Low-dimensional luminescent materials have been broadly investigated due to their distinctive optical and optoelectronic properties, which originate from the quantum size effect[
Journal of Semiconductors, Volume. 44, Issue 1, 011001(2023)
Interface engineering in two-dimensional heterostructures towards novel emitters
Two-dimensional (2D) semiconductors have captured broad interest as light emitters, due to their unique excitonic effects. These layer-blocks can be integrated through van der Waals assembly,i.e., fabricating homo- or heterojunctions, which show novel emission properties caused by interface engineering. In this review, we will first give an overview of the basic strategies that have been employed in interface engineering, including changing components, adjusting interlayer gap, and tuning twist angle. By modifying the interfacial factors, novel emission properties of emerging excitons are unveiled and discussed. Generally, well-tailored interfacial energy transfer and charge transfer within a 2D heterostructure cause static modulation of the brightness of intralayer excitons. As a special case, dynamically correlated dual-color emission in weakly-coupled bilayers will be introduced, which originates from intermittent interlayer charge transfer. For homobilayers and type Ⅱ heterobilayers, interlayer excitons with electrons and holes residing in neighboring layers are another important topic in this review. Moreover, the overlap of two crystal lattices forms moiré patterns with a relatively large period, taking effect on intralayer and interlayer excitons. Particularly, theoretical and experimental progresses on spatially modulated moiré excitons with ultra-sharp linewidth and quantum emission properties will be highlighted. Moiré quantum emitter provides uniform and integratable arrays of single photon emitters that are previously inaccessible, which is essential in quantum many-body simulation and quantum information processing. Benefiting from the optically addressable spin and valley indices, 2D heterostructures have become an indispensable platform for investigating exciton physics, designing and integrating novel concept emitters.Two-dimensional (2D) semiconductors have captured broad interest as light emitters, due to their unique excitonic effects. These layer-blocks can be integrated through van der Waals assembly,i.e., fabricating homo- or heterojunctions, which show novel emission properties caused by interface engineering. In this review, we will first give an overview of the basic strategies that have been employed in interface engineering, including changing components, adjusting interlayer gap, and tuning twist angle. By modifying the interfacial factors, novel emission properties of emerging excitons are unveiled and discussed. Generally, well-tailored interfacial energy transfer and charge transfer within a 2D heterostructure cause static modulation of the brightness of intralayer excitons. As a special case, dynamically correlated dual-color emission in weakly-coupled bilayers will be introduced, which originates from intermittent interlayer charge transfer. For homobilayers and type Ⅱ heterobilayers, interlayer excitons with electrons and holes residing in neighboring layers are another important topic in this review. Moreover, the overlap of two crystal lattices forms moiré patterns with a relatively large period, taking effect on intralayer and interlayer excitons. Particularly, theoretical and experimental progresses on spatially modulated moiré excitons with ultra-sharp linewidth and quantum emission properties will be highlighted. Moiré quantum emitter provides uniform and integratable arrays of single photon emitters that are previously inaccessible, which is essential in quantum many-body simulation and quantum information processing. Benefiting from the optically addressable spin and valley indices, 2D heterostructures have become an indispensable platform for investigating exciton physics, designing and integrating novel concept emitters.
Introduction
Low-dimensional luminescent materials have been broadly investigated due to their distinctive optical and optoelectronic properties, which originate from the quantum size effect[
Thanks to the atomically flat surface and the weak van der Waals (vdW) force, vertically stacked TMDs have provided a fruitful platform for synthesizing 2D luminescent materials with enormous flexibility. Chemical vapor deposition[
We will mainly cover several factors that are important in engineering the interfacial structures of 2D heterostructures, including the electronic structure of each monolayer, the relative band alignment, the interfacial gap as well as the twist angle. Various interface interactions in heterostructures can modulate the intralayer exciton by energy transfer and charge transfer. A specific stacking configuration, such as a twist angle (close to 0° or 60°), will lead to interlayer hybridization, thus the bandgaps of 2D bilayers might evolve from direct into indirect. At the same time, new excitonic states emerge, such as the interlayer excitons with electrons and holes residing in different layers. In addition, the superposition of atomic lattices in a 2D bilayer can produce large-scale periodicity,i.e., the moiré pattern. Moiré pattern arises from the lattice mismatch and/or the twist angle of the two component monolayers. The periodic moiré superlattice introduces a new periodic potential, which has been uncovered to trap intralayer and interlayer excitons, forming arrayed 2D emitters or even arrayed quantum emitters. Based on the huge progresses on twisted heterobilayers during recent years, twisted optoelectronics has grown to be a main stream of optoelectronics.
