Enhancing metallicity and basal plane reactivity of 2D materials via self-intercalation

Intercalation (ic) of metal atoms into the van der Waals (vdW) gap of layered materials constitutes a facile strategy to create new materials whose properties can be tuned via the concentration of the intercalated atoms. Here we perform systematic density functional theory calculations to explore various properties of an emergent class of crystalline 2D materials (ic-2D materials) comprising vdW homobilayers with native metal atoms on a sublattice of intercalation sites. From an initial set of 1348 ic-2D materials, generated from 77 vdW homobilayers, we find 95 structures with good thermodynamic stability (formation energy within 200 meV/atom of the convex hull). A significant fraction of the semiconducting host materials are found to undergo an insulator to metal transition upon self-intercalation with only PdS$_2$, PdSe$_2$, and GeS$_2$ maintaining a finite electronic gap. In five cases, self-intercalation introduces magnetism. In general, self-intercalation is found to promote metallicity and enhance the chemical reactivity on the basal plane. Based on the calculated H binding energy we find that self-intercalated SnS$_2$ and Hf$_3$Te$_2$ are promising candidates for hydrogen evolution catalysis. All the stable ic-2D structures and their calculated properties can be explored in the open C2DB database

Quenching of Exciton Recombination in Strained Two-Dimensional Monochalcogenides

We predict that long-lived excitons with very large binding energies can also exist in a single or few layers of monochalcogenides such as GaSe. Our theoretical study shows that excitons confined by a radial local strain field are unable to recombine despite electrons and holes coexisting in space. The localized single-particle states are calculated in the envelope function approximation based on a three-band k·p Hamiltonian obtained from density-functional-theory calculations. The binding energy and the decay rate of the exciton ground state are computed after including correlations in the basis of electron-hole pairs. The interplay between the localized strain and the caldera-type valence band characteristic of few-layered monochalcogenides creates localized electron and hole states with very different quantum numbers which hinders the recombination even for singlet excitonsResearch supported by the Spanish MINECO through Grant No. FIS2016-80434-P and the María de Maeztu Programme for Units of Excellence in Research and Development (MDM-2014-0377), the Fundación Ramón Areces, and the European Union Seventh Framework Programme under Grant Agreement No. 604391 Graphene Flagship. S. P. was also supported by the VILLUM FONDEN via the Centre of Excellence for Dirac Materials (Grant No. 11744

Emergent properties of van der Waals bilayers revealed by computational stacking

Stacking of two-dimensional (2D) materials has emerged as a facile strategy for realising exotic quantum states of matter and engineering electronic properties. Yet, developments beyond the proof-of-principle level are impeded by the vast size of the configuration space defined by layer combinations and stacking orders. Here we employ a density functional theory (DFT) workflow to calculate interlayer binding energies of 8451 homobilayers created by stacking 1052 different monolayers in various configurations. Analysis of the stacking orders in 247 experimentally known van der Waals crystals is used to validate the workflow and determine the criteria for realizable bilayers. For the 2586 most stable bilayer systems, we calculate a range of electronic, magnetic, and vibrational properties, and explore general trends and anomalies. We identify an abundance of bistable bilayers with stacking order-dependent magnetic or electrical polarisation states making them candidates for slidetronics applications

Antimicrobial Efficacy of Mineral Trioxide Aggregate with and without Silver Nanoparticles

Introduction: Most current root-end filling materials do not provide a perfect seal. Thus, a microscopic space is likely to exist in the interface between walls of the root-end cavity and filling material, which allows microorganisms and their products to penetrate. In addition to good sealing ability and biocompatibility, root-end filling materials should ideally have some antimicrobial activity. Therefore, this in vitro study aimed to evaluate the antimicrobial properties of Angelus white mineral trioxide aggregate (MTA) and the mixture of MTA with silver nanoparticles (1% weight; MTA/SN). Materials and Methods: Antimicrobial properties of MTA and MTA/SN were tested by agar diffusion technique against Enterococcus faecalis, Pseudomonas aeruginosa, Staphylococcus aureus, and Candida albicans. The microbial inhibition zones around the materials were measured by a caliper with 0.1-mm accuracy. Student’s t-test was used for comparison between the two groups in normal data distribution and Man-Whitney U test for non-normal distribution. Results: Student’s t-test revealed that for E. faecalis, C. albicans, and P. aeruginosa, microbial inhibition zone of MTA/SN was significantly greater than that of MTA (P=0.000). Mann-Whitney U test indicated no significant difference between the effect of MTA and MTA/SN on S. aureus (P>0.05). Conclusion: Based on the results of this study, adding silver nanoparticles to MTA improved its antimicrobial efficacy

