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At least 577 records · Page 32

Galileo imaging results from the second Earth-Moon flyby: Lunar Maria and related units

The second flyby of the Earth-Moon System by Galileo occurred on December 7, 1992, on its trajectory toward Jupiter. The flyby took the spacecraft over the lunar north polar region from the dark farside and continued across the illuminated nearside. This provided the first opportunity to observe northern and northeastern limb regions with a modern, multispectral imaging system with high spatial resolution (up to 1.1 km/pixel). Scientific objectives included compositional assessment of previously uncharacterized mare regions, study of various light plains materials, and assessment of dark mantle deposits (DMD) and dark halo craters (DHC). Color composite images were prepared from ratios of Galileo SSI filter data (0.76/0.41 yields red; 0.76/0.99 yields green; 0.41/0.76 yields blue) and used for preliminary comparison of units. The 0.41/0.76 ratio has been empirically correlated to Ti content of mare soils (blue is relatively high, red is relatively low). The relative strengths of the ferrous one micron absorption in mafic minerals can be compared using the 0.76/0.99 ratio. In addition, relative ages of units analyzed spectrally were determined from crater statistics using Lunar Orbiter images following the techniques of Neukum et al. Mare deposits analyzed include Mare Humboldtianum, central and eastern Mare Frigoris, Mare Crisium and other deposits in the Crisium Basin, and isolated mare patches on the northeastern lunar limb. Preliminary results show a diversity of 0.41/0.76 micron signatures, implying a wide range of titanium contents. Some light plains units are similar to units found at the Apollo 16 site; others may be ancient mare materials. Dark mantle deposits (DMD) analyzed also are available.

Greeley, R.↗

Internode and petiole elongation of soybean in response to photoperiod and end-of-day light quality

Elongation of main stem internodes and petioles of soybeans, Glycine max 'Ransom,' was examined in response to various photoperiod/temperature combinations and to end-of-day (EOD) light quality. Photoperiod treatments consisted of 10, 14, and 16 h in combination with day/night temperatures of 18/14, 22/18, 26/22, 30/26, and 34/30 C. The EOD treatments consisted of exposing plants to illumination from either incandescent (high far-red component, FR) or fluorescent (high red component, R) lamps during the final 0.5 h of a 10-h photoperiod. Internode elongation was not significantly promoted by the photoperiod treatments, and, in fact, under the two highest temperature regimes, internode elongation was suppressed under the longer photoperiods. Petiole elongation, however, was enhanced under the longer photoperiods at all temperatures. In the EOD light study, internode and petiole elongation was significantly greater on plants exposed to 0.5 h EOD from incandescent lamps than from fluorescent. Under the incandescent EOD treatment, plants increased dry matter production by 41% and exhibited greater partitioning of assimilates in stem and root portions than under fluorescent EOD.

NASA Program CELSS↗

Depth-Penetrating Measurements Developed for Thermal Barrier Coatings Incorporating Thermographic Phosphors

