Twisted van der Waals Quantum Materials: Fundamentals, Tunability, and Applications.

Twisted van der Waals (vdW) quantum materials have emerged as a rapidly developing field of two-dimensional (2D) semiconductors. These materials establish a new central research area and provide a promising platform for studying quantum phenomena and investigating the engineering of novel optoelectronic properties such as single photon emission, nonlinear optical response, magnon physics, and topological superconductivity. These captivating electronic and optical properties result from, and can be tailored by, the interlayer coupling using moiré patterns formed by vertically stacking atomic layers with controlled angle misorientation or lattice mismatch. Their outstanding properties and the high degree of tunability position them as compelling building blocks for both compact quantum-enabled devices and classical optoelectronics. This paper offers a comprehensive review of recent advancements in the understanding and manipulation of twisted van der Waals structures and presents a survey of the state-of-the-art research on moiré superlattices, encompassing interdisciplinary interests. It delves into fundamental theories, synthesis and fabrication, and visualization techniques, and the wide range of novel physical phenomena exhibited by these structures, with a focus on their potential for practical device integration in applications ranging from quantum information to biosensors, and including classical optoelectronics such as modulators, light emitting diodes, lasers, and photodetectors. It highlights the unique ability of moiré superlattices to connect multiple disciplines, covering chemistry, electronics, optics, photonics, magnetism, topological and quantum physics. This comprehensive review provides a valuable resource for researchers interested in moiré superlattices, shedding light on their fundamental characteristics and their potential for transformative applications in various fields.

Variant Plateau's law in atomically thin transition metal dichalcogenide dome networks.

Since its fundamental inception from soap bubbles, Plateau's law has sparked extensive research in equilibrated states. However, most studies primarily relied on liquids, foams or cellular structures, whereas its applicability has yet to be explored in nano-scale solid films. Here, we observed a variant Plateau's law in networks of atomically thin domes made of solid two-dimensional (2D) transition metal dichalcogenides (TMDs). Discrete layer-dependent van der Waals (vdWs) interaction energies were experimentally and theoretically obtained for domes protruding in different TMD layers. Significant surface tension differences from layer-dependent vdWs interaction energies manifest in a variant of this fundamental law. The equivalent surface tension ranges from 2.4 to 3.6 N/m, around two orders of magnitude greater than conventional liquid films, enabling domes to sustain high gas pressure and exist in a fundamentally variant nature for several years. Our findings pave the way towards exploring variant discretised states with applications in opto-electro-mechanical devices.

Correction: Adsorption of polycyclic aromatic hydrocarbons over CuZnFeAl-LDH modified by sodium dodecyl sulfate.

[This corrects the article DOI: 10.1039/D2RA03968K.].

Enhanced interactions of interlayer excitons in free-standing heterobilayers.

Strong, long-range dipole-dipole interactions between interlayer excitons (IXs) can lead to new multiparticle correlation regimes1,2, which drive the system into distinct quantum and classical phases2-5, including dipolar liquids, crystals and superfluids. Both repulsive and attractive dipole-dipole interactions have been theoretically predicted between IXs in a semiconductor bilayer2,6-8, but only repulsive interactions have been reported experimentally so far3,9-16. This study investigated free-standing, twisted (51°, 53°, 45°) tungsten diselenide/tungsten disulfide (WSe2/WS2) heterobilayers, in which we observed a transition in the nature of dipolar interactions among IXs, from repulsive to attractive. This was caused by quantum-exchange-correlation effects, leading to the appearance of a robust interlayer biexciton phase (formed by two IXs), which has been theoretically predicted6-8 but never observed before in experiments. The reduced dielectric screening in a free-standing heterobilayer not only resulted in a much higher formation efficiency of IXs, but also led to strongly enhanced dipole-dipole interactions, which enabled us to observe the many-body correlations of pristine IXs at the two-dimensional quantum limit. In addition, we firstly observed several emission peaks from moiré-trapped IXs at room temperature in a well-aligned, free-standing WSe2/WS2 heterobilayer. Our findings open avenues for exploring new quantum phases with potential for applications in non-linear optics.

Adsorption of polycyclic aromatic hydrocarbons over CuZnFeAl-LDH modified by sodium dodecyl sulfate.

