Search NASA⌕ Search

SEARCH · Search NASA

Results for “quantum confinement”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 109 records · Page 6

One-Dimensional Electron Gas Confined along Nanowrinkles in a Unidirectional Charge Density Wave Material

Two-dimensional (2D) materials inherently exhibit instabilities. Structurally, this may lead to modulations along the third dimension, e.g., wrinkles. Electronically, 2D instabilities can manifest themselves as charge density waves (CDWs). Although wrinkles can alter anisotropic electronic structures susceptible to forming CDWs, less is known about their impact on broken-symmetry ground states. Here, in this study, using scanning tunneling microscopy and spectroscopy, we investigate the CDW states on the wrinkled surface of DyTe 3 . We identify elongated, parallel nanoscale wrinkles stabilized by ribbon-shaped defects. Interestingly, the CDW order persists across the nanowrinkles with a gradual phase shift but is locally suppressed near the defects, where phase windings occur. In addition, these defects induce quantum confinement effects along the nanowrinkles, indicating the presence of one-dimensional metallic states with hole- like dispersion, while angle-resolved photoemission spectroscopy identifies a gap along the wrinkle direction. We ascribe this discrepancy to strain-induced changes in the Fermi surface, which lead to the closure of the gap at the sites of the nanowrinkles. Taken together, our results underscore the complex interplay between structural features and Fermi surface topology, allowing for the deliberate manipulation of quantum states in strongly correlated systems via local crystal deformations.

nanowrinkles↗

Exciton-Phonon Coupling and Carrier Relaxation in PbS Quantum Dots: The Case of Carboxylate Ligands

Some ligand-nanocrystal combinations exhibit rapid cooling of highly excited electronic states while other nanocrystal/shell combinations do not appear to have this effect. There remains a need to identify the distinguishing properties of ligand-nanocrystal interactions that avoid such rapid relaxation processes to guide the design of colloidal quantum dots (QDs) that take advantage of multiple exciton generation or hot-carrier extraction processes. Here, we use mid-infrared transient absorption spectroscopy to investigate the influence that carboxylate ligands with distinct excited state surface chemistries has on exciton-phonon coupling and hot exciton relaxation in PbS quantum dot (QD) films. Our findings reveal that despite significant differences in the excited state surface chemistry of oleate (OA) and iodide/mercaptopropionic acid (I-/MPA) ligands, PbS QD films passivated with both ligand types exhibit identical electronic relaxation rates and exciton-phonon coupling strengths within experimental precision. The data suggest that the inorganic lattice is the principal source of exciton-phonon coupling that influences hot exciton relaxation, rather than the vibronic modes of carboxylate ligands. The size-dependent nature of the exciton-phonon coupling strength is consistent with the localization of charge on the QD surfaces, which enhances the mixing of electronic and nuclear coordinates particularly when the electronic states are more quantum confined in smaller nanocrystals.

14 SOLAR ENERGY↗

Distance Dependence of Förster Resonance Energy Transfer Rates in 2D Perovskite Quantum Wells via Control of Organic Spacer Length

Two-dimensional (2D) semiconductors are attractive candidates for a variety of optoelectronic applications owing to the unique electronic properties that arise from quantum confinement along a single dimension. Incorporating nonradiative mechanisms that enable directed migration of bound charge carriers, such as Forster resonance energy transfer (FRET), could boost device efficiencies provided that FRET rates outpace undesired relaxation pathways. However, predictive models for FRET between distinct 2D states are lacking, particularly with respect to the distance d between a donor and acceptor. We approach FRET in systems with binary mixtures of donor and acceptor 2D perovskite quantum wells (PQWs), and we synthetically tune distances between donor and acceptor by varying alkylammonium spacer cation lengths. FRET rates are monitored using transient absorption spectroscopy and ultrafast photoluminescence, revealing rapid picosecond lifetimes that scale with spacer cation length. We theoretically model these binary mixtures of PQWs, describing the emitters as classical oscillating dipoles. Finally, we find agreement with our empirical lifetimes and then determine the effects of lateral extent and layer thickness, establishing fundamental principles for FRET in 2D materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of quantum well thickness on efficiency loss in InGaN/GaN LEDs: Challenges for thin-well designs

We investigate the impact of quantum well (QW) thickness on efficiency loss in c-plane InGaN/GaN LEDs using a small-signal electroluminescence technique. Multiple mechanisms related to efficiency loss are independently examined, including injection efficiency, carrier density vs current density relationship, phase space filling, quantum-confined Stark effect, and Coulomb enhancement. An optimal QW thickness of around 2.7 nm in these InGaN/GaN LEDs was determined for QWs having constant In composition. Despite improved control of deep-level defects and lower carrier density at a given current density, LEDs with thin QWs still suffer from an imbalance in enhancement effects on the radiative and intrinsic Auger–Meitner recombination coefficients. The imbalance in enhancement effects results in a decline in internal quantum efficiency and radiative efficiency with decreasing QW thickness at low current density in LEDs with QW thicknesses below 2.7 nm. Here, we also investigate how LED modulation bandwidth varies with QW thickness, identifying the key trends and their implications for device performance.

