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At least 199 records · Page 11

Improving Nocturnal Fire Detection with the VIIRS Day-Night Band

Building on existing techniques for satellite remote sensing of fires, this paper takes advantage of the day-night band (DNB) aboard the Visible Infrared Imaging Radiometer Suite (VIIRS) to develop the Firelight Detection Algorithm (FILDA), which characterizes fire pixels based on both visible-light and infrared (IR) signatures at night. By adjusting fire pixel selection criteria to include visible-light signatures, FILDA allows for significantly improved detection of pixels with smaller and/or cooler subpixel hotspots than the operational Interface Data Processing System (IDPS) algorithm. VIIRS scenes with near-coincident Advanced Spaceborne Thermal Emission and Reflection (ASTER) overpasses are examined after applying the operational VIIRS fire product algorithm and including a modified "candidate fire pixel selection" approach from FILDA that lowers the 4-μm brightness temperature (BT) threshold but includes a minimum DNB radiance. FILDA is shown to be effective in detecting gas flares and characterizing fire lines during large forest fires (such as the Rim Fire in California and High Park fire in Colorado). Compared with the operational VIIRS fire algorithm for the study period, FILDA shows a large increase (up to 90%) in the number of detected fire pixels that can be verified with the finer resolution ASTER data (90 m). Part (30%) of this increase is likely due to a combined use of DNB and lower 4-μm BT thresholds for fire detection in FILDA. Although further studies are needed, quantitative use of the DNB to improve fire detection could lead to reduced response times to wildfires and better estimate of fire characteristics (smoldering and flaming) at night.

Day-night band↗

Mid-day photomixotrophy by Roseiflexus spp. and implications for the 13 C content of hot spring cyanobacterial mats

Microbial mats inhabiting extreme environments have been studied as modern analogs of stromatolites. Mats in Octopus Spring and Mushroom Spring, Yellowstone National Park, are predominated by unicellular photoautotrophic cyanobacteria (Synechococcus spp.), which are thought to cross-feed filamentous photoheterotrophic bacteria (mainly Roseiflexus spp.), except under early morning anoxic conditions when Roseiflexus spp. have been shown to fix dissolved inorganic carbon (DIC). Transcription patterns, however, suggest that Roseiflexus spp. may perform photomixotrophy, in which DIC is incorporated together with organic compounds during the daytime. We investigated the roles played by Synechococcus spp. and Roseiflexus spp. in DIC and organic matter uptake in mid-day light and oxic mats. Mass spectrometry was used to show that 13 C-bicarbonate uptake under infrared (IR) light (utilized by anoxygenic phototrophs) or visible-minus-blue light (V-B) (used by cyanobacteria) was about two-thirds and one-third, respectively, of that incorporated in full light. Laser-ablation mass spectrometry analysis demonstrated that 13 C incorporation under V-B light was restricted to the uppermost portion of the mat, whereas 13 C incorporation under IR light was maximal in deeper mat layers. 13 C-acetate, -propionate, -lactate, and -glycolate were incorporated to an equal or greater extent under IR and full light. Incorporation of 13 C into peptides showed that both Synechococcus spp. and Roseiflexus spp. were active in DIC uptake, whereas Roseiflexus spp. exhibited greater uptake of 13 C-organic acids, especially glycolate and lactate, into peptides. Peptides of proteins of the 3-hydroxypropionate pathway were labeled. Thus, Roseiflexus spp. appears to exhibit photomixotrophy throughout the day.

