Qian Nataly Chen

Mechanisms of electromechanical coupling in strain based scanning probe microscopy

Electromechanical coupling is ubiquitous in nature and underpins the functionality of materials and systems as diverse as ferroelectric and multiferroic materials, electrochemical devices, and biological systems, and strain-based scanning probe microscopy (s-SPM) techniques have emerged as a powerful tool in characterizing and manipulating electromechanical coupling at the nanoscale. Uncovering underlying mechanisms of electromechanical coupling in these diverse materials and systems, however, is a difficult outstanding problem, and questions and confusions arise from recent experiment observations of electromechanical coupling and its apparent polarity switching in some unexpected materials. We propose a series of s-SPM experiments to identify different microscopic mechanisms underpinning electromechanical coupling and demonstrate their feasibility using three representative materials. By employing a combination of spectroscopic studies and different modes of s-SPM, we show that it is possible to distinguish electromechanical coupling arising from spontaneous polarization, induced dipole moment, and ionic Vegard strain, and this offers a clear guidance on using s-SPM to study a wide variety of functional materials and systems.

Mesoporous carbon nanofibers with a high surface area electrospun from thermoplastic polyvinylpyrrolidone

Carbon nanofibers (CNFs) have been synthesized from thermoplastic polyvinylpyrrolidone (PVP) using electrospinning in combination with a novel three-step heat treatment process, which successfully stabilizes the fibrous morphology before carbonization that was proven to be difficult for thermoplastic polymers other than polyacrylonitrile (PAN). These CNFs are both mesoporous and microporous with high surface areas without subsequent activation, and thus overcome the limitations of PAN based CNFs, and are processed in an environmentally friendly and more cost effective manner. The effects of heat treatment parameters and precursor concentration on the morphologies and porous properties of CNFs have been investigated, and their application as anodes for lithium ion batteries has also been demonstrated.

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.

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.

Imaging space charge regions in Sm-doped ceria using electrochemical strain microscopy

Nanocrystalline ceria exhibits a total conductivity several orders of magnitude higher than microcrystalline ceria in air at high temperature. The most widely accepted theory for this enhancement (based on fitting of conductivity data to various transport and kinetic models) is that relatively immobile positively charged defects and/or impurities accumulate at the grain boundary core, leading to a counterbalancing increase in the number of mobile electrons (small polarons) within a diffuse space charge region adjacent to each grain boundary. In an effort to validate this model, we have applied electrochemical strain microscopy to image the location and relative population of mobile electrons near grain boundaries in polycrystalline Sm-doped ceria in air at 20–200 °C. Our results show the first direct (spatially resolved) evidence that such a diffuse space charge region does exist in ceria, and is localized to both grain boundaries and the gas-exposed surface.

High sensitivity piezomagnetic force microscopy for quantitative probing of magnetic materials at the nanoscale.

Accurate scanning probing of magnetic materials at the nanoscale is essential for developing and characterizing magnetic nanostructures, yet quantitative analysis is difficult using the state of the art magnetic force microscopy, and has limited spatial resolution and sensitivity. In this communication, we develop a novel piezomagnetic force microscopy (PmFM) technique, with the imaging principle based on the detection of magnetostrictive response excited by an external magnetic field. In combination with the dual AC resonance tracking (DART) technique, the contact stiffness and energy dissipation of the samples can be simultaneously mapped along with the PmFM phase and amplitude, enabling quantitative probing of magnetic materials and structures at the nanoscale with high sensitivity and spatial resolution. PmFM has been applied to probe magnetic soft discs and cobalt ferrite thin films, demonstrating it as a powerful tool for a wide range of magnetic materials.

Magnetoelectric coupling of multilayered Pb(Zr0.52Ti0.48)O3-CoFe2O4 film by piezoresponse force microscopy under magnetic field

Multiferroic Pb(Zr0.52Ti0.48)O3-CoFe2O4-Pb(Zr0.52Ti0.48)O3 (PCP) laminated film has been synthesized by sol-gel process and spin coating, with the spinel structure of CoFe2O4 and perovskite structure of Pb(Zr0.52Ti0.48)O3 verified by x-ray diffraction. The good multiferroic properties of PCP film have been confirmed by ferroelectric and magnetic hysteresis loops, with leakage current substantially reduced. The local magnetoelectric coupling has been verified using piezoresponse force microscopy under external magnetic field, showing magnetically induced evolution of piezoresponse and ferroelectric switching characteristics, with piezoresponse amplitude reduced and coercive voltage increased. Such technique will be useful in characterizing local magnetoelectric (ME) couplings for a wide range of multiferroic materials.

Piezoelectric and piezomagnetic force microscopies of multiferroic BiFeO3-LiMn2O4 heterostructures

BiFeO3-LiMn2O4 (BFO-LMO) heterostructures were fabricated via pulsed laser deposition, and their ferroelectric and ferromagnetic properties were probed by magnetic force microscopy (MFM), piezoresponse force microscopy (PFM), and the newly developed piezomagnetic force microscopy (PmFM). MFM imaging shows no clear distinction between BFO and LMO phases, while PFM and PmFM mappings clearly distinguish LMO nanopillars from BFO matrix. Linear piezoelectric and piezomagnetic responses have been observed in both phases, with the effects more prominent in BFO. The strong piezomagnetic response in BFO is believed to arise from Mn doping, while piezoelectric-like response of LMO is attributed to ionic activities as well as vertical geometry of the heterostructure. The limitation of global excitation of PmFM is also discussed.

Enhanced lithium ion storage in nanoimprinted carbon

Disordered carbons processed from polymers have much higher theoretical capacity as lithium ion battery anode than graphite, but they suffer from large irreversible capacity loss and have poor cyclic performance. Here, a simple process to obtain patterned carbon structure from polyvinylpyrrolidone was demonstrated, combining nanoimprint lithography for patterning and three-step heat treatment process for carbonization. The patterned carbon, without any additional binders or conductive fillers, shows remarkably improved cycling performance as Li-ion battery anode, twice as high as the theoretical value of graphite at 98 cycles. Localized electrochemical strain microscopy reveals the enhanced lithium ion activity at the nanoscale, and the control experiments suggest that the enhancement largely originates from the patterned structure, which improves surface reaction while it helps relieving the internal stress during lithium insertion and extraction. This study provides insight on fabricating patterned carbon architecture by rational design for enhanced electrochemical performance.

Probing multiferroic heterostructures of BiFeO3 -LiMn2O4 using magnetic, piezoelectric and piezomagnetic force microscopies

In this study magnetic force microscopy (MFM), piezoresponse force microscopy (PFM), and the newly developed piezomagnetic force microscopy (PmFM) techniques are used to probe the ferroelectric and ferromagnetic properties of BiFeO3-LiMn2O4 (BFO-LMO) heterostructures at nano-scale. The PmFM technique is also used to probe the ferromagnetic properties of CoFe2O4 (CFO) as a case study. The PFM and PmFM mappings of the BFO-LMO heterostructures clearly distinguish the BFO matrix and LMO nanopillars while the MFM mapping is ambiguous. The relatively high piezomagnetic response of BFO matrix is believed to be due to the Mn doping while the piezoelectric-like response of LMO nanopillars is due to the ionic activities and the vertical geometry of its heterostructure. Lastly, limitations of the PmFM technique are discussed.Copyright