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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.
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Manipulating electronic polarizations such as ferroelectric or spin polarizations has recently emerged as an effective strategy for enhancing the efficiency of photocatalytic reactions. This study demonstrates the control of electronic polarizations modulated by ferroelectric and magnetic approaches within a two-dimensional (2D) layered crystal of copper indium thiophosphate (CuInP2S6) to boost the photocatalytic reduction of CO2. We investigate the substantial influence of ferroelectric polarization on the photocatalytic CO2 reduction efficiency, utilizing the ferroelectric-paraelectric phase transition and polarization alignment through electrical poling. Additionally, we explore enhancing the CO2 reduction efficiency by harnessing spin electrons through the synergistic introduction of sulfur vacancies and applying a magnetic field. Several advanced characterization techniques, including piezoresponse force microscopy, ultrafast pump-probe spectroscopy, in situ X-ray absorption spectroscopy, and in situ diffuse reflectance infrared Fourier transformed spectroscopy, are performed to unveil the underlying mechanism of the enhanced photocatalytic CO2 reduction. These findings pave the way for manipulating electronic polarizations regulated through ferroelectric or magnetic modulations in 2D layered materials to advance the efficiency of photocatalytic CO2 reduction.
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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.
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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.
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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.
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2D black phosphorus (BP) and rhenium dichalcogenides (ReX2 , X = S, Se) possess intrinsic in-plane anisotropic physical properties arising from their low crystal lattice symmetry, which has inspired their novel applications in electronics, photonics, and optoelectronics. Different from BP with poor environmental stability, ReX2 has low-symmetry distorted 1T structures with excellent stability. In ReX2 , the electronic structure is weakly dependent on layer numbers, which restricts their property tunability and device applications. Here, the properties are tuned, such as optical bandgap, Raman anisotropy, and electrical transport, by alloying 2D ReS2 and ReSe2 . Photoluminescence emission energy of ReS2(1-x) Se2x monolayers (x from 0 to 1 with a step of 0.1) can be continuously tuned ranging from 1.62 to 1.31 eV. Polarization behavior of Raman modes, such as ReS2 -like peak at 212 cm-1 , shifts as the composition changes. Anisotropic electrical property is maintained in ReS2(1-x) Se2x with high electron mobility along b-axis for all compositions of ReS2(1-x) Se2x .
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ReS2 and ReSe2 have recently been enthusiastically studied owing to the specific in-plane electrical, optical and structural anisotropy caused by their distorted one-layer trigonal (1 T) phase, whereas other traditional transition-metal dichalcogenides (TMDCs, e.g. MoS2 and WSe2) have a hexagonal structure. Because of this special property, more and versatile nano-electronics and nano-optoelectronics devices can be developed. In this work, 2D materials in the series ReS2-x Se x (0 ≤ x ≤ 2) have been successfully grown by the method of chemical vapor transport. The direct and indirect resonant emissions of the complete series of layers can be simultaneously detected by polarized micro-photoluminescence (µPL) spectroscopy when the thickness of the ReS2-x Se x is greater than â¼70 nm. When it is less than 70 nm, only three direct excitonic emissions-E 1ex, E 2ex and E Sex-are detected. For the thick (bulk) ReS2-x Se x , more stacking of the ReX2 monolayers even flattens and shifts the valence-band maximum from Γ to the other K- or M-related points, thus leading to the coexistence of direct and indirect resonant light emissions from the c-plane ReX2. The transmittance absorption edge of each bulk ReX2 (a few microns thick) usually has a lower energy than those of the direct E 1ex and E 2ex excitonic emissions to form indirect absorption. The coexistence of direct and indirect emissions in ReX2 is a unique characteristic of a 2D layered semiconductor possessing triclinic low symmetry.