The insulating properties of thermal barrier coatings (TBCs) provide highly beneficial thermal protection to turbine engine components by reducing the temperature sustained by those components. Therefore, measuring the temperature beneath the TBC is critical for determining whether the TBC is performing its insulating function. Currently, noncontact temperature measurements are performed by infrared pyrometry, which unfortunately measures the TBC surface temperature rather than the temperature of the underlying component. To remedy this problem, the NASA Glenn Research Center, under the Information Rich Test Instrumentation Project, developed a technique to measure the temperature beneath the TBC by incorporating a thin phosphor layer beneath the TBC. By performing fluorescence decay-time measurements on light emission from this phosphor layer, Glenn successfully measured temperatures from the phosphor layer up to 1100 C. This is the first successful demonstration of temperature measurements that penetrate beneath the TBC. Thermographic phosphors have a history of providing noncontact surface temperature measurements. Conventionally, a thermographic phosphor is applied to the material surface and temperature measurements are performed by exciting the phosphor with ultraviolet light and then measuring the temperature-dependent decay time of the phosphor emission at a longer wavelength. The innovative feature of the new approach is to take advantage of the relative transparency of the TBC (composed of yttria-stabilized zirconia) in order to excite and measure the phosphor emission beneath the TBC. The primary obstacle to achieving depth-penetrating temperature measurements is that the TBCs are completely opaque to the ultraviolet light usually employed to excite the phosphor. The strategy that Glenn pursued was to select a thermographic phosphor that could be excited and emit at wavelengths that could be transmitted through the TBC. The phosphor that was selected was yttria doped with europia (Y2O3:Eu), which has a minor excitation peak at 532 nm (green) and an emission peak at 611 nm (red)--both are wavelengths that exhibit significant transmission through the TBC. The measurements were performed on specimens consisting of a 25- m-thick phosphor layer beneath a 100- m-thick TBC. The 532-nm (green) excitation light was provided by a frequency-doubled YAG:Nd (yttrium-aluminum-garnet:neodymium) laser, and the fluorescence decay time measurements were acquired with a modified Raman microscope. The preceding graph compares the intensity of the phosphor emission of the phosphor layer above the TBC versus that of the phosphor layer beneath the TBC. Although there was considerable attenuation of the phosphor signal (a factor of 30), the phosphor emission at the reduced intensity was more than sufficient to perform fluorescence decay time measurements. The following graph shows the fluorescence lifetime temperature dependency for the Y2O3:Eu phosphor layers both above and below the TBC. These curves show an excellent match and indicate that, despite the attenuation due to the overlying TBC, the phosphor layer beneath the TBC still functions as an effective temperature indicator.

Eldridge, Jeffrey I.↗

Band Edge Control of Quasi–2D Metal Halide Perovskites for Blue Light–Emitting Diodes with Enhanced Performance

Perovskite light–emitting diodes (PeLEDs) have received great attention for their potential as next–generation display technology. While remarkable progress has been achieved in green, red, and near–infrared PeLEDs with external quantum efficiencies (EQEs) exceeding 20%, obtaining high performance blue PeLEDs remains a challenge. Poor charge balance due to large charge injection barriers in blue PeLEDs has been identified as one of the major roadblocks to achieve high efficiency. Here band edge control of perovskite emitting layers for blue PeLEDs with enhanced charge balance and device performance is reported. By using organic spacer cations with different dipole moments, that is, phenethyl ammonium (PEA), methoxy phenethyl ammonium (MePEA), and 4–fluoro phenethyl ammonium (4FPEA), the band edges of quasi–2D perovskites are tuned without affecting their band gaps. Furthermore, detailed characterization and computational studies have confirmed the effect of dipole moment modification to be mostly electrostatic, resulting in changes in the ionization energies of ≈0.45 eV for MePEA and ≈ –0.65 eV for 4FPEA based thin films relative to PEA–based thin films. With improved charge balance, blue PeLEDs based on MePEA quasi–2D perovskites show twofold increase of the EQE as compared to the control PEA based devices.

36 MATERIALS SCIENCE↗

An Adaptive Cross-Correlation Algorithm for Extended-Scene Shack-Hartmann Wavefront Sensing

This viewgraph presentation reviews the Adaptive Cross-Correlation (ACC) Algorithm for extended scene-Shack Hartmann wavefront (WF) sensing. A Shack-Hartmann sensor places a lenslet array at a plane conjugate to the WF error source. Each sub-aperture lenslet samples the WF in the corresponding patch of the WF. A description of the ACC algorithm is included. The ACC has several benefits; amongst them are: ACC requires only about 4 image-shifting iterations to achieve 0.01 pixel accuracy and ACC is insensitive to both background light and noise much more robust than centroiding,

Terrestrial Planet Finder (TPF)↗

The 2013 FLEX-US Airborne Campaign at the Parker Tract Loblolly Pine Plantation in North Carolina, USA