Strong modulation of optical properties in rippled 2D GaSe via strain engineering

This is the Accepted Manuscript version of an article accepted for publication in Nanotechnology.  IOP Publishing Ltd is not responsible for any errors or omissions in this version of the manuscript or any version derived from it.  The Version of Record is available online at https://doi.org/10.1088/1361-6528/ab0bc1Few-layer GaSe is one of the latest additions to the family of two-dimensional semiconducting crystals whose properties under strain are still relatively unexplored. Here, we study rippled nanosheets that exhibit a periodic compressive and tensile strain of up to 5%. The strain profile modifies the local optoelectronic properties of the alternating compressive and tensile regions, which translates into a remarkable shift of the optical absorption band-edge of up to 1.2 eV between crests and valleys. Our experimental observations are supported by theoretical results from density functional theory calculations performed for monolayers and multilayers (up to seven layers) under tensile and compressive strain. This large band gap tunability can be explained through a combined analysis of the elastic response of Ga atoms to strain and the symmetry of the wave functionsResearch supported by the Spanish MINECO through Grants MAT2017–88693-R, MAT2014-57915-R, FIS2016-80434- P (AEI/FEDER, EU), BES-2015-071316, the Ramón y Cajal programme RYC-2011-09345, the Fundación Ramón Areces and the María de Maeztu Programme for Units of Excellence in R&D (MDM-2014-0377), as well as from the Comunidad Autónoma de Madrid (CAM) MAD2D-CM Program (S2013/MIT-3007) and the European Union Seventh Framework Programme under grant agreement No. 604391 Graphene Flagship. JJP acknowledges Fulbright Fellowship for Sabbatical leave at University of Texas at Austin, EEUU. We acknowledge the computer resources and assistance provided by the Centro de Computación Científica of the Universidad Autónoma de Madri

Exciton diffusion in two-dimensional metal-halide perovskites

Two-dimensional layered perovskites are attracting increasing attention as more robust analogues to the conventional three-dimensional metal-halide perovskites for both light harvesting and light emitting applications. However, the impact of the reduced dimensionality on the optoelectronic properties remains unclear, particularly regarding the spatial dynamics of the excitonic excited state within the two-dimensional plane. Here, we present direct measurements of exciton transport in single-crystalline layered perovskites. Using transient photoluminescence microscopy, we show that excitons undergo an initial fast diffusion through the crystalline plane, followed by a slower subdiffusive regime as excitons get trapped. Interestingly, the early intrinsic diffusivity depends sensitively on the choice of organic spacer. A clear correlation between lattice stiffness and diffusivity is found, suggesting exciton–phonon interactions to be dominant in the spatial dynamics of the excitons in perovskites, consistent with the formation of exciton–polarons. Our findings provide a clear design strategy to optimize exciton transport in these systemsThis work has been supported by the Spanish Ministry of Economy and Competitiveness through The “María de Maeztu” Program for Units of Excellence in R&D (MDM-2014-0377). M.S. acknowledges the financial support of a fellowship from “la Caixa” Foundation (ID 100010434). The fellowship code is LCF/BQ/IN17/11620040. M.S. has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement No. 713673. F.P. acknowledges support from the Spanish Ministry for Science, Innovation, and Universities through the state program (PGC2018-097236-A-I00) and through the Ramón y Cajal program (RYC-2017-23253), as well as the Comunidad de Madrid Talent Program for Experienced Researchers (2016-T1/IND-1209). N.A., M.M. and R. D.B. acknowledges support from the Spanish Ministry of Economy, Industry and Competitiveness through Grant FIS2017-86007-C3-1-P (AEI/FEDER, EU). E.P. acknowledges support from the Spanish Ministry of Economy, Industry and Competitiveness through Grant FIS2016-80434-P (AEI/FEDER, EU), the Ramón y Cajal program (RYC-2011- 09345) and the Comunidad de Madrid through Grant S2018/ NMT-4511 (NMAT2D-CM). S.P. acknowledges financial support by the VILLUM FONDEN via the Centre of Excellence for Dirac Materials (Grant No. 11744