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At least 613 records · Page 34

An optoelectronic heterostructure for neuromorphic computing: CdS/V 3 O 5

Nonvolatile resistive switching is one of the key phenomena for emerging applications in optoelectronics and neuromorphic computing. In most of the cases, an electric field is applied to a two terminal dielectric material device and leads to the formation of a low resistance filament due to ion migration. However, the stochastic nature of the ion migration can be an impediment for the device robustness and controllability, with uncontrolled variations of high and low resistance states or threshold voltages. Here, we report an optically induced resistive switching based on a CdS/V 3 O 5 heterostructure which can overcome this issue. V 3 O 5 is known to have a second order insulator to metal transition around T c ≈ 415 K, with an electrically induced threshold switching at room temperature. Upon illumination, the direct transfer of the photoinduced carriers from the CdS into V 3 O 5 produces a nonvolatile resistive switching at room temperature. The initial high resistance can be recovered by reaching the high temperature metallic phase, i.e., temperatures above T c . Interestingly, this resistive switching becomes volatile around the T c . In conclusion, by locally manipulating the volatile and nonvolatile resistive switching using electric field and light, this system is a promising platform for hardware based neuromorphic computing implementations.

97 MATHEMATICS AND COMPUTING↗

Synthesis of luminescent core/shell α-Zn 3 P 2 /ZnS quantum dots

Metal chalcogenide nanoparticles offer vast control over their optoelectronic properties via size, shape, composition, and morphology which has led to their use across fields including optoelectronics, energy storage, and catalysis. While cadmium and lead-based nanocrystals are prevalent in applications, concerns over their toxicity have motivated researchers to explore alternate classes of nanomaterials based on environmentally benign metals such as zinc and tin. The goal of this research is to identify material systems that offer comparable performance to existing metal chalcogenide systems from abundant, recyclable, and environmentally benign materials. With band gaps that span the visible through the infrared, II–V direct band gap semiconductors such as tetragonal zinc phosphide (α-Zn 3 P 2 ) are promising candidates for optoelectronics. To date, syntheses of α-Zn 3 P 2 nanoparticles have been hindered because of the toxicity of zinc and phosphorus precursors, surface oxidation, and defect states leading to carrier trapping and low photoluminescence quantum yield. Here, we report a colloidal synthesis of quantum confined α-Zn 3 P 2 nanoparticles from common phosphorus precursor tris(trimethylsilyl)phosphine and environmentally benign zinc carboxylates. Shelling of the nanoparticles with zinc sulfide is shown as a method of preventing oxidation and improving the optical properties of the nanoparticles. These results show a route to stabilizing α-Zn 3 P 2 nanoparticles for optoelectronic device applications.

25 ENERGY STORAGE↗

Strain-Modified Raman Responses in Monolayer MoS 2 Nanobubbles Resolved at 5 nm

The formation of nanoscale bubbles is an unavoidable consequence during the transfer of two-dimensional materials onto target substrates, driven by van der Waals interactions at the interface. While often viewed as imperfections, these nanoscale bubbles have garnered considerable scientific interest due to the substantial in-plane strain gradients they induce, which in turn give rise to a variety of intriguing optoelectronic effects, particularly in semiconducting transition metal dichalcogenides. Determining and analyzing the strain distribution within nanobubbles at the nanoscale is crucial for advancing our understanding of these underlying strain-induced effects. Here, we present a high-resolution scanning tunneling microscopy-based tip-enhanced Raman spectroscopic investigation of localized nanoscale strain distribution within the nanobubbles formed between monolayer MoS 2 and Au interface. By employing cryogenic temperature (78 K), we successfully differentiate the nanoscale Raman signatures between nanobubble edge and pristine MoS 2 . We verify a maximum tensile strain of ∽1.15–1.34% at the nanobubble edge, which gradually diminishes toward the center, yielding a cross-sectional strain profile consistent with a doughnut-shaped distribution. Furthermore, we report to achieve ∽5 nm spatial resolution in probing such edge-localized strain within the nanobubble. In addition, comparative average strain analysis of such MoS 2 nanobubbles is conducted via geometric mechanistic analysis such as membrane and nonlinear plate theories, providing key insight into the geometric nature near the bubble edge. Our work provide fundamental information about strain-induced nanoscale chemical understanding of 2D materials on the nanometer scale, paving the way for practical applications of nanobubbles in strain-engineered optoelectronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Strain-Induced Trapping of Indirect Excitons in MoSe 2 /WSe 2 Heterostructures

