Yuanming Liu

Diisopropylammonium Bromide Is a High-Temperature Molecular Ferroelectric Crystal

Environmentally Friendly Ferroelectrics Ferroelectrics—which are widely used as piezo elements, sensors, and actuators—maintain charge polarization even in the absence of an external electric field. The best ferroelectric properties are found in perovskites such as barium titanate (BTO) and lead zirconate titanate; however, environmentally friendly, lead-free alternatives are highly desirable. Fu et al. (p. 425; see the Perspective by Bonnell) find that the organic molecular crystal diisopropylammonium bromide has ferroelectric properties comparable to those of BTO and may represent a viable alternative to perovskites. An organic molecular crystal is found to have ferroelectric properties comparable to those of barium titanate. [Also see Perspective by Bonnell] Molecular ferroelectrics are highly desirable for their easy and environmentally friendly processing, light weight, and mechanical flexibility. We found that diisopropylammonium bromide (DIPAB), a molecular crystal processed from aqueous solution, is a ferroelectric with a spontaneous polarization of 23 microcoulombs per square centimeter [close to that of barium titanate (BTO)], high Curie temperature of 426 kelvin (above that of BTO), large dielectric constant, and low dielectric loss. DIPAB exhibits good piezoelectric response and well-defined ferroelectric domains. These attributes make it a molecular alternative to perovskite ferroelectrics and ferroelectric polymers in sensing, actuation, data storage, electro-optics, and molecular or flexible electronics.

Domain Dynamics During Ferroelectric Switching

The role of defects and interfaces on switching in ferroelectric materials is observed with high-resolution microscopy. The utility of ferroelectric materials stems from the ability to nucleate and move polarized domains using an electric field. To understand the mechanisms of polarization switching, structural characterization at the nanoscale is required. We used aberration-corrected transmission electron microscopy to follow the kinetics and dynamics of ferroelectric switching at millisecond temporal and subangstrom spatial resolution in an epitaxial bilayer of an antiferromagnetic ferroelectric (BiFeO3) on a ferromagnetic electrode (La0.7Sr0.3MnO3). We observed localized nucleation events at the electrode interface, domain wall pinning on point defects, and the formation of ferroelectric domains localized to the ferroelectric and ferromagnetic interface. These results show how defects and interfaces impede full ferroelectric switching of a thin film.

Titanium alkoxide induced BiOBr–Bi2WO6 mesoporous nanosheet composites with much enhanced photocatalytic activity

Here we report a facile hydrothermal route for the preparation of BiOBr–Bi2WO6 mesoporous nanosheet composites (MNCs) in the presence of titanium isopropoxide, Ti(OiPr)4. High resolution transmission electron microscopy, X-ray diffraction, nitrogen adsorption/desorption analysis and X-ray photoelectron spectroscopy were employed for structural and composition analyses of the MNCs. The photogenerated charge transfer and photocatalytic activity of BiOBr–Bi2WO6 MNCs were investigated by Kelvin probe force microscopy and UV-vis spectroscopy. We propose mechanisms to illustrate how titanium alkoxide induces the formation of mesoporous nanosheet heterostructures and the enhanced photodecomposition efficiency of the dye under low light intensity illumination. Overall, our results suggest that titanium alkoxide is not only strongly involved in the growth of BiOBr (001) facets, but also plays a critical role in the pore evolution of the product. Kelvin probe force microscopy analysis allows us to conclude that the resulting nanocomposites demonstrate high photogenerated charge mobility and a long lifetime. Dye molecules can be rapidly and thoroughly decomposed with the photocatalyst under very low light intensity illumination. The enhanced photocatalytic activity is attributed to well matched band edge positions of BiOBr and Bi2WO6 and the large specific surface area of the MNCs in view of the incorporation of mesopores and the highly exposed BiOBr (001) facet due to the use of Ti(OiPr)4 during the synthesis. The results presented here are expected to make a contribution toward the development of delicate nanocomposites for photocatalytic water purification and solar energy utilization.

Nanocrystalline multiferroic BiFeO3 ultrafine fibers by sol-gel based electrospinning

Novel nanocrystalline BiFeO3 ultrafine fibers have been synthesized by sol-gel based electrospinning, with fiber diameter in the range of 100–300 nm and grain size of around 20 nm. Phase pure perovskite BiFeO3 can be obtained if the fibers are fired in Ar atmosphere, eliminating impurity phases often observed when fired in air or N2 atmosphere. Excellent piezoelectricity and clear ferroelectric domain structure of the ultrafine fibers are characterized by high voltage piezoresponse force microscopy. Enhanced weak ferromagnetism arising from the nanocrystalline structure of ultrafine fibers is also observed.

