Integration of 2D Materials with Photonic Nanostructures

Two-dimensional (2D) materials, such as graphene and transition-metal dichalcogenide monolayers, have unique properties that are distinctly different from those of their bulk counterparts, and hopefully possess a wide range of applications in 2D semiconductor device. Structural defects are known to have profound influences on the properties of crystalline materials; thus, correlating the defect structure with local properties in 2D material is of fundamental importance. However, electron microscopy studies of 2D materials on an atomic scale have become a challenge as most of these materials are susceptible to electron beam irradiation damage under high voltage and high dose experimental conditions. The development of low voltage aberration-corrected scanning transmission electron microscopy (STEM) has made it possible to study 2D materials at a single atom level without damaging their intrinsic structures. In addition, controllable structural modification by using electron beam becomes feasible by controlling the electron beam-sample interaction. New nanostructures can be created and novel 2D materials can be fabricated in-situ by using this approach. In this article, we review some of our recent studies of graphene and transition-metal dichalcogenides to showcase the applications of low voltage aberration corrected STEM in 2D material research.

Achieving robust and electrically controlled valley polarization in monolayer transition metal dichalcogenides (ML-TMDs) is a frontier challenge for realistic valleytronic applications. Theoretical investigations show that the integration of 2D materials with ferroelectrics is a promising strategy; however, an experimental demonstration has remained elusive. Here, we fabricate ferroelectric field-effect transistors using a ML-WSe2 channel and an Al0.68Sc0.32N (AlScN) ferroelectric dielectric and experimentally demonstrate efficient tuning as well as non-volatile control of valley polarization. We measure a large array of transistors and obtain a maximum valley polarization of ∼27% at 80 K with stable retention up to 5400 s. The enhancement in the valley polarization is ascribed to the efficient exciton-to-trion (X-T) conversion and its coupling with an out-of-plane electric field, viz., the quantum-confined Stark effect. This changes the valley depolarization pathway from strong exchange interactions to slow spin-flip intervalley scattering. Our research demonstrates a promising approach for achieving non-volatile control over valley polarization for practical valleytronic device applications.

Towards controlled synthesis of 2D crystals by chemical vapor deposition (CVD)

Over the last decade, two-dimensional (2D) materials have drawn much attention for the next-generation electron devices, optoelectronics and bioelectronics [1, 2]. Recently, non-volatile resistance switching (NVRS) behavior has been observed in various 2D materials, including graphene oxide, functionalized MoS2 and partially degraded black phosphorus, etc. [3-5], where the resistance can be modulated between a high-resistance state (HRS) and a low-resistance state (LRS) [6]. In addition, there are several reports about NVRS in multi-layer hexagonal boron-nitride (h-BN) [7]. Although 2D materials are widely regarded as promising candidates to overcome vertical scaling obstacle in NVRS based on conventional metal-insulator-metal (MIM) structure [3], few researchers believe that single-layer 2D material can produce NVRS [8] due to excessive leakage current. Sangwan et al. discovered that grain boundaries in single-layer MoS2 can produce NVRS based on planar (horizontal) structure [9]. However, the planar structure without 3D stacking ability has the limitation of low integration density. Recently, we reported the discovery that NVRS phenomenon is accessible in a variety of single-layer transition metal dichalcogenides (TMDs) in vertical MIM structure [10, 11]. Herein, we report another 2D insulating material, single-layer h-BN, also shows stable and desirable NVRS behavior. Compared with monolayer TMDs with three atomic layers, monolayer h-BN has only one atomic layer and ~0.33 nm in thickness, which is the thinnest active layer in non-volatile resistance memory. These devices can be labelled as “atomristor”, which means the memristor effect in atomically thin nanomaterials.[12] The h-BN atomristors have been studied using a crossbar structure (Au/h-BN/Au) [See Figure a]. Figure b shows a representative I-V curve of h-BN atomristor, demonstrating forming-free switching with large on/off ratio (up to >106) and low switching voltage (down to <1V). In addition, pulse operation proves its fast switching speed (<15 ns), which is comparable to the state-of-the-art in 2D memory. Ab-initio simulation reveals that the metal ion substitution in sulfur vacancies may be related to the switching from HRS to LRS, and area scaling test result is also consistent with this conductive-bridge-like mechanism. The results of this work indicate a potential universal resistive switching behavior in 2D insulating monolayers, which is applicable to memory technology, neuromorphic computing, RF switch and flexible electronics.

