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At least 289 records · Page 16

Ferroelectric Al1 − xBxN thin films integrated on Si

Ferroelectric Al0.93B0.07N thin films are prepared (100) Si substrates. The necessary c-axis out-of-plane orientation to observe macroscopic ferroelectric switching was achieved by implementing an initial Ar/N2 plasma treatment, followed by a thin layer of AlN to initiate the desired texture and a 150 nm W layer. The plasma treatment facilitates crystallinity enhancement of the AlN template layer, allowing for subsequent growth of highly oriented W and Al0.93B0.07N layers. The W layer exhibits random in-plane orientation and exclusive (110) out-of-plane orientation with a rocking curve width of 1.4°. When grown on these W surfaces, 175 nm thick Al0.93B0.07N films exhibit random in-plane orientation and exclusive (001) texture with rocking curve full-width-half-max values of 1.6° and RMS roughness values less than 1 nm. Polarization hysteresis measurements show robust hysteresis with coercive field values of 5.4 MV/cm and remanent polarization values of 136 μC/cm2. XPS depth profile analysis suggests that the plasma treatment converts the existing native oxide to a nitrogen rich oxynitride with approximate composition Si3O0.5N3.67. Cross-sectional TEM reveals that the oxynitride interlayer is amorphous and ∼3.4 nm thick, more than double the native oxide thickness measured by multiwavelength ellipsometry, implying that (oxy)nitride growth continues after conversion of the native oxide. This new family of ferroelectric wurtzites is interesting from an integration perspective given their chemical compatibility with mainstream semiconductors. Developing synthesis routes that promote needed texture while preserving compatible processing windows is an important step toward practical integration.

Physics↗

Polarization Performance Simulation for the GeoXO Atmospheric Composition Instrument: NO2 Retrieval Impacts

NOAA's Geostationary Extended Observations (GeoXO) constellation will continue and expand on the capabilities of the current generation of geostationary satellite systems to support US weather, ocean, atmosphere, and climate operations. It is planned to consist of a dedicated atmospheric composition instrument (ACX) to support air quality forecasting and monitoring by providing capabilities similar to missions such as TEMPO (Tropospheric Emission: Monitoring Pollution), currently planned to launch in 2023, as well as OMI (Ozone Monitoring Instrument), TROPOMI (TROPOspheric Monitoring Instrument), and GEMS (Geostationary Environment Monitoring Spectrometer) currently in operation. As the early phases of ACX development are progressing, design trade-offs are being considered to understand the relationship between instrument design choices and trace gas retrieval impacts. Some of these choices will affect the instrument polarization sensitivity (PS), which can have radiometric impacts on environmental satellite observations. We conducted a study to investigate how such radiometric impacts can affect NO2 retrievals by exploring their sensitivities to time of day, location, and scene type with an ACX instrument model that incorporates PS. The study addresses the basic steps of operational NO2 retrievals: the spectral fitting step and the conversion of slant column to vertical column via the air mass factor (AMF). The spectral fitting step was performed by generating at-sensor radiance from a clear-sky scene with a known NO2 amount, the application of an instrument model including both instrument PS and noise, and a physical retrieval. The spectral fitting step was found to mitigate the impacts of instrument PS. The AMF-related step was considered for clear-sky and partially cloudy scenes, for which instrument PS can lead to errors in interpreting the cloud content, propagating to AMF errors and finally to NO2 retrieval errors. For this step, the NO2 retrieval impacts were small but non-negligible for high NO2 amounts; we estimated that a typical high NO2 amount can cause a maximum retrieval error of 0.25×1015 molec. cm−2 for a PS of 5 %. These simulation capabilities were designed to aid in the development of a GeoXO atmospheric composition instrument that will improve our ability to monitor and understand the Earth's atmosphere.

Aaron Pearlman↗

Relaxor ferroelectric polymer exhibits ultrahigh electromechanical coupling at low electric field

Electromechanical (EM) coupling—the conversion of energy between electric and mechanical forms—in ferroelectrics has been used for a broad range of applications. Ferroelectric polymers have weak EM coupling that severely limits their usefulness for applications. Here, we introduced a small amount of fluorinated alkyne (FA) monomers (<2 mol %) in relaxor ferroelectric poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (PVDF-TrFE-CFE) terpolymer that markedly enhances the polarization change with strong EM coupling while suppressing other polarization changes that do not contribute to it. Under a low–dc bias field of 40 megavolts per meter, the relaxor tetrapolymer has an EM coupling factor (k 33 ) of 88% and a piezoelectric coefficient (d 33 ) >1000 picometers per volt. These values make this solution-processed polymer competitive with ceramic oxide piezoelectrics, with the potential for use in distinct applications.