The first European Space Agency (ESA) and NASA collaboration in an airborne campaign to support ESA's FLuorescence EXplorer (FLEX) mission was conducted in North Carolina, USA during September-October 2013 (FLEX-US 2013) at the Parker Tract Loblolly Pine (LP) Plantation (Plymouth, NC, USA). This campaign combined two unique airborne instrument packages to obtain simultaneous observations of solar-induced fluorescence (SIF), LiDAR-based canopy structural information, visible through shortwave infrared (VSWIR) reflectance spectra, and surface temperature, to advance vegetation studies of carbon cycle dynamics and ecosystem health. We obtained statistically significant results for fluorescence, canopy temperature, and tower fluxes from data collected at four times of day over two consecutive autumn days across an age class chronosequence. Both the red fluorescence (F685) and far-red fluorescence (F740) radiances had highest values at mid-day, but their fluorescence yields exhibited different diurnal responses across LP age classes. The diurnal trends for F685 varied with forest canopy temperature difference (canopy minus air), having a stronger daily amplitude change for young vs. old canopies. The Photochemical Reflectance Index (PRI) was positively correlated with this temperature variable over the diurnal cycle. Tower measurements from mature loblolly stand showed the red/far-red fluorescence ratio was linearly related to canopy light use efficiency (LUE) over the diurnal cycle, but performed even better for the combined morning/afternoon (without midday) observations. This study demonstrates the importance of diurnal observations for interpretation of fluorescence dynamics, the need for red fluorescence to understand canopy physiological processes, and the benefits of combining fluorescence, reflectance, and structure information to clarify canopy function versus structure characteristics for a coniferous forest.

chlorophyll fluorescence; diurnal responses; red S↗

Direct Evidence for a Sequential Electron Transfer–Proton Transfer Mechanism in the PCET Reduction of a Metal Hydroxide Catalyst

Here, the proton-coupled electron transfer (PCET) mechanism for the reaction M ox -OH + e − + H + → M red -OH 2 was de-termined through kinetic resolution of the independent electron transfer (ET) and proton transfer (PT) steps. The reaction of interest was triggered by visible light excitation of [Ru II (tpy)(bpy′)H 2 O] 2+ , Ru II -OH 2 , where tpy is 2,2′:6′,2″-terpyridine and bpy′ is 4,4′-diaminopropylsilatrane-2,2′-bipyridine, anchored to In 2 O 3 :Sn (ITO) thin films in aqueous solutions. Interfacial kinetics for the PCET reduction reaction were quantified by nanosecond transient absorption spectroscopy as a function of solution pH and applied potential. Data acquired from pH = 5-10 revealed a stepwise electron-transfer proton-transfer (ET-PT) mechanism, while kinetic measurements made below the pK a (Ru III -OH/OH 2 ) = 1.3 were used to study the analogous interfacial reaction where electron transfer was the only mechanistic step. Analysis of this data with a recently reported multi-channel kinetic model was used to construct a PCET zone diagram and supported the assignment of an ET-PT mechanism from pH = 5-10. Ultimately, this study represents a unique example amongst M ox -OH/M red -OH 2 reactivity where the protona-tion and oxidation state of the intermediate was kinetically and spectrally resolved to firmly establish the PCET mechanism.