In this review, firstly, we introduce the basic strategies used to engineer the interface which can modulate the luminesce features of 2D emitters. Secondly, we discuss theoretical and experimental demonstration of emergent emissions in terms of intralayer and interlayer excitons, respectively. Finally, we summarize the advance of 2D emitters and emphasize their unique features. We also have a practical outlook on the applications. We hope this review can stimulate new strategies for designing novel 2D emitters and promote the development of optical information technology and optoelectronic devices.
Interface engineering of 2D heterostructures: basic strategies
Components
The intrinsic energy band structures and electronic states of components for fabricating heterostructures are basic determinants for the properties of an assembled structure. During the past decade, various 2D materials with different electronic structures have been used as components of heterostructures, including semiconductors, semi-metals, and insulators[
Here, we focus on the semiconducting MX2 compounds with M being Mo or W and X being S, Se or Te. The MX2 compounds have been broadly studied not only because of their stability at ambient conditions, but also benefited by their unique excitonic and valleytronic features. The band structures of TMD monolayers have the extrema at the K and K′ corners of the hexagonal Brillouin zone, which have distinctive spin and valley indices (
Figure 1.(Color online) Features of lattice and band structures of TMD monolayers and heterostructures. (a) 2D hexagonal lattice representing monolayer TMDs.Ri are the vectors connecting nearest metal atoms. (b) Schematic drawing of valley-contrasting splitting at the K and K′ valley of the band structure at the band edges. (c) Spin and valley coupled optical selection rules. K (K′) valley couple toσ+ (σ−) circularly polarized light[15]. Copyright 2012, American Physical Society. (d) Band structures calculated with exchange-correlation energy functions, and the corresponding Brillouin zone (the top right)[31]. Copyright 2013, American Physical Society. (e) Calculated band-edge energies for various TMDs based on ab initio density functional theory calculation using the Perdew-Burke-Ernzerhof functional (blue) and G0W0 (pink), respectively[32]. Copyright 2016, Institute of Physics.
Homobilayers can be either prepared from direct exfoliation from the bulk crystals, or by stacking two monolayers after exfoliation. These two methods lead to disparate optical features corresponding to distinct interband transitions, since the interlayer hybridization between two identical monolayers is significant and highly sensitive to interlayer coupling conditions (
TMD monolayers (and their alloys[
Interlayer gap
In 2D bilayers, besides the band offset of the components, the interlayer coupling at the interface[
Figure 2.(Color online) Interlayer gap dependence of energy and charge transfer at the 2D interface. (a) The energies of the band-edge states as a function of the interlayer gap in MoS2/WS2 heterostructures[41]. Copyright 2013, American Physical Society. (b, c) Schemes of Fӧrster and Dexter energy transfer mechanism (left), and schemes (right) of representative TMD heterobilayers showing the direction of Fӧrster and Dexter energy transfer[45,46]. Copyright 2016, American Chemical Society (b) and 2019, American Chemical Society (c). (d) Scheme of WSe2/WS2 heterostructures with different BN intermediate layers. (e) Charge transfer kinetics for heterostructures with different BN layer thicknesses[47]. Copyright 2020, American Chemical Society.