36 MATERIALS SCIENCE↗

2D Quantum Mechanical Study of Nanoscale MOSFETs

With the onset of quantum confinement in the inversion layer in nanoscale MOSFETs, behavior of the resonant level inevitably determines all device characteristics. While most classical device simulators take quantization into account in some simplified manner, the important details of electrostatics are missing. Our work addresses this shortcoming and provides: (a) a framework to quantitatively explore device physics issues such as the source-drain and gate leakage currents, DIBL, and threshold voltage shift due to quantization, and b) a means of benchmarking quantum corrections to semiclassical models (such as density-gradient and quantum-corrected MEDICI). We have developed physical approximations and computer code capable of realistically simulating 2-D nanoscale transistors, using the non-equilibrium Green's function (NEGF) method. This is the most accurate full quantum model yet applied to 2-D device simulation. Open boundary conditions and oxide tunneling are treated on an equal footing. Electrons in the ellipsoids of the conduction band are treated within the anisotropic effective mass approximation. We present the results of our simulations of MIT 25, 50 and 90 nm "well-tempered" MOSFETs and compare them to those of classical and quantum corrected models. The important feature of quantum model is smaller slope of Id-Vg curve and consequently higher threshold voltage. Surprisingly, the self-consistent potential profile shows lower injection barrier in the channel in quantum case. These results are qualitatively consistent with ID Schroedinger-Poisson calculations. The effect of gate length on gate-oxide leakage and subthreshold current has been studied. The shorter gate length device has an order of magnitude smaller current at zero gate bias than the longer gate length device without a significant trade-off in on-current. This should be a device design consideration.

Svizhenko, Alexei↗

2D Quantum Transport Modeling in Nanoscale MOSFETs

With the onset of quantum confinement in the inversion layer in nanoscale MOSFETs, behavior of the resonant level inevitably determines all device characteristics. While most classical device simulators take quantization into account in some simplified manner, the important details of electrostatics are missing. Our work addresses this shortcoming and provides: (a) a framework to quantitatively explore device physics issues such as the source-drain and gate leakage currents, DIBL, and threshold voltage shift due to quantization, and b) a means of benchmarking quantum corrections to semiclassical models (such as density- gradient and quantum-corrected MEDICI). We have developed physical approximations and computer code capable of realistically simulating 2-D nanoscale transistors, using the non-equilibrium Green's function (NEGF) method. This is the most accurate full quantum model yet applied to 2-D device simulation. Open boundary conditions, oxide tunneling and phase-breaking scattering are treated on equal footing. Electrons in the ellipsoids of the conduction band are treated within the anisotropic effective mass approximation. Quantum simulations are focused on MIT 25, 50 and 90 nm "well- tempered" MOSFETs and compared to classical and quantum corrected models. The important feature of quantum model is smaller slope of Id-Vg curve and consequently higher threshold voltage. These results are quantitatively consistent with I D Schroedinger-Poisson calculations. The effect of gate length on gate-oxide leakage and sub-threshold current has been studied. The shorter gate length device has an order of magnitude smaller current at zero gate bias than the longer gate length device without a significant trade-off in on-current. This should be a device design consideration.

Svizhenko, Alexei↗

Vertical Architecture Solution-Processed Quantum Dot Photodetectors with Amorphous Selenium Hole Transport Layer

Colloidal quantum dots (CQDs) provide wide spectral tunability and high absorption coefficients owing to quantum confinement and large oscillator strengths, which along with solution processability, allow a facile, low-cost, and room-temperature deposition technique for the fabrication of photonic devices. However, many solution-processed CQD photodetector devices demonstrate low specific-detectivity and slow temporal response. To achieve improved photodetector characteristics, limiting carrier recombination and enhancing photogenerated carrier separation are crucial. In this study, we develop and present an alternate vertical-stack photodetector wherein we use a solution-processed quantum dot photoconversion layer coupled to an amorphous selenium (a-Se) wide-bandgap charge transport layer that is capable of exhibiting single-carrier hole impact ionization and is compatible with active-matrix readout circuitry. This a-Se chalcogenide transport layer enables the fabrication of high-performance and reliable solution-processed quantum dot photodetectors, with enhanced charge extraction capabilities, high specific detectivity (D* ~ 0.5–5 × 10 12 Jones), fast 3 dB electrical bandwidth (3 dB BW ~ 22 MHz), low dark current density (J D ~ 5–10 pA/cm 2 ), low noise current (i n ~ 20–25 fW/Hz 1/2 ), and high linear dynamic range (LDR ~130–150 dB) across the measured visible electromagnetic spectrum (~405–656 nm).

