Stacking Of Monolayers Research Articles

Evidence for moiré excitons in van der Waals heterostructures.

Recent advances in the isolation and stacking of monolayers of van der Waals materials have provided approaches for the preparation of quantum materials in the ultimate two-dimensional limit1,2. In van der Waals heterostructures formed by stacking two monolayer semiconductors, lattice mismatch or rotational misalignment introduces an in-plane moiré superlattice3. It is widely recognized that the moiré superlattice can modulate the electronic band structure of the material and lead to transport properties such as unconventional superconductivity4 and insulating behaviour driven by correlations5-7; however, the influence of the moiré superlattice on optical properties has not been investigated experimentally. Here we report the observation of multiple interlayer exciton resonances with either positive or negative circularly polarized emission in a molybdenum diselenide/tungsten diselenide (MoSe2/WSe2) heterobilayer with a small twist angle. We attribute these resonances to excitonic ground and excited states confined within the moiré potential. This interpretation is supported by recombination dynamics and by the dependence of these interlayer exciton resonances on twist angle and temperature. These results suggest the feasibility of engineering artificial excitonic crystals using van der Waals heterostructures for nanophotonics and quantum information applications.

Impact of the stacking sequence on the bandgap and luminescence properties of bulk, bilayer, and monolayer hexagonal boron nitride

We examine the effects of stacking sequence and number of layers on the electronic and luminescence properties of hexagonal boron nitride (h-BN) structures with first-principles calculations based on density functional and many-body perturbation theory. We explored the variations of the magnitude and character (direct or indirect) of the quasiparticle bandgap and interband optical matrix elements for bulk, bilayer, and monolayer stacking polytypes. Although the fundamental gap for most structures is indirect, phonon-assisted transitions are strong (typically 600 times stronger than bulk Si) and enable efficient deep-ultraviolet (UV) luminescence. The polarization of the emitted light is transverse electric, which facilitates light extraction perpendicularly to the h-BN basal plane. Random stacking in turbostratic BN breaks the crystal symmetry and enables optical transitions across the quasi-direct bandgap, albeit with a weak matrix element. Our results demonstrate that h-BN is a promising material for efficient deep-UV light emitters.

Correction to "Toward a Mechanistic Understanding of Vertical Growth of van der Waals Stacked 2D Materials: A Multiscale Model and Experiments".

Vertical stacking of monolayers via van der Waals (vdW) interaction opens promising routes toward engineering physical properties of two-dimensional (2D) materials and designing atomically thin devices. However, due to the lack of mechanistic understanding, challenges remain in the controlled fabrication of these structures via scalable methods such as chemical vapor deposition (CVD) onto substrates. In this paper, we develop a general multiscale model to describe the size evolution of 2D layers and predict the necessary growth conditions for vertical (initial + subsequent layers) versus in-plane lateral (monolayer) growth. An analytic thermodynamic criterion is established for subsequent layer growth that depends on the sizes of both layers, the vdW interaction energies, and the edge energy of 2D layers. Considering the time-dependent growth process, we find that temperature and adatom flux from vapor are the primary criteria affecting the self-assembled growth. The proposed model clearly demonstrates th...

Direct Measurement of the Magnitude of the van der Waals Interaction of Single and Multilayer Graphene

Vertical stacking of monolayers via van der Waals (vdW) assembly is an emerging field that opens promising routes toward engineering physical properties of two-dimensional materials. Industrial exploitation of these engineering heterostructures as robust functional materials still requires bounding their measured properties so as to enhance theoretical tractability and assist in experimental designs. Specifically, the short-range attractive vdW forces are responsible for the adhesion of chemically inert components and are recognized to play a dominant role in the functionality of these structures. Here, we reliably quantify the strength of ambient vdW forces in terms of an effective Hamaker coefficient for chemical vapor deposition-grown graphene and show how it scales by a factor of two or three from single to multiple layers on standard supporting surfaces such as copper or silicon oxide. Furthermore, direct measurements on freestanding graphene provide the means to discern the interplay between the vdW potential of graphene and its supporting substrate. Our results demonstrated that the underlying substrates could be controllably exploited to enhance or reduce the vdW force of graphene surfaces. We interpret the physical phenomena in terms of a Lifshitz theory-based analytical model.

