Entropy of Liquid Water as Predicted by the Two-Phase Thermodynamic Model and Data-Driven Many-Body Potentials.

We investigate the entropy of liquid water at ambient conditions using the two-phase thermodynamic (2PT) model, applied to both common pairwise-additive water models and the MB-pol and MB-pol(2023) data-driven many-body potentials. Our simulations demonstrate that the 2PT model yields entropy values in semiquantitative agreement with experimental data when using MB-pol and MB-pol(2023). Additionally, our analyses indicate that the entropy values predicted by pairwise-additive water models may benefit from error compensation between the inherent approximations of the 2PT model and the known limitations of these water models in describing many-body interactions. Despite its approximate nature, the simplicity of the 2PT model makes it a valuable tool for estimating relative entropy changes of liquid water across various environments, especially when combined with water models that provide a consistently robust representation of the structural, thermodynamic, and dynamical properties of liquid water.

Cathodoluminescence emission and electron energy loss absorption from a 2D transition metal dichalcogenide in van der Waals heterostructures.

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 MoSe2flakes 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 SiO2make this substrate challenging to use, but we demonstrate that this background can be suppressed by using lower electron energy.

Engineering 2D Material Exciton Line Shape with Graphene/h-BN Encapsulation.

Control over the optical properties of atomically thin two-dimensional (2D) layers, including those of transition metal dichalcogenides (TMDs), is needed for future optoelectronic applications. Here, the near-field coupling between TMDs and graphene/graphite is used to engineer the exciton line shape and charge state. Fano-like asymmetric spectral features are produced in WS2, MoSe2, and WSe2 van der Waals heterostructures combined with graphene, graphite, or jointly with hexagonal boron nitride (h-BN) as supporting or encapsulating layers. Furthermore, trion emission is suppressed in h-BN encapsulated WSe2/graphene with a neutral exciton red shift (44 meV) and binding energy reduction (30 meV). The response of these systems to electron beam and light probes is well-described in terms of 2D optical conductivities of the involved materials. Beyond fundamental insights into the interaction of TMD excitons with structured environments, this study opens an unexplored avenue toward shaping the spectral profile of narrow optical modes for application in nanophotonic devices.

Phosphorus-Doped Multilayer In6Se7: The Study of Structural, Electrical, and Optical Properties for Junction Device.

This work investigates the characteristic of layered In6Se7 with varying phosphorus (P) dopant concentrations (In6Se7:P) from P = 0, 0.5, 1, to P = 5%. X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses indicate that the structure and morphology of the In6Se7:P series compounds remain unchanged, exhibiting a monoclinic structure. Room-temperature micro-Raman (µRaman) result of all the compositions of layered In6Se7:P reveals two dominant peaks at 101 ± 3 cm-1 (i.e., In-In bonding mode) and 201 ± 3 cm-1 (i.e., Se-Se bonding mode) for each P composition in In6Se7. An extra peak at approximately 171 ± 2 cm-1 is observed and it shows enhancement at the highest P composition of In6Se7:P 5%. This mode is attributed to P-Se bonding caused by P doping inside In6Se7. All the doped and undoped In6Se7:P showed n-type conductivity, and their carrier concentrations increased with the P dopant is increased. Temperature-dependent resistivity revealed a reduction in activation energy (for the donor), as the P content is increased in the In6Se7:P samples. Kelvin probe measurement shows a decrease in work function (i.e., an energy increase of Fermi level) of the n-type In6Se7 multilayers with the increase of P content. The indirect and direct band gaps for all of the multilayer In6Se7:P of different P composition are identical. They are determined to be 0.732 eV (indirect) and 0.772 eV (direct) obtained by microtransmittance and microthermoreflectance (µTR) measurements. A rectified n-n+ homojunction was formed by stacking multilayered In6Se7/In6Se7:P 5%. The built-in potential is about Vbi ∼ 0.15 V. It agrees well with the work function difference between the two layer compounds.

