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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.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Edge-Confined Excitons in Monolayer Black Phosphorus

Quantum confinement of two-dimensional excitons in van der Waals materials via electrostatic trapping, lithographic patterning, Moiré potentials, and chemical implantation has enabled significant advances in tailoring light emission from nanostructures. While such approaches rely on complex preparation of materials, natural edges are a ubiquitous feature in layered materials and provide a different approach for investigating quantum-confined excitons. Here, we observe that certain edge sites of monolayer black phosphorus (BP) strongly localize the intrinsic quasi-one-dimensional excitons, yielding sharp spectral lines in photoluminescence, with nearly an order of magnitude line width reduction. Through structural characterization of BP edges using transmission electron microscopy and first-principles GW plus Bethe–Salpeter equation (GW-BSE) calculations of exemplary BP nanoribbons, we find that certain atomic reconstructions can strongly quantum-confine excitons resulting in distinct emission features, mediated by local strain and screening. Here we observe linearly polarized luminescence emission from edge reconstructions that preserve the mirror symmetry of the parent BP lattice, in agreement with calculations. Furthermore, we demonstrate efficient electrical switching of localized edge excitonic luminescence, whose sites act as excitonic transistors for emission. Localized emission from BP edges motivates exploration of nanoribbons and quantum dots as hosts for tunable narrowband light generation, with future potential to create atomic-like structures for quantum information processing applications as well as exploration of exotic phases that may reside in atomic edge structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Large-scale efficient mid-wave infrared optoelectronics based on black phosphorus ink

The mid-wave infrared (MWIR), ranging from 2 to 5 micrometers, is of substantial interest for chemical sensing, imaging, and spectroscopy. Black phosphorus (bP)–based MWIR light emitters and detectors have been shown to outperform the state-of-the-art for commercial devices due to the low Auger recombination coefficient of bP. However, the scalability of these devices remains a challenge. Here, we report a bP ink formula that preserves the exceptional MWIR optoelectronic properties of bP to deposit centimeter-scale, uniform, and pinhole free films with a photoluminescence quantum yield higher than competing III-V and II-VI semiconductors with similar bandgaps at high excitation regime. As a proof of concept, we use bP ink as a “phosphor” on a red commercial light-emitting diode to demonstrate bright MWIR light emission. We also show that these films can be integrated into heterostructure device architectures with electron and hole selective contacts for direct-injected light emission and detection in MWIR.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Broadband electro-optic polarization conversion with atomically thin black phosphorus

Metasurfaces tune polarization In photonic systems, the polarization state of light is typically manipulated with bulky components based on dielectrics and liquid crystals. Active metasurfaces now provide the possibility of shrinking the size of these components to the nanoscale. Biswas et al . demonstrate an active nanophotonic structure capable of versatile electro-optic polarization conversion. Using trilayer black phosphorus sandwiched between electrical gates forming a cavity, they show that the polarization state of light across telecommunication wavelengths can be electrically switched. Such control can be useful for a number of applications in communications, imaging, and beam steering where the wavefront of the propagating light can be actively manipulated. —ISO

Science & Technology - Other Topics↗
DOE OSTI2024

Black Phosphorus for Mid-Infrared Optoelectronics: Photophysics, Scalable Processing, and Device Applications

High efficiency mid-infrared (λ = 3-8 μm) light emitters and photodetectors are pivotal for advancing next-generation optoelectronics. However, narrow-bandgap semiconductors face fundamental challenges such as pronounced nonradiative carrier recombination and thermally generated noise, which impede device performance. Recently, two-dimensional layered black phosphorus (BP) and its alloys have attracted substantial interest for mid-infrared device applications, demonstrating superior performance relative to conventional III-V and II-VI semiconductors with similar bandgaps. In this review, we discuss the optical properties of BP, contrasting these with those of covalent compounds. Owing to its inherently self-terminated surface structure and reduced nonradiative recombination, BP exhibits high performance in light emission and photodetection at room temperature. Furthermore, this review highlights recent advances in the large-area processing of BP thin films, paving the way for practical device applications and integration. Finally, we explore ongoing challenges and emerging opportunities in the utilization of BP for functional mid-infrared devices.

Higashitarumizu, Naoki↗
DOE OSTI2021

Surface Functionalization of Black Phosphorus with Nitrenes: Identification of P=N Bonds by Using Isotopic Labeling

Abstract Surface functionalization of two‐dimensional crystals is a key path to tuning their intrinsic physical and chemical properties. However, synthetic protocols and experimental strategies to directly probe chemical bonding in modified surfaces are scarce. Introduced herein is a mild, surface‐specific protocol for the surface functionalization of few‐layer black phosphorus nanosheets using a family of photolytically generated nitrenes (RN) from the corresponding azides. By embedding spectroscopic tags in the organic backbone, a multitude of characterization techniques are employed to investigate in detail the chemical structure of the modified nanosheets, including vibrational, X‐ray photoelectron, solid state 31 P NMR, and UV‐vis spectroscopy. To directly probe the functional groups introduced on the surface, R fragments were selected such that in conjunction with vibrational spectroscopy, 15 N‐labeling experiments, and DFT methods, diagnostic P=N vibrational modes indicative of iminophosphorane units on the nanosheet surface could be conclusively identified.

