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NASA NTRS2007

Crystal Growth and Characterization of CdTe Grown by Vertical Gradient Freeze

In this study, crystals of CdTe were grown from melts by the unseeded vertical gradient freeze method. The quality of grown crystal were studied by various characterization techniques including Synchrotron White Beam X-ray Topography (SWBXT), chemical analysis by glow discharge mass spectroscopy (GDMS), low temperature photoluminescence (PL), and Hall measurements. The SWBXT images from various angles show nearly strain-free grains, grains with inhomogeneous strains, as well as twinning nucleated in the shoulder region of the boule. The GDMS chemical analysis shows the contamination of Ga at a level of 3900 ppb, atomic. The low temperature PL measurement exhibits the characteristic emissions of a Ga-doped sample. The Hall measurements show a resistivity of 1 x l0(exp 7) ohm-cm at room temperature to 3 x 10(exp 9) ohm-cm at 78K with the respective hole and electron concentration of 1.7 x 10(exp 9) cm(exp -3) and 3.9 x 10(exp 7) cm(exp -3) at room temperature.

Su, Ching-Hua↗

NASA NTRS2004

Arylethynyl Substituted 9,lO-Anthraquinones: Tunable Stokes Shifts by Substitution and Solvent Polarity

2-Arylethynyl- and 2,6- and 2,7-diarylethynyl-substituted 9,lO-anthraquinones were synthesized via Sonogashira coupling reactions of 2-bromo-, 2,6-dibromo-, and 2,7-dibromo-9,10- anthraquinone with para-substituted phenylacetylenes. While the redox properties of those compounds are almost insensitive to substitution, their absorption maxima are linearly related to the Hammett constants with different slopes for electron donors and electron acceptors. ABI compounds are photoluminescent both in solution (quantum yields of emission <= 6 %), and as solids. The emission spectra have the characteristics of charge-transfer bands with large Stokes shifts (100-250 nm). The charge-transfer character of the emitting state is supported by large dipole moment differences between the ground and the excited state as concluded on the basis of molecular modeling and Lippert-Mataga correlations of the Stokes shifts with solvent polarity. Maximum Stokes shifts are attained by both electron-donating and -withdrawing groups. This is explained by a destabilization of the HOMO by electron donors and a stabilization of the LUMO by electron acceptors. X-ray crystallographic analysis of, for example, 2,7-bisphenylethynfl- 9,lO-anthraquinone reveals a monoclinic P21In space group and no indication for pi-overlap that would promote quenching, thus explaining emission from the solid state. Representative reduced forms of the title compounds were isolated as stable acetates of the corresponding dihydrs-9,10- anthraquinones. The emission of these compounds is blue-shifted relative to the parent oxidized forms and is attributed to internal transitions in the dihydro-9,lO-anthraquinone core.

Yang, Jinhua↗

NASA NTRS2007

Temperature Evolution of Excitonic Absorptions in Cd(1-x)Zn(x)Te Materials

The studies consist of measuring the frequency dependent transmittance (T) and reflectance (R) above and below the optical band-gap in the UV/Visible and infrared frequency ranges for Cd(l-x),Zn(x),Te materials for x=0 and x=0.04. Measurements were also done in the temperature range from 5 to 300 K. The results show that the optical gap near 1.49 eV at 300 K increases to 1.62 eV at 5 K. Finally, we observe sharp absorption peaks near this gap energy at low temperatures. The close proximity of these peaks to the optical transition threshold suggests that they originate from the creation of bound electron-hole pairs or excitons. The decay of these excitonic absorptions may contribute to a photoluminescence and transient background response of these back-illuminated HgCdTe CCD detectors.

Quijada, Manuel A.↗

NASA NTRS2008

Control of the Diameter and Chiral Angle Distributions during Production of Single-wall Carbon Nanotubes