Silicon-van der Waals heterointegration for CMOS-compatible logic-in-memory design.

Silicon CMOS-based computing-in-memory encounters design and power challenges, especially in logic-in-memory scenarios requiring nonvolatility and reconfigurability. Here, we report a universal design for nonvolatile reconfigurable devices featuring a 2D/3D heterointegrated configuration. By leveraging the photo-controlled charge trapping/detrapping process and the partially top-gated energy band landscape, the van der Waals heterostacking achieves polarity storage and logic reconfigurable characteristics, respectively. Precise polarity tunability, logic nonvolatility, robustness against high temperature (at 85°C), and near-ideal subthreshold swing (80 mV dec-1) can be done. A comprehensive investigation of dynamic charge fluctuations provides a holistic understanding of the origins of nonvolatile reconfigurability (a trap level of 1013 cm-2 eV-1). Furthermore, we cascade such nonvolatile reconfigurable units into a monolithic circuit layer to demonstrate logic-in-memory computing possibilities, such as high-gain (65 at Vdd = 0.5 V) logic gates. This work provides an innovative 3D heterointegration prototype for future computing-in-memory hardware.

Elucidating the Competitive Adsorption of H2O and CO2 in CALF-20: New Insights for Enhanced Carbon Capture Metal-Organic Frameworks.

In light of the pressing need for efficient carbon capture solutions, our study investigates the simultaneous adsorption of water (H2O) and carbon dioxide (CO2) as a function of relative humidity in CALF-20, a highly scalable and stable metal-organic framework (MOF). Advanced computer simulations reveal that due to their similar interactions with the framework, H2O and CO2 molecules compete for the same binding sites, occupying similar void regions within the CALF-20 pores. This competition results in distinct thermodynamic and dynamical behaviors of H2O and CO2 molecules, depending on whether one or both guest species are present. Notably, the presence of CO2 molecules forces the H2O molecules to form more connected hydrogen-bond networks within smaller regions, slowing water reorientation dynamics and decreasing water entropy. Conversely, the presence of water speeds up the reorientation of CO2 molecules, decreases the CO2 entropy, and increases the propensity for CO2 to be adsorbed within the framework due to stronger water-mediated interactions. Due to the competition for the same void spaces, both H2O and CO2 molecules exhibit slower diffusion when molecules of the other guest species are present. These findings offer valuable strategies and insights into enhancing the differential affinity of H2O and CO2 for MOFs specifically designed for carbon capture applications.

Biexciton and Singlet Trion Upconvert Exciton Photoluminescence in a MoSe2 Monolayer Supported by Acoustic and Optical K-Valley Phonons.

Transition metal dichalcogenide monolayers represent unique platforms for studying both electronic and phononic interactions as well as intra- and intervalley exciton complexes. Here, we investigate the upconversion of exciton photoluminescence in MoSe2 monolayers. Within the nominal transparency window of MoSe2 the exciton emission is enhanced for resonantly addressing the spin-singlet negative trion and neutral biexciton at a few tens of meV below the neutral exciton transition. We identify that the A'1 optical phonon at the K valley provides the energy gain in the upconversion process at the trion resonance, while ZA(K) phonons with their spin- and valley-switching properties support the biexciton driven upconversion of the exciton emission. Interestingly, the latter upconversion process yields unpolarized exciton photoluminescence, while the former also leads to circularly polarized emission. Our study highlights high-order exciton complexes interacting with optical and acoustic K-valley phonons and upconverting light into the bright exciton.

Van der Waals Heterostructure Mid-Infrared Emitters with Electrically Controllable Polarization States and Spectral Characteristics.

