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Phosphorus pentamer (cyclo-P5-) ions are unstable in nature but can be synthesized at the Ag(111) surface. Unlike monolayer black phosphorous, little is known about their electronic properties when in contact with metal electrodes, although this is crucial for future applications. Here we characterize the atomic structure of cyclo-P5 assembled on Ag(111) using atomic force microscopy with functionalized tips and density functional theory. Combining force and tunneling spectroscopy, we find that a strong charge transfer induces an inward dipole moment at the cyclo-P5/Ag interface as well as the formation of an interface state. We probe the image potential states by field-effect resonant tunneling and quantify the increase of the local change of work function of 0.46 eV at the cyclo-P5 assembly. Our results suggest that the high-quality of the cyclo-P5/Ag interface might serve as a prototypical system for electric contacts in phosphorus-based semiconductor devices., Comment: 25 pages, 4 figures

For highly efficient ultrathin solar cells, layered indium selenide (InSe), a van der Waals solid, has shown a great promise. In this paper, we study the coherent dynamics of charge carriers generation in {\gamma}-InSe single crystals. We employ ultrafast transient absorption spectroscopy to examine the dynamics of hot electrons after resonant photoexcitation. To study the effect of excess kinetic energy of electrons after creating A exciton (VB1 to CB transition), we excite the sample with broadband pulses centered at 600, 650, 700 and 750 nm, respectively. We analyze the relaxation and recombination dynamics in {\gamma}-InSe by global fitting approach. Five decay associated spectra with their associated lifetimes are obtained, which have been assigned to intraband vibrational relaxation and interband recombination processes. We extract characteristic carrier thermalization times from 1 to 10 ps. To examine the coherent vibrations accompanying intraband relaxation dynamics, we analyze the kinetics by fitting to exponential functions and the obtained residuals are further processed for vibrational analysis. A few key phonon coherences are resolved and ab-initio quantum calculations reveal the nature of the associated phonons. The wavelet analysis is employed to study the time evolution of the observed coherences, which show that the low-frequency coherences last for more than 5 ps. Associated calculations reveal that the contribution of the intralayer phonon modes is the key determining factor for the scattering between free electrons and lattice. Our results provide fundamental insights into the photophysics in InSe and help to unravel their potential for high-performance optoelectronic devices.

The integrated inplane growth of two dimensional materials with similar lattices, but distinct electrical properties, could provide a promising route to achieve integrated circuitry of atomic thickness. However, fabrication of edge specific GNR in the lattice of hBN still remains an enormous challenge for present approaches. Here we developed a two step growth method and successfully achieved sub 5 nm wide zigzag and armchair GNRs embedded in hBN, respectively. Further transport measurements reveal that the sub 7 nm wide zigzag GNRs exhibit openings of the band gap inversely proportional to their width, while narrow armchair GNRs exhibit some fluctuation in the bandgap width relationship.This integrated lateral growth of edge specific GNRs in hBN brings semiconducting building blocks to atomically thin layer, and will provide a promising route to achieve intricate nanoscale electrical circuits on high quality insulating hBN substrates., Comment: 84 pages,46 figures

The two-dimensional (2D) C3N has emerged as a material with promising applications in high performance device owing to its intrinsic bandgap and tunable electronic properties. Although there are several reports about the bandgap tuning of C3N via stacking or forming nanoribbon, bandgap modulation of bilayer C3N nanoribbons (C3NNRs) with various edge structures is still far from well understood. Here, based on extensive first-principles calculations, we demonstrated the effective bandgap engineering of C3N by cutting it into hydrogen passivated C3NNRs and stacking them into bilayer heterostructures. It was found that armchair (AC) C3NNRs with three types of edge structures are all semiconductors, while only zigzag (ZZ) C3NNRs with edges composed of both C and N atoms (ZZ-CN/CN) are semiconductors. The bandgaps of all semiconducting C3NNRs are larger than that of C3N nanosheet. More interestingly, AC-C3NNRs with CN/CN edges (AC-CN/CN) possess direct bandgap while ZZ-CN/CN have indirect bandgap. Compared with the monolayer C3NNR, the bandgaps of bilayer C3NNRs can be greatly modulated via different stacking orders and edge structures, varying from 0.43 eV for ZZ-CN/CN with AB'-stacking to 0.04 eV for AC-CN/CN with AA-stacking. Particularly, transition from direct to indirect bandgap was observed in the bilayer AC-CN/CN heterostructure with AA'-stacking, and the indirect-to-direct transition was found in the bilayer ZZ-CN/CN with AB-stacking. This work provides insights into the effective bandgap engineering of C3N and offers a new opportunity for its applications in nano-electronics and optoelectronic devices.

Metal heteroatoms dispersed in nitrogen-doped graphene display promising catalytic activity for fuel cell reactions such as the hydrogen evolution reaction (HER). Here we explore the effects of dopant concentration on the synergistic catalytic behaviour of a paired metal atom active site comprised of Co and Pt atoms. The metals are coordinated to six atoms in a vacancy of N-doped graphene. We find that HER activity is enhanced with increasing N concentration, where the free energy of hydrogen atom adsorption ranges from 0.23 to -0.42 eV as the doping changes from a single N atom doped in the pore, to fully doped coordination sites. The results indicated that the effect of N is to make the Co atom more active towards H adsorption and presents a means through which transition metals can be modified to make more effective and sustainable fuel cell catalysts.

Current thermoelectric (TE) materials often have low performance or contain less abundant and/or toxic elements, thus limiting their large-scale applications. Therefore, new TE materials with high efficiency and low cost are strongly desirable. Here we demonstrate that, SiS and SiSe monolayers made from non-toxic and earth-abundant elements intrinsically have low thermal conductivities arising from their low-frequency optical phonon branches with large overlaps with acoustic phonon modes, which is similar to the state-of-the-art experimentally demonstrated material SnSe with a layered structure. Together with high thermal power factors due to their two-dimensional nature, they show promising TE performances with large figure of merit (ZT) values exceeding 1 or 2 over a wide range of temperatures. We establish some basic understanding of identifying layered materials with low thermal conductivities, which can guide and stimulate the search and study of other layered materials for TE applications., Comment: 18 pages, 3 figures

Hexagonal boron nitride (h-BN) has attracted significant attention due to its superior properties as well as its potential as an ideal dielectric layer for graphene-based devices. The h-BN films obtained via chemical vapor deposition in earlier reports are always polycrystalline with small grains due to high nucleation density on substrates. Here we report the successful synthesis of large single-crystal h-BN grains on rational designed Cu-Ni alloy foils. It is found that the nucleation density can be greatly reduced to 60 per mm2 by optimizing Ni ratio in substrates. The strategy enables the growth of single-crystal h-BN grains up to 7,500 um2, about 2 orders larger than that in previous reports. This work not only provides valuable information for understanding h-BN nucleation and growth mechanisms, but also gives an effective alternative to exfoliated h-BN as a high-quality dielectric layer for large-scale nano-electronic applications., Comment: 14 pages, 5 figures