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At least 343 records · Page 19

Spatially Precise Light‐Activated Dedoping in Wafer‐Scale MoS 2 Films

2D materials, particularly transition metal dichalcogenides (TMDCs), have shown great potential for microelectronics and optoelectronics. However, a major challenge in commercializing these materials is the inability to control their doping at a wafer scale with high spatial fidelity. Interface chemistry is used with the underlying substrate oxide and concomitant exposure to visible light in ambient conditions for photo-dedoping wafer scale MoS 2 . It is hypothesized that the oxide layer traps photoexcited holes, leaving behind long-lived electrons that become available for surface reactions with ambient air at sulfur vacancies (defect sites) resulting in dedoping. Additionally, high fidelity spatial control is showcased over the dedoping process, by laser writing, and fine control achieved over the degree of doping by modulating the illumination time and power density. This localized change in MoS 2 doping density is very stable (at least 7 days) and robust to processing conditions like high temperature and vacuum. The scalability and ease of implementation of this approach can address one of the major issues preventing the “Lab to Fab” transition of 2D materials and facilitate its seamless integration for commercial applications in multi-logic devices, inverters, and other optoelectronic devices.

14 SOLAR ENERGY↗

H 2 Evolution at an Electrochemical “Underpotential” with an Iridium-Based Molecular Photoelectrocatalyst

Molecular platforms capable of both photochemical H 2 evolution and electrochemical catalyst regeneration hold promise for the efficient generation of solar fuels. Systems studied to date require a significant electrochemical overpotential (η), so no photon energy is being chemically stored. A detailed study of the parameters that govern the electrochemical overpotential of molecular photoelectrocatalysts is presented. By understanding how tuning the solvent, catalyst structure, and acid pK a affect the kinetics and thermodynamics of the potential- and light-driven H 2 evolution reaction, conditions were identified wherein the solvento complex [Cp*Ir(bpy)(NCCH 3 )][PF 6 ] 2 (Cp* is pentamethylcyclopentadienyl; bpy is 2,2'-bipyridine) mediates photoelectrocatalytic H 2 formation at an electrochemical “underpotential” (η < 0) driven by visible light. Under 460 nm illumination and in the presence of the weak organic acid H-PhTMG + (2-phenyl-1,1,3,3- tetramethylguanidinium), the catalyst facilitates H 2 evolution with Faradaic efficiencies up to 90% and overpotentials as low as –90 mV. As a result, mechanistic studies enabled the construction of graphical “maps” that can guide the choice of catalyst and conditions to minimize overpotential, applicable to both photoelectrocatalysts and dark electrocatalysts.

14 SOLAR ENERGY↗

Hot Stuff? Thermal Imaging Applied to Cryocrystallography

In the past we have used thermal imaging techniques to visualize the cryocooling processes of macromolecular crystals. From these images it was clear that a cold wave progresses through a crystal starting at the face closest to the origin of the cold stream and ending at the point furthest away. During these studies we used large volume crystals, which were clearly distinguished fiom the loop holding them. These large crystals, originally grown for neutron diffiaction studies, were chosen deliberately to enhance the imaging. As an extension to this work, we present used thermal imaging to study small crystals, held in a cryo-loop, in the presence of vitrified mother liquor. The different d a r e d transmission and reflectance properties of the crystal in comparison to the mother liquor surrounding it are thought to be the parameter that produces the contrast that makes the crystal visible. An application of this technology may be the determination of the exact location of small crystals in a cryo-loop. Data fkom initial tests in support of application development was recorded for lysozyme crystals and for bFGF/dna complex crystals, which were cryocooled and imaged in large loops, both with visible light mad with h i k e d rdi&tion. The crystals were clearly distinguished from the vitrified solution in the infiared spectrum, while in the case of the bFGF/dna complex the illumination had to be carefully manipulated to make the crystal visible in the visible spectrum. These results suggest that the thermal imaging may be more sensitive than visual imaging for automated location of small crystals. However, further work on small crystals robotically mounted at SSRL did not clearly visualize those crystals. The depth of field of the camera proved to be limiting and a different cooling geometry was used, compared to the previous, successful experiments. Analysis to exploit multiple images to improve depth of field and experimental work to understand cooling geometry effects is ongoing. These results will be presented along with advantages and disadvantages of the technique and a discussion of how it might be applied.