Polycyclic aromatic hydrocarbons (PAHs) have received extensive attention due to being highly toxic, mutagenic, and carcinogenic organic pollutants. As a result, a series of adsorbents have been designed and developed to solve the problem. In this paper, CuZnFeAl-S has been explored as a highly efficient adsorbent for PAHs. First, CuZnFeAl-LDH was prepared using a coprecipitation method and then calcined at 500 °C to obtain CuZnFeAlO. Finally, CuZnFeAl-S was prepared by modifying CuZnFeAlO with sodium dodecyl sulfate (SDS). The physical and chemical properties of the adsorbents were characterized by XRD, N2 adsorption-desorption, SEM, ICP, FT-IR, TG-DSC, and IGC; subsequently their adsorption performance was investigated. The results show that the surface properties of CuZnFeAl-S changed from hydrophilic to hydrophobic after SDS modification, which enhanced the adsorption of PAHs obviously. The removal of naphthalene and phenanthrene on CuZnFeAl-S reached 97.3% and 90.3%, respectively. And the adsorption process of naphthalene and phenanthrene conforms to Langmuir adsorption and Freundlich adsorption, respectively. Besides, the adsorption thermodynamics indicate that the adsorption of PAHs was a spontaneous exothermic reaction. The highly efficient PAH adsorption performance of CuZnFeAl-S is the synergistic result of various molecule interactions, such as hydrogen bonding, π-π interactions, and electrostatic attraction.

Varied Magnetic Phases in a van der Waals Easy-Plane Antiferromagnet Revealed by Nitrogen-Vacancy Center Microscopy.

Interest in van der Waals materials often stems from a desire to miniaturize existing technologies by exploiting their intrinsic layered structures to create near-atomically thin components that do not suffer from surface defects. One appealing property is an easily switchable yet robust magnetic order, which is only sparsely demonstrated in the case of in-plane anisotropy. In this work, we use widefield nitrogen-vacancy (NV) center magnetic imaging to measure the properties of individual flakes of CuCrP2S6, a multiferroic van der Waals magnet known to exhibit weak easy-plane anisotropy in the bulk. We chart the crossover between the in-plane ferromagnetism in thin flakes down to the trilayer and the bulk behavior dominated by a low-field spin-flop transition. Further, by exploiting the directional dependence of NV center magnetometry, we are able to observe an instance of a predominantly out-of-plane ferromagetic phase near zero field, in contrast with our expectation and previous experiments on the bulk material. We attribute this to the presence of surface anisotropies caused by the sample preparation process or exposure to the ambient environment, which is expected to have more general implications for a broader class of weakly anisotropic van der Waals magnets.

Giant Photoluminescence Enhancement and Resonant Charge Transfer in Atomically Thin Two-Dimensional Cr2Ge2Te6/WS2 Heterostructures.

Hybridization of two-dimensional (2D) magnetic semiconductors with transition-metal dichalcogenides (TMDC) monolayers can significantly engineer the light-matter interactions and provide a promising platform for enhanced excitonic systems with artificially tailored band alignments. Here, we report the fabrication of heterostructures with monolayer WS2 on 2D Cr2Ge2Te6 (CGT), which displayed giant photoluminescence enhancement at specific CGT layer numbers. The highly enhanced quantum yield obtained can be explained by novel photoexcited carrier dynamics, facilitated by alternate relaxation channels, resulting in resonance charge transfer at the heterointerface. 2D CGT revealed a strongly layer-dependent work function (up to ∼750 meV), which greatly modulates the band positioning in the heterostructure. These heterostructures conceived both type I and type II band alignments, which are verified by Kelvin probe force microscopy and PL measurements. In addition to layer modulation, we uncover temperature and power dependence of the resonance charge transfer in the multilayer heterostructure. Our findings provide further insights into the ultrafast charge dynamics occurring at the atomic interfaces. The results may pave the way for novel optoelectronics based on van der Waals heterostructures.

Highly Enhanced Light-Matter Interaction in MXene Quantum Dots-Monolayer WS2 Heterostructure.

Since the Ti3 C2 was discovered in 2011, the family of MXenes has attracted much attention. MXenes offer great potential in the tuning of many fundamental properties by the synthesis of new structures. The synthesis methods of MXene mainly require steps including immersing a MAX phase in hydrofluoric acid (HF) and processing at high temperatures. However, the HF may be hard to acquire in many countries and processing at high temperatures may cause risk issues. In this article, a simple and cost-effective synthesis of Ti3 C2 Tx quantum dots (QDs) via chemical solution method that follows the long-time magnetic stirring process-initiated etching of Al atoms from commercial Ti3 AlC2 powder at room temperature is introduced. With WS2 monolayer sitting over the MXenes QD arrays, a higher level of photoluminescence (PL) enhancement is found in the heterostructure with increasing laser power at room temperature and a few novel quasi-particles species in the heterostructure at -190 °C. The observations show that the possible plasmonic behavior initiated by QD arrays and the suspension state of WS2 may coplay the roles to trigger multiple quasi-particles species. This study can be an important benchmark for the extensive understanding of quasi-particles species, and their dynamics.