36 MATERIALS SCIENCE↗

High SBS-Threshold, Narrowband Pulses Frequency-Doubled to 770.3 nm

We present results of pulsed, narrowband amplification at 1540.6nm using a polarization maintaining, large mode area gain fiber co-doped with erbium and ytterbium. At a repetition rate of 55 kHz, 2.9 W of average 1540.6nm power were generated with a pulse duration of 136 ns, correspondiig to an stimulated Brillouin scattering (SBS) free peak power of 360 W. The amplified signal was frequency doubled in peridically poled potassium titanyl phosphate and conversion efficiencies of up to 56% were generated. When varying the repetition rate between 55- 150 kHz the conversion efficiency changed from 56% to 35% due to the limited pump power.

Dilley, C. E.↗

Optical matter machines: angular momentum conversion by collective modes in optically bound nanoparticle arrays

The creation of optically powered self-assembling nano-to-meso-scale machines that do work is a long-standing goal in photonics. We demonstrate an optical matter (OM) machine that converts the spin angular momentum (SAM) of light into orbital angular momentum (OAM) to do mechanical work. The specific OM machine we study is based on a sixfold symmetric hexagonally ordered nanoparticle array that operates as an OM “gear” that is assembled and made to rotate in a circularly polarized Gaussian beam. The rotational symmetry of the OM gear leads to a selection rule for the allowed scattering modes based on their angular momentum. Electrodynamics calculations show that the collective scattering modes with the largest angular momentum scatter strongly in the transverse direction. Simulations and experiments show that the angular momentum that accompanies the scattered light causes a “negative torque” response on the OM gear and drives a “probe” particle placed outside the OM gear around the gear in an asymmetric force field analogously to Brownian ratchets. The gear–probe OM machine concept can be expanded to applications in nanofluidics and particle sorting.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Manipulating electron redistribution to achieve electronic pyroelectricity in molecular [FeCo] crystals

Pyroelectricity plays a crucial role in modern sensors and energy conversion devices. However, obtaining materials with large and nearly constant pyroelectric coefficients over a wide temperature range for practical uses remains a formidable challenge. Attempting to discover a solution to this obstacle, we combined molecular design of labile electronic structure with the crystal engineering of the molecular orientation in lattice. This combination results in electronic pyroelectricity of purely molecular origin. Here, we report a polar crystal of an [FeCo] dinuclear complex exhibiting a peculiar pyroelectric behavior (a substantial sharp pyroelectric current peak and an unusual continuous pyroelectric current at higher temperatures) which is caused by a combination of Fe spin crossover (SCO) and electron transfer between the high-spin Fe ion and redox-active ligand, namely valence tautomerism (VT). As a result, temperature dependence of the pyroelectric behavior reported here is opposite from conventional ferroelectrics and originates from a transition between three distinct electronic structures. The obtained pyroelectric coefficient is comparable to that of polyvinylidene difluoride at room temperature.

36 MATERIALS SCIENCE↗

Gibberellins promote polar auxin transport to regulate stem cell fate decisions in cambium

Vascular cambium contains bifacial stem cells, which produce secondary xylem to one side and secondary phloem to the other. However, how these fate decisions are regulated is unknown. Here we show that the positioning of an auxin signalling maximum within the cambium determines the fate of stem cell daughters. The position is modulated by gibberellin-regulated, PIN1-dependent polar auxin transport. Gibberellin treatment broadens auxin maximum from the xylem side of the cambium towards the phloem. As a result, xylem-side stem cell daughter preferentially differentiates into xylem, while phloem-side daughter retains stem cell identity. Occasionally, this broadening leads to direct specification of both daughters as xylem, and consequently, adjacent phloem-identity cell reverts to being stem cell. Conversely, reduced gibberellin levels favour specification of phloem-side stem cell daughter as phloem. Together, our data provide a mechanism by which gibberellin regulates the ratio of xylem and phloem production.