Roseiflexus↗

Noncontact measurement of high temperature using optical fiber sensors

The primary goal of this research program was the investigation and application of noncontact temperature measurement techniques using optical techniques and optical fiber methods. In particular, a pyrometer utilizing an infrared optical light pipe and a multiwavelength filtering approach was designed, revised, and tested. This work was motivated by the need to measure the temperatures of small metallic pellets (approximately 3 mm diameter) in free fall at the Microgravity Materials Processing Drop Tube at NASA Marshall Space Flight Center. In addition, research under this program investigated the adaptation of holography technology to optical fiber sensors, and also examined the use of rare-earth dopants in optical fibers for use in measuring temperature. The pyrometer development effort involved both theoretical analysis and experimental tests. For the analysis, a mathematical model based on radiative transfer principles was derived. Key parameter values representative of the drop tube system, such as particle size, tube diameter and length, and particle temperature, were used to determine an estimate of the radiant flux that will be incident on the face of an optical fiber or light pipe used to collect radiation from the incandescent falling particle. An extension of this work examined the advantage of inclining or tilting the collecting fiber to increase the time that the falling particle remains in the fiber field-of-view. Those results indicate that increases in total power collected of about 15 percent may be realized by tilting the fiber. In order to determine the suitability of alternative light pipes and optical fibers, and experimental set-up for measuring the transmittance and insertion loss of infrared fibers considered for use in the pyrometer was assembled. A zirconium fluoride optical fiber and several bundles of hollow core fiber of varying diameters were tested. A prototype two-color pyrometer was assembled and tested at Virginia Tech, and then tested on the Drop Tube at Marshall Space Flight Center. Radiation from 5 mm diameter niobium drops falling in the Drop Tube was successfully detected, and recorded for later analysis. Subsequent analysis indicated that the imaging of light output from the light pipe onto the detector active areas was not identical for both detectors.

Claus, R. O.↗

Metal Side Reflectors for Trapping Light in QWIPs

Focal-plane arrays of quantum-well infrared photodetectors (QWIPs) equipped with both light-coupling diffraction gratings and metal side reflectors have been proposed, and prototypes are expected to be fabricated soon. The purpose served by the metal side reflectors is to increase quantum efficiency by helping to trap light in the photosensitive material of each pixel. The reasons for using diffraction gratings were discussed in several prior NASA Tech Briefs articles. To recapitulate: In an array of QWIPs, the quantum-well layers are typically oriented parallel to the focal plane and therefore perpendicular or nearly perpendicular to the direction of incidence of infrared light. By virtue of the applicable quantum selection rules, light polarized parallel to the focal plane (as normally incident light is) cannot excite charge carriers and, hence, cannot be detected. Diffraction gratings scatter normally or nearly normally incident light into directions more nearly parallel to the focal plane, so that a significant portion of the light attains a component of polarization normal to the focal plane and, hence, can excite charge carriers. Unfortunately, light scattered in directions parallel or nearly parallel to the focal plane can escape sideways from the QWIP of a given pixel, as illustrated in Figure 1. The escaped light has made only a single pass through the interior photosensitive volume of the QWIP. The quantum efficiency of the QWIP would be increased by trapping light so that it makes multiple passes through the photosensitive volume. As shown in Figure 2, the sides of the QWIP of each pixel would be coated with gold to reflect escaping light back into the interior.

Gunapala, Sarath↗

Infrared upconversion as a means of seeing in the dark

A new approach to seeing in the dark is described which is based on the principles of nonlinear optics employing a crystal such as lithium iodate. A nonlinear optical device capable of producing photons at higher frequencies from lower-frequency incident light is shown to upconvert infrared light directly into visible light. The major advantages of the infrared upconversion process is that it permits the infrared signal to be detected by photon-counting devices presently available for the visible spectral region, and that it can provide sensitivity to infrared radiation without the need for cryogenic cooling of the detector used. Early works on infrared upconversion are reviewed. The development of applications is discussed as to astronomical spectroscopy and infrared image upconversion involving either angular or positional resolution elements. The demonstration of infrared upconversion in rectangular waveguides of single-crystal GaAs by Anderson et al. (1971) indicates future possibilities in upconversion by the use of integrated optics devices.

