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Gate-Induced Metal–Insulator Transition in MoS 2 by Solid Superionic Conductor LaF 3
Electric-double-layer (EDL) gating with liquid electrolyte has been a powerful tool widely used to explore emerging interfacial electronic phenomena. Due to the large EDL capacitance, a high carrier density up to 10 14 cm –2 can be induced, directly leading to the realization of field-induced insulator to metal (or superconductor) transition. However, the liquid nature of the electrolyte has created technical issues including possible side electrochemical reactions or intercalation, and the potential for huge strain at the interface during cooling. In addition, the liquid coverage of active devices also makes many surface characterizations and in situ measurements challenging. Here, we demonstrate an all solid-state EDL device based on a solid superionic conductor LaF 3 , which can be used as both a substrate and a fluorine ionic gate dielectric to achieve a wide tunability of carrier density without the issues of strain or electrochemical reactions and can expose the active device surface for external access. Based on LaF 3 EDL transistors (EDLTs), we observe the metal–insulator transition in MoS 2 . Interestingly, the well-defined crystal lattice provides a more uniform potential distribution in the substrate, resulting in less interface electron scattering and therefore a higher mobility in MoS 2 transistors. Finally, this result shows the powerful gating capability of LaF 3 solid electrolyte for new possibilities of novel interfacial electronic phenomena.
Time-Resolved Observation of Hole Tunneling in van der Waals Multilayer Heterostructures
We reported a time-resolved study of quantum-mechanical tunneling of holes between two MoSe 2 monolayers that are separated by a monolayer WS 2 energy barrier. Four-layer heterostructures of MoSe 2 /WS 2 /MoSe 2 /graphene, as well as control samples, were fabricated by mechanical exfoliation and dry transfer techniques. To time-resolve the hole tunneling process, an ultrashort laser pulse was used to excite electrons and holes in both MoSe 2 layers. Here, by utilization of the graphene layer to eliminate carriers in the third MoSe 2 layer, the first MoSe 2 layer is selectively populated with the holes, which then tunnel to the third MoSe 2 layer. By monitoring decay of the hole population with an ultrashort probe pulse, we measure a hole tunneling time of about 20 ps, which is found to slightly increase with the injected carrier density. Besides the fundamental interests of real-time observation of the quantum-mechanical tunneling effect across a nanometer barrier, these results provide quantitative understanding on tunneling mechanisms of charge transfer in van der Waals heterostructures, which is useful for designing sophisticated van der Waals multilayer heterostructures.
Suppressing Polaronic Defect–Photocarrier Interaction in Halide Perovskites by Pre-distorting Its Lattice
In halide perovskites, photocarriers can have strong polaronic interactions with point defects. For iodide-deficient MAPbI 3 , we found that the Fermi level can shift significantly by 0.6–0.7 eV upon light illumination. This energy level shift is accompanied by the formation of deep electron traps. These experimental observations are consistent with the formation of a Pb–Pb dimer when photoexcited electrons are trapped at an iodide vacancy. Interestingly, we found that this polaronic interaction is suppressed when a portion of MA + cations is replaced by smaller Cs + ions. Density functional theory calculations reveal that Cs-doping can reduce the distance between two Pb atoms across an iodide vacancy, even without electron trapping. The predistortion of the lattice induced by cation replacement resembles the Pb–Pb dimer formed by electron trapping at the defect site, which explains the suppression of light-induced effects observed in the experiment. Furthermore, our finding unveils a counterintuitive strategy to enhance the photostability of halide perovskites by preintroducing distortions into its lattice.
Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies
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Brightening of a dark monolayer semiconductor via strong light-matter coupling in a cavity
Engineering the properties of quantum materials via strong light-matter coupling is a compelling research direction with a multiplicity of modern applications. Those range from modifying charge transport in organic molecules, steering particle correlation and interactions, and even controlling chemical reactions. Here, we study the modification of the material properties via strong coupling and demonstrate an effective inversion of the excitonic band-ordering in a monolayer of WSe 2 with spin-forbidden, optically dark ground state. In our experiments, we harness the strong light-matter coupling between cavity photon and the high energy, spin-allowed bright exciton, and thus creating two bright polaritonic modes in the optical bandgap with the lower polariton mode pushed below the WSe 2 dark state. We demonstrate that in this regime the commonly observed luminescence quenching stemming from the fast relaxation to the dark ground state is prevented, which results in the brightening of this intrinsically dark material. We probe this effective brightening by temperature-dependent photoluminescence, and we find an excellent agreement with a theoretical model accounting for the inversion of the band ordering and phonon-assisted polariton relaxation.
Lattice strain effects on the optical properties of MoS 2 nanosheets
‘‘Strain engineering’’ in functional materials has been widely explored to tailor the physical properties of electronic materials and improve their electrical and/or optical properties. Here, we exploit both in plane and out of plane uniaxial tensile strains in MoS 2 to modulate its band gap and engineer its optical properties. We utilize X-ray diffraction and cross-sectional transmission electron microscopy to quantify the strains in the as-synthesized MoS 2 nanosheets and apply measured shifts of Raman-active modes to confirm lattice strain modification of both the out-of-plane and in-plane phonon vibrations of the MoS 2 nanosheets. The induced band gap evolution due to in-plane and out-of-plane tensile stresses is validated by photoluminescence (PL) measurements, promising a potential route for unprecedented manipulation of the physical, electrical and optical properties of MoS 2 .
Three-dimensional mesostructures as high-temperature growth templates, electronic cellular scaffolds, and self-propelled microrobots
Recent work demonstrates that processes of stress release in prestrained elastomeric substrates can guide the assembly of sophisticated 3D micro/nanostructures in advanced materials. Reported application examples include soft electronic components, tunable electromagnetic and optical devices, vibrational metrology platforms, and other unusual technologies, each enabled by uniquely engineered 3D architectures. A vast disadvantage of these systems is that the elastomeric substrates, while essential to the assembly process, can impose significant engineering constraints in terms of operating temperatures and levels of dimensional stability; they also prevent the realization of 3D structures in freestanding forms. In this work, we introduce concepts in interfacial photopolymerization, nonlinear mechanics, and physical transfer that bypass these limitations. The results enable 3D mesostructures in fully or partially freestanding forms, with additional capabilities in integration onto nearly any class of substrate, from planar, hard inorganic materials to textured, soft biological tissues, all via mechanisms quantitatively described by theoretical modeling. Illustrations of these ideas include their use in 3D structures as frameworks for templated growth of organized lamellae from AgCl–KCl eutectics and of atomic layers of WSe 2 from vapor-phase precursors, as open-architecture electronic scaffolds for formation of dorsal root ganglion (DRG) neural networks, and as catalyst supports for propulsive systems in 3D microswimmers with geometrically controlled dynamics. Taken together, these methodologies establish a set of enabling options in 3D micro/nanomanufacturing that lie outside of the scope of existing alternatives.
Electronic properties of single-layer CoO 2 /Au(111)
Here we report direct measurements via angle-resolved photoemission spectroscopy (ARPES) of the electronic dispersion of single-layer (SL) CoO 2 . The Fermi contour consists of a large hole pocket centered at the $\overline{\Gamma}$ point. To interpret the ARPES results, we use density functional theory (DFT) in combination with the multi-orbital Gutzwiller Approximation (DFT+GA), basing our calculations on crystalline structure parameters derived from x-ray photoelectron diffraction and low-energy electron diffraction. Our calculations are in good agreement with the measured dispersion. We conclude that the material is a moderately correlated metal. We also discuss substrate effects, and the influence of hydroxylation on the CoO 2 SL electronic structure.
