately, a desirable energy density of 90.3 J/cm3 with efficiency of 62.3% was achieved. It suggests that strain can serve as a practical means to modulate the energy storage performance of ferroelectric epitaxial film capacitors.

Effect of Lewis acid-base additive on lead-free Cs2SnI6 thin film prepared by direct solution coating process

Abstract Inorganic Cs2SnI6 perovskite has exhibited substantial potential for light harvesting due to its exceptional optoelectronic properties and remarkable stability in ambient conditions. The charge transport characteristics within perovskite films are subject to modulation by various factors, including crystalline orientation, morphology, and crystalline quality. Achieving preferred crystalline orientation and film morphology via a solution-based process is challenging for Cs2SnI6 films. In this work, we employed thiourea as an additive to optimize crystal orientation, enhance film morphology, promote crystallization, and achieve phase purity. Thiourea lowers the surface energy of the (222) plane along the ＜111＞ direction, confirmed by X-ray diffraction, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy studies, and density functional theory calculations. Varying thiourea concentration enables a bandgap tuning of Cs2SnI6 from 1.52 eV to 1.07 eV. This approach provides a novel method for utilizing Cs2SnI6 films in high-performance optoelectronic devices.

Lead-free CsCu2I3 thin films prepared by one-step chemical vapor deposition method for ultraviolet photodetector

In recent years, inorganic lead-free perovskite materials have garnered attention for their non-toxicity, high carrier mobility, and strong light absorption capabilities, showing promising application prospects in photoelectric sensing. CsCu2I3 perovskite has been mentioned as one of the representatives and as a potential material for short-wavelength optoelectronic devices. This study employs a one-step chemical vapor deposition (CVD) process to fabricate CsCu2I3 thin films, which exhibit a vibrant yellow emission at 560 nm. Ultraviolet photodetectors utilizing CsCu2I3 films demonstrate an exceptional responsivity and a detectivity of 1.43 A/W and 1.15 × 1012 Jones (254 nm, 5 V bias), along with rapid response times (trise ≈ 50 ms, tdecay ≈ 70 ms). Moreover, this work examines the factors affecting device performance, including wavelength, operating voltage, and film thickness. It presents a straightforward, ecofriendly CVD method for producing lead-free perovskite films and optoelectronic devices, which has significant implications for the development of lead-free perovskite-based photoelectric technologies.

A phase-field simulation of easily switchable vortex structure for multilevel low-power ferroelectric memory

Ferroelectric materials with multi-directional polarization orders can form a variety of special domain structures, which have a wide range of applications. In this work, lead-free potassium sodium niobate ferroelectric thin films were simulated by solving the Time-Dependent-Landau-Ginzburg (TDLG) equation. Based on vortex topological structure characteristic of perovskite-type ferroelectric, domain types are simplified from 26 to 9 through virtual polarization vectors. By temperature selection, we accomplished a large easily switchable vortex structure with 20% side length. Based on this, as low as 0.04V/nm electric-field pulse was applied to explore vortex domain structures change. Under different low external electric-field pulses, conductance states change in vortex have been calculated and discussed systematically. Free energy computation results reveal that the domain wall (DW) conductance states primarily originate from the competition between electrostatic energy, gradient energy, and elastic energy. Finally, we propose the multilevel data ferroelectric memory through easily switchable vortex topological structures for the first time. Under electric-field pulses, diverse storage states were presented through 0/1 measurement of 8 positions. By achieving an easy-to-distinguish and robust-to-switch data map at the vortex structure, this work might provide a significant idea of vortex structure on low-power ferroelectric memory applications.

Lead-free BaTiO3-based relaxor ferroelectric thin film rendering rapid discharge rate for pulsed power energy application

Ferroelectric thin film capacitors have large application potential in pulsed-power electronic and electrical systems due to their high-power density and rapid discharge capabilities. Although lead-based dielectrics are promising, the pursuit of eco-friendly, lead-free alternatives is gaining research attention. Here, the Bi and Li co-doped BaTiO3 thin film exhibiting relaxor ferroelectric properties was investigated for its energy storage properties. The fabricated polycrystalline Ba0.85(Bi0.5Li0.5)0.15TiO3 thin film by pulsed laser deposition revealed good breakdown strength (∼4 MV cm−1), a slim ferroelectric loop, and low leakage characteristics suitable for energy storage applications. The film exhibits a significant value of recoverable energy density (∼70 J cm−3) with better frequency and thermal stability. Notably, the better overall performance parameters of the film, including a sizable power density (261 MW cm−3) and a fast discharge rate (150 ns), along with good energy density and breakdown strength, make the material suitable for pulsed-power energy applications.