Gurski, T. R.↗

Mid-infrared photodetection with 2D metal halide perovskites at ambient temperature

The detection of mid-infrared (MIR) light is technologically important for applications such as night vision, imaging, sensing, and thermal metrology. Traditional MIR photodetectors either require cryogenic cooling or have sophisticated device structures involving complex nanofabrication. Here, we conceive spectrally tunable MIR detection by using two-dimensional metal halide perovskites (2D-MHPs) as the critical building block. Leveraging the ultralow cross-plane thermal conductivity and strong temperature-dependent excitonic resonances of 2D-MHPs, we demonstrate ambient-temperature, all-optical detection of MIR light with sensitivity down to 1 nanowatt per square micrometer, using plastic substrates. Through the adoption of membrane-based structures and a photonic enhancement strategy unique to our all-optical detection modality, we further improved the sensitivity to sub–10 picowatt-per-square-micrometer levels. The detection covers the mid-wave infrared regime from 2 to 4.5 micrometers and extends to the long-wave infrared wavelength at 10.6 micrometers, with wavelength-independent sensitivity response. Our work opens a pathway to alternative types of solution-processable, long-wavelength thermal detectors for molecular sensing, environmental monitoring, and thermal imaging.

Li, Yanyan [Yale University, New Haven, CT (United↗

Development of flashlamp-pumped Q-switched Ho:Tm:Cr:YAG lasers for mid-infrared LIDAR application

A flashlamp-pumped 2.1 micron Ho:Tm:Cr:YAG laser was studied for both normal mode and Q-switched operations under a wide variety of experimental conditions in order to optimize performance. Laser output energy, slope efficiency, threshold and pulselength were determined as a function of operating temperature, output mirror reflectivity, input electrical energy and Q-switch opening time. The measured normal-mode laser thresholds of a Ho(3+) (0.45 atomic percent):Tm(3+) (2.5 atomic percent):Cr(3+) (0.8 atomic percent):YAG crystal ranged form 26 to 50 J between 120 and 200 K with slope efficiencies up to 0.36 percent with a 60 percent reflective output mirror. Under Q-switched operation the slope efficiency was 90 percent of the normal-mode result. Development of solid state lasers with Ho(3+), Tm(3+) and/or Er(3+) doped crystals has been pursued by NASA for eye-dafe mid-infrared LIDAR (light detection and ranging) application. As a part of the project, the authors have been working on evaluating Ho(3+):Tm(3+):Cr(3+):YAG crystals for normal-mode and Q-switched 2.1 micron laser operations in order to determine an optimum Tm(3+) concentration under flashlamp pumping conditions. Lasing properties of the Ho(3+) in the mid-infrared region have been studied by many research groups since the early 1960's. However, the technology of those lasers is still premature for lidar application. In order to overcome the inefficiency related to narrow absorption bands of the Ho(3+), Tm(3+) and Er(3+), the erbium has been replaced by chromium. The improvement in flashlamp-pumped Ho(3+) laser efficiency has been demonstrated recently by several research groups by utilizing the broad absorption spectrum of Cr(3+) which covers the flashlamp's emission spectrum. Efficient energy transfer to the Tm(3+) and then the Ho(3+) occurs subsequently. It is known that high Tm(3+) concentration and low Ho(3+) concentration are preferred to achieve a quantum efficiency approaching two and to avoid large reabsorption losses. However, determination of the optimum Tm(3+) concentration required to ensure efficient energy transfer from Cr(3+) to Tm(3+) and from Tm(3+) to Ho(3+) has not been made in the Ho:Tm:CR:YAG crystal. The results obtained so far are given.

Choi, Young S.↗

Heterovalent Substitution of K 2 SrP 2 O 7 :Cr 3+ to Achieve Anti-Thermal-Quenching Broadband Near-Infrared Luminescence