π-phase modulated monolayer supercritical lens.

The emerging monolayer transition metal dichalcogenides have provided an unprecedented material platform for miniaturized opto-electronic devices with integrated functionalities. Although excitonic light-matter interactions associated with their direct bandgaps have received tremendous research efforts, wavefront engineering is less appreciated due to the suppressed phase accumulation effects resulting from the vanishingly small thicknesses. By introducing loss-assisted singular phase behaviour near the critical coupling point, we demonstrate that integration of monolayer MoS2 on a planar ZnO/Si substrate, approaching the physical thickness limit of the material, enables a π phase jump. Moreover, highly dispersive extinctions of MoS2 further empowers broadband phase regulation and enables binary phase-modulated supercritical lenses manifesting constant sub-diffraction-limited focal spots of 0.7 Airy units (AU) from the blue to yellow wavelength range. Our demonstrations downscaling optical elements to atomic thicknesses open new routes for ultra-compact opto-electronic systems harnessing two-dimensional semiconductor platforms with integrated functionalities.

Direct Measurement of Folding Angle and Strain Vector in Atomically Thin WS2 Using Second-Harmonic Generation.

Structural engineering techniques such as local strain engineering and folding provide functional control over critical optoelectronic properties of 2D materials. Local strain engineering at the nanoscale level is practically achieved via permanently deformed wrinkled nanostructures, which are reported to show photoluminescence enhancement, bandgap modulation, and funneling effect. Folding in 2D materials is reported to tune optoelecronic properties via folding angle dependent interlayer coupling and symmetry variation. The accurate and efficient monitoring of local strain vector and folding angle is important to optimize the performance of optoelectronic devices. Conventionally, the accurate measurement of both strain amplitude and strain direction in wrinkled nanostructures requires the combined usage of multiple tools resulting in manufacturing lead time and cost. Here, we demonstrate the usage of a single tool, polarization-dependent second-harmonic generation (SHG), to determine the folding angle and strain vector accurately and efficiently in ultrathin WS2. The folding angle in trilayer WS2 folds exhibiting 1-9 times SHG enhancement is probed through variable approaches such as SHG enhancement factor, maxima and minima SHG phase difference, and linear dichroism. In compressive strain induced wrinkled nanostructures, strain-dependent SHG quenching and enhancement is observed parallel and perpendicular, respectively, to the direction of the compressive strain vector, allowing us to determine the local strain vector accurately using a photoelastic approach. We further demonstrate that SHG is highly sensitive to band-nesting-induced transition (C-peak), which can be significantly modulated by strain. Our results show SHG as a powerful probe to folding angle and strain vector.

Controlled Micro/Nanodome Formation in Proton-Irradiated Bulk Transition-Metal Dichalcogenides.

At the few-atom-thick limit, transition-metal dichalcogenides (TMDs) exhibit strongly interconnected structural and optoelectronic properties. The possibility to tailor the latter by controlling the former is expected to have a great impact on applied and fundamental research. As shown here, proton irradiation deeply affects the surface morphology of bulk TMD crystals. Protons penetrate the top layer, resulting in the production and progressive accumulation of molecular hydrogen in the first interlayer region. This leads to the blistering of one-monolayer thick domes, which stud the crystal surface and locally turn the dark bulk material into an efficient light emitter. The domes are stable (>2-year lifetime) and robust, and host strong, complex strain fields. Lithographic techniques provide a means to engineer the formation process so that the domes can be produced with well-ordered positions and sizes tunable from the nanometer to the micrometer scale, with important prospects for so far unattainable applications.

Quantifying Quasi-Fermi Level Splitting and Mapping its Heterogeneity in Atomically Thin Transition Metal Dichalcogenides.

One of the most fundamental parameters of any photovoltaic material is its quasi-Fermi level splitting (∆µ) under illumination. This quantity represents the maximum open-circuit voltage (Voc ) that a solar cell fabricated from that material can achieve. Herein, a contactless, nondestructive method to quantify this parameter for atomically thin 2D transition metal dichalcogenides (TMDs) is reported. The technique is applied to quantify the upper limits of Voc that can possibly be achieved from monolayer WS2 , MoS2 , WSe2 , and MoSe2 -based solar cells, and they are compared with state-of-the-art perovskites. These results show that Voc values of ≈1.4, ≈1.12, ≈1.06, and ≈0.93 V can be potentially achieved from solar cells fabricated from WS2 , MoS2 , WSe2 , and MoSe2 monolayers at 1 Sun illumination, respectively. It is also observed that ∆µ is inhomogeneous across different regions of these monolayers. Moreover, it is attempted to engineer the observed ∆µ heterogeneity by electrically gating the TMD monolayers in a metal-oxide-semiconductor structure that effectively changes the doping level of the monolayers electrostatically and improves their ∆µ heterogeneity. The values of ∆µ determined from this work reveal the potential of atomically thin TMDs for high-voltage, ultralight, flexible, and eye-transparent future solar cells.

