Design for Highly Piezoelectric and Visible/Near‐Infrared Photoresponsive Perovskite Oxides

Defect‐engineered perovskite oxides that exhibit ferroelectric and photovoltaic properties are promising multifunctional materials. Though introducing gap states by transition metal doping on the perovskite B‐site can obtain low bandgap (i.e., 1.1–3.8 eV), the electrically leaky perovskite oxides generally lose piezoelectricity mainly due to oxygen vacancies. Therefore, the development of highly piezoelectric ferroelectric semiconductor remains challenging. Here, inspired by point‐defect‐mediated large piezoelectricity in ferroelectrics especially at the morphotropic phase boundary (MPB) region, an efficient strategy is proposed by judiciously introducing the gap states at the MPB where defect‐induced local polar heterogeneities are thermodynamically coupled with the host polarization to simultaneously achieve high piezoelectricity and low bandgap. A concrete example, Ni²⁺‐mediated (1–x)Na_0.5Bi_0.5TiO₃‐xBa(Ti_0.5Ni_0.5)O_3–δ (x = 0.02–0.08) composition is presented, which can show excellent piezoelectricity and unprecedented visible/near‐infrared light absorption with a lowest ever bandgap ≈0.9 eV at room temperature. In particular, the MPB composition x = 0.05 shows the best ferroelectricity/piezoelectricity (d₃₃ = 151 pC N^–1, Pr = 31.2 μC cm^–2) and a largely enhanced photocurrent density approximately two orders of magnitude higher compared with classic ferroelectric (Pb,La)(Zr,Ti)O₃. This research provides a new paradigm for designing highly piezoelectric and visible/near‐infrared photoresponsive perovskite oxides for solar energy conversion, near‐infrared detection, and other multifunctional applications.     

A Molecular Polycrystalline Ferroelectric with Record‐High Phase Transition Temperature

An outstanding advantage of inorganic ceramic ferroelectrics is their usability in the polycrystalline ceramic or thin film forms, which has dominated applications in the ferroelectric, dielectric, and piezoelectric fields. Although the history of ferroelectrics began with the molecular ferroelectric Rochelle salt in 1921, so far there have been very few molecular ferroelectrics, with lightweight, flexible, low‐cost, and biocompatible superior properties compared to inorganic ceramic ferroelectrics, that can be applied in the polycrystalline form. Here, a multiaxial molecular ferroelectric, guanidinium perchlorate ([C(NH₂)₃]ClO₄), with a record‐high phase transition temperature of 454 K is presented. It is the rectangular polarization–electric field (P –E ) hysteresis loops recorded on the powder and thin film samples (with respective large P _r of 5.1 and 8.1 µC cm^?2) that confirm the ferroelectricity of [C(NH₂)₃]ClO₄ in the polycrystalline states. Intriguingly, after poling, the piezoelectric coefficient (d ₃₃) of the powder sample shows a significant increase from 0 to 10 pC N^?1, comparable to that of LiNbO₃ single crystal (8 pC N^?1). This is the first time that such a phenomenon has been observed in molecular ferroelectrics, indicating the great potential of molecular ferroelectrics being used in the polycrystalline form like inorganic ferroelectrics, as well as being viable alternatives or supplements to conventional ceramic ferroelectrics.     

Giant Polarization Sustainability in Ultrathin Ferroelectric Films Stabilized by Charge Transfer

Ferroelectricity is generally deteriorated or even vanishes when the ferroelectric films are downsized to unit cell scale. To maintain and enhance the polarization in nanoscale ferroelectrics are of scientific and technological importance. Here, giant polarization sustainability is reported in a series of ultrathin PbTiO₃ films scaled down to three unit cells grown on NdGaO₃(110) substrates with La_0.7Sr_0.3MnO₃ as bottom electrodes. Atomic mappings via aberration‐corrected scanning transmission electron microscopy demonstrate the robust ferroelectricity for the sub‐10 nm thick film. For the 1.2 nm thick film, the polarization reaches ≈50 µC cm^?2. The 2 nm thick film possesses a polarization as high as the bulk value. The films ranging from 10 to 35 nm display a giant elongation of out‐of‐plane lattice parameter, which corresponds to a polarization of 100 µC cm^?2, 20% larger than that of the bulk PbTiO₃. The giant enhancement of polarization in the present films is proposed to result from the charge transfer at the La_0.7Sr_0.3MnO₃/PbTiO₃ interface, as supported by the anomalous decrease of Mn valence measured from X‐ray photoelectron spectroscopy. These results reveal the significant role of charge transfer at interfaces in improving large polarizations in ultrathin ferroelectrics and are meaningful for the development of future electronic devices.     