Many applications of single wall carbon nanotubes (SWCNT), especially in microelectronics, will benefit from use of certain (n,m) nanotube types (metallic, small gap semiconductor, etc.). However, as produced SWCNT samples are polydispersed, with many (n,m) types present and typical approximate 1:2 metal/semiconductor ratio. It has been recognized that production of SWCNTs with narrow 'tube type populations' is beneficial for their use in applications, as well as for the subsequent sorting efforts. In the present work, SWCNTs were produced by a pulsed laser vaporization (PLV) technique. The nanotube type populations were studied with respect to the production temperature with two catalyst compositions: Co/Ni and Rh/Pd. The nanotube type populations were measured via photoluminescence, UV-Vis-NIR absorption and Raman spectroscopy. It was found that in the case of Co/Ni catalyst, decreased production temperature leads to smaller average diameter, exceptionally narrow diameter distribution, and strong preference toward (8,7) nanotubes. The other nanotubes present are distributed evenly in the 7-30 deg chiral angle range. In the case of Rh/Pd catalyst, a decrease in the temperature leads to a small decrease in the average diameter, with the chiral angle distribution skewed towards 30 o and a preference toward (7,6), (8,6) and (8,7) nanotubes. However, the diameter distribution remains rather broad. These results demonstrate that PLV production technique can provide at least partial control over the nanotube (n,m) populations. In addition, these results have implications for the understanding the nanotube nucleation mechanism in the laser oven.

Nikolaev, Pavel↗

NASA NTRS2008

Spray Chemical Vapor Deposition of Single-Source Precursors for Chalcopyrite I-III-VI2 Thin-Film Materials

Thin-film solar cells on flexible, lightweight, space-qualified substrates provide an attractive approach to fabricating solar arrays with high mass-specific power. A polycrystalline chalcopyrite absorber layer is among the new generation of photovoltaic device technologies for thin film solar cells. At NASA Glenn Research Center we have focused on the development of new single-source precursors (SSPs) for deposition of semiconducting chalcopyrite materials onto lightweight, flexible substrates. We describe the syntheses and thermal modulation of SSPs via molecular engineering. Copper indium disulfide and related thin-film materials were deposited via aerosol-assisted chemical vapor deposition using SSPs. Processing and post-processing parameters were varied in order to modify morphology, stoichiometry, crystallography, electrical properties, and optical properties to optimize device quality. Growth at atmospheric pressure in a horizontal hotwall reactor at 395 C yielded the best device films. Placing the susceptor closer to the evaporation zone and flowing a more precursor-rich carrier gas through the reactor yielded shinier-, smoother-, and denser-looking films. Growth of (112)-oriented films yielded more Cu-rich films with fewer secondary phases than growth of (204)/(220)-oriented films. Post-deposition sulfur-vapor annealing enhanced stoichiometry and crystallinity of the films. Photoluminescence studies revealed four major emission bands and a broad band associated with deep defects. The highest device efficiency for an aerosol-assisted chemical vapor deposited cell was one percent.

Hepp, Aloysius F.↗

NASA NTRS2009

Enhancing SERS by Means of Supramolecular Charge Transfer

In a proposed method of sensing small quantities of molecules of interest, surface enhanced Raman scattering (SERS) spectroscopy would be further enhanced by means of intermolecular or supramolecular charge transfer. There is a very large potential market for sensors based on this method for rapid detection of chemical and biological hazards. In SERS, the Raman signals (vibrational spectra) of target molecules become enhanced by factors of the order of 108 when those molecules are in the vicinities of nanostructured substrate surfaces that have been engineered to have plasmon resonances that enhance local electric fields. SERS, as reported in several prior NASA Tech Briefs articles and elsewhere, has remained a research tool and has not yet been developed into a practical technique for sensing of target molecules: this is because the short range (5 to 20 nm) of the field enhancement necessitates engineering of receptor molecules to attract target molecules to the nanostructured substrate surfaces and to enable reliable identification of the target molecules in the presence of interferants. Intermolecular charge-transfer complexes have been used in fluorescence-, photoluminescence-, and electrochemistry-based techniques for sensing target molecules, but, until now, have not been considered for use in SERS-based sensing. The basic idea of the proposed method is to engineer receptor molecules that would be attached to nanostructured SERS substrates and that would interact with the target molecules to form receptor-target supramolecular charge-transfer complexes wherein the charge transfer could be photoexcited.

