ZIF-8 derived porous ZnO with grain boundaries for efficient CO2 electroreduction

Journal of Nanoparticle Research - Here, the high-quality single crystal Ni2FeGa nanocrystallines with γ phase or L21 phase were successfully synthesized by using high-temperature hydrogen...     

Dislocations and grain boundaries in quasicrystals

This is a brief review of the theory of topological defects in quasicrystals, within a densitywave picture.     

Benefits of oxygen in CuInSe2 and CuGaSe2 containing Se-rich grain boundaries

Using density functional theory calculation, we show that oxygen (O) exhibits an interesting effect in CuInSe₂ and CuGaSe₂. The Se atoms with dangling bonds in a Se-rich Σ3 (114) grain boundary (GB) create deep gap states due to strong interaction between Se atoms. However, when such a Se atom is substituted by an O atom, the deep gap states can be shifted into valence band, making the site no longer a harmful non-radiative recombination center. We find that O atoms prefer energetically to substitute these Se atoms and induce significant lattice relaxation due to their smaller atomic size and stronger electronegativity, which effectively reduces the anion–anion interaction. Consequently, the deep gap states are shifted to lower energy regions close or even below the top of the valence band.     

Electronic conduction mechanisms of Cs- and B-implanted SiO2-films

Thermal SiO₂-films of MOS-structures have been implanted with Cs-and B-ions so that the distribution maximum was located near the center of the insulating films. The change in conduction mechanism was analysed before and after implantation and annealing at 500°C for 2h. Two major types of effects are observed: 1) Implantation generally changes the conduction mechanism from Fowler-Nordheim tunneling in pure SiO₂ to the Frenkel-Poole mechanism in the implanted film for both types of ions. This effect is caused by traps due to radiation damage. 2) The second effect is dependent on the implanted type of ion. A strong increase of the current at high fields is observed after Cs-implantation while B-implantation leads to a decrease of the current at high fields. This effect is caused by field-enhanced emission and trapping of charge carriers, respectively. The local field in the implanted region is dependent on the charge state of the implanted ion. Cesium is positively and Boron is negatively charged in the oxide. After high-field stressing, a forming process occurs in the oxide which leads to high injection from the contacts. This forming process is very little dependent on the implantation.     

Vertical electrical conduction in pentacene polycrystalline thin films mediated by Au-induced gap states at grain boundaries

Vertical electrical conduction in Au/(polycrystal-line pentacene)/Al diode structures and the influence of the kinetic energy of incident Au atoms on the conduction property have been comprehensively studied using current–voltage–temperature (I–V–T) measurements, ultraviolet photoelectron spectroscopy (UPS), atomic-force-microscope (AFM) current imaging, etc. In the I–V characteristics, a symmetrical ohmic current component appeared when a low voltage was applied, and a super-linear one appeared when a high positive voltage was applied to Au. The component in the high-forward-voltage region was concluded to be a thermionic emission of holes from Au with a 0.23-eV injection barrier, which is the normal hole conduction through the highest occupied molecular orbital of pentacene. On the other hand, the ohmic component was concluded to be a metal-like electron transport through high-density gap states at grain boundaries which were induced by the Au penetration into pentacene. UPS and I–V–T measurements clearly indicated the generation of the gap states and the enhancement of their density by the reduction of Au kinetic energy. For vertical-type devices with polycrystalline organic films, the ohmic conduction through the grain boundary will increase the leakage current. On the contrary, it possibly enhances the carrier injection in lateral-type transistors in the case of top-contact configuration.     

Electrically benign behavior of grain boundaries in polycrystalline CuInSe2 films

The classic grain-boundary (GB) model concludes that GBs in polycrystalline semiconductors create deep levels that are extremely harmful to optoelectronic applications. However, our first-principles density-functional theory calculations reveal that, surprisingly, GBs in CuInSe2 (CIS) do not follow the classic GB model: GBs in CIS do not create deep levels due to the large atomic relaxation in GB regions. Thus, unlike the classic GB model, GBs in CIS are electrically benign, which explains the long-standing puzzling fact that polycrystalline CIS solar cells with remarkable efficiency can be achieved without deliberate GB passivation. This benign electrical character of GBs in CIS is confirmed by our scanning Kelvin probe microscopy measurements on Cu(In,Ga)Se2 chalcopyrite films.     