Modern infrared (IR) microscopy, communication, and sensing systems demand control of the spectral characteristics and polarization states of light. Typically, these systems require the cascading of multiple filters, polarization optics, and rotating components to manipulate light, inevitably increasing their sizes and complexities. Here, we report two-terminal mid-infrared (mid-IR) emitters, in which tuning the polarity of the applied bias can switch their emission peak wavelengths and linear polarization states along two orthogonal orientations. Our devices are composed of two back-to-back p-n junctions formed by stacking anisotropic light-emitting materials, black phosphorus and black arsenic-phosphorus with MoS2. By controlling the crystallographic orientations and engineering the band profile of heterostructures, the emissions of two junctions exhibit distinct spectral ranges and polarization directions; more importantly, these two electroluminescence (EL) units can be independently activated, depending on the polarity of the applied bias. Furthermore, we show that when operating our emitter under the polarity-switched pulse mode, the time-averaged EL exhibits the characteristics of broad spectral coverage, encompassing the entire first mid-IR atmospheric window (λ: 3-5 µm), and electrically tunable spectral shapes.

Structure and thermodynamics of water adsorption in NU-1500-Cr.

Metal-organic frameworks (MOFs) are a class of materials with diverse chemical and structural properties, and have been shown to effectively adsorb various types of guest molecules. The mechanism of water adsorption in NU-1500-Cr, a high-performance atmospheric water harvesting MOF, is investigated using a combination of molecular dynamics simulations and infrared spectroscopy. Calculations of thermodynamic and dynamical properties of water as a function of relative humidity allow for following the adsorption process from the initial hydration stage to complete filling of the MOF pores. Initial hydration begins at the water molecules that saturate the open Cr3+ sites of the framework, which is then followed by the formation of water chains that extend along the channels connecting the hexagonal pores of the framework. Water present in these channels gradually coalesces and fills the hexagonal pores sequentially after the channels are completely hydrated. The development of hydrogen-bond networks inside the MOF pores as a function of relative humidity is characterized at the molecular level using experimental and computational infrared spectroscopy. A detailed analysis of the OH-stretch vibrational band indicates that the low-frequency tail stems from strongly polarized hydrogen-bonded water molecules, suggesting the presence of some structural disorder in the experimental samples. Strategies for designing efficient water harvesting MOFs are also proposed based on the mechanism of water adsorption in NU-1500-Cr.

Resonant Exciton Scattering Reveals Raman Forbidden Phonon Modes in Layered GeS.

Germanium monosulfide with an anisotropic puckered crystalline structure has recently attracted much attention due to its unique optical and electronic properties; however, exciton-phonon interactions were only superficially elucidated. We study the resonant Raman scattering and the photoluminescence of the optically active Γ-exciton in layered GeS flakes and evaluate the exciton and phonon responses on variations in the excitation energy, laser-light and emission polarizations, temperature, and laser power. A double-resonance mechanism allows for observing Raman forbidden (dark) first- and second-order longitudinal-optical phonon modes whose symmetries and energies are moreover calculated by density functional perturbation theory. For (quasi)-resonant exciton excitation, the selection rules become relaxed so that a fourth-order Fröhlich intraband process is mediated by the scattering of the electron with a longitudinal-optical and an acoustic phonon. Our results demonstrate considerable coupling between phonons and photogenerated carriers in GeS flakes and the high efficiency of multiorder scattering in optical processes.

Rydberg polaritons in ReS2 crystals.

Rhenium disulfide belongs to group VII transition metal dichalcogenides (TMDs) with attractive properties such as exceptionally high refractive index and remarkable oscillator strength, large in-plane birefringence, and good chemical stability. Unlike most other TMDs, the peculiar optical properties of rhenium disulfide persist from bulk to the monolayer, making this material potentially suitable for applications in optical devices. In this work, we demonstrate with unprecedented clarity the strong coupling between cavity modes and excited states, which results in a strong polariton interaction, showing the interest of these materials as a solid-state counterpart of Rydberg atomic systems. Moreover, we definitively clarify the nature of important spectral features, shedding light on some controversial aspects or incomplete interpretations and demonstrating that their origin is due to the interesting combination of the very high refractive index and the large oscillator strength expressed by these TMDs.