Snell, E. H.↗

Evidence-Based Recommendations for Optimizing Light in Day-to-Day Spaceflight Operations

NASA Behavioral Health and Performance Element (BHP) personnel have previously reported on efforts to transition evidence‐based recommendations for a flexible lighting system on the International Space Station (ISS). Based on these recommendations, beginning in 2016 the ISS will replace the current fluorescent‐based lights with an LED‐based system to optimize visual performance, facilitate circadian alignment, promote sleep, and hasten schedule shifting. Additional efforts related to lighting countermeasures in spaceflight operations have also been underway. As an example, a recent BHP research study led by investigators at Harvard Medical School and Brigham and Women's Hospital, evaluated the acceptability, feasibility, and effectiveness of blue‐enriched light exposure during exercise breaks for flight controllers working the overnight shift in the Mission Control Center (MCC) at NASA Johnson Space Center. This effort, along with published laboratory studies that have demonstrated the effectiveness of appropriately timed light for promoting alertness, served as an impetus for new light options, and educational protocols for flight controllers. In addition, a separate set of guidelines related to the light emitted from electronic devices, were provided to the Astronaut Office this past year. These guidelines were based on an assessment led by NASA's Lighting Environment Test Facility that included measuring the spectral power distribution, irradiance, and radiance of light emitted from ISS‐grade laptops and I‐Pads, as well as Android devices. Evaluations were conducted with and without the use of off‐the‐shelf screen filters as well as a software application that touts minimizing the short‐wave length of the visible light spectrum. This presentation will focus on the transition for operations process related to lighting countermeasures in the MCC, as well as the evidence to support recommendations for optimal use of laptops, I‐Pads, and Android devices during all phases of spaceflight operations.

Whitmire, Alexandra↗

Investigation of long-term light stability of negative charge injected into oxide-nitride-oxide passivation stack of crystalline silicon solar cells

A negatively charged oxide-nitride-oxide stack for field-effect passivation of crystalline silicon solar cells is discussed. The negative charge was injected into the stack by a plasma charge injection technology. Charge stability was studied by exposing samples to AM1.5 simulation visible light and full-spectrum light at temperatures ranging from 55 to 78 °C for up to 300 h. Charge injection and loss were quantified based on shifts in the flatband voltage of capacitance–voltage curves measured with a mercury probe. The most probable mechanism of charge loss was found to be diffusion of negative charged hydrogen atoms through nitride and bottom oxide. The optimum recipe for each layer of the stack was investigated to minimize the loss of injected charge. The flatband voltage decay of the optimized stack was found to fit a power-law trend, suggesting the dispersive transport of hydrogen atoms with a dispersion parameter of ~0.06–0.07. The optimized stack is projected to maintain a negative charge density of about 3.6 × 10 12 cm –2 or more after 25 years of field operation in an environment such as Arizona, which would be sufficient for field-effect passivation under one-sun illumination. Furthermore, the high stability of the negative injected charge makes the plasma charging technology a safer and lower cost alternative to Al 2 O 3 -passivation technology commonly used to passivate p-type surfaces.

14 SOLAR ENERGY↗

Polar nephelometer for atmospheric particulate studies

A unique polar nephelometer was designed and constructed for the measurement of atmospheric particulate characteristics. The nephelometer produces visible light from a self-contained laser to irradiate an air sample drawn into the instrument. The light scattered from the particulates and molecules in the sample is detected as a function of scattering angle for each of four different incident light polarizations. These measurements are used to determine the particulate scattering matrix which is a function of the size, shape, and index of refraction of the particles. The region of sensitivity for the measurements corresponds to the size range of particles that strongly affects visible radiative transfer in the atmosphere, which is the primary application for the derived information.

Hansen, M. Z.↗

A transmissive concentrator photovoltaic module with cells directly cooled by silicone oil for solar cogeneration systems