Anomalous piezoelectricity in two-dimensional graphene nitride nanosheets

Piezoelectricity is a unique property of materials that permits the conversion of mechanical stimuli into electrical and vice versa. On the basis of crystal symmetry considerations, pristine carbon nitride (C3N4) in its various forms is non-piezoelectric. Here we find clear evidence via piezoresponse force microscopy and quantum mechanical calculations that both atomically thin and layered graphitic carbon nitride, or graphene nitride, nanosheets exhibit anomalous piezoelectricity. Insights from ab inito calculations indicate that the emergence of piezoelectricity in this material is due to the fact that a stable phase of graphene nitride nanosheet is riddled with regularly spaced triangular holes. These non-centrosymmetric pores, and the universal presence of flexoelectricity in all dielectrics, lead to the manifestation of the apparent and experimentally verified piezoelectric response. Quantitatively, an e11 piezoelectric coefficient of 0.758 C m(-2) is predicted for C3N4 superlattice, significantly larger than that of the commonly compared α-quartz.

Molecular ferroelectrics: where electronics meet biology

In the last several years, we have witnessed significant advances in molecular ferroelectrics, with the ferroelectric properties of molecular crystals approaching those of barium titanate. In addition, ferroelectricity has been observed in biological systems, filling an important missing link in bioelectric phenomena. In this perspective, we will present short historical notes on ferroelectrics, followed by an overview of the fundamentals of ferroelectricity. The latest developments in molecular ferroelectrics and biological ferroelectricity will then be highlighted, and their implications and potential applications will be discussed. We close by noting molecular ferroelectric as an exciting frontier between electronics and biology, and a number of challenges ahead are also described.

A Molecular Ferroelectric Thin Film of Imidazolium Perchlorate That Shows Superior Electromechanical Coupling

Molecular ferroelectric thin films are highly desirable for their easy and environmentally friendly processing, light weight, and mechanical flexibility. A thin film of imidazolium perchlorate processed from aqueous solution is an excellent molecular ferroelectric with high spontaneous polarization, high Curie temperature, low coercivity, and superior electromechanical coupling. These attributes make it a molecular alternative to perovskite ferroelectric films in sensing, actuation, data storage, electro-optics, and molecular/flexible electronics.

Delineating local electromigration for nanoscale probing of lithium ion intercalation and extraction by electrochemical strain microscopy

Lithium (Li) ion intercalation and extraction are critically important for high performance Li-ion batteries, and they are highly sensitive to local crystalline morphologies and defects that remain poorly understood. Using electrochemical strain microscopy (ESM) in combination with local transport analysis, we demonstrate that we cannot only probe Li-ion concentration and diffusivity with nanometer resolution but also map local energy dissipation associated with electromigration of Li-ions. Using these techniques, we uncover drastic differences in ESM response and energy dissipation between micro- and nano-crystalline lithium iron phosphate (LiFePO4) under different charging states, which explains the superior capacity observed in Li-ion batteries with nanocrystalline LiFePO4 electrode.

Direct Observations of Retention Failure in Ferroelectric Memories

Nonvolatile ferroelectric random-access memory uses ferroelectric thin films to save a polar state written by an electric field that is retained when the field is removed. After switching, the high energy of the domain walls separating regions of unlike polarization can drive backswitching resulting in a loss of switched domain volume, or in the case of very small domains, complete retention loss.

Ferroelectric switching of elastin

Significance Ferroelectricity has long been speculated to have important biological functions, although its very existence in biology has never been firmly established. Here, we present, to our knowledge, the first macroscopic observation of ferroelectric switching in a biological system, and we elucidate the origin and mechanism underpinning ferroelectric switching of elastin. It is discovered that the polarization in elastin is intrinsic at the monomer level, analogous to the unit cell level polarization in classical perovskite ferroelectrics. Our findings settle a long-standing question on ferroelectric switching in biology and establish ferroelectricity as an important biophysical property of proteins. We believe this is a critical first step toward resolving its physiological significance and pathological implications. Ferroelectricity has long been speculated to have important biological functions, although its very existence in biology has never been firmly established. Here, we present compelling evidence that elastin, the key ECM protein found in connective tissues, is ferroelectric, and we elucidate the molecular mechanism of its switching. Nanoscale piezoresponse force microscopy and macroscopic pyroelectric measurements both show that elastin retains ferroelectricity at 473 K, with polarization on the order of 1 μC/cm2, whereas coarse-grained molecular dynamics simulations predict similar polarization with a Curie temperature of 580 K, which is higher than most synthetic molecular ferroelectrics. The polarization of elastin is found to be intrinsic in tropoelastin at the monomer level, analogous to the unit cell level polarization in classical perovskite ferroelectrics, and it switches via thermally activated cooperative rotation of dipoles. Our study sheds light onto a long-standing question on ferroelectric switching in biology and establishes ferroelectricity as an important biophysical property of proteins. This is a critical first step toward resolving its physiological significance and pathological implications.