Charge transfer↗

Advanced Three-Dimensional Display System

A desktop-scale, computer-controlled display system, initially developed for NASA and now known as the VolumeViewer(TradeMark), generates three-dimensional (3D) images of 3D objects in a display volume. This system differs fundamentally from stereoscopic and holographic display systems: The images generated by this system are truly 3D in that they can be viewed from almost any angle, without the aid of special eyeglasses. It is possible to walk around the system while gazing at its display volume to see a displayed object from a changing perspective, and multiple observers standing at different positions around the display can view the object simultaneously from their individual perspectives, as though the displayed object were a real 3D object. At the time of writing this article, only partial information on the design and principle of operation of the system was available. It is known that the system includes a high-speed, silicon-backplane, ferroelectric-liquid-crystal spatial light modulator (SLM), multiple high-power lasers for projecting images in multiple colors, a rotating helix that serves as a moving screen for displaying voxels [volume cells or volume elements, in analogy to pixels (picture cells or picture elements) in two-dimensional (2D) images], and a host computer. The rotating helix and its motor drive are the only moving parts. Under control by the host computer, a stream of 2D image patterns is generated on the SLM and projected through optics onto the surface of the rotating helix. The system utilizes a parallel pixel/voxel-addressing scheme: All the pixels of the 2D pattern on the SLM are addressed simultaneously by laser beams. This parallel addressing scheme overcomes the difficulty of achieving both high resolution and a high frame rate in a raster scanning or serial addressing scheme. It has been reported that the structure of the system is simple and easy to build, that the optical design and alignment are not difficult, and that the system can be built by use of commercial off-the-shelf products. A prototype of the system displays an image of 1,024 by 768 by 170 (=133,693,440) voxels. In future designs, the resolution could be increased. The maximum number of voxels that can be generated depends upon the spatial resolution of SLM and the speed of rotation of the helix. For example, one could use an available SLM that has 1,024 by 1,024 pixels. Incidentally, this SLM is capable of operation at a switching speed of 300,000 frames per second. Implementation of full-color displays in future versions of the system would be straightforward: One could use three SLMs for red, green, and blue, respectively, and the colors of the voxels could be automatically controlled. An optically simpler alternative would be to use a single red/green/ blue light projector and synchronize the projection of each color with the generation of patterns for that color on a single SLM.

Geng, Jason↗

Comparison of the Forward and Reverse Photocycle Dynamics of Two Highly Similar Canonical Red/Green Cyanobacteriochromes Reveals Unexpected Differences

Cyanobacteriochromes (CBCRs) are cyanobacterial photoreceptors that exhibit photochromism between two states: a thermally stable dark-adapted state and a metastable light-adapted state with bound linear tetrapyrrole (bilin) chromophores possessing 15Z and 15E configurations, respectively. The photodynamics of canonical red/green CBCRs have been extensively studied; however, the time scales of their excited-state lifetimes and subsequent ground-state evolution rates widely differ and, at present, remain difficult to predict. Here, we compare the photodynamics of two closely related red/green CBCRs that have substantial sequence identity (~68%) and similar chromophore environments: AnPixJg2 from Anabaena sp. PCC 7120 and NpR6012g4 from Nostoc punctiforme. Using broadband transient absorption spectroscopy on the primary (125 fs to 7 ns) and secondary (7 ns to 10 ms) time scales together with global analysis modeling, our studies revealed that AnPixJg2 and NpR6012g4 have comparable quantum yields for initiating the forward ( 15Z P r → 15E P g ) and reverse ( 15E P g → 15Z P r ) reactions, which proceed through monotonic and nonmonotonic mechanisms, respectively. In addition to small discrepancies in the kinetics, the secondary reverse dynamics resolved unique features for each domain: intermediate shunts in NpR6012g4 and a Meta-Gf intermediate red-shifted from the 15Z P r photoproduct in AnPixJg2. Altogether, this study supports the conclusion that sequence similarity is a useful criterion for predicting pathways of the light-induced evolution and quantum yield of generating primary intermediate Φ p within subfamilies of CBCRs, but more studies are still needed to develop a comprehensive molecular level understanding of these processes.

59 BASIC BIOLOGICAL SCIENCES↗

Analysis of remotely sensed data for detecting soil limitations

During 1971 and 1972 a detailed study was conducted on a fallow field in the proposed Oahe Irrigation Project to determine the relationship between the tonal variation observed on aerial photographs and the properties of eroded soil. Correlation and regression analysis of digitized, multiemulsion, color infrared film (2443) data and detailed field data revealed a highly significant correlation between film transmittance and several soil properties indicative of the erosion limitation. Computer classification of the multiemulsion film data resulted in maps portraying the eroded soil and the normal soil. Both correlation and computer classification results were best using the reflectance data from the red spectral band. The results showed film transmittance was actually measuring the reflectivity of the soil surface which was increased by the incorporation of the light colored, calcareous parent material exposed by erosion or tillage on soils with thin surface horizons.