Suppressed topological phase transitions due to nonsymmorphism in SnTe stacking

We combine first principles calculations with a group theory analysis to investigate topological phase transitions in the stacking of SnTe monolayers. We show that distinct finite stacking yields different symmetry-imposed degeneracy, which dictates the hybridization properties of opposite surface states. For SnTe aligned along the [001] direction, an (even) odd number of monolayers yields a (non)symmorphic space group. For the symmorphic case, the hybridization of surface states lead to band inversions and topological phase transitions as the sample height is reduced. In contrast, for a nonsymmorphic stacking, an extra degeneracy is guaranteed by symmetry, thus avoiding the hybridization and topological phase transitions, even in the limit of a few monolayers. Our group theory analysis provide a clear picture for this phenomenology and matches well the first principles calculations.

TMDC 2D Materials Synthesis via Two Steps Solution Process at Low Temperature

In nanoelectronics and optoelectronics, two-dimensional transition metal dichalcogenides (2D TMDC) analogous to graphene have drawn considerable attention due to their electrical and innate band gap characteristics. Among them, MoS2 and WS2 show unique properties; direct and indirect band gap of 1.8 eV and 1.2 eV, respectively, depending on the monolayer stacking states. Thin layered WS2 composed of a S-W-S sandwich crystalline with a van der Waals, possessed the coupled spin and valley physics, high photoluminescence efficiency, and composited layered materials with other 2D for many applications. Most studies on 2D TMDC have been focused on the chemical synthesis using chemical vapor deposition (CVD) and mechanical methods like exfoliated flakes by taping or in liquid. In contrast, large scale synthesis of WS2 via solution-process is rare to find. Here, we have prepared new synthetic route combining solution coating and CVD process together. The solution of sodium tungstate soulution and hydrizene hydrate with sodium thiosulphate was coated on the silicon wafer. The coated films from dip coating and spin coating were treated in the CVD with different paramerters to obtain WS2 crystal structures. The temperature and coating conditions were modified to obtain uniform wafer-scale films. The average of 50 um size WS2 crystals with triangle shapes could be obtained at the low temperatures of 700oC and above with sample positions in the CVD.

Electronic structure, optical and photocatalytic performance of SiC-MX2 (M = Mo, W and X = S, Se) van der Waals heterostructures.

The stacking of monolayers in the form of van der Waals heterostructures is a useful strategy for band gap engineering and the control of dynamics of excitons for potential nano-electronic devices. We performed first-principles calculations to investigate the structural, electronic, optical and photocatalytic properties of the SiC-MX2 (M = Mo, W and X = S, Se) van der Waals heterostructures. The stability of most favorable stacking is confirmed by calculating the binding energy and phonon spectrum. SiC-MoS2 is found to be a direct band gap type-II semiconducting heterostructure. Moderate in-plane tensile strain is used to achieve a direct band gap with type-II alignment in the SiC-WS2, SiC-MoSe2 and SiC-WSe2 heterostructures. A difference in the ionization potential of the corresponding monolayers and interlayer charge transfer further confirmed the type-II band alignment in these heterostructures. Furthermore, the optical behaviour is investigated by calculation of the absorption spectra in terms of ε2(ω) of the heterostructures and the corresponding monolayers. The photocatalytic response shows that the SiC-Mo(W)S2 heterostructures can oxidize H2O to O2. An enhanced photocatalytic performance with respect to the parent monolayers makes the SiC-Mo(W)Se2 heterostructures promising candidates for water splitting.

Toward a Mechanistic Understanding of Vertical Growth of van der Waals Stacked 2D Materials: A Multiscale Model and Experiments.

