A Novel Test for the Appraisal of Solid/Solid Interfacial Interactions

The Johnson, Kendall and Roberts (JKR) technique has been used with considerable success for assessing solid/solid interfacial interactions over the past 25 years or so. Nevertheless, the contact zone between the two spherical solids is often small and the energy of adhesion scales with the cube of the contact radius (at low load), thus potentially magnifying errors in adhesion assessment. The theoretical aspects of a novel technique are presented here, in which a hollow, slightly inflated, spherical membrane replaces a full sphere, and is placed in contact with a flat rigid solid. A judicious choice of experimental conditions should lead to increased contact radius and the energy of adhesion scales with its square (at low load), thus reducing possible errors. An added advantage is that the effective elasticity of the sphere depends on internal gas pressure. Thus surface and bulk effects are decoupled.     

Global behavior of the diffusion coefficient for the Van Der Waals binary mixture

We describe the general dependence of the diffusion coefficient associated with the Van der Waals binary mixture on the temperature, number densities, and relative strengths of molecular interaction parameters. The task is facilitated by the fact that for Kac-type intermolecular potentials, in the long-range limit, the diffusion coefficient becomes simply related to the product of a partial compressibility and the curvature of the equilibrium free energy in the space of number densities. Therefore the different kinds of behavior found can be classified according to the scheme of Scott and Van Konynenburg for the global phase diagram of the same model mixture.Paper presented at the Tenth Symposium on Thermophysical Properties, June 20–23, 1988, Gaithersburg, Maryland, U.S.A.     

Phase diagrams beyond the critical point

Following a path in the usual p‐T‐diagrams of one‐component systems via the supercritical region it seems that one can make a transition from the liquid to the gas phase (and in reverse) without traversing a phase boundary curve, whereas in the sub‐critical region one clearly has to pass a phase boundary curve. To solve this paradox situation, the phase diagrams of one‐component systems are analyzed with respect to the phase transition from the liquid to the gas state in the sub‐ and supercritical range. It is shown that the critical point is not an isolated point or an end point on the phase boundary curve between the gaseous and the liquid phase in a p‐T‐diagram. Instead, it marks on the boundary curve just the transition between the section of a first order phase transition in the sub‐critical range and the section of a second or higher order phase transition in the supercritical range. Thus, the present phase diagrams of one‐component systems are incomplete with respect to the phase boundary curve between liquid and gas in the supercritical region. The result is illustrated using the model of a van der Waals gas.     

Impact of superplasticizer concentration and of ultra-fine particles on the rheological behaviour of dense mortar suspensions

This work aims at investigating the impact of the addition of superplasticizer and of ultra-fine particles, namely of silica fume and of precipitated titania, on the rheological behaviour of water-lean mortar pastes. The pastes are characterised in terms of their spread, their flowing behaviour and by means of performing a shear test, giving access to viscosity/shear gradient correlations. Adding superplasticizer is shown to shift the onset of shear thickening of the referring pastes to higher shear rates and to attenuate its otherwise rapid evolution, possibly by means of favouring steric particle-particle interactions. The workability of these mortars, which is characterised in terms of spread values and draining, is also improved. For the case of fly ash based mortars, adding ultra-fine particles is another way of (slightly) “retarding” shear thickening and of attenuating its evolution, possibly because of resulting in - on the average - lower hydrodynamic forces and reduced attractive Van der Waals interactions between particles. However, at the same time these mortars are characterised by a worsening in workability which is attributed to the huge amount of surface area provided by the ultra-fines.     

Type-II van der Waals heterostructures of GeC,ZnO and Al2SO monolayers for promising optoelectronic and photocatalytic applications

Two-dimensional materials stacked via van der Waals (vdW) forces provide a revolutionary route toward high-performance optoelectronic and renewable energy devices. Here, we report vdW heterostructures (vdWHs) consisting of GeC, ZnO and Al₂SO monolayers on first-principles computations. GeC (ZnO)–Al₂SO vdWHs are both stable type-II semiconductors with indirect (direct) band gaps. This significantly suppresses the recombination of photogenerated charge carriers across the interface, making them promising for light detection and harvesting applications. Charge transfer from GeC (Al₂SO) layer to Al₂SO (ZnO) layer leads to p-doping in GeC (Al₂SO) and n-doping in Al₂SO (ZnO) of GeC (ZnO)–Al₂SO vdWHs. In contrast to pristine monolayers, higher carrier mobility promotes charge transfer to the surface and reduces carrier recombination in GeC (ZnO)–Al₂SO vdWHs. Further, the absorption spectra indicate redshift (blueshift) and reveal more solar light is absorbed by GeC (ZnO)–AlS₂O vdWHs in the visible (ultraviolet) region. The band edge positions suggest that GeC–Al₂SO vdWHs can reduce water into H₂ but fails to perform an oxidation reaction at pH = 0. More interestingly, ZnO–Al₂SO vdWHs can perform redox reactions, making them prominent for overall water-splitting reactions. Our computational findings provide a path for the design of vdWHs for future optoelectronic and photovoltaic devices.     