Wong, Eric↗

NASA NTRS2009

Control of the Diameter and Chiral Angle Distributions during Production of Single-Wall Carbon Nanotubes

Many applications of single wall carbon nanotubes (SWCNT), especially in microelectronics, will benefit from use of certain (n,m) nanotube types (metallic, small gap semiconductor, etc.) Especially fascinating is the possibility of quantum conductors that require metallic armchair nanotubes. However, as produced SWCNT samples are polydisperse, with many (n,m) types present and typical approx.1:2 metal/semiconductor ratio. Nanotube nucleation models predict that armchair nuclei are energetically preferential due to formation of partial triple bonds along the armchair edge. However, nuclei can not reach any meaningful thermal equilibrium in a rapidly expanding and cooling plume of carbon clusters, leading to polydispersity. In the present work, SWCNTs were produced by a pulsed laser vaporization (PLV) technique. The carbon vapor plume cooling rate was either increased by change in the oven temperature (expansion into colder gas), or decreased via "warm-up" with a laser pulse at the moment of nucleation. The effect of oven temperature and "warm-up" on nanotube type population was studied via photoluminescence, UV-Vis-NIR absorption and Raman spectroscopy. It was found that reduced temperatures leads to smaller average diameters, progressively narrower diameter distributions, and some preference toward armchair structures. "Warm-up" shifts nanotube population towards arm-chair structures as well, but the effect is small. Possible improvement of the "warm-up" approach to produce armchair SWCNTs will be discussed. These results demonstrate that PLV production technique can provide at least partial control over the nanotube (n,m) population. In addition, these results have implications for the understanding the nanotube nucleation mechanism in the laser oven.

Nikolaev, Pavel↗

NASA NTRS2006

Quantum-Dot Laser for Wavelengths of 1.8 to 2.3 micron

The figure depicts a proposed semiconductor laser, based on In(As)Sb quantum dots on a (001) InP substrate, that would operate in the wavelength range between 1.8 and 2.3 m. InSb and InAsSb are the smallest-bandgap conventional III-V semiconductor materials, and the present proposal is an attempt to exploit the small bandgaps by using InSb and InAsSb nanostructures as midinfrared emitters. The most closely related prior III-V semiconductor lasers are based, variously, on strained InGaAs quantum wells and InAs quantum dots on InP substrates. The emission wavelengths of these prior devices are limited to about 2.1 m because of critical quantum-well thickness limitations for these lattice mismatched material systems. The major obstacle to realizing the proposed laser is the difficulty of fabricating InSb quantum dots in sufficient density on an InP substrate. This difficulty arises partly because of the weakness of the bond between In and Sb and partly because of the high temperature needed to crack metalorganic precursor compounds during the vapor-phase epitaxy used to grow quantum dots: The mobility of the weakly bound In at the high growth temperature is so high that In adatoms migrate easily on the growth surface, resulting in the formation of large InSb islands at a density, usually less than 5 x 10(exp 9) cm(exp -2), that is too low for laser operation. The mobility of the In adatoms could be reduced by introducing As atoms to the growth surface because the In-As bond is about 30 percent stronger than is the In-Sb bond. The fabrication of the proposed laser would include a recently demonstrated process that involves the use of alternative supplies of precursors to separate group-III and group-V species to establish local non-equilibrium process conditions, so that In(As)Sb quantum dots assemble themselves on a (001) InP substrate at a density as high as 4 x 10(exp 10) cm(exp -2). Room-temperature photoluminescence spectra of quantum dots formed by this process indicate that they emit at wavelengths from 1.7 to 2.3 microns.

Qiu, Yueming↗

NASA NTRS2010

Smart materials: strain sensing and stress determination by means of nanotube sensing systems, composites, and devices

The present invention is directed toward devices comprising carbon nanotubes that are capable of detecting displacement, impact, stress, and/or strain in materials, methods of making such devices, methods for sensing/detecting/monitoring displacement, impact, stress, and/or strain via carbon nanotubes, and various applications for such methods and devices. The devices and methods of the present invention all rely on mechanically-induced electronic perturbations within the carbon nanotubes to detect and quantify such stress/strain. Such detection and quantification can rely on techniques which include, but are not limited to, electrical conductivity/conductance and/or resistivity/resistance detection/measurements, thermal conductivity detection/measurements, electroluminescence detection/measurements, photoluminescence detection/measurements, and combinations thereof. All such techniques rely on an understanding of how such properties change in response to mechanical stress and/or strain.

