Interlayer Interaction Research Articles

Borophene/graphene heterostructure for effective hydrogen storage with facile dehydrogenation

A theoretical investigation of the hydrogen adsorption on a β12-borophene monolayer and a β12-borophene/graphene bilayer heterostructure is performed to tailor the substrate properties via functionalization to increase its hydrogen (H2) physisorption strength and enhance its gravimetric capacity. The results using the density-functional theory show that the H2 adsorption energy significantly increases as the substrate changes from monolayer to bilayer heterostructure. This enhancement in H2 adsorption energy is attributed to the synergetic effects of the interlayer interaction in the heterostructure via analysis of the chemical bonding. The lithium decoration of the bilayer heterostructure has indeed increased both the H2 adsorption energy and gravimetric capacity. Further enhancement of these latter attributes is shown to be plausible to achieve through the application of an electric field normal to the surface and directed upward toward the molecules. The thermodynamic analysis based on the Langmuir adsorption model finds that the high storage capacity should be maintained high with an effective gravimetric capacity of 13.64 wt% at ambient conditions. Our findings demonstrated that the Li-decorated β12-borophene/graphene bilayer heterostructure should be a promising candidate for efficient hydrogen storage applications.

Moiré superlattices arising from growth induced by screw dislocations in layered materials

Abstract Moiré superlattices (MSLs) are modulated structures produced from homogeneous or heterogeneous two-dimensional layers stacked with a twist angle and/or lattice mismatch. Enriching the methods for fabricating MSL and realizing the unique emergent properties are key challenges on its investigation. Here we recommend that the spiral dislocation driven growth is another optional method for the preparation of high quality MSL samples. The spiral structure stabilizes the constant out-of-plane lattice distance, causing the variations in electronic and optical properties. Taking SnS2 MSL as an example, we find prominent properties including large band gap reduction (~0.4 eV) and enhanced optical activity. First-principles calculations reveal that these unusual properties can be ascribed to the locally enhanced interlayer interaction associated with the Moiré potential modulation. We believe that the spiral dislocation driven growth would be a powerful method to expand the MSL family and broaden their scope of application.

Intercalation in 2D materials and in situ studies.

Intercalation of atoms, ions and molecules is a powerful tool for altering or tuning the properties - interlayer interactions, in-plane bonding configurations, Fermi-level energies, electronic band structures and spin-orbit coupling - of 2D materials. Intercalation can induce property changes in materials related to photonics, electronics, optoelectronics, thermoelectricity, magnetism, catalysis and energy storage, unlocking or improving the potential of 2D materials in present and future applications. In situ imaging and spectroscopy technologies are used to visualize and trace intercalation processes. These techniques provide the opportunity for deciphering important and often elusive intercalation dynamics, chemomechanics and mechanisms, such as the intercalation pathways, reversibility, uniformity and speed. In this Review, we discuss intercalation in 2D materials, beginning with a brief introduction of the intercalation strategies, then we look into the atomic and intrinsic effects of intercalation, followed by an overview of their in situ studies, and finally provide our outlook.

Understanding mechanism conversion in hydrogen evolution reaction on PtSe2: Role of layer number explored by density functional theory

The emerging two-dimensional (2D) transition metal dichalcogenide PtSe2 is a promising catalyst for hydrogen evolution reactions (HER). In this study, we performed density functional theory (DFT) calculations to investigate the mechanism conversion of the HER over PtSe2 with respect to the changes in the number of layers of the catalyst. We found that the adsorption energy of hydrogen (ΔGH) changed with an increase in the number of 2D material layers, and the most significant change occurred when the number of layers was increased from one to two. Furthermore, we conducted dynamic calculations to reveal the mechanisms of the HER on the basal and Vse surfaces. Owing to the changes in ΔGH, the HER mechanism undergoes a conversion between Volmer–Heyrovsky and Volmer–Volmer'–Tafel mechanisms. Through frontier orbitals analysis, layer-stacking altered the bonding capability between hydrogen and PtSe2 surfaces by altering the electronic structure of the PtSe2 surface. This study demonstrates the synergistic effect of interlayer interactions on the HER over PtSe2 catalysts and can be helpful in stimulating innovative ideas for 2D material design.