The spin singlet ‘bright’ excitons in TMD monolayers have in-plane dipole moments. When the two layers are efficiently coupled in the heterostructure, the Förster energy transfer takes place, with the exchange energy across the interlayer gap by dipole-dipole interaction (
On another hand, interlayer charge transfer processes profoundly affect the features of each individual component and the heterostructure as a whole. The interlayer gap can efficiently affect the strength of the interlayer coupling and is an important determinant for interlayer charge transfer[
Twist angle
Besides component and interlayer gap, the third basic degree of freedom in interface engineering is twist angle. Following discussions in Section 2.2, it shall be noted that the interlayer distance of stacked 2D heterostructures can slightly vary under different relative orientation (twist) angle between the two monolayers (
Figure 3.(Color online) Twist-angle-dependent features of the 2D interface. (a) Twist-angle dependence of the average layer distance of the WS2/WSe2 heterobilayer based on AA-stacking (blue) and AB-stacking (red) configurations, calculated by dispersion-corrected DFT. (b) Calculated K–K (blue) and Γ–K (red) transition energies for AB-stacked heterobilayers with different twist angles[56]. Copyright 2021, Oxford University Press. (c–e) Transient kinetics in the MoS2 layer for WSe2/MoS2 heterobilayers with three different twist angles, including a single exponential rise (CT: charge transfer process) and a single exponential decay (CR: charge recombination process). (f) Interfacial charge transfer lifetime and charge recombination lifetime as a function of Δϕ (bottom axis) and momentum change (top axis) in WSe2/MoS2 heterojunctions. Inset shows scheme illustrating the twist angle in momentum space[42]. Copyright 2017, American Chemical Society.
Intralayer exciton emission modulated by interfacial engineering
Because of the significant excitonic effects caused by the increased Coulomb interaction, TMD monolayers exhibit a variety of unique exciton states, which dominate their optical properties. In 2D bilayers, the intralayer excitons at the K and K′ valleys within each layer are similar to the individual monolayers but accompanied by additional interactions from the neighboring material[
2D emitters with boosted emission
Exfoliated monolayer TMDs usually have a limited quantum yield[
In a 2D heterobilayer, because of large oscillator strength and parallel dipole orientation in two layers, interlayer energy transfer based on dipole-dipole interaction could realize modulation of emission from a 2D emitter pair. Edaet al.[
Figure 4.(Color online) Enhanced emission by interfacial interaction in TMD heterostructures. (a, b) Förster energy transfer in MoSe2/WS2 heterobilayers, including photoluminescence excitation intensity map at 78 K where the color scale represents emission intensity (a) and photoluminescence spectra for MoSe2 emission from different heterostructures excited in resonance with A exciton of WS2 (W-A) at 2.00 eV at room temperature (b)[45]. Copyright 2016, American Chemical Society. (c, d) Trion-mediated Förster energy transfer and optical gating effect in WS2/hBN/MoSe2 heterostructures, including the scheme of trion-mediated energy transfer and optical gating effect (c), and photoluminescence spectra at different positions of heterostructures (d)[48]. Copyright 2020, American Chemical Society. (e, f) Dexter energy transfer in WSe2/MoTe2 heterostructures, including photoluminescence spectra of different domains (e) and schematic depiction of near-unity energy transfer of both bright and dark excitons from WSe2 to MoTe2 (f)[46]. Copyright 2019, American Chemical Society. (g, h) Enhanced emission of MoSe2/MoS2 heterostructures by interlayer charge transfer, including a schematic of the band alignment describing the transfer of electrons and holes (g) and photoluminescence intensity maps of the MoSe2/MoS2 with one or two layers h-BNs at the interface. Scale bars are 5μm[72]. Copyright 2016, American Chemical Society.