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Single crystals of CuAlS2 and AgAlS2 were grown by chemical vapor transport method using ICl3 as the transport. The as-grown CuAlS2 crystals reveal transparent and light-green color. Most of them possess a well-defined (112) surface. The AgAlS2 crystals essentially show transparent and white color in vacuum. As the AgAlS2 was put into the atmosphere, the crystal surface gradually darkened and became brownish because of the surface reaction with humidity or hydrogen gas. After a long-term chemical reaction process, the AgAlS2 will transform into a AgAlO2 oxide with yellow color. From x-ray diffraction measurements, both CuAlS2 and AgAlS2 as-grown crystals show single-phase and isostructural to a chalcopyrite structure. The (112) face is more preferable for the formation of the chalcopyrite crystals. The energies of interband transitions of the CuAlS2 and AgAlS2 were determined accurately by thermoreflectance measurements in a wide energy range of 2-6 eV. The valence-band electronic structures of CuAlS2 and AgAlS2 have been detailed and characterized using polarized-thermoreflectance measurements in the temperature range between 30 and 300 K. The band-edge transitions belonging to the E(â¥) and E(â¥) polarizations have been, respectively, identified. The band edge of AgAlS2 is near 3.2 eV while that of AgAlS2 is about 3.5 eV. On the basis of the experimental analyses, optical and sensing behaviors of the chalcopyrite crystals have been realized.
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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.
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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 â¼ 0.15 V. It agrees well with the work function difference between the two layer compounds.
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Anisotropic optical 2D materials are crucial for achieving multiple-quanta functions within quantum materials, which enables the fabrication of axially polarized electronic and optoelectronic devices. In this work, multiple excitonic emissions owning polarization-sensitive orientations are clearly detected in a multilayered quasi-1D ZrS3 nanoribbon with respect to the nanostripe edge. Four excitons denoted as AS1, AS2, AS, and A2 with E ⥠b polarized direction and one prominent A1 exciton with E || b polarized emission are simultaneously detected in the polarized micro-photoluminescence (µPL) measurement of 1.9-2.2 eV at 10 K. In contrast to light emission, polarized micro-thermoreflectance (µTR) measurements are performed to identify the polarization dependence and verify the excitons in the multilayered ZrS3 nanoribbon from the perspective of light absorption. At 10 K, a prominent and broadened peak on the lower-energy side, containing an indirect resonant emission (DI) observed by µPL and an indirect defect-bound exciton peak (AInd) observed by both µPL and µTR, is simultaneously detected, confirming the existence of a quasi-direct band edge in ZrS3. A van der Waals stacked p-GaSe/n-ZrS3 heterojunction solar cell is fabricated, which demonstrates a maximum axially-polarized conversion efficiency up to 0.412% as the E || b polarized light incident onto the device.
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The α-phase Bi(2)O(3) (α-Bi(2)O(3)) is a crucial and potential visiblelight photocatalyst material needless of intentional doping on accommodating band gap. The understanding on fundamental optical property of α-Bi(2)O(3) is important for its extended applications. In this study, bismuth oxide nanowires with diameters from tens to hundreds nm have been grown by vapor transport method driven with vapor-liquid-solid mechanism on Si substrate. High-resolution transmission electron microscopy and Raman measurement confirm α phase of monoclinic structure for the as-grown nanowires. The axial direction for the as-grown nanowires was along < 122 >. The band-edge structure of α-Bi(2)O(3) has been probed experimentally by thermoreflectance (TR) spectroscopy. The direct band gap was determined accurately to be 2.91 eV at 300 K. Temperaturedependent TR measurements of 30-300 K were carried out to evaluate temperature-energy shift and line-width broadening effect for the band edge of α-Bi(2)O(3) thin-film nanowires. Photoluminescence (PL) experiments at 30 and 300 K were carried out to identify band-edge emission as well as defect luminescence for the α-Bi(2)O(3) nanowires. On the basis of experimental analyses of TR and PL, optical characteristics of direct band edge of α-Bi(2)O(3) nanowires have thus been realized.
Assuntos
Bismuto/química , Medições Luminescentes/métodos , Nanofios/química , Nanofios/ultraestrutura , Teste de MateriaisRESUMO
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.
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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.
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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.
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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.
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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.
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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.
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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.
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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.