Ferroelectric-Driven Exciton and Trion Modulation in Monolayer Molybdenum and Tungsten Diselenides.

In this work, we show how domain-engineered lithium niobate can be used to selectively dope monolayer molybdenum selenide (MoSe2) and tungsten selenide (WSe2) and demonstrate that these ferroelectric domains can significantly enhance or inhibit photoluminescence (PL), with the most dramatic modulation occurring at the heterojunction interface between two domains. A micro-PL and Raman system is used to obtain spatially resolved images of the differently doped transition metal dichalcogenides (TMDs). The domain-inverted lithium niobate causes changes in the TMDs due to electrostatic doping as a result of the remnant polarization from the substrate. Moreover, the differently doped TMDs (n-type MoSe2 and p-type WSe2) exhibit opposite PL modulation. Distinct oppositely charged domains were obtained with a 9-fold PL enhancement for the same single MoSe2 sheet when adhered to the positive (P+) and negative (P-) domains. This sharp PL modulation on the ferroelectric domain results from different free electron or hole concentrations in the material's conduction band or valence band. Moreover, excitons dissociate rapidly at the interface between the P+ and P- domains due to the built-in electric field. We are able to adjust the charge on the P+ and P- domains using temperature via the pyroelectric effect and observe rapid PL quenching over a narrow temperature range, illustrating the observed PL modulation is electronic in nature. This observation creates an opportunity to harness the direct bandgap TMD 2D materials as an active optical component for the lithium niobate platform using domain engineering of the lithium niobate substrate to create optically active heterostructures that could be used for photodetectors or even electrically driven optical sources on-chip.

Modulated interlayer charge transfer dynamics in a monolayer TMD/metal junction.

The performance of optoelectronic devices based on monolayer transition-metal dichalcogenide (mTMD) semiconductors is significantly affected by the contact at the mTMD-metal interface, which is dependent on interlayer interactions and coupling. Here, we report a systematic optical method to investigate the interlayer charge transfer and coupling in a mTMD-metal heterojunction. Giant photoluminescence (PL) quenching was observed in a monolayer MoS2/Pd (1L MoS2/Pd) junction which is mainly due to the efficient interlayer charge transfer between Pd and MoS2. 1L MoS2/Pd also exhibits an increase in the PL quenching factor (η) as the temperature decreases, due to a reduction of the interlayer spacing. Annealing experiments were also performed which supported interlayer charge transfer as the main mechanism for the increase of η. Moreover, a monolayer MoS2/Au (1L MoS2/Au) junction was fabricated for engineering the interlayer charge transfer. Interestingly, a narrowing effect of the full width at half maximum (FWHM) was encountered as the junctions changed from 1L MoS2/SiO2 → 1L MoS2/Au → 1L MoS2/Pd, possibly originating from a change of the doping level induced weakening of exciton-carrier scattering. Our results deepen the understanding of metal-semiconductor junctions for further exploring fundamental phenomena and enabling high-performance devices using mTMD-metal junctions.

Efficient and Layer-Dependent Exciton Pumping across Atomically Thin Organic-Inorganic Type-I Heterostructures.

The fundamental light-matter interactions in monolayer transition metal dichalcogenides might be significantly engineered by hybridization with their organic counterparts, enabling intriguing optoelectronic applications. Here, atomically thin organic-inorganic (O-I) heterostructures, comprising monolayer MoSe2 and mono-/few-layer single-crystal pentacene samples, are fabricated. These heterostructures show type-I band alignments, allowing efficient and layer-dependent exciton pumping across the O-I interfaces. The interfacial exciton pumping has much higher efficiency (>86 times) than the photoexcitation process in MoSe2 , although the pentacene layer has much lower optical absorption than MoSe2 . This highly enhanced pumping efficiency is attributed to the high quantum yield in pentacene and the ultrafast energy transfer between the O-I interface. Furthermore, those organic counterparts significantly modulate the bindings of charged excitons in monolayer MoSe2 via their precise dielectric environment engineering. The results open new avenues for exploring fundamental phenomena and novel optoelectronic applications using atomically thin O-I heterostructures.

