Journal Article•
Nanoscale Ferroelectricity in Crystalline -Glycine
TL;DR: In this paper, it was shown that the polarization vector in {gamma}-glycine can be switched on the nanoscale level, opening a pathway to novel classes of bioelectronic logic and memory devices.
Abstract: Ferroelectrics are multifunctional materials that reversibly change their polarization under an electric field. Recently, the search for new ferroelectrics has focused on organic and bio-organic materials, where polarization switching is used to record/retrieve information in the form of ferroelectric domains. This progress has opened a new avenue for data storage, molecular recognition, and new self-assembly routes. Crystalline glycine is the simplest amino acid and is widely used by living organisms to build proteins. Here, it is reported for the first time that {gamma}-glycine, which has been known to be piezoelectric since 1954, is also a ferroelectric, as evidenced by local electromechanical measurements and by the existence of as-grown and switchable ferroelectric domains in microcrystals grown from the solution. The experimental results are rationalized by molecular simulations that establish that the polarization vector in {gamma}-glycine can be switched on the nanoscale level, opening a pathway to novel classes of bioelectronic logic and memory devices.
Citations
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TL;DR: In the last 20 years, the development of voltage-modulated scanning probe microscopy techniques, exemplified by Piezoresponse force microscopy (PFM) and associated time and voltage spectroscopies, opened a pathway to explore these materials on a single-digit nanometer level as discussed by the authors.
Abstract: Ferroelectric materials have remained one of the major focal points of condensed matter physics and materials science for over 50 years. In the last 20 years, the development of voltage-modulated scanning probe microscopy techniques, exemplified by Piezoresponse force microscopy (PFM) and associated time- and voltage spectroscopies, opened a pathway to explore these materials on a single-digit nanometer level. Consequently, domain structures and walls and polarization dynamics can now be imaged in real space. More generally, PFM has allowed studying electromechanical coupling in a broad variety of materials ranging from ionics to biological systems. It can also be anticipated that the recent Nobel prize [“The Nobel Prize in Chemistry 2016,” http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2016/ (Nobel Media, 2016)] in molecular electromechanical machines will result in rapid growth in interest in PFM as a method to probe their behavior on single device and device assembly levels. However, the br...
242 citations
TL;DR: It is demonstrated that chains of imidazole molecules can often be bistable in electric polarity and electrically switchable, even in the crystalline state, through proton tautomerization, in the quest for lead- and rare-metal-free ferroelectric devices.
Abstract: There are only a few known organic ferroelectrics, particularly ones that operate at high temperatures. Here the discovery of ferroelectricity above room temperature in members of an ubiquitous family of organic molecules reveals the possibility of novel low-cost electronic applications.
193 citations
TL;DR: The results suggest that the glycine–chitosan composite is a promising new biobased piezoelectric material for biodegradable sensors for applications in wearable biomedical diagnostics.
Abstract: This paper presents flexible pressure sensors based on free-standing and biodegradable glycine-chitosan piezoelectric films. Fabricated by the self-assembly of biological molecules of glycine within a water-based chitosan solution, the piezoelectric films consist of a stable spherulite structure of β-glycine (size varying from a few millimeters to 1 cm) embedded in an amorphous chitosan polymer. The polymorphic phase of glycine crystals in chitosan, evaluated by X-ray diffraction, confirms formation of a pure ferroelectric phase of glycine (β-phase). Our results show that a simple solvent-casting method can be used to prepare a biodegradable β-glycine/chitosan-based piezoelectric film with sensitivity (∼2.82 ± 0.2 mV kPa-1) comparable to those of nondegradable commercial piezoelectric materials. The measured capacitance of the β-glycine/chitosan film is in the range from 0.26 to 0.12 nF at a frequency range from 100 Hz to 1 MHz, and its dielectric constant and loss factor are 7.7 and 0.18, respectively, in the high impedance range under ambient conditions. The results suggest that the glycine-chitosan composite is a promising new biobased piezoelectric material for biodegradable sensors for applications in wearable biomedical diagnostics.
184 citations
TL;DR: Guided by quantum mechanical calculations, a high shear piezoelectricity is measured in the amino acid crystal beta (β) glycine, which is of similar magnitude to barium titanate or lead zirconate titanate.
Abstract: Proceeding from quantum mechanical predictions, a high shear piezoelectric constant of 178 pm V−1 was measured for the amino acid crystal beta glycine. This originates from the efficient packing of the molecules of the amino acid.
