Inducing magnetic moment in otherwise nonmagnetic two-dimensional semiconducting materials is the key first step to design spintronic materials. Here, we study the absorption of transition-metals on pristine and defected single-layer phosphorene, within density functional theory. We predict that increased transition-metal diffusivity on pristine phosphorene would hinder any possibility of controlled magnetism, and thus any application. In contrast, the point-defects will anchor metals, and exponentially reduce the diffusivity. Similar to other two-dimensional materials, metals bind strongly on both pristine and defected phosphorene, and we provide a microscopic description of bonding, which explain the qualitative trend with increasing number of valence electrons. We further argue that the divacancy complex is imperative in any practical purpose due to their increased thermodynamic stability over monovacancy. For most cases, the defecttransition metal complexes retain the intrinsic semiconduction properties, and also induce a local magnetic moment with large exchangesplitting and spin-flip energies, which are necessary for spintronic applications. Specifically, the V/Mn/Fe absorbed at the divacancy have tremendous promise in this regard. Further, we provide a simple microscopic model to describe the local moment formation in these transition metal and defect complexes. We also note that metal absorption may completely alter the intrinsic semiconducting nature and give rise to half-metallic and metallic composite system.

An ordered self-assembly of CsPbBr quantum dots (QDs) was generated on the surface of few-layer black phosphorus (FLBP). Strong quenching of the QD fluorescence was observed, and analyzed by time-resolved photoluminescence (TR-PL) studies, DFT calculations, and photoconductivity measurements. Charge transfer by type I band alignment is suggested to be the cause of the observed effects.

Inducing a robust long-range magnetic order in diamagnetic graphene remains a challenge. While nitrogen-doped graphene is reported to be a promising candidate, the corresponding exchange mechanism endures unclear and is essential to tune further and manipulate magnetism. Within the first-principles calculations, we systematically investigate the local moment formation and the concurrent interaction between various defect complexes. The importance of adatom diffusion on the differential defect abundance is discussed. The individual nitrogen complexes that contribute toward itinerant and a local magnetic moment are identified. The magnetic interaction between the complexes is found to depend on the concentration, complex type, sublattice, distance, and orientation. We propose that the direct exchange mechanism between the delocalized magnetic moment originating from the itinerant π-electron at the prevalent graphitic complexes to be responsible for the observed ferromagnetism. We show that B co-doping further improves ferromagnetism. Present results will assist in the microscopic understanding of the current experimental results and motivate experiments to produce robust magnetism following the proposed synthesis strategy. arXiv:1812.10643v1 [cond-mat.mes-hall]

Reduced electron screening in two-dimension plays a fundamental role in determining exciton properties, which dictates optoelectronic and photonic device performances. Considering the explicit electron-hole interaction within the GW −Bethe-Salpeter formalism, we first study the excitonic properties of pristine phosphorene and investigate the effects of strain and impurity coverage. The calculations reveal strongly bound exciton in these systems with anisotropic spatial delocalization. Further, we present a simplified hydrogenic model with anisotropic exciton mass and effective electron screening as parameters, and the corresponding results are in excellent agreement with the present GW −BSE calculations. The simplified model is then used to investigate exciton renormalization in few-layer and heterostructure phosphorene. The changes in carrier effective mass along with increasing electron screening renormalizes the exciton binding in these systems. We establish that the present model, where the parameters are calculated within computationally less expensive first-principles calculations, can predict exciton properties with excellent accuracy for larger two-dimensional systems, where the many-body GW −BSE calculations are impossible. arXiv:1810.11994v1 [cond-mat.mes-hall]

An ordered self‐assembly of CsPbBr3 quantum dots (QDs) was generated on the surface of few‐layer black phosphorus (FLBP). Strong quenching of the QD fluorescence was observed, and analyzed by time‐resolved photoluminescence (TR‐PL) studies, DFT calculations, and photoconductivity measurements. Charge transfer by type I band alignment is suggested to be the cause of the observed effects.

Li metal is the most promising choice for anode in high-energy rechargeable batteries, but the dendrite growth upon cycling leads to safety concerns and poor cycle life. Herein, we demonstrate a novel and scalable approach for direct writing of a thin layer of carbon nano-onions on copper substrate to stabilize the Li metal anode and prevent the dendrite growth. The F-doped carbon nano-onion film (F-CNOF) scaffold enables reversible electroplating for over 1500 hours (300 cycles) with a coulombic efficiency of ∼100%. The F-CNOF is capable of depositing Li equivalent to a capacity of 10 mA h cm-2 (gravimetric capacity 3218 mA h g-1) at 1 mA cm-2, operating at a high current density of 6 mA cm-2. More importantly, these features of long-term cyclic stability and excellent rate capability are attributed to the very high curvature due to nano dimension (∼108 m-1) of the nano-onions that develop a very uniform Li flux due to the negative surface charge, thus preventing the dendrite formation. We have also shown via first-principles DFT calculations that the high curvature achieved herein can significantly enhance the binding energy of Li to the carbon surface, which helps to improve lithiophilicity. A full cell fabricated using Li4Ti5O12 as the positive electrode showed cyclic stability of 450 cycles.

Kinetics of vacancy defect in graphene drives structural modifications leading to disorder, multivacancy complex and edge reconstruction. Within the first-principles calculations, we study the dynamic Jahn-Teller distortion and diffusion of a vacancy defect. Further, the intricate dependence of carrier doping is systematically investigated. The experimental observation of dynamic Jahn-Teller distortion is argued to be blocked by defect functionalization and charge doping. We demonstrate that lattice relaxation perpendicular to the graphene sheet along with the in-plane strain relaxation play predominant roles in predicting the correct microscopic mechanism for vacancy diffusion. The importance of quantum correction to the classical barrier is discussed. The calculated activation barrier increases upon both electron and hole doping and the observed trends are explained by the differential charge density distribution and hardening of the responsible low-energy phonon modes. Electron doping essentially freezes the vacancy motion, and thus any degradation mediated by it. While tracking and analyzing the vacancy diffusion experimentally in graphene is a difficult task, the present results will motivate new experimental efforts and assist interpretation of the results. arXiv:1803.04384v2 [cond-mat.mes-hall]

Converting solar energy into chemical energy by splitting water is a promising means to generate a sustainable and renewable solution without detrimental environmental impact. The two-dimensional semiconductors serve as potential catalysts in this regard, and here we combine Janus transitionmetal dichalcogenides (MoXY, X/Y = S, Se, Te) and graphitic carbon nitride in a van der Waals heterostructure. Within the first-principles calculations, we investigate the electronic, optical and excitonic properties that determine the photocatalytic activity. Due to the internal electric field, the photogenerated electrons and holes are separated in the MoXY layers, and also generates high overpotentials for the redox reactions. The high optical absorptions span throughout the entire visible and near ultraviolet regime in these heterostructure nanocomposites. Further, the lower exciton binding, calculated within the two-dimensional hydrogenic model, indicates efficient charge separation. Enormous tunability of photocatalytic properties in such heterostructures should attract considerable theoretical and experimental attention in future.