Hybrid concentrator photovoltaic-thermal systems can cogenerate electricity and heat by beam-splitting incoming concentrated light onto photovoltaic cells and a thermal receiver to increase total conversion efficiency and potentially reduce system cost. To demonstrate this, we have designed and prototyped a transmissive spectrum-splitting concentrator photovoltaic module that maximizes solar energy conversion by utilizing the entire solar spectrum. Visible light is collected using infrared-transmissive triple-junction photovoltaic cells to achieve an in-band module efficiency of 43.3% for light of wavelength λ < 873 nm, while 44.2% of out-of-band light with λ > 873 nm is transmitted through for collection by a thermal receiver. During testing on a dual-axis tracked parabolic concentrator dish at up to 166 suns, cell temperatures were maintained at 119 °C or below via a novel active cooling method. This cooling system strictly flows silicone oil directly across both sides of the cells, without inhibiting optical transmission, as verified through experimentation and simulation. The module was validated outdoors for 572 sun·hrs, and achieved a maximum thermal receiver temperature of 180 °C. 86.1% of incident solar power is collected at 166 suns average concentration collectively among the electrical, cooling, and thermal receiver subsystems. The remaining 13.9% is lost to mirror reflectivity, dish shadowing, receiver reflection, and thermal losses. The ability to directly cool the cells with an inert silicone oil offers the potential for reduced system cost relative to previous transmissive hybrid concentrator photovoltaic-thermal systems, including microfluidic-cooled designs. This solar cogeneration capability is valuable in a wide range of commercial and industrial applications.

14 SOLAR ENERGY↗

Light-induced transitions of polar state and domain morphology of photoferroelectric nanoparticles

Using the Landau-Ginzburg-Devonshire approach, we study light-induced phase transitions, evolution of polar state and domain morphology in photo-ferroelectric nanoparticles (NPs). Light exposure increases the free carrier density near the NP surface and may in turn induce phase transitions from the nonpolar paraelectric to the polar ferroelectric phase. Using the uniaxial photo-ferroelectric Sn 2 P 2 S 6 as an example, here we show that visible light exposure induces the appearance and vanishing of striped, labyrinthine or curled domains and changes in the polarization switching hysteresis loop shape from paraelectric curves to double, pinched and single loops, as well as the shifting in the position of the tricritical point. Furthermore, we demonstrate that an ensemble of non-interacting photo-ferroelectric NPs may exhibit superparaelectric-like features at the tricritical point, such as strongly frequency-dependent giant piezoelectric and dielectric responses, which can potentially be exploited for piezoelectric applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Absorption and scattering limits of silicon nitride integrated photonics in the visible spectrum

Visible-light photonic integrated circuits (PICs) promise scalability for technologies such as quantum information, biosensing, and scanning displays, yet extending large-scale silicon photonics to shorter wavelengths has been challenging due to the higher losses. Silicon nitride (SiN) has stood out as the leading platform for visible photonics, but the propagation losses strongly depend on the film’s deposition and fabrication processes. Current loss measurement techniques cannot accurately distinguish between absorption and surface scattering, making it difficult to identify the dominant loss source and reach the platform’s fundamental limit. Here we demonstrate an ultra-low loss, high-confinement SiN platform that approaches the limits of absorption and scattering across the visible spectrum. Leveraging the sensitivity of microresonators to loss, we probe and discriminate each loss contribution with unparalleled sensitivity, and derive their fundamental limits and scaling laws as a function of wavelength, film properties and waveguide parameters. Through the design of the waveguide cross-section, we show how to approach the absorption limit of the platform, and demonstrate the lowest propagation losses in high-confinement SiN to date across the visible spectrum. We envision that our techniques for loss characterization and minimization will contribute to the development of large-scale, dense PICs that redefine the loss limits of integrated platforms across the electromagnetic spectrum.

Corato-Zanarella, Mateus (ORCID:0000000327318046)↗

A fully light-driven approach to separate carbon dioxide from emission streams

Carbon capture from industrial point sources is an essential component of the global effort to mitigate climate risks. However, traditional approaches require significant energy input—often provided, counterproductively, by fossil fuel combustion. Using sunlight directly as the energy source would significantly improve the energy efficiency of carbon capture processes. Herein, we report the first fully visible-light-driven CO 2 separation system, in which carbon capture is achieved via the photoenolization/addition reaction of inexpensive 2-methylbenzophenone with CO 2 , and CO 2 release is realized through an intramolecular photodecarboxylation reaction. Finally, this system operates isothermally, works with natural sunlight, and facilitates CO 2 removal from natural gas flue emissions, providing a blueprint for other non-thermal chemical separations.