Interlayer charge transfer is another extensively studied interaction with emerging optical and electrical properties. For semiconductors, the injection of electrons and holes will introduce extra free charges. When these extra charges interact with excitons, they will bind to form charged excitons, called trions[
Blinking 2D emitters
Fluorescence intermittency, namely fluorescence blinking, has been extensively studied in zero-dimensional systems including quantum dots and molecules[
Figure 5.(Color online) Fluorescence blinking of 2D emitters. (a) Optical image (left) and fluorescence images (three panels on the right) of a WS2/MoSe2 heterobilayer showing bright, neutral, and dark emission state of WS2 at the heterobilayer region. (b) Spectra of WS2 and MoSe2, and optical image of WS2/MoSe2 heterobilayer (inset). (c) Time-dependent intensity of WS2 (red curve) and MoSe2 (blue curve) emission from the spectra shown in (b)[36]. Copyright 2017, The Authors. (d) Capture of interfacial photocurrent in a blinking WSe2/WS2 circuit at zero bias. The photocurrent and fluorescence intensities are recorded synchronously[39]. Copyright 2021, American Chemical Society.
Intralayer moiré excitons
Owing to the similar hexagonal lattices of TMD monolayers, the superposition of two monolayers with small mismatches forms a superlattice with a relatively larger periodicity as compared to the pristine lattice constant, called the moiré superlattice. The large periodic lattices can dramatically modify the electronic states and create a new periodic potential for carriers and excitons, namely moiré potential[
Figure 6.(Color online) Intralayer moiré excitons in TMD heterostructures. (a) Left: schematic illustration of the moiré superlattice with a twist angleθ and moiré potential periodaM. Right: the moiré Brillouin zone corresponding to the moiré unit cell. (b) Schematic diagram of excitons trapped by the periodic moiré potential. (c) Observation of moiré excitons in twisted WS2/WS2 homobilayer superlattices. (d) Linear energy distribution of different peaks fitted by the Lorentzian function[87]. Copyright 2022, American Physical Society. (e, f) Excitons in a reconstructed moiré potential. (e) Scanning electron microscopy image of twisted WSe2 bilayer showing a reconstructed moiré pattern[90]. Copyright 2021, Wiley-VCH GmbH. (f) Photoluminescence spectra at five positions in a WSe2 homobilayer[91]. Copyright 2022, Royal Society of Chemistry.
Interlayer exciton emission modulated by interfacial engineering
Most combinations of common TMD monolayers (e.g., WS2, MoS2, WSe2, and MoSe2) feature ultrafast interlayer charge transfer, causing electrons and holes to separate and reside in different layers, respectively. The Coulomb interactions between adjacent layers allow the generation of electron-hole pairs with out-of-plane electrical dipole moments, to form the interlayer excitons. Lots of interest has been attracted into the unique properties of interlayer excitons like their long lifetime[
Interlayer excitons
The efficient formation of interlayer excitons requires certain prerequisites: suitable interlayer gap and proper twist angle between TMD monolayers in heterostructures. In type Ⅱ heterostructures, owing to the small interlayer gap that contributes to the interlayer charge transfer, the Coulomb interaction between two layers is strong enough to produce interlayer excitons, with smaller binding energy and lower emission energy compared to the intralayer excitons of both components (
Figure 7.(Color online) Emission features of interlayer excitons in TMD heterostructures. (a) Photoluminescence of WSe2 and MoSe2 monolayers and the heterobilayers[95]. Copyright 2022, Royal Society of Chemistry. (b) Interlayer exciton energies and calculated transition energies for heterobilayers with different twist angles. (c) Left: band alignment diagram. Right: the misaligned Brillouin zones of MoS2 (blue) and WSe2 (green) where both K–K and Γ–K transitions arek-space indirect[96]. Copyright 2020, Royal Society of Chemistry. (d) Intensity and (e) energy of the interlayer exciton emission versus the twist angle. The inset in (d) shows the schema of MoSe2/WSe2 heterobilayers[97]. Copyright 2017, American Chemical Society. (f, g) Spin-valley polarization of the interlayer exciton in MoSe2/WSe2 heterostructures. (f) Circular polarization-resolved photoluminescence spectra of the interlayer exciton showing the generation of strong valley polarization. (g) Spatial maps ofσ+ (left) andσ− (right) interlayer exciton photoluminescence[98]. Copyright 2016, Science.