A study on the electrical properties of Pb(Zr, Ti)O3 thin films crystallized by the electrical resistive heating of Pt thin film

The electrical properties of Pb(Zr, Ti)O₃ thin films annealed by Pt thin film heater were investigated. By the thin film heater, we successfully crystallized Pb(Zr, Ti)O₃ thin films at a high temperature above 750 °C in a few seconds. The thin film heater has some advantages, such as a low thermal budget, little Pb-loss and enhanced surface morphology compared with the conventional furnace because it has a fast heating rate. The electrical properties of the Pb(Zr, Ti)O₃ thin film crystallized by thin film heater improved considerably comparing to those crystallized in conventional furnace. The remanent polarization, breakdown field, and leakage current density measured to be 22.7 μC/cm², 853 kV/cm, and 6.93 × 10⁻⁷ A/cm², respectively.     

Lead‐Free Antiferroelectric Silver Niobate Tantalate with High Energy Storage Performance

Antiferroelectric materials that display double ferroelectric hysteresis loops are receiving increasing attention for their superior energy storage density compared to their ferroelectric counterparts. Despite the good properties obtained in antiferroelectric La‐doped Pb(Zr,Ti)O₃‐based ceramics, lead‐free alternatives are highly desired due to the environmental concerns, and AgNbO₃ has been highlighted as a ferrielectric/antiferroelectric perovskite for energy storage applications. Enhanced energy storage performance, with recoverable energy density of 4.2 J cm^?3 and high thermal stability of the energy storage density (with minimal variation of ≤±5%) over 20–120 °C, can be achieved in Ta‐modified AgNbO₃ ceramics. It is revealed that the incorporation of Ta to the Nb site can enhance the antiferroelectricity because of the reduced polarizability of B‐site cations, which is confirmed by the polarization hysteresis, dielectric tunability, and selected‐area electron diffraction measurements. Additionally, Ta addition in AgNbO₃ leads to decreased grain size and increased bulk density, increasing the dielectric breakdown strength, up to 240 kV cm^?1 versus 175 kV cm^?1 for the pure counterpart, together with the enhanced antiferroelectricity, accounting for the high energy storage density.     

Advanced fabrication and characterization of epitaxial ferroelectric thin films and multilayers

Understanding the behavior of ferroelectrics on the nanoscale level requires the production of materials of the highest quality and advanced characterization techniques for probing the fascinating properties of these systems with reduced dimensions. Here we give an overview of our recent achievements in this area, which includes the detailed study of the suppression of ferroelectricity in PbTiO3 thin films, the fabrication of PbTiO3/SrTiO3 superlattices in which ferroelectricity shows some surprising behavior, and finally the manipulation of nanoscale ferroelectric domains using the atomic force microscope which leads to the precise analysis of domain wall creep and roughness in Pb(Zr,Ti)O3 thin films.     

Enhanced ferro- and piezoelectric properties in (100)-textured Nb-doped Pb(ZrxTi1 − x)O3 films with compositions at morphotropic phase boundary

To develop high-performance piezoelectric films on conventional Pt(111)/Ti/SiO₂/Si(100) substrates, sol-gel-derived highly [100]-textured Nb-doped Pb(Zr_xTi_1 − x)O₃ (PNZT) thin films with different Zr/Ti ratios ranging from 20/80 to 80/20 were prepared and characterized. The phase structure, ferroelectric and piezoelectric properties of the PZNT films were investigated as a function of Zr/Ti ratios, and it was confirmed that there was distinct phase transition of the PNZT system from tetragonal to rhombohedral when the Zr/Ti ratio varied across the morphotropic phase boundary (MPB). The Nb-doped PZT films showed enhanced remanent polarization but reduced coercive field, whose best values reached 75 μC/cm² and 82 kV/cm, respectively at the composition close to MPB. In addition, the [100]-textured PNZT film at MPB also shows a high piezoelectric coefficient up to 161 pm/V. All these properties are superior to those for undoped PZT films.     