Fabrication of high quality lead-free double perovskite Cs2AgBiBr6 thin film and its application in memristor with ultralow operation voltage

Recently, the lead-free double perovskite Cs2AgBiBr6 has been considered as a promising candidate for next-generation nonvolatile memory and artificial synapse devices due to its high stability and low toxicity compared to its lead-based counterparts. In this work, we developed a simple and effective method to produce high-quality lead-free double perovskite Cs2AgBiBr6 thin films without pinholes and particles by applying a low-pressure assisted method under ambient condition with a relative humidity (RH) of about 45%. The formation of pinholes and Ag precipitation in the perovskite Cs2AgBiBr6 films is effectively suppressed by the proper ratio of N,N-dimenthylformamide (DMF) mixed in dimethyl sulfoxide (DMSO) solvents. Furthermore, the grain size of the Cs2AgBiBr6 films can be significantly increased by increasing the post-annealing temperature. Finally, a sandwiched structure memristor with an ITO/Cs2AgBiBr6/Ta configuration was successfully demonstrated, featuring ultralow operation voltage (V Set ∼ 57 ± 23 mV, V Reset ∼ −692 ± 68 mV) and satisfactory memory window (the ratio of R HRS/R LRS ∼ 10 times), which makes it suitable for low-power consumption information storage devices.

Giant electrostriction-like response from defective non-ferroelectric epitaxial BaTiO3 integrated on Si (100)

Lead-free, silicon compatible materials showing large electromechanical responses comparable to, or better than conventional relaxor ferroelectrics, are desirable for various nanoelectromechanical devices and applications. Defect-engineered electrostriction has recently been gaining popularity to obtain enhanced electromechanical responses at sub 100 Hz frequencies. Here, we report record values of electrostrictive strain coefficients (M31) at frequencies as large as 5 kHz (1.04×10−14 m2/V2 at 1 kHz, and 3.87×10−15 m2/V2 at 5 kHz) using A-site and oxygen-deficient barium titanate thin-films, epitaxially integrated onto Si. The effect is robust and retained upon cycling upto 6 million times. Our perovskite films are non-ferroelectric, exhibit a different symmetry compared to stoichiometric BaTiO3 and are characterized by twin boundaries and nano polar-like regions. We show that the dielectric relaxation arising from the defect-induced features correlates well with the observed giant electrostriction-like response. These films show large coefficient of thermal expansion (2.36 × 10−5/K), which along with the giant M31 implies a considerable increase in the lattice anharmonicity induced by the defects. Our work provides a crucial step forward towards formulating guidelines to engineer large electromechanical responses even at higher frequencies in lead-free thin films.

Transformation of Polarization Mechanisms by Dimensional Reduction in Lead-Free Silver Bismuth Bromide Double-Perovskite Thin Films

Transformation of Polarization Mechanisms by Dimensional Reduction in Lead-Free Silver Bismuth Bromide Double-Perovskite Thin Films

Self-assembly ordered domain configurations serve the high electromechanical response lead-free thin films

Micro-electromechanical systems (MEMS) urgently require high-performance lead-free piezoelectric thin films, which is rather difficult to achieve via the existing strategy of designing a morphotropic phase boundary. How to update the optimization methods for piezoelectric performance is a challenge. Here, we proposed a simple and interesting way, that is, constructing the self-assembly ordered domain configurations in our oriented lead-free thin films. Driven by the local strain, we realized a periodic arrangement of disordered nano-domains and ordered striped domain structures, and thus obtained an outstanding electrostrain of 1.55%. Multi-scale characterization and phase-field simulations suggest the underlying mechanism of this giant strain as the synergy between the high polarization brought about by the periodic nano-pillar-like striped domains, the highly sensitive electrical stimulation response of defective dipoles and disordered nano-domains. The presented high electrostrain supports the potential MEMS application, the proposed optimization strategy serves the next generation lead-free thin films with higher electromechanical response.