Exceptional electronic transport and quantum oscillations in thin bismuth crystals grown inside van der Waals materials
Confining materials to two-dimensional forms changes the behaviour of the electrons and enables the creation of new devices. However, most materials are challenging to produce as uniform, thin crystals. Here we present a synthesis approach where thin crystals are grown in a nanoscale mould defined by atomically flat van der Waals (vdW) materials. Here, by heating and compressing bismuth in a vdW mould made of hexagonal boron nitride, we grow ultraflat bismuth crystals less than 10 nm thick. Due to quantum confinement, the bismuth bulk states are gapped, isolating intrinsic Rashba surface states for transport studies. The vdW-moulded bismuth shows exceptional electronic transport, enabling the observation of Shubnikov–de Haas quantum oscillations originating from the (111) surface state Landau levels. By measuring the gate-dependent magnetoresistance, we observe multi-carrier quantum oscillations and Landau level splitting, with features originating from both the top and bottom surfaces. Our vdW mould growth technique establishes a platform for electronic studies and control of bismuth’s Rashba surface states and topological boundary modes1,2,3. Beyond bismuth, the vdW-moulding approach provides a low-cost way to synthesize ultrathin crystals and directly integrate them into a vdW heterostructure.
Foam With Direction: Unraveling the Anisotropic Radiation Shielding Properties of 2D Boron Nitride Nanoplatelet Foams
Neutron radiation exposure is one of the main challenges faced during space missions. There is a critical need for advanced lightweight radiation shielding materials. Two-dimensional (2D) boron nitride nanoplatelets (BNNP) are excellent candidates for polymer matrix nanofillers due to their superior neutron shielding and thermal and mechanical properties. Furthermore, the 2D material anisotropic behavior unlocks the potential for composite property tailoring. This study fabricated ultra- lightweight lamellar BNNP foams (density 0.05 g cm –3 and 97.5% porous) via freeze-drying processing. The neutron shielding effectiveness or mass absorption coefficient of the BNNP foams with walls perpendicular to the direction of the radiation source was 14.47 cm 2 g –1 , while that of the foam with parallel configuration was only 8.51 cm 2 g –1 . The orientation-dependent neutron radiation shielding properties were modeled using the Beer-Lambert law for porous composite materials. The BNNP foam in this study has the potential to benefit advanced tailorable radiation shielding technologies for future aerospace missions.
Electronic transport in two-dimensional high dielectric constant nanosystems
There has been remarkable recent progress in engineering high-dielectric constant two dimensional (2D) materials, which are being actively pursued for applications in nanoelectronics in capacitor and memory devices, energy storage, and high-frequency modulation in communication devices. Yet many of the unique properties of these systems are poorly understood and remain unexplored. Here we report a numerical study of hopping conductivity of the lateral network of capacitors, which models two-dimensional insulators, and demonstrate that 2D long-range Coulomb interactions lead to peculiar size effects. We find that the characteristic energy governing electronic transport scales logarithmically with either system size or electrostatic screening length depending on which one is shorter. Our results are relevant well beyond their immediate context, explaining, for example, recent experimental observations of logarithmic size dependence of electric conductivity of thin superconducting films in the critical vicinity of superconductor-insulator transition where a giant dielectric constant develops. Our findings mark a radical departure from the orthodox view of conductivity in 2D systems as a local characteristic of materials and establish its macroscopic global character as a generic property of high-dielectric constant 2D nanomaterials.