Broadband near-infrared (NIR) light sources based on phosphor-converted light-emitting diodes are highly desirable for biochemical analysis and medical diagnosis applications. However, thermal quenching remains a demanding challenge for developing efficient NIR phosphors. Herein, we report the enhancement of both quantum efficiency and thermal stability in Cr 3+ -activated K 2 SrP 2 O 7 phosphors through a heterovalent substitution strategy by replacing Sr 2+ with Al 3+ in K 2 Sr 1–x Al x P 2 O 7 (0.05 ≤ x ≤ 0.2) to obtain optimized broadband NIR emission. Structural modulation via Al 3+ substitution leads to the optimized composition, K 2 Sr 0.88 Al 0.1 P 2 O 7 :0.02Cr 3+ , which emits across a broad NIR range of 650–1100 nm peaking at 807 nm with a full width at half-maximum of ∼130 nm under 448 nm excitation. Remarkably, its emission intensity at 150 °C remains 120% of the initial value at room temperature, demonstrating a rare antithermal-quenching behavior. Temperature-dependent XRD studies further reveal that Al 3+ substitution effectively suppresses lattice expansion at elevated temperatures, indicating enhanced lattice stability under thermal excitation. Detailed structural and spectral analyses show that the substitution enhances local site symmetry, reduces electron–phonon coupling, increases thermally induced absorption probability, and fortifies energetic barriers against nonradiative transitions. These synergistic effects collectively endow this NIR phosphor with a superior thermal stability. Furthermore, NIR light-emitting diodes fabricated with this phosphor exhibit strong potential for applications in information identification, nondestructive detection, and night vision technologies. This study demonstrates a local structure engineering strategy for designing thermally robust Cr 3+ -activated NIR phosphors, offering valuable insights into material discovery and NIR spectroscopy device development.

Cr3+↗

H-cluster Intermediates and Catalytic Properties of Clostridium pasteurianum [FeFe]-Hydrogenase III

[FeFe]-Hydrogenases are structurally diverse enzymes that catalyze reversible H2 activation at a catalytic cofactor or H-cluster. The H-cluster is a [4Fe-4S] cubane linked by a cysteine thiolate to a diiron subsite containing unique CO, CN-, and dithiomethylamine ligands. The established H-cluster resting state of [4Fe-4S]2+-[FeII-FeI], or Hox, functions in H2 binding and oxidation, or by proton-coupled reduction initiates H2 evolution. In contrast, in Clostridium pasteurianum [FeFe]-hydrogenase III (CpIII) the resting state of the H-cluster is fully oxidized, [4Fe-4S]2+-[FeII-FeII], or Hox+1. To begin to understand if Hox+1 has a role in the mechanism of CpIII, we determined the spectroscopic and redox properties of CpIII H-cluster states under catalytic conditions. CpIII poised in Hox+1 and either equilibrated under 1 atm of H2 or reduced with sodium dithionite, resulted in a mixture of reduced states including Hox (Em8 = -407 mV), Htrans-like [4Fe-4S]+-[FeII-FeII] (Em8 = -418 mV), Hred [4Fe-4S]+-[FeII-FeI], and HredH+ [4Fe-4S]2+-[FeI-FeI] (Em8 = -455-480 mV). Under H2 the population of the Htrans-like state was >20-fold higher than Hox, implicating a role in CpIII catalysis. Unlike other enzymes, there was no spectral evidence of fully reduced states, such as HsredH+ ([4Fe-4S]+-[FeI-FeI]) or Hhyd ([4Fe-4S]+-[FeII-FeII]-H-). Thus, while the H-cluster states of CpIII encompass most of the catalytic intermediates, it is either unable to form HsredH+ and Hhyd, or these states are highly destabilized in CpIII. Thus, these results demonstrate that catalytic intermediates of reduced CpIII differ from the typical intermediates of other catalytic [FeFe]-hydrogenases and may explain the catalytic preference for H2 production.

08 HYDROGEN↗

Near-Infrared Photoluminescence from Spin-Flip Excited States of π-Conjugated Tris(quinolinolate) Chromium(III) Complexes