Ahmad, Bayu I. Z. [Cornell Univ., Ithaca, NY (Unit↗

2D Covalent Organic Frameworks with an Incorporated Manganese Complex for Light Driven Carbon Dioxide Reduction

Covalent organic frameworks (COFs) have emerged as a novel class of crystalline porous photocatalytic materials due to their unique properties such as large surface area, tunable porosity, and rigid structure. Here in this work, we report the direct incorporation of a manganese CO 2 molecular catalyst (MC) into COFs (Mn-TTA-COF) and the evaluation of its capability as photocatalyst for visible light driven CO 2 reduction to form CO. We found that the photocatalytic activity of Mn-TTA-COF is quite low, which mainly results from the elimination of the CO ligand in the Mn MC upon light illumination, rendering its short duration in the catalytic reaction. While this is a central concern for the further use Mn-TTA-COF as a CO 2 reduction catalyst, here we found that the stability and efficiency of Mn MC is largely enhanced after being incorporated into COFs with respect to its homogeneous version, suggesting the capability of COFs as heterogeneous platform to incorporate MC and improve the catalytic performance of MC. Moreover, transient absorption spectroscopic studies show that the intramolecular charge transfer lifetime of the Mn-incorporated COF is longer than that in the parent COF, which suggests that charge separation (CS) may occur from the parent COF to the Mn moiety. These results together suggest that COFs may show promise as a platform for creating next-generation photocatalysts with a built-in photosensitizer and MC, which can facilitate CS and enhance the stability and efficiency of the incorporated MC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photorefractivity in WGM resonators

We report on observation of photorefractive effects in whispering gallery mode resonators made of as-grown and magnesium doped lithium niobate and lithium tantalate in the near as well as far infrared. The effects manifested themselves as dynamic modification of the spectra as well as quality factors of the resonators coupled to the laser radiation. We have observed a significant (exceeding 10-4) change of the ordinary index of refraction of all the materials exposed with 780 nm light. Photorefractive effects have also been detected at 1550 nm. Our experiments support the conclusion that the photorefractivity does not have a distinct red boundary. We show that the maximum saturated refractive index change in the infrared is of the same order of magnitude as in the visible light.

optical resonator↗

Atmospheric-pressure ammonia synthesis on AuRu catalysts enabled by plasmon-controlled hydrogenation and nitrogen-species desorption

The Haber–Bosch process for ammonia synthesis contributes up to ~3% of global greenhouse gas emissions. Plasmonic catalysts strongly concentrate light and can alter the reaction intermediates via out-of-equilibrium processes, providing the potential for an alternative, less-energy-intensive pathway to synthesize ammonia. Here, in this study, we show that gold-ruthenium (AuRu) bimetallic nanoparticles can synthesize ammonia at room temperature and pressure using visible light. We create AuRu alloys with varying compositions and achieve ammonia production rates of ~60 μmol per gram of catalyst bed per hour. In situ infrared spectroscopy reveals that light accelerates the hydrogenation of nitrogen intermediates compared to conventional thermal catalysis. Through computational modelling, we demonstrate that photo-excited electrons enable associative hydrogenation pathways for nitrogen activation rather than direct nitrogen–nitrogen bond breaking. This light-assisted mechanism requires both hydrogen and light working together to overcome the nitrogen activation barrier, mimicking how biological enzymes produce ammonia naturally and providing fundamental insights for developing sustainable, energy-efficient chemical synthesis.

Yuan, Lin [Stanford Univ., CA (United States)] (OR↗

Hydrophilic, light active coating for membranes

A porous membrane provides enhanced filtration of pollutants and particles by coating the membrane with conformal thin films of doped titanium dioxide via atomic layer deposition or, alternatively, sequential infiltration synthesis. The membrane can either be organic or inorganic, and the doping of the membrane, usually with nitrogen, is an important feature that shifts the optical absorption of the TiO2 from the UV range into the visible-light range. This enables the use of lower energy light, including sunlight, to activate the photocatalytic function of the film. The coating described in the present invention is compatible with virtually any porous membrane and allows for precise tuning of the pore size with molecular precision. The present invention presents a new coating process and chemical structure that provides catalytic activity, strongly enhanced by light, to both mitigate fouling and break down various organic pollutants in the process stream.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Finely tunable dynamical coloration using bicontinuous micrometer-domains

Nanostructures similar to those found in the vividly blue wings of Morpho butterflies and colorful photonic crystals enable structural color through constructive interference of light waves. Different from commonly studied structure-colored materials using periodic structures to manipulate optical properties, we report a previously unrecognized approach to precisely control the structural color and light transmission via a novel photonic colloidal gel without long-range order. Nanoparticles in this gel form micrometer-sized bicontinuous domains driven by the microphase separation of binary solvents. This approach enables dynamic coloration with a precise wavelength selectivity over a broad range of wavelengths extended well beyond the visible light that is not achievable with traditional methods. The dynamic wavelength selectivity is thermally tunable, reversible, and the material fabrication is easily scalable.