The spin-valley information of electrons in TMD monolayers is a unique quantum index of intralayer excitons. For interlayer excitons, due to the breaking of the out-of-plane mirror symmetry, the restriction of spin conservation is no longer valid. As a result, the optical transition dipole of the spin-triplet exciton is in the same order of magnitude as that of the spin-singlet exciton[
Interlayer moiré excitons
As discussed in Section 2.3, the moiré superlattice formed by two TMD monolayers produces a periodic potential that can localize intralayer excitons. Similarly, there is also a potential landscape for interlayer excitons in the moiré superlattice (
Figure 8.(Color online) Modulated emissions of interlayer moiré excitons in TMD heterostructures. (a) A moiré superlattice formed by a MoSe2/WSe2 vertical heterostructure, showing three highlighted regions with three-fold rotational symmetry. (b) Optical selection rules of different atomic configurations in K valley. (c) Left: the moiré potential of the interlayer exciton transition, showing a local minimum and maximum at different sites. Right: spatial map of the degree of circular polarization for K-valley excitons[111]. Copyright 2021, Springer Nature. (d, e) Helicity-resolved photoluminescence spectra of trapped interlayer excitons in MoSe2/WSe2 heterobilayers with twist angles of (d) 57° and (e) 2°[112]. Copyright 2021, Royal Society of Chemistry. (f-h), Modulation of interlayer moiré excitons by strain, which changes the moiré patterns. (f, g) Piezoresponse force microscopy (PFM) images at two locations of the heterostructure subjected to stress[113]. Copyright 2021, Wiley‐VCH GmbH. (h) Excitation power-dependent emission spectra of 1D moiré exciton[114]. Copyright 2021, American Chemical Society. (i) Trapped interlayer trions in a moiré superlattice[115]. Copyright 2021, Nature.
In addition to the twist angle that determines the superlattice geometry, in-plane and out-of-plane strain is another decisive factor to influence the periodicity of moiré potentials. The spatially inhomogeneous superlattice structure with different periodicity induced by strain exhibits different emission characteristics in different regions[
Moiré quantum emitters
Quantum emitters, known as “single-photon emitters”, are crucial for photon-based quantum information processing in quantum technologies. In TMD monolayers, the localized excitons trapped by defects can show the single-photon nature with narrow line widths of around 100μeV and strong photon antibunching[
Figure 9.(Color online) Quantum emission from moiré excitons. (a) Nano-patterned quantum emitter arrays. Left: distribution of oscillator strength of the interlayer exciton. Right: nanodot confinements atA points, realizing a periodic array of excitonic quantum emitters. Three high-symmetry points corresponding to the moiré superlattices are labeled asA,B, andC, respectively[109]. Copyright 2017, Science. (b) Normalized emission spectra excited by photon energy of 1.55 eV with different excitation power densities[118]. Copyright 2021, American Chemical Society. (c–f) Quantum features of moiré interlayer excitons. (c) Photoluminescence spectrum of MoSe2/WSe2 moiré superlattices at 4 K. (d) Time-resolved normalized PL intensity of the single emitter fitted by single exponential decay fit (red line), which reveals a lifetime of 12.1 ± 0.3 ns. (e) Integrated PL intensity of the same single emission peak (1.401 eV) at different excitation powers. (f) Photon antibunching revealed by second-order photon correlation statistics (g(2)(τ)) of emission with the experimental data (red solid line) and the Poissonian interval error (red shadowed area)[119]. Copyright 2020, Science.
Summary and outlook
In summary, we have reviewed progress on novel van der Waals emitters based on well-designed homo- or heterojunctions, representative observations are summarized in
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Hua Li, Jinyang Ling, Jiamin Lin, Xin Lu, Weigao Xu. Interface engineering in two-dimensional heterostructures towards novel emitters[J]. Journal of Semiconductors, 2023, 44(1): 011001
Category: Articles
Received: Oct. 9, 2022
Accepted: --
Published Online: Feb. 22, 2023
The Author Email: Xu Weigao (xuwg@nju.edu.cn)