Understanding and control of excitons in transition metal dichalcogenide (TMD) materials are essential for the exploration of the rich many-body physics in TMDs and their applications in photonic and optoelectronic devices. Local strain modulation has been utilized as an effective approach for creating potential traps and localizing intralayer excitons in TMD monolayers. Here, we investigate the effect of strains on indirect excitons in TMD heterostructures. The emergence of narrow spectral peaks from the strained sites together with their drastically reduced lifetimes indicates the formation of potential traps in the heterostructures and the trapping of indirect excitons in them. The absence of photon-antibunching from these trapped indirect excitons further reveals their weak localization in the potential traps. Here, our study indicates that, compared to the case of intralayer excitons, narrower potential traps are required for obtaining highly localized indirect excitons due to their unique properties. These findings have important implications for creating long-wavelength quantum emitters in TMD heterostructures and the exploration of indirect exciton condensation and motion in TMDs.

36 MATERIALS SCIENCE↗

Charge transport in mixed metal halide perovskite semiconductors

Investigation of the inherent field-driven charge transport behaviour of three-dimensional lead halide perovskites has largely remained challenging, owing to undesirable ionic migration effects near room temperature and dipolar disorder instabilities prevalent specifically in methylammonium-and-lead-based high-performing three-dimensional perovskite compositions. Here, in this paper, we address both these challenges and demonstrate that field-effect transistors based on methylammonium-free, mixed metal (Pb/Sn) perovskite compositions do not suffer from ion migration effects as notably as their pure-Pb counterparts and reliably exhibit hysteresis-free p-type transport with a mobility reaching 5.4 cm 2 V –1 s -1 . The reduced ion migration is visualized through photoluminescence microscopy under bias and is manifested as an activated temperature dependence of the field-effect mobility with a low activation energy (~48 meV) consistent with the presence of the shallow defects present in these materials. An understanding of the long-range electronic charge transport in these inherently doped mixed metal halide perovskites will contribute immensely towards high-performance optoelectronic devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Versatile acid solvents for pristine carbon nanotube assembly

Chlorosulfonic acid and oleum are ideal solvents for enabling the transformation of disordered carbon nanotubes (CNTs) into precise and highly functional morphologies. Currently, processing these solvents using extrusion techniques presents complications due to chemical compatibility, which constrain equipment and substrate material options. Here, we present a novel acid solvent system based on methanesulfonic or p-toluenesulfonic acids with low corrosivity, which form true solutions of CNTs at concentrations as high as 10 g/liter (≈0.7 volume %). The versatility of this solvent system is demonstrated by drop-in application to conventional manufacturing processes such as slot die coating, solution spinning continuous fibers, and 3D printing aerogels. Through continuous slot coating, we achieve state-of-the-art optoelectronic performance (83.6 %T and 14 ohm/sq) at industrially relevant production speeds. This work establishes practical and efficient means for scalable processing of CNT into advanced materials with properties suitable for a wide range of applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Colloidal Synthesis of Single-Layer Quasi-Ruddlesden–Popper Phase Bismuth-Based Two-Dimensional Perovskite Nanosheets with Controllable Optoelectronic Properties

Single- and few-layered two-dimensional (2D) nanomaterials have attracted intense research interest in the last two decades due to their unique electronic and optoelectronic properties leading to various potential applications. Herein, we report the colloidal synthesis of Bi-based 2D perovskite nanosheets (PEG6-NH 3 +) n Cs 3-n Bi 2 X 9 , where X = CI, Br, and I, through careful design of reaction conditions and selection of poly(ethylene glycol) (PEG6) surface passivating ligands. The 2D nanosheets are similar to 5 nm in thickness with micron-sized lateral dimensions and display composition-dependent band gap and work function modulation. Furthermore, small-angle X-ray scattering analysis substantiates that the individual inorganic crystal layer, Cs 3-n Bi 2 X 9 , is separated by the spacer, PEG6 ligand. Additionally, we determined that PEG6-NH 2 is an essential passivating ligand and spacer for the formation of Bi-based 2D nanosheets. Most importantly, controlled crystallization of the colloidal dispersion of nanosheets results in the formation of superlattice microstructures of the quasi-Ruddlesden-Popper phase. These microstructures can be exfoliated to ultrathin nanosheets by overcoming the van der Waals interaction between the organic passivating layers. The controlled synthesis of lead-free 2D perovskite nanosheets presented here can expand their utility to photocatalytic and optoelectronic applications with reduced toxicity.