Electrostatic Gating of Ionic Conductance through Heterogeneous van der Waals Nanopores
Nanofluidic ionic transistors typically require gate voltages above 1 V and operate only at submillimolar ionic strengths, limiting their biocompatible applications. We demonstrate ionic transistors consisting of single sub-10 nm nanopores drilled in van der Waals (vdW) heterostructures with internal gate electrodes made of few-layer graphene. These devices deliver up to 10-fold current modulation at gate voltages as low as 0.3 V in 10 mM KCl, and ∼2-fold modulation at near-physiological 100 mM KCl. Baseline conductance with no gate shows surface-charge-dominated transport below 100 mM KCl, consistent with negatively charged hBN walls and ∼5 nm opening of the pores. The surface charge and the electrochemical asymmetry introduced by the three-electrode configuration govern the device’s behavior: negative gate voltage (V G ) enriches ionic concentrations and enhances current, whereas positive V G induces a local depletion zone that suppresses transport. The current modulation by V G is dependent on the polarity of the transmembrane potential and leads to ion current rectification. Molecular dynamics simulations of a nanopore in a hBN–graphene–hBN stack reveal confinement and surface charge-dependent suppression of the relative permittivity of interfacial water. Continuum modeling with radially varying interfacial water permittivity reproduces the asymmetric I–V characteristics and explains how the embedded gate sculpts local potential and ion concentrations. By enabling sub-0.5 V control of ionic transport at up to 100 mM salt concentrations, these devices address a key need in nanofluidics to create low-power ionic circuits and biosensing.
Designed 2D protein crystals as dynamic molecular gatekeepers for a solid-state device
The sensitivity and responsiveness of living cells to environmental changes are enabled by dynamic protein structures, inspiring efforts to construct artificial supramolecular protein assemblies. However, despite their sophisticated structures, designed protein assemblies have yet to be incorporated into macroscale devices for real-life applications. We report a 2D crystalline protein assembly of C98/E57/E66 L-rhamnulose-1-phosphate aldolase ( CEE RhuA) that selectively blocks or passes molecular species when exposed to a chemical trigger. CEE RhuA crystals are engineered via cobalt(II) coordination bonds to undergo a coherent conformational change from a closed state (pore dimensions <1 nm) to an ajar state (pore dimensions ~4 nm) when exposed to an HCN(g) trigger. When layered onto a mesoporous silicon (pSi) photonic crystal optical sensor configured to detect HCN (g) , the 2D CEE RhuA crystal layer effectively blocks interferents that would otherwise result in a false positive signal. The 2D CEE RhuA crystal layer opens in selective response to low-ppm levels of HCN (g) , allowing analyte penetration into the pSi sensor layer for detection. These findings illustrate that designed protein assemblies can function as dynamic components of solid-state devices in non-aqueous environments.
Evaluating the Sources of Graphene’s Resistivity Using Differential Conductance
We explore the contributions to the electrical resistance of monolayer and bilayer graphene, revealing transitions between different regimes of charge carrier scattering. In monolayer graphene at low densities, a nonmonotonic variation of the resistance is observed as a function of temperature. Such behaviour is consistent with the influence of scattering from screened Coulomb impurities. At higher densities, the resistance instead varies in a manner consistent with the influence of scattering from acoustic and optical phonons. The crossover from phonon-, to charged-impurity, limited conduction occurs once the concentration of gate-induced carriers is reduced below that of the residual carriers. In bilayer graphene, the resistance exhibits a monotonic decrease with increasing temperature for all densities, with the importance of short-range impurity scattering resulting in a “universal” density-independent (scaled) conductivity at high densities. At lower densities, the conductivity deviates from this universal curve, pointing to the importance of thermal activation of carriers out of charge puddles. These various assignments, in both systems, are made possible by an approach of “differential-conductance mapping”, which allows us to suppress quantum corrections to reveal the underlying mechanisms governing the resistivity.