Upconversion photoluminescence excitation reveals exciton-trion and exciton-biexciton coupling in hBN/WS[Formula: see text]/hBN van der Waals heterostructures.

Monolayers of transition-metal dichalcogenides with direct band gap located at the binary [Formula: see text] points of the Brillouin zone are promising materials for applications in opto- and spin-electronics due to strongly enhanced Coulomb interactions and specific spin-valley properties. They furthermore represent a unique platform to study electron-electron and electron-phonon interactions in diverse exciton complexes. Here, we demonstrate processes in which the neutral biexciton and two negative trions, namely the spin-triplet and spin-singlet trions, upconvert light into a bright intravalley exciton in an hBN-encapsulated WS[Formula: see text] monolayer. We propose that the energy gains required in the polarized upconversion photoluminescence originate from different interactions including resonant optical phonons, a cooling of resident electrons and a non-local and an anisotropic electron-hole exchange, respectively. The temperature dependence (7-120 K) of the excitonic upconversion intensity obtained at excitation energies corresponding to the biexciton and trions provides insight into an increasing phonon population as well as a thermally enhanced electron scattering. Our study sheds new light on the understanding of excitonic spin and valley properties of van der Waals heterostructures and improves the understanding of photonic upconversion mechanisms in two-dimensional quantum materials.

Van der Waals Heterostructure Photodetectors with Bias-Selectable Infrared Photoresponses.

A bias-selectable photodetector, which can sense the wavelength of interest by tuning the polarity of applied bias, is useful for target discrimination and identification applications. So far, those detectors are generally based on the back-to-back photodiode configuration via exploiting epitaxial semiconductors as optoelectronic materials, which inevitably lead to high fabrication costs and complex device architectures. Here, we demonstrate that our band-engineered van der Waals heterostructures can be applied as bias-selectable photodetectors. Our first prototypical device is mainly composed of black phosphorus (BP) and MoTe2 light absorbers sandwiching a thin MoS2 hole blocking layer. By varying the bias polarity, its spectral photoresponse can be switched between near-infrared and short-wave infrared bands, and our optoelectronic characterizations indicate that the detector can exhibit high external quantum efficiency (EQE) and fast operation speed. With this framework, we further demonstrate the detector with bias-selectable photoresponses within the mid-wave infrared band using BP/MoS2/arsenic-doped BP heterostructures and show that our developed detectors can be integrated into a single-pixel imaging system to capture dual-band infrared imaging.

Internal Built-In Electric Fields at Organic-Inorganic Interfaces of Two-Dimensional Ruddlesden-Popper Perovskite Single Crystals.

Two-dimensional (2D) organic-inorganic hybrid Ruddlesden-Popper perovskites (OIRPPs), which consist of naturally formed "multiple quantum well (MQW)-like" structure, have received considerable interest in optoelectronic applications, owing to their outstanding optical properties and tailorable functionalities. While the quantum-confined electrons and holes at an MQW structure are under an applied electric field, the tilt of the energy bands may cause a significant influence on their optical properties. This work demonstrates the presence of internal built-in electric fields (BIEFs) at the as-synthesized 2D OIRPP single crystals. Spontaneous Franz-Keldysh oscillations, which usually act as the fingerprint to account for the presence of BIEFs in the MQW-like structures, are observed at 2D OIRPPs by the highly sensitive differential technique of modulated thermoreflectance spectroscopy. The strength of BIEFs at 2D OIRPP single crystals reduces with increased n values due to the increased width of the quantum well. The origin of the presence of BIEFs at 2D OIRPPs is further unveiled by atomically resolved scanning tunneling microscopy on their electronic band structures at organic-inorganic interfaces. Unlike the conventional III-V MQW semiconductors with the BIEFs, which are dominated by the spatial concentration gradients at heterointerfaces, the presence of BIEFs at the 2D OIRPP single crystals is attributed to the molecular dipoles within organic spacers pointing to the organic-inorganic interfaces. The discovery of internal BIEFs at the 2D OIRPPs may provide deep insight into understanding the fundamental optical properties for the future design of large-area and low-cost perovskite optoelectronic devices.