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Reversible Interfacial Charge Transfer and Delayed Emission in InP/ZnSe/ZnS Quantum Dots with Hexadecanethiol

The results in this paper show that holes are rapidly and reversibly transferred from red-emitting InP/ZnSe/ZnS quantum dots (QDs) to adsorbed hexadecanethiol (HDT) forming an equilibrium between the thiols and the QD valence band. Photoexcitation results in populations of holes in the valence band and in slightly higher-energy shell-localized traps. Trap to valence band hole tunneling results in a photoluminescence risetime having time constants varying from 300 ps to 2 ns. The presence of adsorbed HDT eliminates the slower risetime component, indicating that hole transfer from the shell-localized traps that are closest to the particle surface efficiently competes with tunneling to the QD core. This shows that the interfacial charge transfer equilibrium is established in less than 2 ns. The population of the shell-localized traps corresponds to a reservoir of hole states that eventually tunnel to the core-localized valence band, resulting in delayed emission. The amount of delayed emission increases rapidly with ZnSe shell thickness and is slightly blue-shifted from the prompt photoluminescence. We propose an energetic model in which the HDT/valence band equilibrium is affected by the extent of valence band quantum confinement and an electric field produced by core–shell interfacial dipoles. Furthermore, this model explains the core size, shell thickness, and photoluminescence (PL) wavelength dependence of this equilibrium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photoinduced charge transfer in transition metal dichalcogenide heterojunctions – towards next generation energy technologies

Increasing interest in using two-dimensional transition metal dichalcogenides (2D TMDCs) in optical energy conversion technologies creates a demand for improving the yields and lifetimes of photogenerated charge carriers. Despite inherently fast photocarrier decay in neat 2D TMDCs, the unique photophysics in these quantum-confined systems motivates continued effort to control the evolution of photoexcited states and create functional devices. Here, an intriguing strategy to accomplish this goal is to employ TMDCs in heterojunctions with appropriate semiconductors, where energy level offsets drive photoinduced charge transfer (PCT) across material interfaces. PCT in TMDC-based systems can be optimized for many different applications, such as driving free carriers to photocatalytic sites for redox reactions like water splitting, extracting charge to perform work in photovoltaics or photodetectors, and manipulating the spin and momentum valley electronic degrees of freedom for quantum computing systems. Here, we review recent strides in optimizing PCT for such applications through greater fundamental understanding of the photophysics that occurs at TMDC/semiconductor interfaces. After giving an overview of isolated TMDC properties, synthetic methods, and the basics of PCT, we discuss TMDCs in heterojunctions with several classes of materials, including other TMDCs, small molecule semiconductors, polymers, single-walled carbon nanotubes, quantum dots, perovskites, and electrolytes. In addition to highlighting the unique benefits of each materials category, we also identify parallels across common themes, such as the roles of charge-transfer states, spin, electronic coupling, delocalization, interfacial atomic morphology, and the precise design of energy landscapes to direct charge and energy motion. We hope to capture a broad range of the valuable work in this fast-paced field to inspire new research directions for employing PCT in targeted TMDC-based systems.

30 DIRECT ENERGY CONVERSION↗

Identity of the reversible hole traps in InP/ZnSe core/shell quantum dots

Density functional theory calculations are combined with time-resolved photoluminescence experiments to identify the species responsible for reversible trapping of holes following photoexcitation of InP/ZnSe/ZnS core/shell/shell quantum dots (QDs) having excess indium in the shell. Several possible assignments are considered, and a substitutional indium adjacent to a zinc vacancy, In 3+ /V Zn 2- , is found to be the most likely. This assignment is consistent with the observation that trapping occurs only when the QD has excess indium and is supported by experiments showing that the addition of zinc oleate or acetate decreases the extent of trapping, presumably by filling some of the vacancy traps. We also show that addition of alkyl carboxylic acids causes increased trapping, presumably by creation of additional zinc vacancies. The calculations show that either a single In 2+ ion or an In 2+ -In 3+ dimer is much too easily oxidized to form the reversible traps observed experimentally, while In 3+ is far too difficult to oxidize. Additional experimental data on InP/ZnSe/ZnS QDs synthesized in the absence of chloride demonstrates that the reversible traps are not associated with Cl - . Furthermore, a zinc vacancy adjacent to a substitutional indium is calculated to have its highest occupied orbitals about 1 eV above the top of the valence band of bulk ZnSe, in the appropriate energy range to act as reversible traps for quantum confined holes in the InP valence band. The associated orbitals are predominantly composed of p orbitals on the Se atoms adjacent to the Zn vacancy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multireference diffusion Monte Carlo reaches 2D materials

