Resistance switching of graphene by gate-controlled polarization reorientation of polyvinylidene fluoride in a field effect transistor.

Ferroelectric ß-phase crystals of a polyvinylidene fluoride (PVDF) polymer grown or deposited on a graphene channel of a field effect transistor would induce various degrees of electrostatic doping (i.e., various amounts of charge carriers) into graphene and in turn ON/OFF switching of the device, only if the electric field applied at the gate can reorient its polarization (i.e., the well-aligned F-to-H dipole moments perpendicular to the all-trans polymer backbone) around the polymer backbone. To assess the feasibility of achieving a ß-PVDF/graphene ferroelectric field effect transistor or memory device, we mimic (1) the electric-field-controlled PVDF polarization reversal (with density functional theory calculations and molecular dynamics simulations) and (2) the conductance switching of ß-PVDF/graphene by PVDF reorientations (F-, H- and FH-down) representing a cycle of gate-voltage sweep (with density functional theory combined with non-equilibrium Green's function formalism). The low energy barrier of the collective synchronous PVDF chain rotation around the backbone (0.22 eV per monomer) and the high electric field required to initiate the chain rotation (16 V nm-1) are compatible with the domain nucleation-growth theory and would support the polarization-induced resistance switching mechanism if the PVDF film is ultrathin and partially amorphous.

Pentagons and Heptagons on Edges of Graphene Nanoflakes Analyzed by X-ray Photoelectron and Raman Spectroscopy.

Identifying pentagons and heptagons in graphene nanoflake (GNF) structures at the atomic scale is important to completely understand the chemical and physical properties of these materials. Herein, we used X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy to analyze the spectral features of GNFs according to the position of pentagons and heptagons introduced onto their zigzag and armchair edges. The XPS peak maxima were shifted to higher binding energies by introducing the pentagons or heptagons on armchair rather than zigzag edges, and the structures could be distinguished depending on the positions of the introduced pentagons or heptagons. Raman spectroscopic analyses also revealed that the position of edges with introduced pentagons or heptagons could also be identified using Raman spectroscopy, with characteristic bands appearing at 800-1200 cm-1, following the introduction of either pentagons or heptagons on armchair edges. This precise spectroscopic identification of pentagons and heptagons in GNFs provides the groundwork for the analysis of graphene-related materials.

Distinguishing Zigzag and Armchair Edges on Graphene Nanoribbons by X-ray Photoelectron and Raman Spectroscopies.

Graphene nanoribbons (GNRs) have recently emerged as alternative 2D semiconductors owing to their fascinating electronic properties that include tunable band gaps and high charge-carrier mobilities. Identifying the atomic-scale edge structures of GNRs through structural investigations is very important to fully understand the electronic properties of these materials. Herein, we report an atomic-scale analysis of GNRs using simulated X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Tetracene with zigzag edges and chrysene with armchair edges were selected as initial model structures, and their XPS and Raman spectra were analyzed. Structurally expanded nanoribbons based on tetracene and chrysene, in which zigzag and armchair edges were combined in various ratios, were then simulated. The edge structures of chain-shaped nanoribbons composed only of either zigzag edges or armchair edges were distinguishable by XPS and Raman spectroscopy, depending on the edge type. It was also possible to distinguish planar nanoribbons consisting of both zigzag and armchair edges with zigzag/armchair ratios of 4:1 or 1:4, indicating that it is possible to analyze normally synthesized GNRs because their zigzag to armchair edge ratios are usually greater than 4 or less than 0.25. Our study on the precise identification of GNR edge structures by XPS and Raman spectroscopy provides the groundwork for the analysis of GNRs.

In Situ Spectroscopic and Computational Studies on a MnO2-CuO Catalyst for Use in Volatile Organic Compound Decomposition.

In situ near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and density functional theory calculations were conducted to demonstrate the decomposition mechanism of propylene glycol methyl ether acetate (PGMEA) on a MnO2-CuO catalyst. The catalytic activity of MnO2-CuO was higher than that of MnO2 at low temperatures, although the pore properties of MnO2 were similar to those of MnO2-CuO. In addition, whereas the chemical state of MnO2 remained constant following PGMEA dosing at 150 °C, MnO2-CuO was reduced under identical conditions, as confirmed by in situ NEXAFS spectroscopy. These results indicate that the presence of Cu in the MnO2-CuO catalyst enables the release of oxygen at lower temperatures. More specifically, the released oxygen originated from the Mn-O-Cu moiety on the top layer of the MnO2-CuO structure, as confirmed by calculation of the oxygen release energies in various oxygen positions of MnO2-CuO. Furthermore, the spectral changes in the in situ NEXAFS spectrum of MnO2-CuO following the catalytic reaction at 150 °C corresponded well with those of the simulated NEXAFS spectrum following oxygen release from Mn-O-Cu. Finally, after the completion of the catalytic reaction, the quantities of lactone and ether functionalities in PGMEA decreased, whereas the formation of C=C bonds was observed.

Aluminum oxide formation at Al/La(1-x)Sr(x)MnO3 interface: a computational study for resistance random access memory applications.

Resistance random access memory (ReRAM) is emerging as a next-generation nonvolatile memory. One of the most promising materials for the ReRAM application is a composite of a reactive metal [such as aluminum (Al)] and a mixed-valance manganite [such as La(1-x)Ca(x)MnO3 (LCMO) and La(1-x)Sr(x)MnO3 (LSMO)]. One of the current hypotheses regarding the origin of the resistive switching of such systems is a voltage-controlled reversible formation of a high-resistance aluminum oxide (AlO(x)) layer at the Al/LC(S)MO interface through oxygen migration from LC(S)MO. To validate this hypothesis, quantum mechanics (density functional theory) calculations were carried out on an atomistic model of the resistive-switching phenomena at the Al/LSMO interface (the composite systems of Al/LSMO and AlO(x)/LSMO) as well as on the component materials such as Al, AlO(x), LaMnO3, LaMnO(3-delta), La(1-x)Sr(x)MnO3, and La(1-x)Sr(x)MnO(3-delta). The changes in the structure, energy, and electronic structure of these systems during the oxygen vacancy formation in LSMO, the oxygen migration through the Al/LSMO interface, and the AlO(x) formation were investigated.