An all two-dimensional vertical heterostructure graphene/CuInP2S6/MoS2for negative capacitance field effect transistor.

As scaling down the size of metal oxide semiconductor field-effect transistors (FETs), power dissipation has become a major challenge. Lowering down the sub-threshold swing (SS) is known as an effective technique to decrease the operating voltage of FETs and hence lower down the power consumption. However, the Boltzmann distribution of electrons (so-called 'Boltzmann tyranny') implements a physical limit to the SS value. Use of negative capacitance (NC) effect has enabled a new path to achieve a low SS below the Boltzmann limit (60 mV dec-1at room temperature). In this work, we have demonstrated a NC-FET from an all two-dimensional (2D) metal ferroelectric semiconductor (MFS) vertical heterostructure: Graphene/CuInP2S6/MoS2. The negative capacitance from the ferroelectric CuInP2S6has enabled the breaking of the 'Boltzmann tyranny'. The heterostructure based device has shown steep slopes switching below 60 mV dec-1(lowest to < 10 mV dec-1) over 3 orders of source-drain current, which provides an avenue for all 2D material based steep slope FETs.

Upconversion of Light into Bright Intravalley Excitons via Dark Intervalley Excitons in hBN-Encapsulated WSe2 Monolayers.

Semiconducting monolayers of transition-metal dichalcogenides are outstanding platforms to study both electronic and phononic interactions as well as intra- and intervalley excitons and trions. These excitonic complexes are optically either active (bright) or inactive (dark) due to selection rules from spin or momentum conservation. Exploring ways of brightening dark excitons and trions has strongly been pursued in semiconductor physics. Here, we report on a mechanism in which a dark intervalley exciton upconverts light into a bright intravalley exciton in hBN-encapsulated WSe2 monolayers. Excitation spectra of upconverted photoluminescence reveals resonances at energies 34.5 and 46.0 meV below the neutral exciton in the nominal WSe2 transparency range. The required energy gains are theoretically explained by cooling of resident electrons or by exciton scattering with Λ- or K-valley phonons. Accordingly, an elevated temperature and a moderate concentration of resident electrons are necessary for observing the upconversion resonances. The interaction process observed between the inter- and intravalley excitons elucidates the importance of dark excitons for the optics of two-dimensional materials.

Pressure induced structural phase crossover of a GaSe epilayer grown under screw dislocation driven mode and its phase recovery.

Hydrostatically pressurized studies using diamond anvil cells on the structural phase transition of the free-standing screw-dislocation-driven (SDD) GaSe thin film synthesized by molecular beam epitaxy have been demonstrated via in-situ angle-dispersive synchrotron X-ray diffraction and Raman spectroscopy. The early pressure-driven hexagonal-to-rock salt transition at approximately ~ 20 GPa as well as the outstandingly structural-phase memory after depressurization in the SDD-GaSe film was recognized, attributed to the screw dislocation-assisted mechanism. Note that, the reversible pressure-induced structural transition was not evidenced from the GaSe bulk, which has a layer-by-layer stacking structure. In addition, a remarkable 1.7 times higher in bulk modulus of the SDD-GaSe film in comparison to bulk counterpart was observed, which was mainly contributed by its four times higher in the incompressibility along c-axis. This is well-correlated to the slower shifting slopes of out-of-plane phonon-vibration modes in the SDD-GaSe film, especially at low-pressure range (< 5 GPa). As a final point, we recommend that the intense density of screw dislocation cores in the SDD-GaSe lattice structure plays a crucial role in these novel phenomena.

Investigations of Electron-Electron and Interlayer Electron-Phonon Coupling in van der Waals hBN/WSe2/hBN Heterostructures by Photoluminescence Excitation Experiments.