Benson, L. A.↗

The Development of a 30-125 Micron Array for Airborne Astronomy

The development of a 30-125 micron Ge:Sb photoconductor array for AIRES (Airborne Infra-Red Echelle Spectrometer) is described. The prototype array is a 2x24 module which can be close-stacked to provide larger two-dimensional formats. Light is focused onto each detector using a collecting cone with a 2 mm pitch. The array is read out by two Raytheon SBRC-190 cryogenic multiplexers that also provide a CTIA (capacitive transimpedance amplifier) unit cell for each detector. We discuss our results from a test series conducted to measure the array performance and to evaluate its suitability for airborne astronomy.

Mason, C. G.↗

The Development of a 30-125 Micron Array for Airborne Astronomy

The development of a 30-125 micron Ge:Sb photoconductor array for AIRES (Airborne Infra-Red Echelle Spectrometer) is described. The prototype array is a 2x24 module which can be close-stacked to provide larger two-dimensional formats. Light is focused onto each detector using a collecting cone with a 2 mm pitch. The array is read out by two Raytheon SBRC-190 cryogenic multiplexers that also provide a CTIA (capacitive transimpedance amplifier) unit cell for each detector. We discuss our results from a test series conducted to measure the array performance and to evaluate its suitability for airborne astronomy.

Mason, C. G.↗

The Gamma-Ray Burst Next Door

I hesitate to spawn a thousand bad sci-fi flicks, but here it goes: Scientists now say that some gamma-ray bursts, the most powerful explosions in the universe, originate in nearby galaxy clusters. If one were to occur nearby, it could wipe out life on Earth. Fortunately, the chances of mass extinction are slimmer than the Chicago Cubs meeting the Boston Red Sox in the World Series (. . . and the Red Sox winning). But a new analysis of over 1400 archived gamma-ray bursts reveals that about 100 bursts originated within 325 million light-years of Earth, and not billions of light-years away as previously thought. If so, there's no reason why a burst couldn't go off in our galaxy.

Wanjek, Christopher↗

First Earth-Based Detection of a Superbolide on Jupiter

Cosmic collisions can planets cause detectable optical flashes that range from terrestrial shooting stars to bright fireballs. On 2010 June 3 a bolide in Jupiter's atmosphere was simultaneously observed from the Earth by two amateur astronomers observing Jupiter in red and blue wavelengths, The bolide appeared as a flash of 2 s duration in video recording data of the planet. The analysis of the light carve of the observations results in an estimated energy of the impact of (0.9-4,0) x 10(exp 15) J which corresponds to a colliding body of 8-13 m diameter assuming a mean density of 2 g/cu cm. Images acquired a few days later by the Hubble Space Telescope and other large ground-based facilities did not show any signature of aerosol debris, temperature, or chemical composition anomaly, confirming that the body was small and destroyed in Jupiter's upper atmosphere. Several collisions of this size may happen on Jupiter on a yearly basis. A systematic study of the impact rate and size of these bolides can enable an empirical determination. of the flux of meteoroids in Jupiter with implications for the populations of small bodies in the outer solar system and may allow a better quantification of the threat of impacting bodies to Earth. The serendipitous recording of this optical flash opens a new window in the observation of Jupiter with small telescopes.

Hueso, R.↗

Flash Formation of I-Rich Clusters during Multistage Halide Segregation Studied in MAPbI 1.5 Br 1.5