P-Type electronic conduction in CeO2- and LaGaO3-based solid electrolytes

Modifications of the e.m.f. and faradaic efficiency techniques, taking into account electrode polarization in the measuring cells, in combination with the use of electrodes having sufficiently high polarization resistances enable a precise determination of minor electronic contributions to the conductivity of solid electrolytes. These methods were used to determine the p-type conductivity of compositions based on La(Sr)Ga(Mg)O_3-δ (LSGM) and Ce(Gd)O_2-δ (CGO) at 900–1270 K. The oxygen ion transference numbers of these materials under oxygen/air gradient vary in the range 0.999–0.970, increasing with decreasing temperature. Substitution of 2 % gadolinium in Ce_0.80Gd_0.20O_2-δ with praseodymium was found to increase the electron-hole conduction by 2.5 – 4 times. At temperatures above 700 K, both the partial oxygen ionic and p-type electronic conductivities of LaGaO₃-based phases are higher than those in CGO. The electron-hole transport in LSGM tends to increase with the magnesium concentration, while the activation energy is essentially independent of composition. Electronic conduction in CGO and LSGM electrolytes was also found to be influenced by the ceramic microstructure. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Conductivity degradation of NiO-containing 8YSZ and 10YSZ electrolyte during reduction

Yttria-stabilized zirconia (YSZ) electrolyte containing dissolved nickel as a result of co-sintering in air with NiO was shown by TEM and magnetic measurements to develop isolated, nano-sized metallic nickel precipitates during treatments in hydrogen-containing atmosphere. During exposure to hydrogen containing atmosphere at 1000 °C for 500 h, an exponential decrease in oxygen ion conductivity was observed in Ni-doped 8YSZ, while no conductivity change was observed in Ni-doped 10YSZ.     

Electrical resistance of grain boundaries in platinum

In platinum strips and wires subjected to long annealing the electrical resistance of grain boundaries was measured by a direct method. The measurement shows that the concentration of impurities on grain boundaries may attain relatively large values, which are very variable in different parts of the sample.     

Poole-Frenkel conduction in Al/ZrO2 /SiO 2 /Si structures

Leakage currents through Al/ZrO₂/SiO₂/n-Si metal-insulator-semiconductor (MIS) capacitors were studied. Thin SiO₂ films were chemically grown on monocrystalline phosphorous doped silicon wafers. Zirconia films with thicknesses of 15 and 50 nm were deposited by radio frequency (rf) magnetron sputtering and, then, annealed in oxygen ambient at 850 ^○C, for 1 h. The dielectric constant of the sputtered and annealed ZrO₂ layer was of about 17.8. The equivalent oxide thickness (EOT) of the stack 15 nm and 50 nm-ZrO₂/SiO₂ structure was estimated to be 3.2 nm and 10.7 nm, respectively. The temperature dependence of the leakage currents was explained by Poole-Frenkel (PF) conduction mechanism. Shallow trap levels in the studied structure of about 0.2 eV and 0.46 eV were calculated. The existence of A and D-defects, due to the sputtering and high temperature annealing in oxygen, was suggested.     

General theory of grain boundaries in crystal

Presented is a microscopic derivation of the theory of grain boundaries in crystal. Fundamental properties of the grain boundaries are also discussed.     

Theory and simulation of coupled grain boundary migration and grain rotation in low angle grain boundaries

Abstract

Microstructure evolution due to coupled grain boundary migration and grain rotation in low angle grain boundaries is studied through a combination of molecular dynamics and phase field modeling. We have performed two dimensional molecular dynamics simulations on a bicrystal with a circular grain embedded in a larger grain. Both size and orientation of the embedded grain are observed to evolve with time. The shrinking embedded grain is observed to have two regimes: constant dislocation density on the grain boundary followed by constant rate of increase in dislocation density. Based on these observations from the molecular dynamics simulations, a theoretical formulation of the kinetics of coupled grain rotation is developed. The grain rotation rate is derived for the two regimes of constant dislocation density and constant rate of change of dislocation density on the grain boundary during evolution. The theoretical calculation of the grain rotation rate shows strong dependence on the grain size and compares very well with the molecular dynamics simulations. A multi-order parameter based phase field model with coupled grain rotation is developed using the theoretical formulation to model polycrystalline microstructure evolution.     