Monolayers of transition metal dichalcogenides (TMDs) with their unique physical properties are very promising for future applications in novel electronic devices. In TMDs monolayers, strong and opposite spin splittings of the energy gaps at the K points allow for exciting carriers with various combinations of valley and spin indices using circularly polarized light, which can further be used in spintronics and valleytronics. The physical properties of van der Waals heterostructures composed of TMDs monolayers and hexagonal boron nitride (hBN) layers significantly depend on different kinds of interactions. Here, we report on observing both a strong increase in the emission intensity as well as a preservation of the helicity of the excitation light in the emission from hBN/WSe2/hBN heterostructures related to interlayer electron-phonon coupling. In combined low-temperature (T = 7 K) reflectivity contrast and photoluminescence excitation experiments, we find that the increase in the emission intensity is attributed to a double resonance, where the laser excitation and the combined Raman mode A'1 (WSe2) + ZO (hBN) are in resonance with the excited (2s) and ground (1s) states of the A exciton in a WSe2 monolayer. In reference to the 2s state, our interpretation is in contrast with previous reports, in which this state has been attributed to the hybrid exciton state existing only in the hBN-encapsulated WSe2 monolayer. Moreover, we observe that the electron-phonon coupling also enhances the helicity preservation of the exciting light in the emission of all observed excitonic complexes. The highest helicity preservation of more than 60% is obtained in the emission of the neutral biexciton and negatively charged exciton (trion) in its triplet state. Additionally, to the best of our knowledge, the strongly intensified emission of the neutral biexciton XX0 at double resonance condition is observed for the first time.

High-responsivity broad-band sensing and photoconduction mechanism in direct-Gap α-In2Se3 nanosheet photodetectors.

Photoconductivities (PCs) with high responsivity in two-dimensional (2D) diindium triselenide (In2Se3) nanostructures with α-phase hexagonal structure were studied. The In2Se3 nanosheet photodetectors fabricated by focused-ion beam technique exhibit broad spectral response with wavelength range from 300 nm to 1000 nm. The In2Se3 nanosheets achieve optimal responsivity of 720 A W-1 in near-infrared region (808 nm), and detectivity of 2.2 × 1012 Jones, which were higher than several 2D material photodetectors. The physical origins that result in high photoresponse in In2Se3 nanosheets such as carrier lifetime and mobility were also characterized by time-resolved PC and field-effect transistor measurements. The fast (hundred microseconds to milliseconds) and slow (seconds and longer) current rise or decay processes were both observed during the photoresponse. The narrowing (or relaxation) of depletion region and oxygen-sensitized photoconduction mechanism were suggested to be the causes of the efficient photoresponse in the In2Se3 nanostructure detectors. All these observations suggest that α-In2Se3 nanosheets could be a promising candidate for photosensitive material applications.

Ga2Se3 Defect Semiconductors: The Study of Direct Band Edge and Optical Properties.

Direct band edge is a crucial factor for a functional chalcogenide to be applied in luminescence devices, photodetectors, and solar-energy devices. In this work, the room-temperature band-edge emission of III-VI Ga2Se3 has been first observed by micro-photoluminescence (µPL) measurement. The emission peak is at 1.85 eV, which matches well with the band-edge transition that is measured by micro-thermoreflectance (µTR) and micro-transmittance (µTransmittance) for verification of the direct band edge of Ga2Se3. The temperature-dependent µTR spectra of Ga2Se3 show a general semiconductor behavior with its temperature-energy shift following Varshni-type variation. With the well-evident direct band edge, the peak responsivities of photovoltaic response (∼6.2 mV/µW) and photocurrent (∼2.25 µA/µW at f = 30 Hz) of defect zincblende Ga2Se3 can be, respectively, detected at ∼2.22 and ∼1.92 eV from a Cu/Ga2Se3 Schottky solar cell and a Ga2Se3 photoconductor. On the basis of experimental analysis, the optical band edge and photoresponsivity properties of a III-VI Ga2Se3 defect semiconductor are thus realized.