Wide band gap mixed halide perovskites such as MAPb(I 1–x Br x ) 3 sparked great research interest because of their outstanding optoelectronic properties, ease of fabrication, and band gap tunability. Their application thus far is however limited by light-induced halide segregation in which microscopic clusters with a high iodide content are formed and act as recombination centers. The key mechanism(s) underlying this halide segregation process are still debated. Here, we present a study on the photoluminescence evolution in MAPb(I 1.5 Br 1.5 ) perovskites with varying microstructures under constant illumination at room temperature and at elevated temperature. Our findings reveal a more complicated picture of the segregation mechanism occurring in three stages instead of two as commonly reported. The process starts with a flash formation of I-rich domains. Following is a rapid blue shift before the gradual and typically observed red shift occurs. The evolution of the three stages is fully reversible in the dark and is also present at elevated temperatures (50 °C). We explain the existence of multiple stages during light-induced halide segregation by natural compositional fluctuations of the halides and the formation of halide clusters with a dynamically changing distribution in I–Br content. The variation in the I–Br ratio depends on the grain size and film heterogeneity. Overall, these findings add further details in the quest of unraveling the underlying segregation mechanism(s), which need to be identified to stabilize halides in wide band gap perovskites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Changes in SSL Device Efficiency and Optical Performance Under Accelerated Aging Conditions