Walz Mitra, Kendahl L.↗
DOE OSTI2025

Mechanically flexible mid-wave infrared imagers using black phosphorus ink films

The mid-wave infrared (MWIR) spectral range (λ = 3–8 μm) enables important sensing and imaging applications, including non-invasive bioimaging, night vision, and autonomous navigation. Commercial MWIR photodetectors are limited to rigid imagers based on heteroepitaxial materials. There is an emerging need for mechanically flexible MWIR imagers to broaden their functionality and practicality. Recently, photodetectors using van der Waals (vdW) black phosphorus (BP) flakes have demonstrated highly sensitive room-temperature photodetection. Additionally, vdW materials are solution-processable, facilitating scalable processing and flexible device fabrication. In this work, we present flexible MWIR imagers consisting of photodiodes fabricated on thin plastic substrates using BP ink films. We demonstrate mechanically robust responsivity up to 2.5-mm bending radii and after 5000 bending cycles. Leveraging this flexibility, we achieve full-azimuthal imaging, detecting directional light sources with precision. These results establish a scalable approach for large-area, conformable MWIR imaging and pave the way for integration with flexible electronics.

Wijaya, Theodorus Jonathan↗
DOE OSTI2021

Tunable Photocatalytic Production of Syngas Using Co@C 3 N 4 and Black Phosphorus

Photocatalytic syngas production is an attractive option to efficiently generate a feedstock for the Fischer-Tropsch processes that can produce liquid fuels and other chemicals. Here, one-pot photocatalytic production of syngas (H 2 +CO) with specific and controllable ratios of H 2 /CO has proven to be a significant challenge to date. In this work, single Co 2+ sites loaded onto carbon nitride (Co@C 3 N 4 ) is combined with black phosphorus (BP) to form a hybrid material, which is capable of simultaneous photocatalytic evolution of H 2 and CO. H 2 /CO syngas ratios can be controlled in the range from 0.30 to 5.16 by changing the % weight of BP in this system or by the addition of CoCl 2 in the reaction solution. Maximum total gas evolution of 70 μmol g –1 h –1 was achieved with 20 wt % BP (BP 20% /Co@C 3 N 4 ) at a H 2 /CO ratio of 2.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Electrochemical Li Intercalation in Black Phosphorus: In Situ and Ex Situ Studies

A systematic study on electrochemical charge transfer in Li-doped black phosphorous (BP) was carried out by both in-situ and ex-situ Raman scattering. Galvanostatic discharge of dedicated in-situ electrochemical cell for Raman spectroscopy was used to study time evolution of vibrational modes under lithiation. In addition to the peak broadening which is a result of structural expansion, peaks corresponding to all three atomic vibrational modes A 1 g , B 2 g and A 2 g were found to red-shift as a result of lithiation. Peaks B 2 g and A 2 g were shifted about 1.6 times more towards lower wavenumbers in comparison to A 1 g . Further characterizations using optical and electron microscopy showed that the intercalation of BP is highly anisotropic, where channels along the zigzag direction were found to be the easy direction for intercalation. X-ray diffraction on intercalated samples confirmed a reduction of thickness as lithiation weakens interlayer bonding, thus resulting in a partial exfoliation of BP flakes. Here, first principle studies using density function theory (DFT) were used to develop a theoretical model for the intercalation mechanism. The discrepancy between the experimental and the theoretical results was also addressed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Structural and Thermoelectric Properties of Black Arsenic–Phosphorus

Here, we report the structural and temperature dependent transport properties of As x P 1-x (x = 0, 0.2, 0.5, 0.83, 1) alloys. It is observed that black phosphorous (BP)-related phonon modes in the alloy samples are red-shifted with increasing arsenic concentration, while black arsenic-related modes in these samples are blue-shifted with increasing phosphorus concertation. As the arsenic concentration, x increases from 0 to 1, the 4-probe resistance of the As x P 1-x alloys is found to decrease by more than 3 orders of magnitude. The transport studies reveal that samples with the highest arsenic concentration (x = 1 and 0.83) show metallic behavior in the temperature dependence of resistance with a small thermopower at room temperature with an anomalous temperature dependence. In contrast, the samples with high phosphorus concentration (x = 0, 0.2, and 0.5) show very large thermopower values at room temperature reaching a value as high as 803 μV/k for x = 0.2. The temperature dependence of the thermopower of these samples can be well described by the variable range hopping (VRH) mechanism in two-dimensions (2-d), S ~ T 1/3 . Similarly, their 4-probe resistance (R) values can be fitted with 2-d VRH mechanism, R ~ exp(T -1/3 ).

36 MATERIALS SCIENCE↗
DOE OSTI2026

Plasmon and Photon Excitations in Two-Dimensional and Layered Materials

Light-matter interactions in layered and two-dimensional materials allows one to achieve extreme optical confinement approaching the atomic scale, enabling exploration of new materials phenomena. Layered narrow bandgap and zero bandgap materials, such as black phosphorus and graphene, support unusual and intriguing quantum-confined electronic states in thin layers and surface electronic states. The incomplete screening of applied electrostatic fields in ultrathin materials permits the exploration of light-matter interactions at high electric fields and over a wide range of carrier densities in a single sample, facilitating exploration of the optical and plasmonic properties of ultrathin and layered materials under electrochemical potential control. We have made advances in understanding the nature of optical interband and intraband plasmon excitations in layered materials such as graphene, black phosphorus, molybdenum diselenide, and molybdenum ditelluride.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Non-Carbon 2D Materials-Based Field-Effect Transistor Biosensors: Recent Advances, Challenges, and Future Perspectives

In recent years, field-effect transistors (FETs) have been very promising for biosensor applications due to their high sensitivity, real-time applicability, scalability, and prospect of integrating measurement system on a chip. Non-carbon 2D materials, such as transition metal dichalcogenides (TMDCs), hexagonal boron nitride (h-BN), black phosphorus (BP), and metal oxides, are a group of new materials that have a huge potential in FET biosensor applications. In this work, we review the recent advances and remarkable studies of non-carbon 2D materials, in terms of their structures, preparations, properties and FET biosensor applications. We will also discuss the challenges facing non-carbon 2D materials-FET biosensors and their future perspectives.

2D-materials↗