Investigation on the effects of PbO content and seeding layers of TiO2 and ZrO2 on the orientation and microstructure of Pb(Zr0.52Ti0.48)O3 ferroelectric films grown by reverse dip-coating method of sol–gel

Lead zirconate titanate Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films were grown on Si (100) and Pt(111)/Ti/SiO₂/Si(100) substrates by a new reverse dip-coating method of sol–gel process. The method was first proposed and applied to coat films. It has several advantages over the conventional sol–gel coating method, including: no consideration of the mechanical transmission that is difficult to manipulate with costly exact apparatus in classical dip-coating procession, convenient processing control, simplicity, low cost, less pollution, and easy fabrication films on large areas and irregular shaped devices etc. This paper studied the factors including PbO content of precursor, TiO₂ and ZrO₂ layers, which are related to raw materials of PZT precursor and influence greatly the crystal orientation of the final thin films. We find that the PZT films deposited by precursor with 20% mole excess Pb displayed strong (111) preferred orientation, with 5% mole excess Pb showed a little (100) orientation and pyrochlore phase. The precursor with 10% mole excess Pb was found prompting the PZT films phase transformation with (110) preferred orientation. In addition, the results show that the TiO₂ and ZrO₂ seeding layers had totally different effects on the preferred orientation of PZT films. The films with TiO₂ seeding layer were highly (111) oriented and exhibited better ferroelectric properties (remnant polarization Pr = 14.2 μC cm^− 2, coercive field Ec = 59.1 Kv cm^− 1) than those of the films with ZrO₂ seeding layer shown (100) orientation (Pr = 7.4 μC cm^− 2, Ec = 42.9 Kv cm^− 1).     

Facile Control of Ferroelectricity Driven by Ingenious Interaction Engineering

Construction of ferroelectric and optimization of macroscopic polarization has attracted tremendous attention for next generation light weight and flexible devices, which brings fundamental vitality for molecular ferroelectrics. However, effective molecular tailoring toward cations makes ferroelectric synthesis and modification relatively elaborate. Here, the study proposes a facile method to realize triggering and optimization of ferroelectricity. The experimental and theoretical investigation reveals that orientation and alignment of polar cations, dominated factors in molecular ferroelectrics, can be controlled by easily processed anionic modification. In one respect, ferroelectricity is induced by strengthened intermolecular interaction. Moreover, ≈50% of microscopic polarization enhancement (from 8.07 to 11.68 µC cm⁻²) and doubling of equivalent polarization direction (from 4 to 8) are realized in resultant ferroelectric FEtQ2ZnBrI₃ (FEQZBI, FEtQ = N-fluoroethyl-quinuclidine). The work offers a totally novel platform for control of ferroelectricity in organic–inorganic hybrid ferroelectrics and a deep insight of structure–property correlations.     

Enhanced ferroelectric properties of Pb(Zr0.80Ti0.20)O3/PbO thin films prepared by radio frequency magnetron sputtering

The Pb(Zr_0.80Ti_0.20)O₃ (PZT) thin films with and without a PbO buffer layer were deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by radio frequency (rf) magnetron sputtering method. The PbO buffer layer improves the microstructure and electrical properties of the PZT thin films. High phase purity and good microstructure of the PZT thin films with a PbO buffer layer were obtained. The effect of the PbO buffer layer on the ferroelectric properties of the PZT thin films was also investigated. The PZT thin films with a PbO buffer layer possess better ferroelectric properties with higher remnant polarization (P_r = 25.6 μC/cm²), and lower coercive field (E_c = 60.5 kV/cm) than that of the films without a PbO buffer layer (P_r = 9.4 μC/cm², E_c = 101.3 kV/cm). Enhanced ferroelectric properties of the PZT thin films with a PbO buffer layer is attributed to high phase purity and good microstructure.     

Hafnium and zirconium tetramethylnonanedionates as new MOCVD precursors for oxide films

New bulky Zr and Hf β-diketonates (2,2,8,8-tetramethyl-4,6-nonanedionates, tmnd) were synthesized and characterized by elemental analyses, ¹H NMR, FT-IR and mass spectrometry. A volatile copper compound Cu(tmnd)₂, an intermediate product of ligand synthesis, was isolated and characterized as well. The M(tmnd)₄ (M=Zr, Hf) compounds were tested as precursors for MOCVD of ZrO₂ and HfO₂ films. Preferentially (001)/(010)/(100) textured and in-plane oriented films of monoclinic oxides have been deposited by pulsed liquid injection MOCVD on R plane sapphire. Smooth films could be grown, especially on sapphire and at low temperature (500 °C). The films on Si(100) were polycrystalline and had rougher surface. XPS study showed 3–4 and 7–8 at.% of carbon in HfO₂ and ZrO₂ films, respectively. Zr(tmnd)₄ and Hf(tmnd)₄ lead to significantly higher growth rates of ZrO₂ and HfO₂ films at low temperature than conventional Zr(thd)₄ and Hf(thd)₄ precursors (thd=2,2,6,6-tetramethyl-3,5-heptanedionate) and are attractive precursors for oxide films.     