Highly Enhanced Many-Body Interactions in Anisotropic 2D Semiconductors.

Atomically thin two-dimensional (2D) semiconductors have presented a plethora of opportunities for future optoelectronic devices and photonics applications, made possible by the strong light matter interactions at the 2D quantum limit. Many body interactions between fundamental particles in 2D semiconductors are strongly enhanced compared with those in bulk semiconductors because of the reduced dimensionality and, thus, reduced dielectric screening. These enhanced many body interactions lead to the formation of robust quasi-particles, such as excitons, trions, and biexcitons, which are extremely important for the optoelectronics device applications of 2D semiconductors, such as light emitting diodes, lasers, and optical modulators, etc. Recently, the emerging anisotropic 2D semiconductors, such as black phosphorus (termed as phosphorene) and phosphorene-like 2D materials, such as ReSe2, 2D-perovskites, SnS, etc., show strong anisotropic optical and electrical properties, which are different from conventional isotropic 2D semiconductors, such as transition metal dichalcogenide (TMD) monolayers. This anisotropy leads to the formation of quasi-one-dimensional (quasi-1D) excitons and trions in a 2D system, which results in even stronger many body interactions in anisotropic 2D materials, arising from the further reduced dimensionality of the quasi-particles and thus reduced dielectric screening. Many body interactions have been heavily investigated in TMD monolayers in past years, but not in anisotropic 2D materials yet. The quasi-particles in anisotropic 2D materials have fractional dimensionality which makes them perfect candidates to serve as a platform to study fundamental particle interactions in fractional dimensional space. In this Account, we present our recent progress related to 2D phosphorene, a 2D system with quasi-1D excitons and trions. Phosphorene, because of its unique anisotropic properties, provides a unique 2D platform for investigating the dynamics of excitons, trions, and biexcitons in reduced dimensions and fundamental many body interactions. We begin by explaining the fundamental reasons for the highly enhanced interactions in the 2D systems influenced by dielectric screening, resulting in high binding energies of excitons and trions, which are supported by theoretical calculations and experimental observations. Phosphorene has shown much higher binding energies of excitons and trions than TMD monolayers, which allows robust quasi-particles in anisotropic materials at room temperature. We also discuss the role of extrinsic defects induced in phosphorene, resulting in localized excitonic emissions in the near-infrared range, making it suitable for optical telecommunication applications. Finally, we present our vision of the exciting device applications based on the highly enhanced many body interactions in phosphorene, including exciton-polariton devices, polariton lasers, single-photon emitters, and tunable light emitting diodes (LEDs).

Defect Engineering in Few-Layer Phosphorene.

Defect engineering in 2D phosphorene samples is becoming an important and powerful technique to alter their properties, enabling new optoelectronic applications, particularly at the infrared wavelength region. Defect engineering in a few-layer phosphorene sample via introduction of substrate trapping centers is realized. In a three-layer (3L) phosphorene sample, a strong photoluminescence (PL) emission peak from localized excitons at ≈1430 nm is observed, a much lower energy level than free excitonic emissions. An activation energy of ≈77 meV for the localized excitons is determined in temperature-dependent PL measurements. The relatively high activation energy supports the strong stability of the localized excitons even at elevated temperature. The quantum efficiency of localized exciton emission in 3L phosphorene is measured to be approximately three times higher than that of free excitons. These results could enable exciting applications in infrared optoelectronics.

An effort to use human-based exome capture methods to analyze chimpanzee and macaque exomes.

Non-human primates have emerged as an important resource for the study of human disease and evolution. The characterization of genomic variation between and within non-human primate species could advance the development of genetically defined non-human primate disease models. However, non-human primate specific reagents that would expedite such research, such as exon-capture tools, are lacking. We evaluated the efficiency of using a human exome capture design for the selective enrichment of exonic regions of non-human primates. We compared the exon sequence recovery in nine chimpanzees, two crab-eating macaques and eight Japanese macaques. Over 91% of the target regions were captured in the non-human primate samples, although the specificity of the capture decreased as evolutionary divergence from humans increased. Both intra-specific and inter-specific DNA variants were identified; Sanger-based resequencing validated 85.4% of 41 randomly selected SNPs. Among the short indels identified, a majority (54.6%-77.3%) of the variants resulted in a change of 3 base pairs, consistent with expectations for a selection against frame shift mutations. Taken together, these findings indicate that use of a human design exon-capture array can provide efficient enrichment of non-human primate gene regions. Accordingly, use of the human exon-capture methods provides an attractive, cost-effective approach for the comparative analysis of non-human primate genomes, including gene-based DNA variant discovery.