Fast Exfoliation and Functionalisation of Two-Dimensional Crystalline Carbon Nitride by Framework Charging.

Two-dimensional (2D) layered graphitic carbon nitride (gCN) nanosheets offer intriguing electronic and chemical properties. However, the exfoliation and functionalisation of gCN for specific applications remain challenging. We report a scalable one-pot reductive method to produce solutions of single- and few-layer 2D gCN nanosheets with excellent stability in a high mass yield (35 %) from polytriazine imide. High-resolution imaging confirmed the intact crystalline structure and identified an AB stacking for gCN layers. The charge allows deliberate organic functionalisation of dissolved gCN, providing a general route to adjust their properties.

H atom adsorption and diffusion on Si(110)-(1×1) and (2×1) surfaces.

We present a periodic density-functional study of hydrogen adsorption and diffusion on the Si(110)-(1×1) and (2×1) surfaces, and identify a local reconstruction that stabilizes the clean Si(110)-(1×1) by 0.51 eV. Hydrogen saturates the dangling bonds of surface Si atoms on both reconstructions and the different structures can be identified from their simulated scanning tunneling microscopy/current image tunneling spectroscopy (STM/CITS) images. Hydrogen diffusion on both reconstructions will proceed preferentially along zigzag rows, in between two adjacent rows. The mobility of the hydrogen atom is higher on the (2×1) reconstruction. Diffusion of a hydrogen vacancy on a monohydride Si(110) surface will proceed along one zigzag row and is slightly more difficult (0.2 eV and 0.6 eV on (1×1) and (2×1), respectively) than hydrogen atom diffusion on the clean surface.

Crystal structure and vibrational spectra of AlVO4. A DFT study.

We present periodic density functional calculations within the generalized gradient approximation (Perdew-Wang 91) on structure and vibrational properties of bulk AlVO(4). The optimized structure agrees well with crystallographic data obtained by Rietveld refinement (the mean absolute deviation of bond distances is 0.032 A), but the deviations are larger for the lighter oxygen atoms than for the heavier Al and V atoms. All observed bands in the Raman and IR spectrum have been assigned to calculated harmonic frequencies. Bands in the 1020-900 cm(-1) region have been assigned to V-O((2)) stretches in V-O((2))-Al bonds. The individual bands do not arise from vibrations of only one bond, not even from vibrations of several bonds of one VO(4) tetrahedron. The results confirm that vibrations around 940 cm(-1) observed for vanadia particles supported on thin alumina film are V-O-Al interface modes with 2-fold coordinated oxygen atoms in the V-O((2))-Al interface bonds.

Vanadium oxides on aluminum oxide supports. 2. Structure, vibrational properties, and reducibility of V2O5 clusters on alpha-Al2O3(0001).

The structure, stability, and vibrational properties of isolated V2O5 clusters on the Al2O3(0001) surface have been studied by density functional theory and statistical thermodynamics. The most stable structure does not possess vanadyl oxygen atoms. The positions of the oxygen atoms are in registry with those of the alumina support, and both vanadium atoms occupy octahedral sites. Another structure with one vanadyl oxygen atom is only 0.12 eV less stable. Infrared spectra are calculated for the two structures. The highest frequency at 922 cm(-1) belongs to a V-O stretch in the V-O-Al interface bonds, which supports the assignment of such a mode to the band observed around 941 cm(-1) for vanadia particles on alumina. Removal of a bridging oxygen atom from the most stable cluster at the V-O-Al interface bond costs 2.79 eV. Removal of a (vanadyl) oxygen atom from a thin vanadia film on alpha-Al2O3 costs 1.3 eV more, but removal from a V2O5(001) single-crystal surface costs 0.9 eV less. Similar to the V2O5(001) surface, the facile reduction is due to substantial structure relaxations that involve formation of an additional V-O-V bond and yield a pair of V(IV)(d1) sites instead of a V(III)(d2)/V(V)(d0) pair.

Hydrogen adsorption and diffusion around Si(0 0 1)/Si(1 1 0) corners in nanostructures.

While the diffusion of hydrogen on silicon surfaces has been relatively well characterized, both experimentally and theoretically, diffusion around corners between surfaces, as will be found on nanowires and nanostructures, has not been studied. Motivated by nanostructure fabrication by Patterned Atomic Layer Epitaxy, we present a density functional theory study of the diffusion of hydrogen around the edge formed by the orthogonal (0 0 1) and (1 1 0) surfaces in silicon. We find that the barrier from (0 0 1) to (1 1 0) is approximately 0.3 eV lower than from (1 1 0) to (0 0 1), and that it is comparable to diffusion between rows on a clean surface, with no significant effect on the hydrogen patterns at the growth temperatures used.

Investigating individual arsenic dopant atoms in silicon using low-temperature scanning tunnelling microscopy.

We study subsurface arsenic dopants in a hydrogen-terminated Si(001) sample at 77 K, using scanning tunnelling microscopy and spectroscopy. We observe a number of different dopant-related features that fall into two classes, which we call As1 and As2. When imaged in occupied states, the As1 features appear as anisotropic protrusions superimposed on the silicon surface topography and have maximum intensities lying along particular crystallographic orientations. In empty-state images the features all exhibit long-range circular protrusions. The images are consistent with buried dopants that are in the electrically neutral (D0) charge state when imaged in filled states, but become positively charged (D+) through electrostatic ionization when imaged under empty-state conditions, similar to previous observations of acceptors in GaAs. Density functional theory calculations predict that As dopants in the third layer of the sample induce two states lying just below the conduction-band edge, which hybridize with the surface structure creating features with the surface symmetry consistent with our STM images. The As2 features have the surprising characteristic of appearing as a protrusion in filled-state images and an isotropic depression in empty-state images, suggesting they are negatively charged at all biases. We discuss the possible origins of this feature.

Site-dependent ambipolar charge states induced by group V atoms in a silicon surface.

We report that solitary bismuth and antimony atoms, incorporated at Si(111) surfaces, induce either positive or negative charge states depending on the site of the surface reconstruction in which they are located. This is in stark contrast to the hydrogenic donors formed by group V atoms in silicon bulk crystal and therefore has strong implications for the design and fabrication of future highly scaled electronic devices. Using scanning tunnelling microscopy (STM) and density functional theory (DFT) we determine the reconstructions formed by different group V atoms in the Si(111)2 × 1 surface. Based on these reconstructions a model is presented that explains the polarity as well as the location of the observed charges in the surface. Using locally resolved scanning tunnelling spectroscopy we are furthermore able to map out the spatial extent over which a donor atom influences the unoccupied surface and bulk electronic states near the Fermi-level. The results presented here therefore not only show that a dopant atom can induce both positive and negative charges but also reveal the nature of the local electronic structure in the region of the silicon surface where an individual donor atom is present.