Tuning metal–ligand covalency offers promising design strategies to tailor the photoluminescence (PL) emission energies of metal-centered, spin-flip excited states. Herein, we report a series of tris(quinolinolate) chromium(III) complexes that exhibit record-low near-infrared II emission energies in a fluid solution at room temperature, afforded by their strong metal–ligand covalencies. Appending π-conjugated arylethynyl substituents to quinolinolate ligands resulted in minimal changes to metal–ligand bond lengths, facilitating nearly indiscriminate metal–ligand covalencies for each tris(quinolinolate) chromium(III) complex. As a result, near-infrared II emission was observed across the series, while simultaneously affording careful tuning of the 4 LMCT/ 4 ( 1 ILCT) electronic transition energies across the visible region. Here, detailed analyses of ground-state electronic structures and excited-state electronic transitions revealed that PL arises from a ligand-field, 2 E excited state, admixed with charge-transfer character. This assignment was supported by solvent-dependent near-infrared emission energies and long excited-state lifetimes, consistent with spin-forbidden relaxation (ranging from 115 ± 5 to 123 ± 1 ns across the series). Utilizing spectroscopic data, ligand-field parameters were quantified, further rationalizing the role of strong metal–ligand covalency in enabling near-infrared II emission. Supported by these results, this study presents a new class of ligands that enable room-temperature near-infrared II emission in chromium(III)-based spin-flip excited states.

Absorption spectroscopy↗

High-Resolution Photoelectron Spectroscopy of NO3 – Vibrationally Excited Along Its ν3 Mode

The nitrate (NO3) radical has long been the subject of both experimental and theoretical studies due to its complex electronic structure resulting from vibronic interactions between its X̃2A2' and B̃2E' states. In particular, the definite assignment of the fundamental of its degenerate stretching vibration (ν3) is still under debate. Here, we report high-resolution photoelectron spectra of vibrationally pre-excited NO3- using the recently developed IR-cryo-SEVI technique. The anions are excited through infrared (IR) excitation near 1350 cm-1, accessing the ν3 and 2ν3(e') vibrational levels with band centers at 1350.5 and ∼2700 cm-1, respectively. The IR-cryo-SEVI spectrum for 2ν3 pre-excitation shows clear evidence for an intense 321 transition. From the position of this feature (30031 cm-1), the electron affinity of NO3 also determined in this work (31680 cm-1), and the IR excitation energy, we obtain a fundamental frequency of 1051 cm-1 for the ν3 fundamental of the NO3 radical. This assignment and other features in the IR-cryo-SEVI spectra are supported by spectral simulations based on a vibronic Köppel-Domcke-Cederbaum Hamiltonian. The simulations also show that nearly all features in the IR-cryo-SEVI spectra arise because of pseudo-Jahn-Teller coupling between the X̃ and B̃ states of NO3. The results and analysis presented here settle a long-standing controversy regarding the ν3 frequency of NO3.

Anions↗

Photodissociation and Infrared Spectroscopy of U + (CO 2 ) n , UO + (CO 2 ) n , and UO 2+ (CO 2 ) n Cation-Molecular Complexes

Laser vaporization of uranium in a pulsed supersonic expansion of carbon dioxide is used to produce complexes of the form U + (CO 2 ) n , UO + (CO 2 ) n , and UO 2+ (CO 2 ) n . These ions are selected in a reflectron time-offlight mass spectrometer and studied with visible laser photodissociation and tunable infrared laser photodissociation spectroscopy in the region of the CO 2 antisymmetric stretch. The dissociation patterns and spectroscopy of these ions indicate that CO 2 ligands are intact molecules. Although reaction products that form oxide-carbonyl or oxalate species are predicted to be stable, there is no direct evidence in the frequency range studied for the formation of these species. There is no clear indication for the coordination numbers for singly charged uranium and its oxide complexes with CO 2 . However, there is strong support in the vibrational patterns for an eight-coordinate complex of the doubly charged UO 2+ species, i.e., UO 2+ (CO 2 ) 8 .

Cluster chemistry↗

Above the Energy Gap Law: Heavy Chalcogenide Substitution in NIR II-Emissive Diradicaloid Qubits

Near-infrared (NIR, 700–1700 nm)- and telecom (∼1260–1625 nm)-emissive molecules are good candidates for biological imaging and quantum sensing applications, respectively; however, bright low energy emission is rare due to exponentially increasing nonradiative decay rates in these regions, a phenomenon known as the energy gap law. Recent literature has emphasized the importance of minimizing skeletal modes to prevent increased nonradiative decay rates, but most organic lumiphores in these regions utilize large, conjugated scaffolds containing many C═C modes. Here we report a compact, telecom-emissive scaffold, tetrathiafulvalene-2,3,6,7-tetraselenate, or TTFts, that displays remarkable air, water, and acid stability, exhibits record quantum yields and brightness values, and retains quantum coherence under ambient conditions. These properties are enabled through methodical selenium substitution, which bathochromically shifts emission while shifting skeletal vibrations to lower energies. This new scaffold validates heavy heteroatom substitution strategies and establishes a new class of bright telecom emitters and robust qubits.