36 MATERIALS SCIENCE↗

Local ordering in Ge/Ge–Sn semiconductor alloy core/shell nanowires revealed by extended x-ray absorption fine structure (EXAFS)

Short-range atomic order in semiconductor alloys is a relatively unexplored topic that may promote design of new materials with unexpected properties. Here, local atomic ordering is investigated in Ge–Sn alloys, a group-IV system that is attractive for its enhanced optoelectronic properties achievable via a direct gap for Sn concentrations exceeding ≈10 at. %. The substantial misfit strain imposed on Ge–Sn thin films during growth on bulk Si or Ge substrates can induce defect formation; however, misfit strain can be accommodated by growing Ge–Sn alloy films on Ge nanowires, which effectively act as elastically compliant substrates. In this work, Ge core/Ge 1–x Sn x (x ≈ 0.1) shell nanowires were characterized with extended x-ray absorption fine structure (EXAFS) to elucidate their local atomic environment. Simultaneous fitting of high-quality EXAFS data collected at both the Ge K-edge and the Sn K-edge reveals a large (≈ 40%) deficiency of Sn in the first coordination shell around a Sn atom relative to a random alloy, thereby providing the first direct experimental evidence of significant short-range order in this semiconductor alloy system. Furthermore, comparison of path length data from the EXAFS measurements with density functional theory simulations provides alloy atomic structures consistent with this conclusion.

36 MATERIALS SCIENCE↗

Electrochemical ion insertion from the atomic to the device scale

Electrochemical ion insertion involves coupled ion–electron transfer reactions, transport of guest species and redox of the host. The hosts are typically anisotropic solids with 2D conduction planes but can also be materials with 1D or isotropic transport pathways. These insertion compounds have traditionally been studied in the context of energy storage but also find extensive applications in electrocatalysis, optoelectronics and computing. Recent developments in operando, ultrafast and high-resolution characterization methods, as well as accurate theoretical simulation methods, have led to a renaissance in the understanding of ion-insertion compounds. In this Review, we present a unified framework for understanding insertion compounds across timescales and length scales ranging from atomic to device levels. Using graphite, transition metal dichalcogenides, layered oxides, oxyhydroxides and olivines as examples, we explore commonalities in these materials in terms of point defects, interfacial reactions and phase transformations. We illustrate similarities in the operating principles of various ion-insertion devices, ranging from batteries and electrocatalysts to electrochromics and thermal transistors, with the goal of unifying research across disciplinary boundaries.

36 MATERIALS SCIENCE↗

Photocarrier Dynamics in MoTe 2 Nanofilms with 2 H and Distorted 1 T Lattice Structures

Molybdenum telluride (MoTe 2 ), an emerging layered two-dimensional (2D) material, possesses excellent phase-changing properties. Previous studies revealed its reversible transition between 2H and 1T' phases with a transition energy as small as 35 meV. Since 1T'-MoTe 2 is metallic, it can serve as an electrical contact for semiconducting 2H-MoTe 2 -based optoelectronic devices. Here, the photocarrier dynamics in MoTe 2 nanofilms synthesized by a one-step method and with coexisting multiple phases are investigated by transient absorption measurements. Both the energy relaxation time and the recombination lifetime of the excitons are shorter in the 1T'-MoTe 2 compared to its 2H phase. Furthermore, these results provide information on the different photocarrier dynamical properties of these two phases, which is important for future 2D optoelectronic and phase-change electronic devices based on MoTe 2 .

36 MATERIALS SCIENCE↗

Anharmonic Exciton‐Phonon Coupling in Metal‐Organic Chalcogenides Hybrid Quantum Wells

Abstract In contrast to inorganic quantum wells, hybrid quantum wells (HQWs) based on metal‐organic semiconductors are characterized by relatively soft lattices, in which excitonic states can strongly couple to lattice phonons. Therefore, understanding the lattice's impact on exciton dynamics is essential for harnessing the optoelectronic potential of HQWs. Beyond 2D metal halide perovskites, layered metal‐organic chalcogenides (MOCs), which are an air‐stable, underexplored material class hosting room‐temperature excitons, can be exploited as photodetectors, light emitting devices, and ultrafast photoswitches. Here, the role of phonons in the optical transitions of the prototypical MOC [AgSePh] ∞ is elucidated. Impulsive stimulated Raman scattering (ISRS) allows the detection of coherent exciton oscillations driven by Fröhlich interaction with low‐energy optical phonons. Steady state absorption and Raman spectroscopies reveal a strong exciton‐phonon coupling (Huang‐Rhys parameter ≈1.7) and its anharmonicity, manifested as a nontrivial temperature‐dependent Stokes shift. The ab initio calculations support these observations, hinting at an anharmonic behavior of the low‐energy phonons <200 cm −1 . These results untangle complex exciton‐phonon interactions in MOCs, establishing an ideal testbed for room‐temperature many‐body phenomena.