Lighting application efficiency (LAE) describes the efficient delivery of light from the light source to the lighted task and is viewed as a new frontier—increasing energy savings with solid-state lighting (SSL) technologies. The framework for LAE that is proposed by the U.S. Department of Energy (DOE) consists of four major elements: light source efficiency, optical delivery efficiency, spectral efficiency, and intensity effectiveness. This report focuses on a sampling of the available SSL products that can be broadly defined as having modified spectral output because the method of spectra modification has a significant impact on light source efficiency and long-term optical delivery and spectral efficiencies. This report focused on the changes in light source, optical delivery, and spectral efficiencies that occur during aging of SSL devices. An accelerated stress test (AST) regiment was developed for the devices under test (DUTs) examined in this report to provide insights into how the performance of SSL devices change with aging. The AST protocols demonstrate that the SSL products discussed in this report often reduce light source efficiency to achieve different spectral characteristics. In addition, aging of the optical components (e.g., lenses, solder masks) in SSL devices can produce increased light absorption, which negatively impacts optical delivery efficiency and light source efficiency. The modified spectral outputs of the selected SSL products discussed in this report come in a variety of form factors and achieve enhanced optical performance by using a variety of methods. All of the products examined in this study use mid-power light-emitting diodes (MP-LEDs), although the number, configuration, phosphor content, and light-emitting diode (LED) pump of the MP-LEDs differ. Product MS-1 is a 60-watt (W) replacement A19 lamp with a hermetically sealed glass globe, which contains an embedded optical filter to absorb green and yellow emissions, thereby creating a “sunlike” modified spectrum. Product MS-2 is a 60-W replacement A19 lamp with 30 MP-LEDs, and it uses a violet LED pump, along with green and red phosphor emissions, to produce a “healthy” spectrum. This spectrum omits blue emissions in an effort to reduce melanopic lux. Product MS-3 is an LED module consisting of 21 MP-LEDs that use a violet LED pump, along with blue, green, and red phosphors, to produce a “sunlike” spectrum. Products MS-4 and MS-5 are both 6-inch (in) downlights that use a manual switching mechanism so that users can select application-specific correlated color temperatures before installation. Products MS-4 and MS-5 both contain two LED primaries (2,700 Kelvin [K] and 5,000 K) for spectral tuning. Product MS-4 contains 12 MP-LEDs for each LED primary, and Product MS-5 contains 10 MP-LEDs for each LED primary. This report summarizes the overall findings from up to 8,000 hours (hrs) of AST on the lamp DUTs (Products MS-1 and MS-2); up to 5,000 hrs of AST on the LED light engine DUTs (Product MS-3); and up to 7,000 hrs of AST on the downlight DUTs (Products MS-4 and MS-5). The AST procedures used in this study included a room temperature operational life (RTOL) test, an operational life test conducted at 45 degrees Celsius (°C; 45OL) test, an operational life test conducted at 75°C (75OL), a wet high-temperature operational life test performed at 65°C and 90% relative humidity (6590), and a wet high-temperature operational life test performed at 75°C and 75% relative humidity (7575). The AST procedures used for Products MS-1 and MS-2 were RTOL, 45OL, and 6590. The AST procedures used for Products MS-3, MS-4, and MS-5 were RTOL, 75OL, and 7575. During the ASTs described herein, separate populations of each product (three DUTs in each population for Products MS-1, MS-2, MS-4, and MS-5; four DUTs in each population for Product MS-3) were subjected to power cycling of 1 hr on and 1 hr off. The key findings from this study include the following. Enhanced optical performance came at the cost of reduced light source efficiency for the lamps and light engines examined in this study. The optical filter used to produce a “sunlike” spectrum for Product MS-1 reduced light source efficiency by 26%, from 113 lumens per watt (lm/W) to 85 lm/W. Products MS-2 and MS-3 that used a violet-pumped LED to achieve “healthy” and “sunlike” enhanced optical performance, respectively, suffered the largest reduction in initial light source efficiency (49 lm/W for Product MS-2 and 68 lm/W for Products MS-3) perhaps because of the use of violet LED as the optical pump. Product MS-2 also had the poorest color fidelity because of undersaturation of blues and oversaturation of greens and yellows. Chromaticity maintenance of the products in this study was generally good, with parametric failure only occurring for one product at one AST condition (i.e., Product MS-3 at 7575). The chromaticity shift for Product MS-3 in 7575 test conditions resulted from reduced emissions of the broad green and red phosphors used to mimic sunlight in the 500–750 nanometer (nm) range. As a result of these phosphor emission losses, chromaticity shifted toward the more stable violet-pumped LED and blue phosphor. Although chromaticity maintenance was acceptable for most products tested, different chromaticity shift mechanisms were observed for temperature and humidity tests compared with temperature alone for Products MS-1, MS-2, and MS-3. For Product MS-1, a relative increase in green emissions was observed with humidity, which may indicate humidity-accelerated degradation of the optical filter at green wavelengths (optical delivery efficiency reduction) or degradation of the emitters in the red region (spectral efficiency reduction). The violet-pumped products (i.e., MS-2 and MS-3) exhibited different chromaticity shift behavior in the temperature-humidity environments, with Product MS-2 shifting generally yellow because of photo-induced oxidation of the plastic globe (i.e., a reduction of optical delivery efficiency) and Product MS-3 shifting toward violet and blue emitters because of faster loss of emission from green and red phosphors (i.e., a reduction in spectral efficiency). Because of an initial drop in power consumption, the light source efficiency of downlights (Products MS-4 and MS-5) increased at RTOL throughout the test duration. The light source efficiency initially increased during 75OL until a decay in luminous flux maintenance (LFM) dominated light source efficiency, whereas the light source efficiency decreased for the entire 7575 test duration. It was found that increasing the ambient environment of an SSL device from 25°C to 75°C decreases the LFM by 2.7 to 5.5, depending on design of the SSL device. Adding humidity to the system (75OL to 7575) was found to decrease LFM by another factor of approximately 3.0. A common location of failure was identified for the downlights (Products MS-4 and MS-5) operated in the 7575 environment. This failure abruptly occurred between 3,000 to 5,000 hrs of testing on the film capacitor of the electromagnetic interference (EMI) filter near the diode bridge for 11 of the 12 downlights. It is likely that this failure was caused by a combination of the high electrical voltage across the capacitor, the location of the capacitor near the heat sources (e.g., transformers, diode bridges, power resistors), and the high stress environment of 7575. Longer test times are needed to fully understand the LFM, luminous efficacy changes, and chromaticity shifts for some of the products. Because of the high reliability, light source efficiency, and spectral tuning capabilities of LEDs, the expectations of LAE for SSL products are greatly increased over traditional lighting products. The data gathered in this report begin to provide an understanding of the tradeoffs that current SSL products undergo when optimizing the different efficiency elements of LAE. As discussed in this report, the findings from the tests conducted show that the optimization of spectral efficiency can come at the cost of initial light source efficiency. Furthermore, the introduction of violet LEDs can promote long-term optical delivery efficiency degradation, and the introduction of optical filters or new phosphors can lead to unwanted spectral efficiency changes because the ratio of phosphor emitters changes with aging. The data presented in this report also identified a common failure location in 6-in downlights. The results regarding long-term behavior of the modified spectra devices studied provide valuable information about changes to the light source, spectral, and optical delivery efficiencies as the devices age. This information can be used to improve future SSL designs.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Ligand Control of Structural Diversity in Luminescent Hybrid Copper(I) Iodides