biological imaging↗

Vibrational Dynamics and Phase Transitions of Hydrazine to 50 GPa

The high pressure behavior of hydrazine, N 2 H 4 , has been investigated to 50 GPa at room temperature using infrared and Raman spectroscopy to explore pressure induced phase transitions and changes in hydrogen bonding. Three solid–solid phase transitions were detected at 11, 21, and 32 GPa on room temperature compression through dramatic changes in the lattice vibration and N–H stretching regions with increasing pressure in both measurement techniques. The transition to phase IV, which appears at 32 GPa, exhibits increased hydrogen bonding with significant hysteresis, persisting to 9 GPa on decompression. This work presents a detailed analysis of the pressure dependence of mode shifts and calculations of mode Grüneisen parameters as well as a determination of an approximate thermodynamic Grüneisen parameter. We compare these results to the behavior of other small molecular materials such as ammonia and water and explore the evolution of hydrogen bonding in hydrazine toward the symmetrically hydrogen bonded state, which has previously been suggested by theoretical computations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Near-Infrared Optical Gain of Colloidal Quantum Wells via Intraband Transitions

Tunable, unipolar, near-infrared intraband optical gain is demonstrated in semiconductor colloidal quantum wells, expanding the form and optical range for potential infrared applications. Atomically flat colloidal quantum wells of cadmium selenide display photoinduced absorption features in the near-infrared assigned to intraband (alternatively intersubband) transitions from the first to second electron subbands of the quantum wells. Under ultraviolet optical excitation, these same transitions from the first to second electron subbands are shown to exhibit stimulated emission, resulting in optical gain covering the near-infrared spectral region. The modal gain, bandwidth, and lifetime of this intraband gain are manipulated by using excitation energy, fluence, temperature, and surface chemistry. Unlike previous demonstrations of intraband optical gain in epitaxial quantum wells (e.g., quantum cascade lasers), the colloidal quantum wells are undoped. As a result, nearly thresholdless gain is in principle possible and limited in practice by the measurement of small optical losses of the samples in the near-infrared. Furthermore, the observations may be understood as a modified "quantum fountain" employing the valence band, a strategy that may be applied to many other materials.

Optical gain↗

Surface-Functionalized, Two-Dimensional Polymer Electrochromic Layers as Ultrafast, Multi-State Infrared Optical Gates

Electrochromic devices have widespread application potential, but the currently available switching speeds limit broad real-world implementation of this technology. Here, we report surface-engineered two-dimensional polymers with ionophilic pores that offer unprecedented switching speeds in solid-state, two-terminal, electrochromic devices. In particular, we demonstrate that a crystalline donor–acceptor 2DP functionalized with ethylene glycol oligomers exhibits multistate infrared absorption that is 4× faster (t c = 320 ms) with 3× coloration efficiency (491 cm 2 C –1 ) compared to an alkyl functionalized 2DP constructed from the same chromophores. The functionalized nanoporous surfaces enable rapid switching in these materials under either oxidative or reductive conditions, allowing us to access a range of robust, stable optical responses in a single electrochromic layer. These attributes led us to leverage surface-functionalized 2DPs as multistate infrared logic gates. Collectively, this work demonstrates that surface engineering of nanoporous crystalline lattices is a promising approach to co-optimize the electronic and ionic conductivities required to achieve rapidly switchable electrochromic layers. Beyond speed and efficiency, the demonstration of multistate infrared characteristics shows that electrochromic frameworks are useful in integrated optoelectronic circuits. This positions surface-engineered 2DPs as improved electrochromic coatings and a new material platform for photonic information processing and adaptive devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