Barrera, Enrique V.↗

NASA NTRS2003

Study of Dislocation-Ordered In(x)Ga(1-x)As/GaAs Quantum Dots

A report describes an experimental study of dislocation-induced spatial ordering of quantum dots (QDs) comprising nanometer-sized In(x)Ga(1-x)As islands surrounded by GaAs. Metastable heteroepitaxial structures were grown by molecular-beam epitaxy of In(x)Ga(1-x)As onto n+ GaAs and semi-insulating GaAs substrates. Then the structures were relaxed during a post-growth annealing/self-organizing process leading to the formation of surface undulations that acted as preferential sites for the nucleation of QDs. Structural effects of annealing times and temperatures on the strain-relaxed In(x)Ga(1-x)As/GaAs and the subsequent spatial ordering of the QDs were analyzed by atomic-force microscopy and transmission electron microscopy. Continuous-wave spectral and time-resolved photoluminescence (PL) measurements were performed to study the effects, upon optical properties, of increased QD positional ordering, increased QD uniformity, and proximity of QDs to arrays of dislocations. PL spectral peaks of ordered QD structures formed on strain-relaxed In(x)Ga(1-x)As/GaAs layers were found to be narrower than those of structures not so formed and ordered. Rise and decay times of time-resolved PL were found to be lower at lower temperatures -- apparently as a consequence of decreased carrier-transport times within the barriers surrounding the QDs.

Leon, Rose↗

NASA NTRS2011

Temperature-Sensitive Coating Sensor Based on Hematite

A temperature-sensitive coating, based on hematite (iron III oxide), has been developed to measure surface temperature using spectral techniques. The hematite powder is added to a binder that allows the mixture to be painted on the surface of a test specimen. The coating dynamically changes its relative spectral makeup or color with changes in temperature. The color changes from a reddish-brown appearance at room temperature (25 C) to a black-gray appearance at temperatures around 600 C. The color change is reversible and repeatable with temperature cycling from low to high and back to low temperatures. Detection of the spectral changes can be recorded by different sensors, including spectrometers, photodiodes, and cameras. Using a-priori information obtained through calibration experiments in known thermal environments, the color change can then be calibrated to yield accurate quantitative temperature information. Temperature information can be obtained at a point, or over an entire surface, depending on the type of equipment used for data acquisition. Because this innovation uses spectrophotometry principles of operation, rather than the current methods, which use photoluminescence principles, white light can be used for illumination rather than high-intensity short wavelength excitation. The generation of high-intensity white (or potentially filtered long wavelength light) is much easier, and is used more prevalently for photography and video technologies. In outdoor tests, the Sun can be used for short durations as an illumination source as long as the amplitude remains relatively constant. The reflected light is also much higher in intensity than the emitted light from the inefficient current methods. Having a much brighter surface allows a wider array of detection schemes and devices. Because color change is the principle of operation, the development of high-quality, lower-cost digital cameras can be used for detection, as opposed to the high-cost imagers needed for intensity measurements with the current methods. Alternative methods of detection are possible to increase the measurement sensitivity. For example, a monochrome camera can be used with an appropriate filter and a radiometric measurement of normalized intensity change that is proportional to the change coating temperature. Using different spectral regions yields different sensitivities and calibration curves for converting intensity change to temperature units. Alternatively, using a color camera, a ratio of the standard red, green, and blue outputs can be used as a self-referenced change. The blue region (less than 500 nm) does not change nearly as much as the red region (greater than 575 nm), so a ratio of color intensities will yield a calibrated temperature image. The new temperature sensor coating is easy to apply, is inexpensive, can contour complex shape surfaces, and can be a global surface measurement system based on spectrophotometry. The color change, or relative intensity change, at different colors makes the optical detection under white light illumination, and associated interpretation, much easier to measure and interpret than in the detection systems of the current methods.

Bencic, Timothy J.↗

NASA NTRS2013

Spectroscopic chemical analysis methods and apparatus

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. Chemical analysis instruments employed in some embodiments include capillary and gel plane electrophoresis, capillary electrochromatography, high performance liquid chromatography, flow cytometry, flow cells for liquids and aerosols, and surface detection instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted along with photoluminescence spectroscopy (i.e. fluorescence and/or phosphorescence spectroscopy) to provide high levels of sensitivity and specificity in the same instrument.

Hug, William F.↗

NASA NTRS2014

The Use of Photo-Luminescence as an Emergency Egress Guidance System on ISS

Because ever increasing performance, photoluminescence has moved from “glow in the dark” toys to greatly expanded use in offices, factories, homes and many other places where it can be charged regularly by light and seen clearly and effectively in the dark for extended periods of time.