Vertical stacking of monolayers via van der Waals (vdW) interaction opens promising routes toward engineering physical properties of two-dimensional (2D) materials and designing atomically thin devices. However, due to the lack of mechanistic understanding, challenges remain in the controlled fabrication of these structures via scalable methods such as chemical vapor deposition (CVD) onto substrates. In this paper, we develop a general multiscale model to describe the size evolution of 2D layers and predict the necessary growth conditions for vertical (initial + subsequent layers) versus in-plane lateral (monolayer) growth. An analytic thermodynamic criterion is established for subsequent layer growth that depends on the sizes of both layers, the vdW interaction energies, and the edge energy of 2D layers. Considering the time-dependent growth process, we find that temperature and adatom flux from vapor are the primary criteria affecting the self-assembled growth. The proposed model clearly demonstrates the distinct roles of thermodynamic and kinetic mechanisms governing the final structure. Our model agrees with experimental observations of various monolayer and bilayer transition metal dichalcogenides grown by CVD and provides a predictive framework to guide the fabrication of vertically stacked 2D materials.

Structure and Stability of Hydrolysis Reaction Products of MgO Nanoparticles Leading to the Formation of Brucite

The bottom-up formation of MgxOy(OH)z nanoparticles leading to Mg(OH)2 nanoparticles was modeled in two steps by using an evolutionary global optimization approach: (1) the formation of small MgnOm+nH2m clusters via the hydrolysis of (MgO)n and (2) the formation of multilayered (Mg(OH)2)n clusters via monolayer stacking. The sheet-like (Mg(OH)2)n structures were predicted as the energetically favorable reaction products for the (MgO)n + nH2O reaction, whereas more compact structures were found to dominate for the products of (MgO)n + mH2O, m < n. The stepwise hydrolysis reactions most likely follow the compact reaction path until the crossover point is reached. Multistep structural rearrangements are required for the conversion between the compact products and the sheet-like products even after the crossover point. The protective shell formed by the hydroxyl groups may inhibit the further hydrolysis reaction of the compact products, even though the hydrolysis reactions are both exothermic and exergonic; s...

Cell sheet engineering for integrating functional tissue in vivo: Successes and challenges

Abstract

Reprint of: Optical properties of wurtzite GaN/AlN quantum dots grown on non-polar planes: The effect of stacking faults in the reduction of the internal electric field

The optical emission of non-polar GaN/AlN quantum dots has been investigated. The presence of stacking faults inside these quantum dots is evidenced in the dependence of the photoluminescence with temperature and excitation power. A theoretical model for the electronic structure and optical properties of non-polar quantum dots, taking into account their realistic shapes, is presented which predicts a substantial reduction of the internal electric field but a persisting quantum confined Stark effect, comparable to that of polar GaN/AlN quantum dots. Modeling the effect of a 3 monolayer stacking fault inside the quantum dot, which acts as zinc-blende inclusion into the wurtzite matrix, results in an additional 30% reduction of the internal electric field and gives a better account of the observed optical features.

Band Gap Engineering of Two-Dimensional Nitrogene.

In our previous study, we have predicted the novel two-dimensional honeycomb monolayers of pnictogen. In particular, the structure and properties of the honeycomb monolayer of nitrogen, which we call nitrogene, are very unusual. In this paper, we make an in-depth investigation of its electronic structure. We find that the band structure of nitrogene can be engineered in several ways: controlling the stacking of monolayers, application of biaxial tensile strain, and application of perpendicular electric field. The band gap of nitrogene is found to decrease with the increasing number of layers. The perpendicular electric field can also reduce the band gap when it is larger than 0.18 V/Å, and the gap closes at 0.35 V/Å. A nearly linear dependence of the gap on the electric field is found during the process. Application of biaxial strain can decrease the band gap as well, and eventually closes the gap. After the gap-closing, we find six inequivalent Dirac points in the Brillouin zone under the strain between 17% and 28%, and the nitrogene monolayer becomes a Dirac semimetal. These findings suggest that the electronic structure of nitrogene can be modified by several techniques, which makes it a promising candidate for electronic devices.

Conductive Hybrid Crystal Composed from Polyoxomolybdate and Deprotonatable Ionic-Liquid Surfactant.