59 BASIC BIOLOGICAL SCIENCES↗

Outstanding Platinum Group Metal-free Bifunctional Catalysts for Rechargeable Zinc-Air Batteries

Developing highly active and durable catalysts for zinc-air batteries (ZAB) is critical for energy conversion and storage. Herein, we prepared Fe-N-C catalysts at a kilogram scale by the commercial VariPore™ method and the effect of synthesis conditions on the catalyst performance at ZAB air electrode was investigated. The results show the PA-450-HT exhibits excellent electrocatalytic activity toward oxygen reduction reaction (ORR) and it is the most suitable catalyst for primary ZAB with the galvanostatic polarization discharge peak power density of 149 mW cm -2 , outperforming commercial Pt-Ru/C catalysts. Additionally, the NCB-600-HT catalyst displays the half-wave potential of 0.87 V vs. RHE for ORR and ΔE value of 0.81 V (indicating outstanding ORR and OER reversibility) and exhibits excellent charge-discharge cycling durability similar to NCB-550-LT around 160 h for the secondary ZAB. This work reports outstanding bifunctional Fe-N-C catalysts for rechargeable ZAB at mass production for the first time.

25 ENERGY STORAGE↗

Circular polarimetry of fifteen interesting objects.

The results of a search are presented for circular polarization of visible light in 15 objects, including two eclipsing binaries, six magnetic Ap stars, three planetary nebulae, Hubble's Nebula, M87, Sirius, and the Orion A region. On the whole, the results were null, down to typical upper limits for q of 0.01 per cent. A complete description of the used photoelastic polarimeter is given, with special attention to the incidental linear-circular conversion.

Kemp, J. C.↗

Conversion and Extraction of Insoluble Organic Materials in Meteorites

We endeavor to develop and implement methods in our laboratory to convert and extract insoluble organic materials (IOM) from low car-bon bearing meteorites (such as ordinary chondrites) and Precambrian terrestrial rocks for the purpose of determining IOM structure and prebiotic chemistries preserved in these types of samples. The general scheme of converting and extracting IOM in samples is summarized in Figure 1. First, powdered samples are solvent extracted in a micro-Soxhlet apparatus multiple times using solvents ranging from non-polar to polar (hexane - non-polar, dichloromethane - non-polar to polar, methanol - polar protic, and acetonitrile - polar aprotic). Second, solid residue from solvent extractions is processed using strong acids, hydrochloric and hydrofluoric, to dissolve minerals and isolate IOM. Third, the isolated IOM is subjected to both thermal (pyrolysis) and chemical (oxidation) degradation to release compounds from the macromolecular material. Finally, products from oxidation and pyrolysis are analyzed by gas chromatography - mass spectrometry (GCMS). We are working toward an integrated method and analysis scheme that will allow us to determine prebiotic chemistries in ordinary chondrites and Precambrian terrestrial rocks. Powerful techniques that we are including are stepwise, flash, and gradual pyrolysis and ruthenium tetroxide oxidation. More details of the integrated scheme will be presented.

Locke, Darren R.↗

Shallow-etched thin-film lithium niobate waveguides for highly-efficient second-harmonic generation

High-fidelity periodic poling over long lengths is required for robust, quasi-phase-matched second-harmonic generation using the fundamental, quasi-TE polarized waveguide modes in a thin-film lithium niobate (TFLN) waveguide. Here, a shallow-etched ridge waveguide is fabricated in x-cut magnesium oxide doped TFLN and is poled accurately over 5 mm. The high fidelity of the poling is demonstrated over long lengths using a non-destructive technique of confocal scanning second-harmonic microscopy. We report a second-harmonic conversion efficiency of up to 939 %.W −1 (length-normalized conversion efficiency 3757 %.W −1 .cm −2 ), measured at telecommunications wavelengths. The device demonstrates a narrow spectral linewidth (1 nm) and can be tuned precisely with a tuning characteristic of 0.1 nm/°C, over at least 40 °C without measurable loss of efficiency.