Abstract Quantum confinement in 2D materials strongly enhances electronic correlation effects. Therefore, predicting the properties of these unique materials, with both a high level of accuracy and computational efficiency, without relying on adjustable parameters or functionals, remains an outstanding theoretical challenge. The majority of theoretical studies are based on the approximations of density functional theory (DFT). The reliability of DFT predictions are heavily dependent on the choice of an approximated exchange-correlation functional. Here, we estimate the magnitude of impact of correlation on the total energy for the quintessential 2D material, graphene, by performing and comparing state-of-the-art selected CI and quantum Monte Carlo extrapolated calculations for a single unit cell at the$$\Gamma$$point. We demonstrate that Self-Healing Diffusion Monte Carlo (SHDMC) obtains a very compact, but high-quality wavefunction for this system that lacks the strong basis set dependence displayed by state of the art quantum chemistry methods. The SHDMC wavefunction is of higher quality compared to that obtained from sCI, in the same orbital basis, while being$$\sim$$ 1000 times smaller in terms of determinant count compared to sCI. We also demonstrate that extrapolating SHDMC results to the infinite determinant limit compares extremely well with complete basis set extrapolated sCI. Our work paves the way for future validation of SHDMC applied to challenging 2D materials.

Science & Technology - Other Topics↗

Dielectric screening and vacancy formation for large neutral and charged Si n H m ( n > 1500 ) nanocrystals using real-space pseudopotentials

A commonly used procedure for computing the properties of defects in crystalline materials is to consider a large supercell that includes the defect of interest. This is a straightforward technique as standard energy band codes can be used for such computations. For neutral defects, the only impediment of such an approach is to avoid defect-defect interactions between adjoining cells. However, this procedure can be complex if the defect of interest is charged as the system at large contains Coulombic divergences. Moreover, some have recently argued that the conventional definition of formation energies for charged defects cannot be reconciled with statistical mechanics. Here, we focus on an alternative approach. We consider large nanocrystals wherein a charged defect can be placed. Since the system is confined, a charged defect within the nanocrystal does not result in a Coulombic divergence. The chief impediment is computational, i.e., while no defect-defect or Coulombic divergences are present, the nanocrystal must be sufficiently large to allow the system to properly replicate a bulklike configuration. With the development of new algorithms and hardware advances, computations for systems of sufficient size to address this issue are feasible. In particular, we solve the Kohn-Sham equation in real space using pseudopotential-density-functional theory for large silicon nanocrystals, which contain thousands of atoms. Further, we focus on (i) the screening of a point charge and (ii) the formation of a charged vacancy in hydrogen-terminated silicon nanocrystals. This approach allows us to examine the role of quantum confinement in addition to exploring the bulk limit. Comparisons to other methods confirm the viability of this approach.

36 MATERIALS SCIENCE↗

Simulations of nonradiative processes in semiconductor nanocrystals

The description of carrier dynamics in spatially confined semiconductor nanocrystals (NCs), which have enhanced electron–hole and exciton–phonon interactions, is a great challenge for modern computational science. These NCs typically contain thousands of atoms and tens of thousands of valence electrons with discrete spectra at low excitation energies, similar to atoms and molecules, that converge to the continuum bulk limit at higher energies. Computational methods developed for molecules are limited to very small nanoclusters, and methods for bulk systems with periodic boundary conditions are not suitable due to the lack of translational symmetry in NCs. This perspective focuses on our recent efforts in developing a unified atomistic model based on the semiempirical pseudopotential approach, which is parameterized by first-principle calculations and validated against experimental measurements, to describe two of the main nonradiative relaxation processes of quantum confined excitons: exciton cooling and Auger recombination. Here, we focus on the description of both electron–hole and exciton–phonon interactions in our approach and discuss the role of size, shape, and interfacing on the electronic properties and dynamics for II–VI and III–V semiconductor NCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Floquet engineering of strongly driven excitons in monolayer tungsten disulfide