Two-dimensional materials like graphene or transition metal dichalcogenides have remarkable properties, making them very attractive from a technological point of view and incredibly fun to work with. The intrinsic properties of 2D materials change drastically when going from the bulk into the true 2D limit, where they exhibit exotic quantum properties. While many groups have focused on studying and exploiting these materials, very little work has been devoted to engineering their intrinsic properties. The “all-surface” nature makes device fabrication complex, and so far, only the most conventional nanofabrication or tailoring routes have been explored. In this talk, I will present novel routes currently under exploration in our group to tailor and exploit the properties of TMDS and MOF devices based on mechanical deformation or physical nanopatterning.Also, the integration of 2D materials into superconducting circuits can lead to novel technological applications of interest for photon and radiation detectors or quantum computing.In this talk, I will present some results concerning the development of retroreflectors based on MoS2 oscillating membranes and how they can be turned into electroluminescent diodes. I will also present the tailoring of conductive channels on MoS2 FET devices. Preliminary results on lateral PN homo-junctions, memristive field-effect transistors and photonic crystal cavities will also be presented. I will present preliminary results on the integration of MOF into Hall bar structures for metrology applications. To finish, I will also present results on the integration of Graphene and MoS2 onto Superconducting nanowire single photon detectors. Figure 1

Two-dimensional (2D) materials have captured the attention of the scientific community due to the wide range of unique properties at nanometer-scale thicknesses. While significant exploratory research in 2D materials has been achieved, the understanding of 2D electronic transport and carrier dynamics remains in a nascent stage. Furthermore, because prior review articles have provided general overviews of 2D materials or specifically focused on charge transport in graphene, here we instead highlight charge transport mechanisms in post-graphene 2D materials, with particular emphasis on transition metal dichalcogenides and black phosphorus. For these systems, we delineate the intricacies of electronic transport, including band structure control with thickness and external fields, valley polarization, scattering mechanisms, electrical contacts, and doping. In addition, electronic interactions between 2D materials are considered in the form of van der Waals heterojunctions and composite films. This review concludes with a perspective on the most promising future directions in this fast-evolving field.

The valley degree of freedom in two-dimensional crystalline materials is another promising candidate for designing dissipationless information devices in addition to the spin degree of freedom. The primary challenge for the application of valley degree of freedom is to achieve a significant and controllable valley polarization. Here, we discover an electrical tunable mechanism for generating valley polarization caused by the backscattering induced by Rashba spin-orbit coupling in monolayer nanoribbon of transition-metal dichalcogenides. Since the Rashba spin-orbit coupling in monolayer transition-metal dichalcogenides can be induced by the external electric field, the valley polarization here can be dynamically controlled by means of the external gating. The results of the valley-dependent transport calculations show that a pronounced valley polarization can be generated when the external electric field-induced Rashba spin-orbit coupling is present in the central scattering region of the nanoribbon. Moreover, the efficiency and direction of the valley polarization can be controlled by tuning the Fermi energy and the strength of Rashba spin-orbit coupling. The calculated results also confirm that the valley polarization remains significant in the presence of atomic vacancy defects. This finding opens up a potential possibility for realizing electrical control of the valleytronics devices.

Two dimensional (2D) materials have become a growing subject in the last 15 years mainly due to the isolation of graphene, which created a completely different class of material based on its unique, monolayer design. Since then, various stable materials of few atoms thick are showing emerging capabilities in optical electronics and photonics. Semiconducting monolayers of transition metal dichalcogenides (TMDs) such as MoS2, Mo1-xWxS2, and WS2 exhibit direct electronic band gaps; bulk crystals display indirect band gaps. Interestingly, these 2D materials show significant light interaction over a broad bandwidth ranging from infrared to ultraviolet wavelengths. The materials allow photodetection in this bandwidth without the need of cooling, thus creating new potential for uncooled detection. In this review, we discuss various 2D materials and their interaction with light for photodetection applications.