Zhao, Jie (ORCID:0000000306230125)↗

An Assessment of Stratospheric Water Vapor Trends and Variations Above the Boulder Region

This study analyzes time series of stratospheric water vapor (SWV) data at 30 hPa, based on frost-point hygrometer (FPH) measurements at Boulder, CO (40°N, 255°E), and on sets of HALOE scans above that region for 1993 through 2005; their differing trends agree with previously published findings. Yet, there is an apparent switch over in 2002 from positive to negative trends in the HALOE time series, and that change follows the episodic decrease of tropical, lower stratospheric SWV in early 2001. The HALOE data points only resolve medium to large scale spatial variations, as they are based on an average of four or more limb scans within a latitude/longitude sector near Boulder. The FPH time series do not indicate a similar change of trend in 2002, although its time series points have variations about the mean that are twice as large as those from HALOE. The FPH soundings are sensitive to variations from all spatial scales, however, including the effects of a local vertical mixing of the air due to gravity waves. The vertical gradient SWV mixing ratio with altitude is positive at 30 hPa. There is also a positive trend in methane and its conversion to water vapor during this time that may explain a slightly larger SWV trend from the local FPH data than from the HALOE data. The Nimbus 7 LIMS experiment provides daily SWV plots at medium to large scales during the dynamically active, winter and springtime periods, for assessing the effects of meridional transport of SWV from its source regions. There is transport of high SWV from polar regions and of lower SWV from the subtropics at those times. SWV variations and trends from both the FPH and HALOE time series are reasonable and in accord with the spatial scales that they observed.

Ellis Remsberg↗

Insight of BaCe 0.5 Fe 0.5 O 3– δ twin perovskite oxide composite for solid oxide electrochemical cells

One-pot synthesized twin perovskite oxide composite of BaCe 0.5 Fe 0.5 O 3–δ (BCF), comprising cubic and orthorhombic perovskite phases, shows triple-conducting properties for promising solid oxide electrochemical cells. Phase composition evolution of BCF under various conditions was systematically investigated, revealing that the cubic perovskite phase could be fully/partially reduced into the orthorhombic phase under certain conditions. The reduction happened between the two phases at the interface, leading to the microstructure change. As a result, the corresponding apparent conducting properties also changed due to the difference between predominant conduction properties for each phase. Based on the revealed phase composition, microstructure, and electrochemical properties changes, a deep understanding of BCF's application in different conditions (oxidizing atmospheres, reducing/oxidizing gradients, cathodic conditions, and anodic conditions) was achieved. Triple-conducting property (H + /O 2– /e – ), fast open-circuit voltage response (~16–~470 mV) for gradients change, and improved single-cell performance (~31% lower polarization resistance at 600°C) were comprehensively demonstrated. Besides, the performance was analyzed under anodic conditions, which showed that the microstructure and phase change significantly affected the anodic behavior.

08 HYDROGEN↗

Control over Charge Separation by Imine Structural Isomerization in Covalent Organic Frameworks with Implications on CO 2 Photoreduction

Two-dimensional covalent organic frameworks (COFs) are an emerging class of photocatalytic materials for solar energy conversion. In this work, we report a pair of structurally isomeric COFs with reversed imine bond directions, which leads to drastic differences in their physical properties, photophysical behaviors, and photocatalytic CO 2 reduction performance after incorporating a Re(bpy)(CO) 3 Cl molecular catalyst through bipyridyl units on the COF backbone (Re-COF). Using the combination of ultrafast spectroscopy and theory, we attributed these differences to the polarized nature of the imine bond that imparts a preferential direction to intramolecular charge transfer (ICT) upon photoexcitation, where the bipyridyl unit acts as an electron acceptor in the forward imine case (f-COF) and as an electron donor in the reverse imine case (r-COF). These interactions ultimately lead the Re-f-COF isomer to function as an efficient CO 2 reduction photocatalyst, while the Re-r-COF isomer shows minimal photocatalytic activity. Furthermore, these findings not only reveal the essential role linker chemistry plays in COF photophysical and photocatalytic properties but also offer a unique opportunity to design photosensitizers that can selectively direct charges.