Maida, James C.↗

NASA NTRS2015

Laser Induced Fluorescence Spectroscopy of Neutral and Ionized Polycyclic Aromatic Hydrocarbons in the Cosmic Simulation Chamber

Polycyclic aromatic hydrocarbon (PAH) molecules are considered the best carriers to account for the ubiquitous infrared emission bands. PAHs have also been proposed as candidates to explain the diffuse interstellar bands (DIBs), a series of absorption features seen on the interstellar extinction curve and are plausible carriers for the extended red emission (ERE), a photoluminescent process associated with a wide variety of interstellar environments. Extensive efforts have been devoted over the past two decades to characterize the physical and chemical properties of PAH molecules and ions in space. Absorption spectra of PAH molecules and ions trapped in solid matrices have been compared to the DIBs. Absorption spectra of several cold, isolated gas-phase PAHs have also been measured under experimental conditions that mimic the interstellar conditions. The purpose of this study is to provide a new dimension to the existing spectroscopic database of neutral and single ionized PAHs that is largely based on absorption spectra by adding emission spectroscopy data. The measurements are based on the laser induced fluorescence (LIF) technique and are performed with the Pulsed Discharge Nozzle (PDN) of the COSmIC laboratory facility at NASA Ames laboratory. The PDN generates a plasma in a free supersonic jet expansion to simulate the physical and the chemical conditions in interstellar environments. We focus, here, on the fluorescence spectra of large neutral PAHs and their cations where there is a lack of fluorescence spectroscopy data. The astronomical implications of the data (e.g., ERE) are examined.

Laboratory↗

NASA NTRS2017

Spectroscopic Chemical Analysis Methods and Apparatus

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted along with photoluminescence spectroscopy (i.e. fluorescence and/or phosphorescence spectroscopy) to provide high levels of sensitivity and specificity in the same instrument.

Hug, William F.↗

NASA NTRS2017

Multi-Functional BN-BN Composite

Multifunctional Boron Nitride nanotube-Boron Nitride (BN-BN) nanocomposites for energy transducers, thermal conductors, anti-penetrator/wear resistance coatings, and radiation hardened materials for harsh environments. An all boron-nitride structured BN-BN composite is synthesized. A boron nitride containing precursor is synthesized, then mixed with boron nitride nanotubes (BNNTs) to produce a composite solution which is used to make green bodies of different forms including, for example, fibers, mats, films, and plates. The green bodies are pyrolized to facilitate transformation into BN-BN composite ceramics. The pyrolysis temperature, pressure, atmosphere and time are controlled to produce a desired BN crystalline structure. The wholly BN structured materials exhibit excellent thermal stability, high thermal conductivity, piezoelectricity as well as enhanced toughness, hardness, and radiation shielding properties. By substituting with other elements into the original structure of the nanotubes and/or matrix, new nanocomposites (i.e., BCN, BCSiN ceramics) which possess excellent hardness, tailored photonic bandgap and photoluminescence, result.

Kang, Jin Ho↗

NASA NTRS2018

Spectroscopic Chemical Analysis Methods and Apparatus

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted along with photoluminescence spectroscopy (i.e. fluorescence and/or phosphorescence spectroscopy) to provide high levels of sensitivity and specificity in the same instrument.

Hug, William F.↗

NASA NTRS2004

Self-assembled InAsSb quantum dots on (001) InP substrates

Self-assembled InAsSb quantum dots (QD) on (001) InP substrates have been grown using metalorganic vapor phase epitaxy. The dot density and size are found to be strongly dependent on the presence of arsine. Direct deposition of InSb on InP and GaSb substrates formed large islands of InSb with low density of less than 53109/cm², however, InAsSb QDs of density as high as 4 X10¹º/cm² could be self-assembled by alternating group III and group V precursors, and high density almost pure InSb QDs were achieved on In0.53Ga0.47As/InP. The formation of high density InAsSb QDs is a result of a local nonequilibrium process and a reduction in mobility of In adatoms on the growth surface due to the presence of arsenic atoms, and in the case of high density almost pure InSb QDs on InGaAs/InP, the InAs interface layer is believed to be responsible. Photoluminescence shows that InSb QDs emit light at room temperature in the range of 1.7–2.2µm.

Uhl, David↗