Fluorinated 2D Lead Iodide Perovskite Ferroelectrics

Hybrid perovskite materials are famous for their great application potential in photovoltaics and optoelectronics. Among them, lead‐iodide‐based perovskites receive great attention because of their good optical absorption ability and excellent electrical transport properties. Although many believe the ferroelectric photovoltaic effect (FEPV) plays a crucial role for the high conversion efficiency, the ferroelectricity in CH₃NH₃PbI₃ is still under debate, and obtaining ferroelectric lead iodide perovskites is still challenging. In order to avoid the randomness and blindness in the conventional method of searching for perovskite ferroelectrics, a design strategy of fluorine modification is developed. As a demonstration, a nonpolar lead iodide perovskite is modified and a new 2D fluorinated layered hybrid perovskite material of (4,4‐difluorocyclohexylammonium)₂PbI₄, 1 , is obtained, which possesses clear ferroelectricity with controllable spontaneous polarization. The direct bandgap of 2.38 eV with strong photoluminescence also guarantees the direct observation of polarization‐induced FEPV. More importantly, the 2D structure and fluorination are also expected to achieve both good stability and charge transport properties. 1 is not only a 2D fluorinated lead iodide perovskite with confirmed ferroelectricity, but also a great platform for studying the effect of ferroelectricity and FEPV in the context of lead halide perovskite solar cells and other optoelectronic applications.     

Ferroelectric properties of neodymium-doped Bi4Ti3O12 thin films crystallized in different environments

Neodymium (Nd)-doped Bi₄Ti₃O₁₂ (Bi_3.15Nd_0.85Ti₃O₁₂, BNT) ferroelectric films have been deposited on Pt/Ti/SiO₂/Si substrates by a sol–gel process and crystallized in nitrogen, air and oxygen environments, respectively. The crystallization environment was found to be important in determining the crystallization and ferroelectric properties of the BNT films. The film crystallized in nitrogen at a relatively low temperature of 650 °C, and exhibits excellent crystallinity and ferroelectricity with a remanent polarization of 2P_r=63.6 μC/cm², a coercive field of 130 kV/cm and a fatigue-free characteristic. While the films annealed in air and oxygen, they did not show good crystallinity and ferroelectricity until they were annealed at 710 and 730 °C, respectively. A correlation between the remanent polarization and dielectric constants of the BNT films has been observed.     

MXene‐Derived Ferroelectric Crystals

This study demonstrates the first synthesis of MXene‐derived ferroelectric crystals. Specifically, high‐aspect‐ratio potassium niobate (KNbO₃) ferroelectric crystals is successfully synthesized using 2D Nb₂C, MXene, and potassium hydroxide (KOH) as the niobium and potassium source, respectively. Material analysis confirms that a KNbO₃ orthorhombic phase with Amm2 symmetry is obtained. Additionally, ferroelectricity in KNbO₃ is confirmed using standard ferroelectric, dielectric, and piezoresponse force microscopy measurements. The KNbO₃ crystals exhibit a saturated polarization of ≈21 µC cm^?2, a remnant polarization of ≈17 µC cm^?2, and a coercive field of ≈50 kV cm^?1. This discovery illustrates that the 2D nature of MXenes can be exploited to grow ferroelectric crystals.     

Orientation controlling of Pb(Zr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript> thin films prepared on silicon substrates with the thickness of La<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>CoO<Subscript>3</Subscript> electrodes

Pb(Zr_0.53Ti_0.47)O₃ (PZT) thin films were prepared on La_0.5Sr_0.5CoO₃ (LSCO) coated Si substrates by a sol–gel route. The thickness of LSCO electrode was found to modify the preferential orientation of PZT thin films, which consequently affected the dielectric and ferroelectric properties. (100) textured PZT films with dense columnar structure could be obtained on the top of (110) textured LSCO with thickness of 230 nm. PZT thin films prepared on the optimized LSCO films exhibit the enhanced dielectric constant and remnant polarization of 980 and 20 μC/cm², respectively.     

Effect of processing on the properties of Bi3.15Nd0.85Ti3O12 thin films

Various crystallization parameters were studied during the fabrication of Bi_3.15Nd_0.85Ti₃O₁₂ (BNdT) thin films on Pt/Ti/SiO₂/Si (100) by metal organic solution decomposition method. The effect of crystallization processes, crystallization ambients on the properties of BNdT thin films such as orientation, ferroelectric properties were examined. By adopting different fabrication processes, it is possible to get both highly c-axis oriented as well as randomly oriented thin films. Highly c-axis oriented BNdT thin film showed a large remnant polarization (2P_r) of 70 μC/cm² at an applied voltage of 10 V and exhibited a fatigue free behavior unto 2 × 10⁹ switching cycles. The improved ferroelectric properties of BNdT thin films suggest their suitability for high density ferroelectric random access memory applications.     