Tunable Photocarrier Dynamics in CuS Nanoflakes under Pressure Modulation.

Two-dimensional materials with a unique layered structure have attracted intense attention all around the world due to their extraordinary physical properties. Most importantly, the internal Coulomb coupling can be regulated, and thus electronic transition can be realized by manipulating the interlayer interaction effectively through adding external fields. At present, the properties of two-dimensional materials can be tuned through a variety of methods, such as adding pressure, strain, and electromagnetic fields. For optoelectronic applications, the lifetime of the photogenerated carriers is one of the most crucial parameters for the materials. Here, we demonstrate effective modulation of the optical band gap structure and photocarrier dynamics in CuS nanoflakes by applying hydrostatic pressure via a diamond anvil cell. The peak differential reflection signal shows a linear blueshift with the pressure, suggesting effective tuning of interlayer interaction inside CuS by pressure engineering. The results of transient absorption show that the photocarrier lifetime decreases significantly with pressure, suggesting that the dissociation process of the photogenerated carriers accelerates. It could be contributed to the phase transition or the decrease of the phonon vibration frequency caused by the pressure. Further, Raman spectra reveal the change of Cu-S and S-S bonds after adding pressure, indicating the possible occurrence of structural phase transition. Interestingly, all of the variation modes are reversible after releasing pressure. This work has provided an excellent sight to show the regulation of pressure on the photoelectric properties of CuS, exploring CuS to wider applications that can lead toward the realization of future excitonic and photoelectric devices modulated by high pressure.

Stacking-dependent interlayer magnetic interactions in CrSe2.

Recently, CrSe2, a new ferromagnetic van der Waals two-dimensional material, was discovered to be highly stable under ambient conditions, making it an attractive candidate for fundamental research and potential device applications. Here, we study the interlayer interactions of bilayer CrSe2using first-principles calculations. We demonstrate that the interlayer interaction depends on the stacking structure. The AA and AB stackings exhibit antiferromagnetic (AFM) interlayer interactions, while the AC stacking exhibits ferromagnetic (FM) interlayer interaction. Furthermore, the interlayer interaction can be further tuned by tensile strain and charge doping. Specifically, under large tensile strain, most stacking structures exhibit FM interlayer interactions. Conversely, under heavy electron doping, all stacking structures exhibit AFM interlayer interactions. These findings are useful for designing spintronic devices based on CrSe2.

Thermally Activated Photoluminescence Induced by Tunable Interlayer Interactions in Naturally Occurring van der Waals Superlattice SnS/TiS2.

van der Waals (vdW) superlattices, comprising different 2D materials aligned alternately by weak interlayer interactions, offer versatile structures for the fabrication of novel semiconductor devices. Despite their potential, the precise control of optoelectronic properties with interlayer interactions remains challenging. Here, we investigate the discrepancies between the SnS/TiS2 superlattice (SnTiS3) and its subsystems by comprehensive characterization and DFT calculations. The disappearance of certain Raman modes suggests that the interactions alter the SnS subsystem structure. Specifically, such structural changes transform the band structure from indirect to direct band gap, causing a strong PL emission (∼2.18 eV) in SnTiS3. In addition, the modulation of the optoelectronic properties ultimately leads to the unique phenomenon of thermally activated photoluminescence. This phenomenon is attributed to the inhibition of charge transfer induced by tunable intralayer strains. Our findings extend the understanding of the mechanism of interlayer interactions in van der Waals superlattices and provide insights into the design of high-temperature optoelectronic devices.

Modulating electronic structure by interlayer spacing and twist on bilayer bismuthene.

Modulation of the electronic structure has played a crucial role in advancing the field of two-dimensional materials, but there are still many unexplored directions, such as the twist angle for a novel degree of freedom, for modulating the properties of heterostructures. We observed a distinct pattern in the energy bands of bilayer bismuthene, demonstrating that modulating the twist angle and interlayer spacing significantly influences interlayer interactions. Our study of various interlayer spacings and twist angles revealed a close relationship between bandgap size and interlayer spacing, while the twist angle notably affects the shape of the energy bands. Furthermore, we observed a synergistic effect between these two factors. As the twist angle decreases, the energy bands become flat, and flat bands can be generated without requiring a specific angle on bilayer bismuthene. Our results suggest a promising way to tailor the energy band structure of bilayer 2D materials by varying the interlayer spacing and twist angle.