42 ENGINEERING↗

Handheld White Light Interferometer for Measuring Defect Depth in Windows

Accurate quantification of defects (scratches and impacts) is vital to the certification of flight hardware and other critical components. The amount of damage to a particular component contributes to the performance, reliability, and safety of a system, which ultimately affects the success or failure of a mission or test. The launch-commit criteria on a Space Shuttle Orbiter window are governed by the depth of the defects that are identified by a visual inspection. This measurement of a defect is not easy to obtain given the environment, size of the defect, and location of the window(s). The determination of depth has typically been performed by taking a mold impression and measuring the impression with an optical profiling instrument. Another method of obtaining an estimate of the depth is by using a refocus microscope. To use a refocus microscope, the surface of the glass and bottom of the defect are, in turn, brought into focus by the operator. The amount of movement between the two points corresponds to the depth of the defect. The refocus microscope requires a skilled operator and has been proven to be unreliable when used on Orbiter windows. White light interferometry was chosen as a candidate to replace the refocus microscope. The White Light Interferometer (WLI) was developed to replace the refocus microscope as the instrument used for measuring the depth of defects in Orbiter windows. The WLI consists of a broadband illumination source, interferometer, detector, motion control, displacement sensor, mechanical housing, and support electronics. The illumination source for the WLI is typically a visible light emitting diode (LED) or a near-infrared superluminescent diode (SLD) with power levels of less than a milliwatt. The interferometer is a Michelson configuration consisting of a 1-in. (2.5-cm) cube beam splitter, a 0.5-in. (1.3-cm) optical window as a movable leg (used to closely match the return intensity of the fixed leg from the window), and a mirrored prism to fold the optics into the mechanical housing. The detector may be one of many C-mount CCD (charge-coupled device) cameras. Motion is provided by a commercial nanostepping motor with a serial interface. The displacement sensor is a custom device specifically designed for this application. The mechanical housing and support electronics were designed to integrate the various components into an instrument that could be physically handled by a technician and easily transported.

Youngquist, Robert↗

Depolymerization of Hydroxylated Polymers via Light-Driven C–C Bond Cleavage

The accumulation of persistent plastic waste in the environment is widely recognized as an ecological crisis. New chemical technologies are necessary both to recycle existing plastic waste streams into high-value chemical feedstocks and to develop next-generation materials that are degradable by design. Here, we report a catalytic methodology for the depolymerization of a commercial phenoxy resin and high molecular weight hydroxylated polyolefin derivatives upon visible light irradiation near ambient temperature. Proton-coupled electron transfer (PCET) activation of hydroxyl groups periodically spaced along the polymer backbone furnishes reactive alkoxy radicals that promote chain fragmentation through C–C bond β-scission. The depolymerization produces well-defined and isolable product mixtures that are readily diversified to polycondensation monomers. In addition to controlling depolymerization, the hydroxyl group modulates the thermomechanical properties of these polyolefin derivatives, yielding materials with diverse properties. Furthermore, these results demonstrate a new approach to polymer recycling based on light-driven C–C bond cleavage that has the potential to establish new links within a circular polymer economy and influence the development of new degradable-by-design polyolefin materials.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Helical allophycocyanin nanotubes absorb far-red light in a thermophilic cyanobacterium

To compete in certain low-light environments, some cyanobacteria express a paralog of the light-harvesting phycobiliprotein, allophycocyanin (AP), that strongly absorbs far-red light (FRL). Using cryo–electron microscopy and time-resolved absorption spectroscopy, we reveal the structure-function relationship of this FRL-absorbing AP complex (FRL-AP) that is expressed during acclimation to low light and that likely associates with chlorophyll a–containing photosystem I. FRL-AP assembles as helical nanotubes rather than typical toroids due to alterations of the domain geometry within each subunit. Spectroscopic characterization suggests that FRL-AP nanotubes are somewhat inefficient antenna; however, the enhanced ability to harvest FRL when visible light is severely attenuated represents a beneficial trade-off. The results expand the known diversity of light-harvesting proteins in nature and exemplify how biological plasticity is achieved by balancing resource accessibility with efficiency.

59 BASIC BIOLOGICAL SCIENCES↗