Reduced leakage current and enhanced energy storage performance of BZNT/BTO multilayer structures: Implications in electronic devices

The extremely high recoverable energy density (Wrec) and efficiency (η) of lead-free thin films make them a promising candidate for application in miniature power devices. Here, a stable design of multilayered structures of BaTiO3 (BTO) and Bi[Zn2/3(Nb0.85Ta0.15)1/3]O3 (BZNT) have been fabricated using the pulsed laser deposition (PLD) technique on n-type Si, and Pt/Ti/SiO2/Si (Pt-Si) substrates. The effect of a number of stacking of alternate BTO and BZNT layers on the structural, microstructural, electrical, and ferroelectric properties is investigated. The films exhibited a polycrystalline nature, and the tetra-layer stacked film (BZNT/BTO3) exhibited better crystallinity, improvement in microstructure, and grain growth than that of the bi-layer stacked film (BZNT/BTO1). The improvement in ferroelectric response in the tetra-layer film is well correlated to the low leakage current density (∼10-7 A/cm2 at ±500 kV/cm) owing to reduced defects in the film. The reduced oxygen vacancies and dielectric loss tangent of order 10-3 validate the high quality of BZNT/BTO3 film exhibiting a large Wrec of 52.19 J/cm3 and high energy efficiency of 92.21 % achieved through interface engineering. These findings demonstrate the promising future for BTO-based multilayer thin film in high-power and energy-storage device applications.

Substrate temperature dependence of vapor phase deposition of all-inorganic lead-free CsSnBr3 perovskite thin films

We report the effect of substrate temperature on the vapor phase deposition of all-inorganic lead-free tin halide perovskite CsSnBr3 thin films by co-evaporation of CsBr and SnBr2. The amount of SnBr2 supplied had little effect on the thin film when the substrate temperature exceeded the SnBr2 effusion cell temperature (∼180 °C) indicating that the three-temperature growth was realized. The polycrystalline CsSnBr3 thin films obtained by three-temperature growth showed micrometer-scale grains and no by-products. The average grain size increased for higher substrate temperatures following the Arrhenius law with an activation energy of 6.6 kJ mol−1.

Probing compositional engineering effects on lead-free perovskite-inspired nanocrystal thin films using correlative nonlinear optical microscopy.

We introduce the use of correlative third-harmonic generation and multiphoton-induced luminescence microscopy to investigate the impact of manganese (Mn) doping on bismuth (Bi)-based perovskite-inspired nanocrystal thin films. The technique was found to be extremely sensitive to the microscopic features of the perovskite film and its structural compositions, allowing the unambiguous detection of compositionally different emitters in the perovskite film and manipulation of their nonlinear optical responses. Our work unveils a new way to investigate, manipulate, and exploit perovskite-inspired functional materials for nonlinear optical conversion at the nanoscale.

Lead-Free Perovskite Thin Films for Gas Sensing through Surface Acoustic Wave Device Detection.

Thin film technology shows great promise in fabricating electronic devices such as gas sensors. Here, we report the fabrication of surface acoustic wave (SAW) sensors based on thin films of (1 - x) Ba(Ti0.8Zr0.2)O3-x(Ba0.7Ca0.3)TiO3 (BCTZ50, x = 50) and Polyethylenimine (PEI). The layers were deposited by two laser-based techniques, namely pulsed laser deposition (PLD) for the lead-free material and matrix assisted pulsed laser evaporation (MAPLE) for the sensitive polymer. In order to assay the impact of the thickness, the number of laser pulses was varied, leading to thicknesses between 50 and 350 nm. The influence of BCTZ film's crystallographic features on the characteristics and performance of the SAW device was studied by employing substrates with different crystal structures, more precisely cubic Strontium Titanate (SrTiO3) and orthorhombic Gadolinium Scandium Oxide (GdScO3). The SAW sensors were further integrated into a testing system to evaluate the response of the BCTZ thin films with PEI, and then subjected to tests for N2, CO2 and O2 gases. The influence of the MAPLE's deposited PEI layer on the overall performance was demonstrated. For the SAW sensors based on BCTZ/GdScO3 thin films with a PEI polymer, a maximum frequency shift of 39.5 kHz has been obtained for CO2; eight times higher compared to the sensor without the polymeric layer.