Simulation of interlayer coupling for electroactive covalent organic framework design.

Porous, stacked two-dimensional covalent organic frameworks (2D COFs) bearing semiconducting linkers can support directional charge transfer across adjacent layers of the COF. To better inform the current and possible future design rules for enhancing electron and hole transport in such materials, an understanding of how linker selection and functionalization affects interlayer electronic couplings is essential. We report electronic structure simulation and analysis of electronic couplings across adjacent linker units and to encapsulated species in functionalized electroactive 2D COFs. The detailed dependence of these electronic couplings on interlayer interactions is examined through scans along key interlayer degrees of freedom and through configurational sampling from equilibrium molecular dynamics on semiempirical potential energy surfaces. Beyond affirming the sensitivity of the electronic coupling to interlayer distance and orientation, these studies offer guidance toward linker functionalization strategies for enhancing charge carrier transport in electroactive 2D COFs.

Biomimetic artificial nacre-like microfiber of Co/C modified cellulose nanofiber/Ti3C2Tx MXene with efficient microwave absorption

Although considerable efforts have been made in the fabrication of MXene-based composites for microwave absorption (MA), there is a great challenge to assemble MXene into regularly arranged microfibers prepared by wet-spinning technique for application in the field of MA due to insufficient interlayer interactions between Ti3C2Tx flakes. Heterogeneous interface design by optimizing material components to construct ingenious microstructure is crucial for efficient microwave absorbers. Herein, artificial nacre-like supramolecular microfibers of Co/C modified cellulose nanofiber/Ti3C2Tx MXene (Co/C/CNF/Ti3C2Tx) with plenty of heterogeneous interfaces were prepared by a simple wet-spinning technology through a self-assembly process induced by hydrogen bonding interactions between CNF and Ti3C2Tx. The artificial nacre-like microfibers with layered structure possess abundant heterogeneous interfaces, which facilitate multiple reflections/scattering of electromagnetic waves (EMW) between these interfaces, and at the same time promote interfacial and dipole polarization. The introduction of magnetic Co/C nanoparticles not only offer additional magnetic loss ability and improved impedance matching, but also enhance conductivity loss and polarization loss. Benefiting from these advantages, Co/C/CNF/Ti3C2Tx (1:1:1) fiber exhibits superior MA performance with a minimum reflection loss (RLmin) of up to −62.32 dB (>99.9999 % energy absorption) and a broad effective absorption bandwidth (EAB) of 5.86 GHz. The work provides a promising method for the preparation of biomimetic artificial nacre-like MXene-based microfibers with efficient MA performance, which is expected to be applied in the field of flexible wearable electromagnetic protection.

CVD-growth and interlayer interaction of multilayer WS2-based vertical heterostructures with the evolution of bottom section from MoS2 to alloyed MoxW1-xS2

The construction of vertical van der Waals (vdW) heterostructures (HSs) via stacking various two-dimensional (2D) transition-metal dichalcogenide (TMDC) crystals supplies an alternative pathway to modifying relative physical characteristics through a transfer method. However, fabrication of 2D multilayer TMDC vdW HSs is still challenging by a one-step chemical vapor deposition (CVD). In this work, high-yield 2D TMDC vdW HSs, for example, 1 L-MoS2/1 L-WS2, 4 L-MoS2/2 L-WS2, 4 L-MoxW1-xS2/3 L-WS2, and 1 L-MoxW1-xS2/2 L-WS2, have been realized through a strategy combining the precursors’ spin-coating and one-step CVD method. The structure, composition distribution, exciton behavior, and interlayer interaction of these unique multilayer vdW HSs are systematically estimated by optical microscopy, atomic force microscopy, and Raman/photoluminescence measurements. We further reveal the effect of layer number and compositions on the evolution of interlayer exciton in the range of 848–955 nm, and the possible growth mechanism of as-grown WS2-based multilayer vdW HSs. Our results demonstrate the prospects of regulating light emission from interlayer excitons and facilitate the development of novel optoelectronics based on multilayer 2D TMDC vdW HSs.