36 MATERIALS SCIENCE↗

Poly(cyclosilane) Connectivity Tunes Optical Absorbance

We report herein the influence of skeletal connectivity on the conformation-dependent optical properties of cyclosilane homo- and copolymers. 1,3-Linked cyclosilanes were bathochromically shifted by 20 nm in solution relative to 1,4-linked cyclosilanes, an effect reproduced by quantum chemical calculations on oligomeric model systems. Polysilane optical properties are conformation-dependent, and 1,3-linked cyclosilanes were hypothesized to adopt a favorable conformation unavailable to 1,4-linked cyclosilanes constrained to an endocyclic gauche conformation. Copolymerization of the isomeric cyclosilanes 1,3Si 6 and 1,4Si 6 afforded linear statistical copolymers, as characterized by 1 H and 29 Si NMR spectroscopies. The distinct connectivity of each comonomer was found to give rise to tunable absorption spectra, where the position of the absorption band systematically increased with the increased corporation of 1,3Si 6 . Computational studies pointed to conformation-dependent changes in orbital symmetry in shifting the most intense transition from the low-energy highest occupied molecular orbital (HOMO) → lowest unoccupied molecular orbital (LUMO) transition to a higher-energy HOMO → LUMO + n transition. Here, the results of these studies demonstrate for the first time the role of silicon skeletal connectivity in controlling conformation and optoelectronic properties and provide new insight into the structure-based design of solution-processable silicon-based polymeric materials.

36 MATERIALS SCIENCE↗

Snapshots of a light-induced metastable hidden phase driven by the collapse of charge order

Nonequilibrium hidden states provide a unique window into thermally inaccessible regimes of strong coupling between microscopic degrees of freedom in quantum materials. Understanding the origin of these states allows the exploration of far-from-equilibrium thermodynamics and the development of optoelectronic devices with on-demand photoresponses. However, mapping the ultrafast formation of a long-lived hidden phase remains a longstanding challenge since the initial state is not recovered rapidly. Here, using state-of-the-art single-shot spectroscopy techniques, we present a direct ultrafast visualization of the photoinduced phase transition to both transient and long-lived hidden states in an electronic crystal, 1T-TaS 2 , and demonstrate a commonality in their microscopic pathways, driven by the collapse of charge order. We present a theory of fluctuation-dominated process that helps explain the nature of the metastable state. Our results shed light on the origin of this elusive state and pave the way for the discovery of other exotic phases of matter.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Quantum Dots on Silicon-on-Insulator (QD/SOI): Nanoscale Strain and Band Structure Engineering (Final Report)

As the project titles indicate, the work focused on Group IV nanomembranes (NMs), thin functional layers, and interfaces, all with one or more dimensions at the nanoscale. The primary focus was discovery driven fundamental science. This approach led to surprising new, unexpected results that ended up being patentable and creating commercial value, but that were also high-impact science. Our effort divided into several overlapping thrusts: 1) strain engineering of NMs, via both lattice strain and externally applied strain, 2) interfaces between crystalline semiconductor NMs and other 2D sheets that are stacked or grown on each other, and 3) charge transport (electronics and optoelectronics) in thin layers, sheets, and surfaces. We accomplish these goals via 1) fabrication of new or higher-quality materials using NM approaches, 2) growth of new combinations, or 3) transfer and stacking to create new composites. The range of materials included combinations of Si, Ge, graphene, and several III-V compounds. The work has foundations in both nano- and mesoscale science.