182 citations
TL;DR: Strain and electromechanical coupling are ubiquitous in nature, and exist in many processes involved in information technology, energy conversion, and biological phenomena as discussed by the authors, and they have emerged as powerful tools to probe and manipulate materials, structures, and systems at the nanoscale.
122 citations
References
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TL;DR: An efficient scheme for calculating the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set is presented and the application of Pulay's DIIS method to the iterative diagonalization of large matrices will be discussed.
Abstract: We present an efficient scheme for calculating the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set. In the first part the application of Pulay's DIIS method (direct inversion in the iterative subspace) to the iterative diagonalization of large matrices will be discussed. Our approach is stable, reliable, and minimizes the number of order ${\mathit{N}}_{\mathrm{atoms}}^{3}$ operations. In the second part, we will discuss an efficient mixing scheme also based on Pulay's scheme. A special ``metric'' and a special ``preconditioning'' optimized for a plane-wave basis set will be introduced. Scaling of the method will be discussed in detail for non-self-consistent and self-consistent calculations. It will be shown that the number of iterations required to obtain a specific precision is almost independent of the system size. Altogether an order ${\mathit{N}}_{\mathrm{atoms}}^{2}$ scaling is found for systems containing up to 1000 electrons. If we take into account that the number of k points can be decreased linearly with the system size, the overall scaling can approach ${\mathit{N}}_{\mathrm{atoms}}$. We have implemented these algorithms within a powerful package called VASP (Vienna ab initio simulation package). The program and the techniques have been used successfully for a large number of different systems (liquid and amorphous semiconductors, liquid simple and transition metals, metallic and semiconducting surfaces, phonons in simple metals, transition metals, and semiconductors) and turned out to be very reliable. \textcopyright{} 1996 The American Physical Society.
81,985 citations
TL;DR: A detailed description and comparison of algorithms for performing ab-initio quantum-mechanical calculations using pseudopotentials and a plane-wave basis set is presented in this article. But this is not a comparison of our algorithm with the one presented in this paper.
47,666 citations
TL;DR: The development, current features, and some directions for future development of the Amber package of computer programs, which contains a group of programs embodying a number of powerful tools of modern computational chemistry, focused on molecular dynamics and free energy calculations of proteins, nucleic acids, and carbohydrates.
Abstract: We describe the development, current features, and some directions for future development of the Amber package of computer programs. This package evolved from a program that was constructed in the late 1970s to do Assisted Model Building with Energy Refinement, and now contains a group of programs embodying a number of powerful tools of modern computational chemistry, focused on molecular dynamics and free energy calculations of proteins, nucleic acids, and carbohydrates.
7,672 citations
TL;DR: In this paper, the authors present an approach to generate electrostatic potential (ESP) derived charges for molecules, which optimally reproduce the intermolecular interaction properties of molecules with a simple two-body additive potential, provided that a suitably accurate level of quantum mechanical calculation is used to derive the ESP around the molecule.
Abstract: We present a new approach to generating electrostatic potential (ESP) derived charges for molecules. The major strength of electrostatic potential derived charges is that they optimally reproduce the intermolecular interaction properties of molecules with a simple two-body additive potential, provided, of course, that a suitably accurate level of quantum mechanical calculation is used to derive the ESP around the molecule. Previously, the major weaknesses of these charges have been that they were not easily transferable between common functional groups in related molecules, they have often been conformationally dependent, and the large charges that frequently occur can be problematic for simulating intramolecular interactions
6,266 citations
Book•
06 Oct 1977
TL;DR: In this paper, the theory of ferroelectricity in terms of soft modes and lattice dynamics is developed and modern techniques of measurement, including X-ray, optic, and neutron scattering, infra-red absorption, and magnetic resonance.
Abstract: The book develops the modern theory of ferroelectricity in terms of soft modes and lattice dynamics and also describes modern techniques of measurement, including X-ray, optic, and neutron scattering, infra-red absorption, and magnetic resonance. It includes a discussion of the related phenomena of antiferroelectricity, pyroelectricity, and ferroelasticity and seconds on domains, thin films, ceramics, and polymers, leading on to a comprehensive survey of potential and actual device capabilities for pyroelectric detection, memories, display, and modulation. It should provide an authoritative account for those engaged in research or graduate ferroelectric or pyroelectric devices.
4,931 citations