Microstructure and electrical properties of Pb(Zr0.52Ti0.48)O3 ferroelectric films on different bottom electrodes

The crystalline quality, dielectric and ferroelectricity of the Pb(Zr_0.52Ti_0.48)O₃ (PZT) films deposited on the LaNiO₃ (LNO), LNO/Pt and Pt bottom electrodes were comparatively analyzed to investigate the possibility for their application. LNO thin films were successfully prepared on Si (100) and Pt(111)/Ti/SiO₂/Si substrates by modified metallorganic decomposition (MOD). The PZT thin films were spin-coated onto the LNO, LNO/Pt and Pt bottom electrodes by sol–gel method. The crystallographic orientation and the microstructure of the resulting LNO films and PZT thin films on the different bottom electrodes were characterized by X-ray diffraction analysis. The dielectric and ferroelectric properties of PZT films on the different bottom electrodes are discussed. The PZT films deposited onto Pt/Ti/SiO₂/Si and LNO/Si substrates show strong (110) and (100) preferred orientation, respectively, while the films deposited onto LNO/Pt/Ti/SiO₂/Si substrates show the peaks of mixed orientations. PZT films on LNO and LNO/Pt bottom electrodes have larger dielectric constant and remnant polarizations compared with those grown on the Pt electrode.     

BaPbO3 conductive coating layers on platinized Si substrate for the growth of PbZr1−xTixO3 thin films

Barium metaplumbate (BaPbO₃, BPO) thin films were prepared on Pt/Ti/SiO₂/Si substrates by a sol–gel method and a rapid thermal annealing (RTA) process. X-ray diffraction (XRD) was used to characterize the crystalline structure of the resultant films. It was shown that the formation of perovskite BPO greatly depends on the lead concentration and the final annealing temperature. In terms of the semi-quantitative energy dispersion spectrum (EDS) analysis, the ratio of Pb/Ba in the BPO ceramic films increases as the final heating temperature increases. Using BPO as buffer layers, PZT thin films with a pure perovskite structure were grown at a very low temperature of 500 °C by the sol–gel technique and the RTA process. The remanent polarization of Pt/PZT/BPO/Pt ferroelectric capacitors is about 17 μC/cm² at an applied voltage of 3 V.     

Linear and nonlinear optical properties of RF sputtered (Pb,La)(Zr,Ti)O<Subscript>3</Subscript> ferroelectric thin films

Linear and nonlinear optical properties of (Pb,La)(Zr,Ti)O₃ (PLZT) ferroelectric thin films were presented in this paper. The PLZT ferroelectric thin films have been in situ grown on quartz substrates by radio-frequency (RF) magnetron sputtering at 650 °C. Their crystalline structure and surface morphologies were examined by X-ray diffraction and atomic force microscopy, respectively. It can be found that the PLZT thin films exhibit well-crystallized perovskite structure and good surface morphology. The fundamental optical constants (the band gap energy, linear refractive index, and linear absorption coefficient) were obtained through the optical transmittance measurements. A Z-scan technique was used to investigate the optical nonlinearity of the PLZT thin films on quartz substrates. The films display the strong third-order nonlinear optical effect. A large and negative nonlinear refractive index n ₂ is determined to be 1.21 × 10⁻⁶ esu for the PLZT thin films. All results show that the PLZT ferroelectric thin films have potential applications in optical limiting, switching, and modulated-type optical devices.     

Thermal treatment effects on interfacial layer formation between ZrO2 thin films and Si substrates

This paper describes the growth condition of stoichiometric ZrO₂ thin films on Si substrates and the interfacial structure of ZrO₂ and Si substrates. The ZrO₂ thin films were prepared by rf-magnetron sputtering from Zr target with mixed gas of O₂ and Ar at room temperature followed by post-annealing in O₂ ambient. The stoichiometric ZrO₂ thin films with smooth surface were grown at high oxygen partial pressure. The thick Zr-free SiO₂ layer was formed with both Zr silicide and Zr silicate at the interface between ZrO₂ and Si substrate during the post-annealing process due to rapid diffusion of oxygen atoms through the ZrO₂ thin films. After post annealing at 650-750 °C, the multi-interfacial layer shows small leakage current of less than 10⁻⁸ A/cm² that is corresponding to the high-temperature processed thermal oxidized SiO₂.