The isolation of graphene has sparked an unprecedented world wide research activity on the topic of two-dimensional (2D) materials. However, even though graphene has a high potential for various applications, its metallic character is a significant limitation for a large variety of electron devices, starting with the conventional field effect transistor. This limitation could be overcome in the near future by the use of layered van der Waals crystals such as black phosphorus (i.e., phosphorene, which is one to few layers of black phosphorus) and also by other semiconducting 2D materials such as transition metal dichalcogenides (TMDCs) of general formula MX2, where M is the metal and X the chalcogen (S, Se and Te). For instance, phosphorene exhibits a direct band gap varying between ~ 0.3 eV for bulk crystals to ~ 2 eV for a monolayer. In layered TMDC structures, each layer typically comprises 3 atomic planes (corresponding to a thickness below 8 Å), and consists of an hexagonally-organized atomic layer of metal atoms sandwiched between two planes of chalcogen atoms, also in hexagonal configurations. M–X bonds inside each layer are covalent; however, the sandwiching chalcogen layers are linked by weak van der Waals bonds, so that a bulk crystal is easy to cleave along the chalcogen planes. As with phosphorene, most semiconducting TMDC materials also see their band gap increasing as thickness decreases and they switch from indirect to direct band gap for a monolayer. To date, the most studied semiconductor TMDCs are MoS2 and WS2. Because they are atomically thin, 2D materials are particularly well suited for flexible electronics applications. After a brief description of the major features of phosphorene and TMDCs (crystal structures, relevant electronic properties as a function of thickness …), the talk will highlight recent results concerning field effect transistor characteristics. In particular, carrier mobility values as high as 5000 cm2/Vs have been measured in phosphorene films. Since local substitutional-type doping cannot be used in 2D materials, there is a general contacting problem (Schottky barrier formation), which is of paramount importance for device applications. In particular, two types of contacts can be formed: the top contact and the edge contact, which behave differently. Generally speaking, the semiconductor thickness is much smaller than the depletion length at the contact, which is an intriguing and novel situation. In the second part of the talk, various synthesis methods will be presented and discussed, particularly in view of their possible use in the field of large area electronics. For most devices fabricated so far, the 2D layers were obtained by exfoliation of bulk crystals. However, recent progress in synthesis include molecular beam epitaxy, controlled chemical vapour deposition and vapour phase transport. Those various approaches will be discussed, as well as the newly-introduced atomic layer deposition (ALD) process. As most 2D materials are grown on a separate substrate, the transfer problem will be highlighted, particularly concerning phosphorene which is highly hygroscopic, and sensitive to the presence of light. The presentation will be concluded by some perspectives concerning the industrialization of 2D materials.

The field of valleytronics, which exploits the valley degree of freedom in two-dimensional (2D) materials, has emerged as a promising frontier in next-generation electronic and photonic devices. In this context, a valley refers to an energy extremum in the electronic band structure of a material, which can serve as a discrete quantum number — akin to charge or spin — for information encoding. Because many 2D materials possess two inequivalent valleys in momentum space, they can naturally represent binary logic states, making them attractive for low-power electronics and quantum computing. This topical review explores the valley-dependent Berry phase effects and their significant role in various valleytronic applications. We begin by introducing the fundamentals of topology in solid-state physics, emphasizing the Berry phase — a geometric phase with profound quantum mechanical implications — and its associated Berry curvature, which acts as an effective magnetic field in momentum space. Next, we review key 2D materials, including monolayer and bilayer graphene as well as transition metal dichalcogenides, to illustrate how valley-dependent Berry curvature gives rise to orbital magnetic moments and the valley Hall effect. Advanced concepts, such as Chern numbers and valley Chern numbers, are discussed to quantify the topological order in these systems. The review also highlights the emergence of topological kink states and domain wall states in graphene, which are linked to robust edge conduction. Furthermore, we examine the valley Zeeman effect and the mechanisms underlying valley polarization (VP), wherein an imbalance of electrons between distinct momentum valleys enables novel device functionalities. Recent experimental breakthroughs — such as observations of the exciton Hall effect — demonstrate the technological potential of Berry phase effects in controlling VP and current. Finally, we underscore the critical role of these geometric and topological phenomena in driving future valleytronic innovations in 2D materials.

Two-dimensional (2D) materials have brought a spectacular revolution in fundamental research and industrial applications due to their unique physical properties of atomically thin thickness, strong light-matter interaction, unity valley polarization and enhanced many-body interactions. To fully explore their exotic physical properties and facilitate potential applications in electronics and optoelectronics, an effective and versatile characterization method is highly demanded. Among the many methods of characterization, optical second harmonic generation (SHG) has attracted broad attention because of its sensitivity, versatility and simplicity. The SHG technique is sufficiently sensitive at the atomic scale and therefore suitable for studies on 2D materials. More importantly, it has the capacity to acquire abundant information ranging from crystallographic, and electronic, to magnetic properties in various 2D materials due to its sensitivity to both spatial-inversion symmetry and time-reversal symmetry. These advantages accompanied by its characteristics of non-invasion and high throughput make SHG a powerful tool for 2D materials. This review summarizes recent experimental developments of SHG applications in 2D materials and also provides an outlook of potential prospects based on SHG.