Air‐Stable 2D van der Waals MgTeMoO6 Exhibits Strong In‐plane Optical Anisotropy

AbstractExploring 2D van der Waals (vdW) materials is of great importance to the various optoelectronics‐based applications. Herein, mono‐ and few‐layer nanoflakes of a novel 2D vdW MgTeMoO6 are prepared by facile mechanical exfoliation method. These nanoflakes remain highly stable when being exposed in air even for 1 month, which is unique compared to most of 2D materials. Temperature‐dependent Raman spectroscopy reveals that 2D MgTeMoO6 nanosheets exhibit stronger interlayer interaction than that of graphene. In situ, angle‐resolved polarized Raman spectroscopy investigation show evidences for the anisotropic photo–phonon interactions. Notably, strong in‐plane anisotropy for the second harmonic generation (SHG) independent of layer number is observed for 2D MgTeMoO6, making 2D MgTeMoO6 promising in polarization‐sensitive optoelectronic applications.

Self-condensation-assisted chemical vapour deposition growth of atomically two-dimensional MOF single-crystals

Two-dimensional metal-organic frameworks (MOFs) have a wide variety of applications in molecular separation and other emerging technologies, including atomically thin electronics. However, due to the inherent fragility and strong interlayer interactions, high-quality MOF crystals of atomic thickness, especially isolated MOF crystal monolayers, have not been easy to prepare. Here, we report the self-condensation-assisted chemical vapour deposition growth of atomically thin MOF single-crystals, yielding monolayer single-crystals of poly[Fe(benzimidazole)2] up to 62 μm in grain sizes. By using transmission electron microscopy and high-resolution atomic force microscopy, high crystallinity and atomic-scale single-crystal structure are verified in the atomically MOF flakes. Moreover, integrating such MOFs with MoS2 to construct ultrathin van der Waals heterostructures is achieved by direct growth of atomically MOF single-crystals onto monolayer MoS2, and enables a highly selective ammonia sensing. These demonstrations signify the great potential of the method in facilitating the development of the fabrication and application of atomically thin MOF crystals.

Regulation of Ethanol on Ferrous Oxalate Particle Size and Properties: Theoretical and Experimental Study

AbstractSurfactants containing hydroxyl functional groups have a significant influence on the morphology of ferrous oxalate dihydrate. However, few studies have provided a theoretical explanation for this effect. In this investigation, the size of ferrous oxalate dihydrate was reduced from micron to nanometer scale using anhydrous ethanol, and its mechanism was elucidated through density functional theory calculations. The calculational results reveal that anhydrous ethanol molecules bound to the ferrous oxalate dihydrate crystal via hydrogen bonding and van der Waals forces, thereby controlling crystal growth. It means that anhydrous ethanol molecules preferentially affected the interlayer interaction in the structure of ferrous oxalate dihydrate, leading to a significant impact on its overall crystal growth way. Furthermore, the electrochemical properties of ferrous oxalate dihydrate synthesized in aqueous and anhydrous ethanol systems were compared and tested. The specific capacitance (242 F ⋅ g−1 at 0.5 A ⋅ g−1 current density) of ferrous oxalate dihydrate synthesized in anhydrous ethanol system is obvious higher than that of ferrous oxalate dihydrate synthesized in water system (186 F ⋅ g−1), due to its smaller particle size (75 nm). Furthermore, the specific capacitance of this material can be improved to 469 F ⋅ g−1 during composite process of ferrous oxalate dihydrate with graphene oxide.

Adsorption of Zn atoms by monolayer WS2 doped with different atoms X (X = O, Se, N, P, F, Cl): first principles study.