14 SOLAR ENERGY↗

Plasmonically assisted channels of photoemission from metals

We analyze recently measured nonlinear photoemission spectra from Ag surfaces that reveal resonances whose energies do not scale with the applied photon energy but stay pinned to multiples of bulk plasmon energy $\hbar$ω p above the Fermi level. To elucidate these unexpected and peculiar features we investigate the spectra of plasmons generated in a solid by the optically pumped electronic polarization and their effect on photoemission. By combining quadratic response formalism for calculations of photoemission yield, a nonperturbative approach to inelastic electron scattering, and first-principles calculations for the electronic structure, we demonstrate the dependence of probability amplitude for single- and multiplasmon excitations on the basic parameters characterizing the photon pulse and the system. The resulting multiexcitation spectrum evolves towards a truncated plasmonic coherent state. Analogous concept is extrapolated to interpret plasmon generation by multiphoton excited electronic polarization. Based on this we elaborate a scenario that the thus created real plasmons act as supplementary frequency-locked pump field for non-Einsteinian plasmonically assisted channels of photoemission from metals. The established paradigm enables assignment and assessment of the observed linear $\hbar$ω p and nonlinear 2$\hbar$ω p electron yields from Ag. Such effects may be exploited for selective filtering of optical energy conversion in electronic systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Mid-Infrared Nonlinear Frequency Conversion Using Monolithic Barium Titanate on Silicon-on-Insulator

In this work, efficient nonlinear frequency conversion in the mid-infrared (mid-IR) region was demonstrated by a barium titanate (BTO) on a silicon-on-insulator (SOI) substrate. The BTO thin film was epitaxially grown by pulsed-laser deposition (PLD). The tensorial second order optical nonlinearity and the ferroelectric domain property of the BTO were characterized by the polarimetric mid-IR second harmonic generation (SHG) measurements. Azimuthal-dependent polarized SHG was modeled at different combinations of the nonlinear coefficient $d_{ij}$ and the domain fraction factor $ΔD^Y/ΔD^X$. Strong SHG intensity was experimentally observed over a broad spectrum at λ = 3.1 μm - 3.7 μm. A characteristic linear dependence between the SHG signal and the square of the pumping laser intensity was observed. The monolithic integration between the epitaxial BTO and the Si provides a compact platform for efficient on-chip light generation and quantum photonic technologies.

25 ENERGY STORAGE↗

Photochemistry of the atmosphere of Uranus

A detailed one-dimensional photochemical model incorporating vertical transport by eddy and molecular diffusion is used to study the importance of chemical and physical processes that control the hydrocarbon abundances in the stratosphere of Uranus. The study includes updated photochemical reaction rates and photolysis branching ratios; explicit calculation of the condensation rate of condensing species; and appropriate boundary conditions at the tropopause. It is found that the basic photochemical process generally produces low net conversion efficiencies of methane to higher hydrocarbons. However, even with these low efficiencies, the total condensation rate, which represents the net rate of conversion of methane to hydrocarbons, is roughly 2 x 10 to the -16th g/cm sec, in agreement with the upper range of the low condensation rate for the production of the stratospheric aerosol layer as determined by Pollack et al. (1987). Furthermore, a range of vertical transport rates is required to separately match the observational constraints on hydrocarbon abundances. The solar reflection data refer to the sunlit polar region of Uranus and require an eddy diffusion coefficient of K approx. = 50 sq cm/sec for globally averaged insolation or K approx = 1500 (Nh/N) exp 1/2 for overhead sun. The Voyager 2 Utraviolet Spectrometer solar occultation data refer to the equatorial regions, thus implying a large latitudinal gradient in stratospheric hydrocarbon abundance.

Summers, Michael E.↗

Distinguishing resonance symmetries with energy-resolved photoion angular distributions from ion-pair formation in O 2 following two-photon absorption of a 9.3 eV femtosecond pulse

We present a combined experimental and theoretical study on the photodissociation dynamics of ion-pair formation in O 2 following resonant two-photon absorption of a 9.3 eV femtosecond pulse, where the resulting O + ions are detected using 3-D momentum imaging. Ion-pair formation states of $^3\Sigma^-_g$ and $^3\Pi_g$ symmetry are accessed through predissociation of optically dark continuum Rydberg states converging to the B $^2\Sigma^-_g$ ionic state, which are resonantly populated via a mixture of both parallel-parallel and parallel-perpendicular two-photon transitions. This mixture is evident in the angular distribution of the dissociation relative to the light polarization, and varies with the kinetic energy release (KER) of the fragmenting ion-pair. The KER-dependent photoion angular distribution reveals the underlying two-photon absorption dynamics involved in the ion-pair production mechanism and indicates the existence of two nearly degenerate continuum resonances possessing different symmetries, which can both decay by coupling to ion-pair states of the same total symmetry through internal conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