Nonlinear optics in 2D materials: From classical to quantum
Nonlinear optics has long been a cornerstone of modern photonics, enabling a wide array of technologies, from frequency conversion to the generation of ultrafast light pulses. Recent breakthroughs in two-dimensional (2D) materials have opened a frontier in this field, offering new opportunities for both classical and quantum nonlinear optics. These atomically thin materials exhibit strong light–matter interactions and large nonlinear responses, thanks to their tunable lattice symmetries, strong resonance effects, and highly engineerable band structures. In this paper, we explore the potential that 2D materials bring to nonlinear optics, covering topics from classical nonlinear optics to nonlinearities at the few-photon level. We delve into how these materials enable possibilities, such as symmetry control, phase matching, and integration into photonic circuits. The fusion of 2D materials with nonlinear optics provides insights into the fundamental behaviors of elementary excitations—such as electrons, excitons, and photons—in low-dimensional systems and has the potential to transform the landscape of next-generation photonic and quantum technologies.
Exploring and Embracing Heterogeneity in Atomically Thin Energy Materials
Atomically thin semiconductors offer extraordinary opportunities for the manipulation of charge carriers, many-body optical excitations, quantum light emitters, and non-charge based quantum numbers. Confinement and reduced dielectric screening in these two-dimensional (2D) materials give rise to large characteristic energies so that many-body and quantum effects are important even at room temperature. Optical excitations in extended homogeneous areas have been investigated intensely, albeit mostly focusing on a limited set of materials, particularly transition metal dichalcogenides. Much less understood are light-matter interactions for other classes of 2D semiconductors, as well as effects that arise in heterogeneous materials, either near naturally occurring defects, impurities, edges and grain boundaries, or as a result of intentional interface formation in heterostructures. Addressing such systems experimentally involves significant challenges: Understanding the atomistic growth mechanisms of 2D semiconductors, so that novel systems with designed properties, specific ‘imperfections’, or controlled interfaces can be realized; and probing of local excitations at scales that match the relevant (micrometer to nanometer) length scales in heterogeneous materials. In this research project, we addressed these challenges by harnessing quantitative in-situ microscopy to study the growth of 2D and layered semiconductors and heterostructures, combined with local spectroscopic measurements of quasiparticles excited at the nanometer scale. An integral part of the research has been the development of novel experimental approaches, both for in-situ microscopy of synthesis and for nanometer-scale spectroscopy. In particular, advanced techniques were developed for cathodoluminescence in scanning transmission electron microscopy (STEM-CL) where a nanometer-focused electron beam is used to locally excite electron-hole pairs, excitons, as well as propagating hybrid light-matter modes such as exciton-polaritons. Experiments were guided and analyzed via computations of structure, chemistry, and excitation spectra. The particular materials focus has been on group IV chalcogenides, a family of less explored 2D/layered semiconductors whose diversity in crystal structure and properties promises access to novel materials architectures and the discovery of phenomena that can support emerging technology needs.
Sequential Dual Alignments Introduce Synergistic Effect on Hexagonal Boron Nitride Platelets for Superior Thermal Performance
Planarly aligning 2D platelets is challenging due to their additional orientational freedom compared to 1D materials. Here, this study reports a sequential dual-alignment approach, employing an extrusion-printing-induced shear force and rotating-magnetic-field-induced force couple for platelet planarly alignment in a yield-stress support bath. It is hypothesized that the partial alignment induced by a directional shear force facilitates subsequent axial rotation of the platelets for planar alignment under an external force couple, resulting in a synergistic alignment effect. This sequential dual-alignment approach achieves better planar alignment of 2D modified hexagonal boron nitride (mhBN). Specifically, the thermal conductivity of the 40 wt% mhBN/epoxy composite is significantly higher (692%) than that of unaligned composites, surpassing the cumulative effect of individual methods (only 133%) with a 5 times more synergistic effect. For 30, 40, and 50 wt% mhBN composites, the thermal conductivity values (5.9, 9.5, and 13.8 W m –1 K –1 ) show considerable improvement compared to the previously reported highest values (5.3, 6.6, and 8.6 W m –1 K –1 ). Additionally, a 3D mhBN/epoxy heat sink is printed and evaluated to demonstrate the feasibility of device fabrication. The approach enables the planar alignment of electrically or thermally conducting 2D fillers during 3D fabrication.