The effect of X (X = O, Se, N, P, F, Cl) doping on the adsorption of Zn atoms by WS2 was investigated based on first principles. The electronic structure and optical properties of the adsorbed system after atomic doping were calculated. It is found that the Zn atom adsorbed on the W top (Tw) site has the most stable structure. When an S atom is replaced with an X atom based on the adsorption system, where the adsorption energy decreases after doping of O, P, F, and Cl atoms compared to the undoped system, it means that each system is more stable after doping of these atoms; charge transfer shows that the adsorption system after P-atom doping the system around the Zn atom loses electrons while S-atom gains electrons, which indicates that P-atom doping is favorable for the adsorption of Zn by WS2, N, P-atom is introduced as p-type doping and F, Cl-atom is introduced undoped by n-type doping, and the band gap of the doped system is less than that of the undoped one. With the introduction of different dopant atoms, certain impurity energy levels are introduced into the adsorption system. The prohibited bandwidth around the Fermi energy level reduces the density of states, causing the doped system's density of states to shift to lower energies, among which the shifts of N, P, F, and Cl are more pronounced. The P-doped adsorption system shows a new peak near the energy of - 11 eV. In addition, the study of optical properties showed that the peak reflections of both doped and non-doped systems adsorbing Zn atoms appeared in the ultraviolet region; the absorbance coefficient of the doped system is moved in the lower energy direction and red-shifted after atom doping; in addition, the absorption coefficients and reflectance of the P, Se doped systems are enhanced in the wavelength range of 200-300 nm compared with that before doping, the dielectric function and CBM and VBM positions were also calculated further indicating the potential of Se-doped systems in improving photocatalytic efficiency. In this paper, the structure optimization of X (X = O, Se, N, P, F, Cl) doping on WS2 adsorbed Zn atom model is performed based on the CASTEP module in Materials-Studio software under the first principles using GGA and PBE generalized function. The corresponding binding energies, bond lengths, bond angles, charge densities, energy band structures, densities of states, and optical properties were also analyzed. The Monkhorst-Pack particular K-point sampling method is used in the calculations; the K-point grid is 6 × 6 × 1, and the cutoff energy for the plane wave expansion is 500 eV. After geometric optimization, the iterative accuracy converges to a value of less than 1 × 10-5 eV/atom for the total energy of each atom and less than 0.03 eV/Å for all atomic forces. The thickness of the vacuum layer was set to 20 Å to avoid the effect of interlayer interaction forces. In this paper, 27 atoms were used to form a 3 × 3 × 1 supercellular tungsten disulfide system consisting of 18 S atoms and 9 W atoms.

Temperature-dependent local structure and lattice dynamics of 1T-TiSe[formula omitted] and 1T-VSe[formula omitted] probed by X-ray absorption spectroscopy

The local atomic structure and lattice dynamics of two isostructural layered transition metal dichalcogenides (TMDs), 1T-TiSe2 and 1T-VSe2, were studied using temperature-dependent X-ray absorption spectroscopy at the Ti, V, and Se K-edges. Analysis of the extended X-ray absorption fine structure (EXAFS) spectra, employing reverse Monte Carlo (RMC) simulations, enabled tracking of the temperature evolution of the local environment in the range of 10–300 K. The atomic coordinates derived from the final atomic configurations obtained using the RMC method were used to calculate the partial radial distribution functions (RDFs) and the mean-square relative displacement (MSRD) factors for the first ten coordination shells around the absorbing atoms. Characteristic Einstein frequencies and effective force constants were determined for TiSe, TiTi, VSe, VV, and SeSe atom pairs from the temperature dependencies of MSRDs. The obtained results reveal differences in the temperature evolution of lattice dynamics and the strengths of intralayer and interlayer interactions in TiSe2 and VSe2.

Materials properties and device applications of semiconducting bismuth oxyselenide

AbstractLayered two‐dimensional (2D) materials have garnered marvelous attention in diverse fields, including sensors, capacitors, nanocomposites and transistors, owing to their distinctive structural morphologies and superior physicochemical properties. Recently, layered quasi‐2D materials, especially layered bismuth oxyselenide (Bi2O2Se), are of particular interest, because of their different interlayer interactions from other layered 2D materials. On this basis, this material offers richer and more intriguing physics, including high electron mobility, sizeable bandgap, and remarkable thermal and chemical durability, rendering it an utterly prospective contender for use in advanced electronic and optoelectronic applications. Herein, this article reviews the recent advances related with Bi2O2Se. Initially, its structural characterization, band structure, and basic properties are briefly introduced. Further, the synthetic strategies for the preparation of Bi2O2Se are presented. Furthermore, the diverse applications of Bi2O2Se in the field of electronics and optoelectronics, photocatalytic, solar cells and sensing were summarized in detail. Ultimately, the challenges and future perspectives of Bi2O2Se are included.image