Interactions of quantum materials with strong-laser fields can induce exotic nonequilibrium electronic states. Monolayer transition-metal dichalcogenides, a new class of direct-gap semiconductors with prominent quantum confinement, offer exceptional opportunities toward Floquet engineering of quasiparticle electron-hole states, or excitons. Strong-field driving has a potential to achieve enhanced control of electronic band structure, thus a possibility to open a new realm of exciton light-matter interactions. However, experimental implementation of strongly-driven excitons has so far remained out of reach. Here, we use mid-infrared laser pulses below the optical bandgap to excite monolayer tungsten disulfide up to a field strength of 0.3 V/nm, and demonstrate strong-field light dressing of excitons in the excess of a hundred millielectronvolt. Our high-sensitivity transient absorption spectroscopy further reveals formation of a virtual absorption feature below the 1s-exciton resonance, which is assigned to a light-dressed sideband from the dark 2p-exciton state. Quantum-mechanical simulations substantiate the experimental results and enable us to retrieve real-space movies of the exciton dynamics. Here, this study advances our understanding of the exciton dynamics in the strong-field regime, and showcases the possibility of harnessing ultrafast, strong-field phenomena in device applications of two-dimensional materials.

36 MATERIALS SCIENCE↗

Triplet Energy Transfer from Lead Halide Perovskite for Highly Selective Photocatalytic 2 + 2 Cycloaddition

Triplet excitons are generally confined within a semiconductor. Hence, solar energy utilization via direct triplet energy transfer (TET) from semiconductors is challenging. TET from lead halide perovskite semiconductors to nearby organic molecules has been illustrated with ultrafast spectroscopy. Direct utilization of solar energy, i.e., visible light, via TET for photocatalysis is an important route but has not yet been demonstrated with lead halide perovskite semiconductors. Here, we show that a photocatalytic reaction, focusing on a 2 + 2 cycloaddition reaction, can been successfully demonstrated via TET from lead halide perovskite nanocrystals (PNCs). In this work, the triplet excitons are shown to induce a highly diastereomeric syn-selective 2 + 2 cycloaddition starting from olefins. Such photocatalytic reactions probe the TET process previously only observed spectroscopically. Moreover, our observation demonstrates that bulk-like PNCs (size, >10 nm; PL = 530 nm), in addition to quantum-confined smaller PNCs, are also effective for TET. Our findings may render a new energy conversion pathway to employ PNCs via direct TET for photocatalytic organic synthesis.

14 SOLAR ENERGY↗

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↗

Strong Structural and Electronic Coupling in Metavalent PbS Moiré Superlattices

Moiré superlattices are twisted bilayer materials in which the tunable interlayer quantum confinement offers access to new physics and novel device functionalities. Previously, moiré superlattices were built exclusively using materials with weak van der Waals interactions, and synthesizing moiré superlattices with strong interlayer chemical bonding was considered to be impractical. Here, in this study, using lead sulfide (PbS) as an example, we report a strategy for synthesizing moiré superlattices coupled by strong chemical bonding. We use water-soluble ligands as a removable template to obtain free-standing ultrathin PbS nanosheets and assemble them into direct-contact bilayers with various twist angles. Atomic-resolution imaging shows the moiré periodic structural reconstruction at the superlattice interface due to the strong metavalent coupling. Electron energy loss spectroscopy and theoretical calculations collectively reveal the twist-angle-dependent electronic structure, especially the emergent separation of flat bands at small twist angles. The localized states of flat bands are similar to well-arranged quantum dots, promising an application in devices. This study opens a new door to the exploration of deep energy modulations within moiré superlattices alternative to van der Waals twistronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fano Resonance in CO 2 Reduction Catalyst Functionalized Quantum Dots

Molecular catalyst functionalized semiconductor quantum dots (QDs) are a promising modular platform for developing novel hybrid photocatalysts. The interaction between adsorbed catalyst vibrations and the QD electron intraband absorption can influence the photophysical properties of both the QD and the catalysts and potentially their photocatalysis. In CdSe QDs functionalized by the CO 2 reduction catalyst, Re(CO) 3 (4,4’-bipyridine-COOH)Cl, we observe that the transient Fano resonance signal resulting from coupling of the catalyst CO stretching mode and the QD conduction band electron mid-IR intraband absorption appears on an ultrafast time scale and decays with the electron population, irrespective of the occurrence of photoreduced catalysts. The Fano asymmetry factor increases with an increase in the adsorbed catalyst number and a decrease in QD sizes. The latter can be attributed to an enhanced charge transfer interaction between the more strongly quantum-confined QD conduction band and catalyst LUMO levels. These results provide a more in-depth understanding of interactions in excited QD-catalyst hybrid photocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