Copper(I) iodide hybrids are of interest for next-generation lighting technologies because of their efficient luminescence in the absence of rare-earth elements. Here, we report 10 structurally diverse hybrid copper(I) iodides that emit in the green–red region with quantum yields reaching 67%. The compounds display a diversity of structures including ones with one-dimensional (1D) Cu–1 chains, Cu 2 I 2 rhomboid dimers, and structures with two different arrangements of Cu 4 I 4 tetramers. The compounds with Cu 2 I 2 rhomboid dimers or Cu 4 I 4 cubane tetramers have higher photoluminescence quantum yields than those with Cu–I 1D chains and octahedral Cu 4 I 4 tetramers, owing to the optimal degree of condensation of the inorganic motifs, which suppresses nonradiative processes. Electronic structure calculations on these compounds point out the critical influence of the inorganic motif and organic ligand on the nature of the band gaps and thus the excitation characteristics. Temperature-dependent photoluminescence spectra are presented to better understand the nature of luminescence in compounds with different inorganic motifs. Here. the emerging understanding of composition–structure–property correlations in this family provides inspiration for the rational design of hybrid phosphors for general lighting applications.

36 MATERIALS SCIENCE↗

Filling-in of Far-Red and Near-Infrared Solar Lines by Terrestrial and Atmospheric Effects: Simulations and Space-Based Observations from SCHIAMACHY and GOSAT

Mapping of terrestrial vegetation fluorescence from space is of interest because it can potentially provide global information on the functional status of vegetation including light use efficiency and global primary productivity that can be used for global carbon cycle modeling. Space-based measurement of solar-induced chlorophyll fluorescence is challenging, because its signal is small as compared with the much larger reflectance signal. Ground- and aircraft-based approaches have made use of the dark and spectrally-wide 02-A (approx 760 nm) and O2-B (approx 690 nm) atmospheric features to detect the weak fluorescence signal. More recently, Joiner et a1. and Frankenberg et a1. focused on longer-wavelength solar Fraunhofer lines that can be observed with space-based instruments such as the currently operational GOSAT. They showed that fluorescence can be detected using Fraunhofer lines away from the far-red chlorophyll-a fluorescence peak even when the surface is relatively bright. Here, we build on that work by developing methodology to correct for instrumental artifacts that produce false filling-in signals that can bias fluorescence retrievals. We also examine other potential sources of filling-in at far-red and NIR wavelengths. Another objective is to explore the possibility of making fluorescence measurements from space with lower spectral resolution instrumentation than the GOSAT interferometer. We focus on the 866 nm Ca II solar Fraunhofer line. Very few laboratory and ground-based measurements of vegetation fluorescence have been reported at wavelengths longer than 800 mn. Some results of fluorescence measurements of corn leaves acquired in the laboratory using polychromatic excitation at wavelengths shorter than 665 nm show that at 866 nm, the measured signal is of the order of 0.1-0.2 mw/sq m/nm/sr. In this work we use the following satellite observations: We use SCIAMACHY channel 5 in nadir mode that covers wavelengths between 773 and 1063 nm at a spectral resolution of 0.54 nm. GOSAT has two instrument packages: the Thermal And Near-infrared Sensor for carbon Observation-Fourier Transform Spectrometer (TANSO-FTS) and the Cloud and Aerosol Imager (CAI). We use TANSO-FTS band 1, which extends from approximately 758 to 775 mn and we use cloud fraction derived from the CAL We compare satellite-derived fluorescence with the Enhanced Vegetation Index (EVI), an Aqua/MODIS-derived vegetation reflectance-based index that indicates relative greenness and is used to infer photosynthetic function.

Joiner, J.↗