skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Large enhancement of ferroelectric properties of perovskite oxides via nitrogen incorporation
Perovskite oxides have a wide variety of physical properties that make them promising candidates for versatile technological applications including nonvolatile memory and logic devices. Chemical tuning of those properties has been achieved, to the greatest extent, by cation-site substitution, while anion substitution is much less explored due to the difficulty in synthesizing high-quality, mixed-anion compounds. Here, nitrogen-incorporated BaTiO3thin films have been synthesized by reactive pulsed-laser deposition in a nitrogen growth atmosphere. The enhanced hybridization between titanium and nitrogen induces a large ferroelectric polarization of 70 μC/cm2and high Curie temperature of ~1213 K, which are ~2.8 times larger and ~810 K higher than in bulk BaTiO3, respectively. These results suggest great potential for anion-substituted perovskite oxides in producing emergent functionalities and device applications.  more » « less
Award ID(s):
2102895
PAR ID:
10618409
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; more » ; ; ; ; « less
Publisher / Repository:
Science
Date Published:
Journal Name:
Science Advances
Volume:
11
Issue:
2
ISSN:
2375-2548
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract The removal of lead from commercialized perovskite‐oxide‐based piezoceramics has been a recent major topic in materials research owing to legislation in many countries. In this regard, Sn(II)‐perovskite oxides have garnered keen interest due to their predicted large spontaneous electric polarizations and isoelectronic nature for substitution of Pb(II) cations. However, they have not been considered synthesizable owing to their high metastability. Herein, the perovskite lead hafnate, i.e., PbHfO3in space groupPbam, is shown to react with SnClF at a low temperature of 300 °C, and resulting in the first complete Sn(II)‐for‐Pb(II) substitution, i.e. SnHfO3. During this topotactic transformation, a high purity and crystallinity is conserved withPbamsymmetry, as confirmed by X‐ray and electron diffraction, elemental analysis, and119Sn Mössbauer spectroscopy. In situ diffraction shows SnHfO3also possesses reversible phase transformations and is potentially polar between ≈130–200 °C. This so‐called ‘de‐leadification’ is thus shown to represent a highly useful strategy to fully remove lead from perovskite‐oxide‐based piezoceramics and opening the door to new explorations of polar and antipolar Sn(II)‐oxide materials. 
    more » « less
  2. Abstract Defect chemistry that results in the thermal processing of dielectric and piezoelectric films, crystals and ceramics ultimately controls the properties and long‐term performance of materials and devices. This paper reviews several thermochemical defect reactions using important perovskite base composition dielectrics including Pb(Zr,Ti)O3, (Na,K)NbO3, (Bi0.5Na0.5)TiO3‒BaTiO3, and Ca(Hf,Ti,Mn)O3. Within this group of perovskite‐based functional materials, we note ways the point defects can be formed to create non‐stoichiometric compositions changing the overall cation‐to‐anion ratios during the synthesis process. These reactions can be developed with the loss of volatile species such as metal and oxygen ions. The relative concentrations of these can impact the over conductions in terms of the mixed contributions of ionic conductivity from the oxygen vacancies and the electronic conductivity, along with microstructure and properties in some cases. 
    more » « less
  3. Abstract BaTiO3is a technologically relevant material in the perovskite oxide class with above‐room‐temperature ferroelectricity and a very large electro‐optical coefficient, making it highly suitable for emerging electronic and photonic devices. An easy, robust, straightforward, and scalable growth method is required to synthesize epitaxial BaTiO3thin films with sufficient control over the film's stoichiometry to achieve reproducible thin film properties. Here the growth of BaTiO3thin films by hybrid molecular beam epitaxy is reported. A self‐regulated growth window is identified using complementary information obtained from reflection high energy electron diffraction, the intrinsic film lattice parameter, film surface morphology, and scanning transmission electron microscopy. Subsequent optical characterization of the BaTiO3films by spectroscopic ellipsometry revealed refractive index and extinction coefficient values closely resembling those of stoichiometric bulk BaTiO3crystals for films grown inside the growth window. Even in the absence of a lattice parameter change of BaTiO3thin films, degradation of optical properties is observed, accompanied by the appearance of a wide optical absorption peak in the IR spectrum, attributed to optical transitions involving defect states present. Therefore, the optical properties of BaTiO3can be utilized as a much finer and more straightforward probe to determine the stoichiometry level present in BaTiO3films. 
    more » « less
  4. null (Ed.)
    The past decade has witnessed tremendous advances in synthesis of metal halide perovskites and their use for a rich variety of optoelectronics applications. Metal halide perovskite has the general formula ABX 3 , where A is a monovalent cation (which can be either organic ( e.g. , CH 3 NH 3 + (MA), CH(NH 2 ) 2 + (FA)) or inorganic ( e.g. , Cs + )), B is a divalent metal cation (usually Pb 2+ ), and X is a halogen anion (Cl − , Br − , I − ). Particularly, the photoluminescence (PL) properties of metal halide perovskites have garnered much attention due to the recent rapid development of perovskite nanocrystals. The introduction of capping ligands enables the synthesis of colloidal perovskite nanocrystals which offer new insight into dimension-dependent physical properties compared to their bulk counterparts. It is notable that doping and ion substitution represent effective strategies for tailoring the optoelectronic properties ( e.g. , absorption band gap, PL emission, and quantum yield (QY)) and stabilities of perovskite nanocrystals. The doping and ion substitution processes can be performed during or after the synthesis of colloidal nanocrystals by incorporating new A′, B′, or X′ site ions into the A, B, or X sites of ABX 3 perovskites. Interestingly, both isovalent and heterovalent doping and ion substitution can be conducted on colloidal perovskite nanocrystals. In this review, the general background of perovskite nanocrystals synthesis is first introduced. The effects of A-site, B-site, and X-site ionic doping and substitution on the optoelectronic properties and stabilities of colloidal metal halide perovskite nanocrystals are then detailed. Finally, possible applications and future research directions of doped and ion-substituted colloidal perovskite nanocrystals are also discussed. 
    more » « less
  5. Abstract All‐inorganic lead halide perovskite nanocrystals (NCs) have great optoelectronic properties with promising applications in light‐emitting diodes (LEDs), lasers, photodetectors, solar cells, and photocatalysis. However, the intrinsic toxicity of Pb and instability of the NCs impede their broad applications. Shell‐coating is an effective method for enhanced environmental stability while reducing toxicity by choosing non‐toxic shell materials such as metal oxides, polymers, silica, etc. However, multiple perovskite NCs can be encapsulated within the shell material and a uniform epitaxial‐type shell growth of well‐isolated NCs is still challenging. In this work, lead‐free vacancy‐ordered double perovskite Cs2SnX6(X = Cl, Br, and I) shells are epitaxially grown on the surface of CsPbX3NCs by a hot‐injection method. The effectiveness of the non‐toxic double perovskite shell protection is demonstrated by the enhanced environmental and phase stability against UV illumination and water. In addition, the photoluminescence quantum yields (PL QYs) increase for the CsPbCl3and CsPbBr3NCs after shelling because of the type I band alignment of the core/shell materials, while enhanced charge transport properties obtained from CsPbI3/Cs2SnI6core/shell NCs are due to the efficient charge separation in the type II core/shell band alignment. 
    more » « less