Oxide ion conduction in Nd9.33(SiO4)6O2 and Sr2Nd8(SiO4)6O2 single crystals grown by floating zone method

Single crystals of Nd_9.33(SiO₄)₆O₂ and Sr₂Nd₈(SiO₄)₆O₂ oxide ion conductors with the oxyapatite structure were grown without any macroscopic defect by the floating zone method. The oxide ion conductivity of the Sr₂Nd₈(SiO₄)₆O₂ single crystal varied with the distance from its seed crystal along the growth direction, because of its changing deficiency in Sr content. Its stoichiometric portion had a lower electrical conductivity by about five orders of magnitude at 600 °C than the value for Nd_9.33(SiO₄)₆O₂ single crystal. Structural refinement of neutron diffraction data for powdered Nd_9.33(SiO₄)₆O₂ single crystal showed that the previous structure analysis was misleading. Cation vacancies were present only at 4f site and its channel oxygen site was fully occupied in space group of P6₃/m. The oxygen had an anisotropic displacement along the channel in the refined oxyapatite structure.     

Multi-timescale investigation of radiation damage near TiO2 rutile grain boundaries

To understand the interactions between defects and grain boundaries (GBs) in oxides, two atomistic modeling methods were used to examine the role of GBs in a model system, rutile TiO₂, in modifying radiation-induced defect production and annealing. Molecular dynamics was used to investigate defect production near a symmetric tilt GB at both 300?K and 1000?K. The damage production is found to be sensitive to the initial distance of the primary knock-on atom from the GB. We find three distinct regimes in which GBs have different effects. Similar to GBs in metals, the GB absorbs more interstitials than vacancies at certain distances while this behavior of biased loading of interstitials diminishes at other distances. Further, we obtain the statistics of both interstitial and vacancy clusters produced in collision cascades in terms of their compositions at two temperatures. Perfectly stoichiometric defect clusters represent a small fraction of the total clusters produced. Moreover, a significant reduction in the number of interstitial clusters at 1000?K compared to 300?K is thought to be a consequence of enhanced migration of interstitials towards the GB. Finally, the kinetic properties of certain defect clusters were investigated with temperature accelerated dynamics, without any a priori assumptions of migration mechanisms. Small interstitial clusters become mobile at high temperatures while small vacancy clusters do not. Multiple migration pathways exist and are typically complex and non-intuitive. We use this kinetic information to explain experimental observations and predict their long-time migration behavior near GBs.     

Effect of graphene grain boundaries on MoS_2/graphene heterostructures

The grain boundaries of graphene are disordered topological defects, which would strongly affect the physical and chemical properties of graphene. In this paper, the spectral characteristics and photoresponse of MoS_2/graphene heterostructures are studied. It is found that the blueshift of the G and 2 D peaks of graphene in Raman spectrum is due to doping. The lattice mismatch at the graphene boundaries results in a blueshift of MoS_2 features in the photoluminescence spectra, comparing to the MoS_2 grown on SiO_2. In addition, the photocurrent signal in MoS_2/hexagonal single-crystal graphene heterostructures is successfully captured without bias, but not in MoS_2/polycrystalline graphene heterostructures.The electron scattering at graphene grain boundaries affects the optical response of MoS_2/graphene heterostructures. The photoresponse of the device is attributed to the optical absorption and response of MoS_2 and the high carrier mobility of graphene. These findings offer a new approach to develop optoelectronic devices based on two-dimensional material heterostructures.     

Analysis of faceting of grain boundaries in GaN

Faceting of coincidence grain boundaries was experimentally observed in an MBE GaN layer. The energy of a few configurations including special facets as the first and the second shortest periods of the CSL unit cell was calculated with the empirical potential of Stillinger and Weber adapted to GaN. It is shown that the experimental configuration presents the lowest increase of energy by comparison to the two individual periods.     

Density of states of grain boundaries in silicon

A new spectroscopic method for the evaluation of the density of states in semiconductor grain boundaries is presented. The method is based on a measurement of the intensity and wavelength dependence of the zero-bias photo capacitance of grain boundaries under sub-bandgap illumination. Experiments are performed on p-type silicon bicrystals. Bandtails and states close to midgap are observed.