A polyoxomolybdate inorganic-organic hybrid crystal was synthesized with deprotonatable ionic-liquid surfactant. 1-dodecylimidazolium cation was employed for its synthesis. The hybrid crystal contained δ-type octamolybdate (Mo8) isomer, and possessed alternate stacking of Mo8 monolayers and interdigitated surfactant bilayers. The crystal structure was compared with polyoxomolybdate hybrid crystals comprising 1-dodecyl-3-methylimidazolium surfactant, which preferred β-type Mo8 isomer. The less bulky hydrophilic moiety of the 1-dodecylimidazolium interacted with the δ-Mo8 anion by N–H···O hydrogen bonds, which presumably induced the formation of the δ-Mo8 anion. Anhydrous conductivity of the hybrid crystal was estimated to be 5.5 × 10−6 S·cm−1 at 443 K by alternating current (AC) impedance spectroscopy.

Optical properties of wurtzite GaN/AlN quantum dots grown on non-polar planes: The effect of stacking faults in the reduction of the internal electric field

The optical emission of non-polar GaN/AlN quantum dots has been investigated. The presence of stacking faults inside these quantum dots is evidenced in the dependence of the photoluminescence with temperature and excitation power. A theoretical model for the electronic structure and optical properties of non-polar quantum dots, taking into account their realistic shapes, is presented which predicts a substantial reduction of the internal electric field but a persisting quantum confined Stark effect, comparable to that of polar GaN/AlN quantum dots. Modeling the effect of a 3 monolayer stacking fault inside the quantum dot, which acts as zinc-blende inclusion into the wurtzite matrix, results in an additional 30% reduction of the internal electric field and gives a better account of the observed optical features.

Atomic structures of a liquid-phase bonded metal/nitride heterointerface.

Liquid-phase bonding is a technologically important method to fabricate high-performance metal/ceramic heterostructures used for power electronic devices. However, the atomic-scale mechanisms of how these two dissimilar crystals specifically bond at the interfaces are still not well understood. Here we analyse the atomically-resolved structure of a liquid-phase bonded heterointerface between Al alloy and AlN single crystal using aberration corrected scanning transmission electron microscopy (STEM). In addition, energy-dispersive X-ray microanalysis, using dual silicon drift X-ray detectors in STEM, was performed to analyze the local chemistry of the interface. We find that a monolayer of MgO is spontaneously formed on the AlN substrate surface and that a polarity-inverted monolayer of AlN is grown on top of it. Thus, the Al alloy is bonded with the polarity-inverted AlN monolayer, creating a complex atomic-scale layered structure, facilitating the bonding between the two dissimilar crystals during liquid-phase bonding processes. Density-functional-theory calculations confirm that the bonding stability is strongly dependent on the polarity and stacking of AlN and MgO monolayers. Understanding the spontaneous formation of layered transition structures at the heterointerface will be key in fabricating very stable Al alloy/AlN heterointerface required for high reliability power electronic devices.

Resonant surface plasmon-exciton interaction in hybrid MoSe2@Au nanostructures.

In this work we investigate the interaction between plasmonic and excitonic resonances in hybrid MoSe2@Au nanostructures. The latter were fabricated by combining chemical vapor deposition of MoSe2 atomic layers, Au disk processing by nanosphere lithography and a soft lift-off/transfer technique. The samples were characterized by scanning electron and atomic force microscopy. Their optical properties were investigated experimentally using optical absorption, Raman scattering and photoluminescence spectroscopy. The work is focused on a resonant situation where the surface plasmon resonance is tuned to the excitonic transition. In that case, the near-field interaction between the surface plasmons and the confined excitons leads to interference between the plasmonic and excitonic resonances that manifests in the optical spectra as a transparency dip. The plasmonic-excitonic interaction regime is determined using quantitative analysis of the optical extinction spectra based on an analytical model supported by numerical simulations. We found that the plasmonic-excitonic resonances do interfere thus leading to a typical Fano lineshape of the optical extinction. The near-field nature of the plasmonic-excitonic interaction is pointed out experimentally from the dependence of the optical absorption on the number of monolayer stacks on the Au nanodisks. The results presented in this work contribute to the development of new concepts in the field of hybrid plasmonics.