Electric Field Tunable Interlayer Relaxation Process and Interlayer Coupling in WSe2/Graphene Heterostructures

Transition metal dichalcogenides van der Waals (vdWs) heterostructures present fascinating optical and electronic phenomena, and bear tremendous significance for electronic and optoelectronic applications. As the significant merits in vdWs heterostructures, the interlayer relaxation of excitons and interlayer coupling at the heterointerface reflect the dynamic behavior of charge transfer and the coupled electronic/structural characteristics, respectively, which may give rise to new physics induced by quantum coupling. In this work, upon tuning the photoluminescence (PL) properties of WSe₂/graphene and WSe₂/MoS₂/graphene heterostructures by virtue of electric field, it is demonstrated that the interlayer relaxation of excitons at the heterointerface in WSe₂/graphene, which is even stronger than that in MoS₂/graphene and WSe₂/MoS₂ , plays a dominant role in PL tuning in WSe₂/graphene, while the carrier population in WSe₂ induced by electric field has a minor contribution. In addition, it is discovered that the interlayer coupling between monolayer WSe₂ and graphene is enhanced under high electric field, which breaks the momentum conservation of first order Raman‐allowed phonons in graphene, yielding the enhanced Raman scattering of defects in graphene. The interplay between electric field and vdWs heterostructures may provide versatile approaches to tune the intrinsic electronic and optical properties of the heterostructures.     

Healing of Planar Defects in 2D Materials via Grain Boundary Sliding

Understanding the mechanisms and kinetics of defect annihilations, particularly at the atomic scale, is important for the preparation of high‐quality crystals for realizing the full potential of 2D transition metal dichalcogenides (TMDCs) in electronics and quantum photonics. Herein, by performing in situ annealing experiments in an atomic resolution scanning transmission electron microscope, it is found that stacking faults and rotational disorders in multilayered 2D crystals can be healed by grain boundary (GB) sliding, which works like a “wiper blade” to correct all metastable phases into thermodynamically stable phases along its trace. The driving force for GB sliding is the gain in interlayer binding energy as the more stable phase grows at the expanse of the metastable ones. Density functional theory calculations show that the correction of 2D stacking faults is triggered by the ejection of Mo atoms in mirror twin boundaries, followed by the collective migrations of 1D GB. The study highlights the role of the often‐neglected interlayer interactions for defect repair in 2D materials and shows that exploiting these interactions has significant potential for obtaining large‐scale defect‐free 2D films.     

Salt‐Assisted Growth of P‐type Cu9S5 Nanoflakes for P‐N Heterojunction Photodetectors with High Responsivity

P‐n junctions based on two dimensional (2D) van der Waals (vdW) heterostructure are one of the most promising alternatives in next‐generation electronics and optoelectronics. By choosing different 2D transition metal dichalcogenides (TMDCs), the p‐n junctions have tailored energy band alignments and exhibit superior performance as photodetectors. The p‐n diodes working at reverse bias commonly have high detectivity due to suppressed dark current but suffer from low responsivity resulting from small quantum efficiency. Greater build‐in electric field in the depletion layer can improve the quantum efficiency by reducing recombination of charge carriers. Herein, Cu₉S₅, a novel p‐type semiconductor with direct bandgap and high optical absorption coefficient, is synthesized by salt‐assisted chemical vapor deposition (CVD) method. The high density of holes in Cu₉S₅ endows the constructed p‐n junction, Cu₉S₅/MoS₂, with strong build‐in electric field according to Anderson heterojunction model. Consequently, the Cu₉S₅/MoS₂ p‐n heterojunction has low dark current at reverse bias and high photoresponse under illumination due to the efficient charge separation. The Cu₉S₅/MoS₂ photodetector exhibits good photodetectivity of 1.6 × 10¹² Jones and photoresponsivity of 76 A W^?1 under illumination. This study demonstrates Cu₉S₅ as a promising p‐type semiconductor for high‐performance p‐n heterojunction diodes.     

Atomically Thin MoS2: A Versatile Nongraphene 2D Material

Two‐dimensional inorganic materials are emerging as a premiere class of materials for fabricating modern electronic devices. The interest in 2D layered transition metal dichalcogenides is especially high. Particularly, 2D MoS₂ is being heavily researched due to its novel functionalities and its suitability for a wide range of electronic and optoelectronic applications. In this article, the progress in mono/few layer(s) MoS₂ research is reviewed by focusing primarily on the layer dependent evolution of crystal, phonon, and electronic structure. The review includes extensive detail into the methodologies adapted for single or few layer(s) MoS₂ growth. Further, the review covers the versatility of 2D MoS₂ for a broad range of device applications. Recent advancements in the field of van der Waals heterostructures are also highlighted at the end of the review.