36 MATERIALS SCIENCE↗

Rugged, Portable, Real-Time Optical Gaseous Analyzer for Hydrogen Fluoride

Hydrogen fluoride (HF) is a primary evolved combustion product of fluorinated and perfluorinated hydrocarbons. HF is produced during combustion by the presence of impurities and hydrogen- containing polymers including polyimides. This effect is especially dangerous in closed occupied volumes like spacecraft and submarines. In these systems, combinations of perfluorinated hydrocarbons and polyimides are used for insulating wiring. HF is both highly toxic and short-lived in closed environments due to its reactivity. The high reactivity also makes HF sampling problematic. An infrared optical sensor can detect promptly evolving HF with minimal sampling requirements, while providing both high sensitivity and high specificity. A rugged optical path length enhancement architecture enables both high HF sensitivity and rapid environmental sampling with minimal gaseous contact with the low-reactivity sensor surfaces. The inert optical sample cell, combined with infrared semiconductor lasers, is joined with an analog and digital electronic control architecture that allows for ruggedness and compactness. The combination provides both portability and battery operation on a simple camcorder battery for up to eight hours. Optical detection of gaseous HF is confounded by the need for rapid sampling with minimal contact between the sensor and the environmental sample. A sensor is required that must simultaneously provide the required sub-parts-permillion detection limits, but with the high specificity and selectivity expected of optical absorption techniques. It should also be rugged and compact for compatibility with operation onboard spacecraft and submarines. A new optical cell has been developed for which environmental sampling is accomplished by simply traversing the few mm-thick cell walls into an open volume where the measurement is made. A small, low-power fan or vacuum pump may be used to push or pull the gaseous sample into the sample volume for a response time of a few seconds. The optical cell simultaneously provides for an enhanced optical interaction path length between the environmental sample and the infrared laser. Further, the optical cell itself is comprised of inert materials that render it immune to attack by HF. In some cases, the sensor may be configured so that the optoelectronic devices themselves are protected and isolated from HF by the optical cell. The optical sample cell is combined with custom-developed analog and digital control electronics that provide rugged, compact operation on a platform that can run on a camcorder battery. The sensor is inert with respect to acidic gases like HF, while providing the required sensitivity, selectivity, and response time. Certain types of combustion events evolve copious amounts of HF, very little of other gases typically associated with combustion (e.g., carbon monoxide), and very low levels of aerosols and particulates (which confound traditional smoke detectors). The new sensor platform could warn occupants early enough to take the necessary countermeasures.

Pilgrim, Jeffrey↗

All-Inorganic Halide Perovskites as Potential Thermoelectric Materials: Dynamic Cation off-Centering Induces Ultralow Thermal Conductivity

Halide perovskites are anticipated to impact next generation high performance solar cells because of their extraordinary charge transport and optoelectronic properties. However, their thermal transport behavior has received limited attention. In this work, we studied the thermal transport and thermoelectric properties of the CsSnBr 3–x I x perovskites. We find a strong correlation between lattice dynamics and an ultralow thermal conductivity for series CsSnBr 3–x I x reaching 0.32 Wm –1 K –1 at 550 K. The CsSnBr 3–x I x also possess a decent Seebeck coefficient and controllable electrical transport properties. The crystallography data and theoretical calculations suggest the Cs atom deviates from its ideal cuboctahedral geometry imposed by the perovskite cage and behaves as a heavy atom rattling oscillator. This off-center tendency of Cs, together with the distortion of SnX 6 (X = Br or I) octahedra, produces a highly dynamic and disordered structure in CsSnBr 3–x I x , which gives rise to a very low Debye temperature and phonon velocity. Moreover, the low temperature heat capacity data suggests strong coupling between the low frequency optical phonons and heat carrying acoustical phonons. In conclusion, this induces strong phonon resonance scattering that induces the ultralow lattice thermal conductivity of CsSnBr 3–x I x .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dopants, Isotope, Pressure and Lead Sequestration for Hybrid Perovskite Materials

Dopants, Isotope, Pressure and Lead Sequestration for Hybrid Perovskite Materials The soaring power conversion efficiency (PCE) of solution process-based organic-inorganic hybrid perovskites solar cells (PSCs) assures their membership in the competitive photovoltaic technologies. However, stability, toxicity and scalability are the three grand challenges that still impedes the market adoption of PSCs. Careful fundamental studies on how their fascinating optoelectronic properties is related to their structures may provide leads to these challenges and also spin off new applications. In this talk, I will present our recent study on the dopants, isotope and pressure effects on hybrid perovskite materials (HPMs). We discovered an interesting bipolar electron injection in LiCl-doped MAPbI 3 -based UV detectors that respond to the energy of UV photons in distinguished photocurrents polarity. We also investigated how the underline interaction between the mass of the cationic rotors and the inorganic lattice in HPMs by isotope effect. In-situ synchrotron X-ray and time-resolved photoluminescence revealed abnormal optoelectronic properties of HPMs by modulating their bond angles and bond lengths using high pressure techniques. Moreover, I will also discuss our new technology to sequestrate lead leakage on perovskite solar cells that can absorb >99% leaked Pb ions under severe device damge while without sacrificing the PCE under normal operational conditions.

Xu, Tao↗