Interlayer orientation-dependent light absorption and emission in monolayer semiconductor stacks

Two-dimensional stacks of dissimilar hexagonal monolayers exhibit unusual electronic, photonic and photovoltaic responses that arise from substantial interlayer excitations. Interband excitation phenomena in individual hexagonal monolayer occur in states at band edges (valleys) in the hexagonal momentum space; therefore, low-energy interlayer excitation in the hexagonal monolayer stacks can be directed by the two-dimensional rotational degree of each monolayer crystal. However, this rotation-dependent excitation is largely unknown, due to lack in control over the relative monolayer rotations, thereby leading to momentum-mismatched interlayer excitations. Here, we report that light absorption and emission in MoS2/WS2 monolayer stacks can be tunable from indirect- to direct-gap transitions in both spectral and dynamic characteristics, when the constituent monolayer crystals are coherently stacked without in-plane rotation misfit. Our study suggests that the interlayer rotational attributes determine tunable interlayer excitation as a new set of basis for investigating optical phenomena in a two-dimensional hexagonal monolayer system.

Relationship between monolayer stacking faults and twins in nanocrystals

A density functional theory–phase field dislocation dynamics model is used to study stress-induced emission of defects from grain boundaries in nanoscale face-centered cubic (fcc) crystals under ambient conditions. The propensity for stable stacking fault formation and the maximum grain size DSF below which a stacking fault is stable are found to scale inversely with the normalized intrinsic stacking fault energy, γI/μb, where μ is the shear modulus and b is the value of the Burgers vector. More significantly, we reveal that a grain size smaller than DSF is a necessary but not sufficient condition for twinning. Rather, it is shown that deformation twinning additionally scales with ΔSFE=(γU-γI)/μb, where γU is the unstable stacking fault energy. The combined effects of the material γ-surface and nanograin size for several pure fcc metals are presented in the form of a twinnability map. The findings may provide useful information in controlling nanostructures for improved mechanical performance.

Thickness and rotational effects in simulated HRTEM images of graphene on hexagonal boron nitride.

Recent studies have shown that when graphene is placed on a thin hexagonal boron nitride (h-BN) substrate, unlike when it is placed on a typical SiO2 surface, it can closely approach the ideal carrier mobility observed in suspended graphene samples. This study further examines the epitaxial relationship between graphene and h-BN substrate with high-resolution transmission electron microscopy simulation. Virtual monolayer and multilayer stacks of h-BN were produced with a monolayer of graphene on top, on bottom, and in between h-BN layers, in order to study this interface. Once the simulations were performed, the phase contrast image and Moiré pattern created by this heterostack were analyzed for local and global intensity minima and maxima. In addition, h-BN substrate thickness and rotations between h-BN and graphene were probed and analyzed. The simulated images produced in this work will be used to help understand subsequent transmission electron microscopy images and electron energy-loss studies.

Spectroscopic signatures for interlayer coupling in MoS2-WSe2 van der Waals stacking.

Stacking of MoS2 and WSe2 monolayers is conducted by transferring triangular MoS2 monolayers on top of WSe2 monolayers, all grown by chemical vapor deposition (CVD). Raman spectroscopy and photoluminescence (PL) studies reveal that these mechanically stacked monolayers are not closely coupled, but after a thermal treatment at 300 °C, it is possible to produce van der Waals solids consisting of two interacting transition metal dichalcogenide (TMD) monolayers. The layer-number sensitive Raman out-of-plane mode A(2)1g for WSe2 (309 cm(-1)) is found sensitive to the coupling between two TMD monolayers. The presence of interlayer excitonic emissions and the changes in other intrinsic Raman modes such as E″ for MoS2 at 286 cm(-1) and A(2)1g for MoS2 at around 463 cm(-1) confirm the enhancement of the interlayer coupling.