Transition metal dichalcogenide (TMDC) monolayers exhibit great photocatalytic performances and tunabilities. By using first-principles simulations based on density functional theory, we demonstrate here that external electric bias can be employed to further improve the photocatalytic hydrogen production efficiencies of the six AB2 (A = Mo, W and B = S, Se, Te) TMDC monolayers since these are influenced by their piezoelectric response. In particular, when subjected to a proper amount of electrically induced tensile biaxial strain, most TMDC monolayers turn into potentially ideal photocatalysts toward the hydrogen evolution reaction (HER). The beneficial effects of introducing tensile biaxial strain on the TMDC monolayers are not limited to the reduction of the band gap and proper adjustment of the band edge positions; the concomitant hydrogen adsorption free energies are also modified in such a way that the HER reaction is noticeably favored.

The integration of two-dimensional (2D) materials with photonic structures has catalyzed a wide spectrum of optical and optoelectronic applications. Conventional nanophotonic structures generally lack efficient reconfigurability and multifunctionality. The atomically thin 2D van der Waals materials can thus infuse new functionality and reconfigurability to the well-established library of photonic structures such as integrated waveguides, optical fibers, photonic crystals, micro-cavities, and metasurface, to name a few. Thanks to the handiness of van der Waals interfaces, the 2D materials can be easily transferred and mixed with other prefabricated photonic templates with high degrees of freedom, and can act as the optical gain, modulation, sensing, or plasmonic media for diverse applications. Here we review recent advents on combining 2D materials to nanophotonic structures for new functionality development or performance enhancements. Challenges and emerging opportunities in integrating van der Waals building blocks beyond 2D materials are also discussed.

Significant progress has been made in growing large-area transition metal dichalcogenide (TMD) monolayers, but most rely on stitching small flakes, which can affect electronic and optical performance. High-quality single-crystal monolayers are needed for device applications. Here, we report a wafer-bonder-assisted transfer (WBAT) method to produce uniform, crack-free, single-crystal TMD monolayers over large areas. This technique integrates gold-tape exfoliation with wafer-scale bonding, enabling flake sizes over 106 times larger than those from traditional Scotch tape exfoliation. Compared to hand-press transfer, WBAT yields higher-quality monolayers with fewer cracks, reduced strain, and over 2-fold improvement in photoluminescence uniformity, as confirmed by Raman and PL mapping. Fabricated field-effect transistor arrays show high mobility and on-off ratio. The WBAT method offers high yield, reproducibility, and compatibility with various 2D materials, heterostructures, and substrates, aligning with standard semiconductor processes. It provides a scalable solution for integrating high-quality TMD monolayers into next-generation electronic and optoelectronic devices.

Nanoscale variations of optical properties in transition metal dichalcogenide (TMD) monolayers can be explored with cathodoluminescence (CL) and electron energy loss spectroscopy (EELS) using electron microscopes. To increase the CL emission intensity from TMD monolayers, the MoSe2 flakes are encapsulated in hexagonal boron nitride (hBN), creating van der Waals (VdW) heterostructures. Until now, the studies have been exclusively focused on scanning transmission electron microscopy (STEM-CL) or scanning electron microscopy (SEM-CL), separately. Here, we present results, using both techniques on the same sample, thereby exploring a large acceleration voltage range. We correlate the CL measurements with STEM-EELS measurements acquired with different energy dispersions, to access both the low-loss region at ultra-high spectral resolution, and the core-loss region. This provides information about the weight of the various absorption phenomena including the direct TMD absorption, the hBN interband transitions, the hBN bulk plasmon, and the core losses of the atoms present in the heterostructure. The S(T)EM-CL measurements from the TMD monolayer only show emission from the A exciton. Combining the STEM-EELS and S(T)EM-CL measurements, we can reconstruct different decay pathways leading to the A exciton CL emission. The comparison with SEM-CL shows that this is also a good technique for TMD heterostructure characterization, where the reduced demands on sample preparation are appealing. To demonstrate the capabilities of SEM-CL imaging, we also measured on a SiO2/Si substrate, quintessential in the sample preparation of two-dimensional materials, which is electron-opaque and can only be measured in SEM-CL. The CL-emitting defects of SiO2 make this substrate challenging to use, but we demonstrate that this background can be suppressed by using lower electron energy.