Precise structure and energy of group 6 transition metal dichalcogenide homo- and heterobilayers in high-symmetry configurations

Two-dimensional group 6 transition metal dichalcogenide (2D TMDC) bilayers show various high-symmetry stacking configurations, which have also been observed in extended domains formed in their twisted homo- and heterobilayers. The interlayer energy varies for these stacking configurations, and the energy differences determine the relative size of the stacking domains. Therefore, the precise prediction of the composition- and stacking-dependent interlayer energy is crucial to model the domain structure of 2D TMDCs in their twisted bilayer homo- and heterostructures. For the validation of approximate methods that are necessary to tackle these systems encompassing thousands of atoms precise reference data is still lacking. Here, we employ the random phase approximation (RPA) on previously validated SCAN-rVV10 geometries to obtain interaction energies of state-of-the-art accuracy on the six high-symmetry stacking configurations ( Hhh , HhM , HhX , Rhh , RhM , and RhX ) of MX2 (M = Mo, W; X = S, Se) bilayers and compare them with the dispersion-corrected density-functional theory (DFT) functionals Perdew–Burke–Ernzerhof (PBE)+D3(BJ), PBE-rVV10L, and SCAN-rVV10. We identify SCAN-rVV10 as most reliable DFT variant with an average deviation of 1.2 meV/atom in relative energies from the RPA reference, and a root mean squared error of less than 2 meV/atom for interlayer interaction energies. We find interlayer distances obtained by PBE+D3(BJ) as being too short, with an impact on the electronic structure, resulting in the incorrect prediction of the band gap character in some cases. A further result of this work is the significant lowering of the interlayer energy and increasing of the interlayer distance in the high-energy stacking configurations. These stackings can be accessible via shear strain and promote exfoliation.

Bi2Te3-Based Thermoelectric Modules for Efficient and Reliable Low-Grade Heat Recovery.

Bismuth-telluride-based alloy has long been considered as the most promising candidate for low-grade waste heat power generation. However, optimizing the thermoelectric performance of n-type Bi2Te3 is more challenging than that of p-type counterparts due to its greater sensitivity to texture, and thus limits the advancement of thermoelectric modules. Herein, the thermoelectric performance of n-type Bi2Te3 is enhanced by incorporating a small amount of CuGaTe2, resulting in a peak ZT of 1.25 and a distinguished average ZT of 1.02 (300-500 K). The decomposed Cu+ strengthens interlayer interaction, while Ga+ optimizes carrier concentration within an appropriate range. Simultaneously, the emerged numerous defects, such as small-angle grain boundaries, twin boundaries, and dislocations, significantly suppresses the lattice thermal conductivity. Based on the size optimization by finite element modelling, the constructed thermoelectric module yields a high conversion efficiency of 6.9% and output power density of 0.31W cm-2 under a temperature gradient of 200 K. Even more crucially, the efficiency and output power little loss after subjecting the module to 40 thermal cycles lasting for 6 days. This study demonstrates the efficient and reliable Bi2Te3-based thermoelectric modules for broad applications in low-grade heat harvest.

High-quality 2D Ruddlesden-Popper perovskites single crystal and its intrinsic spectral properties

High-quality 2D Ruddlesden-Popper perovskite (RPP) single crystals with large size are highly desirable for fundamental research and different related applications, which also is critical to understand the reported divergent spectral properties of 2D RPP. In this study, we successfully prepared crack free (n-C12H25NH3)2(CH3NH3)Pb2I7 single crystal with a lateral size up to centimeter by regulating the interlayer interaction and aggregate behavior of this layered self-assembly lattice. The RPP crystals show step-like absorbance band with a clear cutoff at 588 nm. The optical band gap was determined as 2.1 eV, which was consistent with previous theoretical calculation results, and clarified its divergent spectral properties. Moreover, a narrow photoluminescence (PL) peak at 623 nm was observed near the band edge. Time-resolved PL measurements revealed a highly reproducible decaying pathway, comprising three distinct components with lifetime as τ1 ∼ 0.57, τ2 ∼ 2.33 ns and τ3 ∼ 11.40 ns respectively. This crystal has demonstrated remarkable long-term chemical stability under ambient conditions.