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NASA NTRS2011

Atomic Data for Neutron-capture Elements I. Photoionization and Recombination Properties of Low-charge Selenium Ions

We present multi-configuration Breit-Pauli AUTOSTRUCTURE calculations of distorted-wave photoionization (PI) cross sections. and total and partial final-state resolved radiative recombination (RR) and dielectronic recombination (DR) rate coefficients for the first six ions of the trans-iron element Se. These calculations were motivated by the recent detection of Se emission lines in a large number of planetary nebulae. Se is a potentially useful tracer of neutron-capture nucleosynthesis. but accurate determinations of its abundance in photoionized nebulae have been hindered by the lack of atomic data governing its ionization balance. Our calculations were carried out in intermediate coupling with semi re1ativistic radial wavefunctions. PI and recombination data were determined for levels within the ground configuration of each ion, and experimental PI cross-section measurements were used to benchmark our results. For DR, we allowed (Delta)n = 0 core excitations, which are important at photoionized plasma temperatures. We find that DR is the dominant recombination process for each of these Se ions at temperatures representative of photoionized nebulae (approx.10(exp 4) K). In order to estimate the uncertainties of these data, we compared results from three different configuration-interaction expansions for each ion, and also tested the sensitivity of the results to the radial scaling factors in the structure calculations. We find that the internal uncertainties are typically 30-50% for the direct PI cross sections and approx.10% for the computed RR rate coefficients, while those for low-temperature DR can be considerably larger (from 15-30% up to two orders of magnitude) due to the unknown energies of near-threshold autoionization resonances. These data are available at the CDS, and fitting coefficients to the total RR and DR rate coefficients are presented. The results are suitable for incorporation into photoionization codes used to numerically simulate astrophysical nebulae, and will enable robust determinations of nebular Se abundances.

Sterling, N. C.↗

NASA NTRS2012

Visible Light Responsive Catalysts Using Quantum Dot-Modified Ti02 for Air and Water Purification

The method of photocatalysis utilizing titanium dioxide, TiO2, as the catalyst has been widely studied for trace contaminant control for both air and water applications because of its low energy consumption and use of a regenerable catalyst. Titanium dioxide requires ultraviolet light for activation due to its band gap energy of 3.2 eV. Traditionally, Hg-vapor fluorescent light sources are used in PCO reactors and are a setback for the technology for space application due to the possibility of Hg contamination. The development of a visible light responsive (VLR) TiO2-based catalyst could lead to the use of solar energy in the visible region (approx.45% of the solar spectrum lies in the visible region; > 400 nm) or highly efficient LEDs (with wavelengths > 400 nm) to make PCO approaches more efficient, economical, and safe. Though VLR catalyst development has been an active area of research for the past two decades, there are few commercially available VLR catalysts; those that are available still have poor activity in the visible region compared to that in the UV region. Thus, this study was aimed at the further development of VLR catalysts by a new method - coupling of quantum dots (QD) of a narrow band gap semiconductor (e.g., CdS, CdSe, PbS, ZnSe, etc.) to the TiO2 by two preparation methods: 1) photodeposition and 2) mechanical alloying using a high-speed ball mill. A library of catalysts was developed and screened for gas and aqueous phase applications, using ethanol and 4-chlorophenol as the target contaminants, respectively. Both target compounds are well studied in photocatalytic systems serve as model contaminants for this research. Synthesized catalysts were compared in terms of preparation method, type of quantum dots, and dosage of quantum dots.

Coutts, Janelle L.↗

NASA NTRS2013

Application of Statistically Derived CPAS Parachute Parameters

The Capsule Parachute Assembly System (CPAS) Analysis Team is responsible for determining parachute inflation parameters and dispersions that are ultimately used in verifying system requirements. A model memo is internally released semi-annually documenting parachute inflation and other key parameters reconstructed from flight test data. Dispersion probability distributions published in previous versions of the model memo were uniform because insufficient data were available for determination of statistical based distributions. Uniform distributions do not accurately represent the expected distributions since extreme parameter values are just as likely to occur as the nominal value. CPAS has taken incremental steps to move away from uniform distributions. Model Memo version 9 (MMv9) made the first use of non-uniform dispersions, but only for the reefing cutter timing, for which a large number of sample was available. In order to maximize the utility of the available flight test data, clusters of parachutes were reconstructed individually starting with Model Memo version 10. This allowed for statistical assessment for steady-state drag area (CDS) and parachute inflation parameters such as the canopy fill distance (n), profile shape exponent (expopen), over-inflation factor (C(sub k)), and ramp-down time (t(sub k)) distributions. Built-in MATLAB distributions were applied to the histograms, and parameters such as scale (sigma) and location (mu) were output. Engineering judgment was used to determine the "best fit" distribution based on the test data. Results include normal, log normal, and uniform (where available data remains insufficient) fits of nominal and failure (loss of parachute and skipped stage) cases for all CPAS parachutes. This paper discusses the uniform methodology that was previously used, the process and result of the statistical assessment, how the dispersions were incorporated into Monte Carlo analyses, and the application of the distributions in trajectory benchmark testing assessments with parachute inflation parameters, drag area, and reefing cutter timing used by CPAS.

Romero, Leah M.↗

NASA NTRS2013

Compound Specific Hydrogen Isotope Composition of Type II and III Kerogen Extracted by Pyrolysis-GC-MS-IRMS

The use of Hydrogen (H) isotopes in understanding oil and gas resource plays is in its infancy. Described here is a technique for H isotope analysis of organic compounds pyrolyzed from oil and gas shale-derived kerogen. Application of this technique will progress our understanding. This work complements that of Pernia et al. (2013, this meeting) by providing a novel method for the H isotope analysis of specific compounds in the characterization of kerogen extracted by analytically diverse techniques. Hydrogen isotope analyses were carried out entirely "on-line" utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC Ultra interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make semi-quantitative compositional measurements of the extracted compounds. Kerogen samples from five different basins (type II and III) were dehydrated (heated to 80 C overnight in vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C) which quantitatively forms H2, following a modified method of Burgoyne and Hayes, (1998, Anal. Chem., 70, 5136-5141). Samples ranging from approximately 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. Compounds were separated on a Poraplot Q GC column. Hydrogen isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight compounds. Water (H2O) average deltaD = -215.2 (V-SMOW), ranging from -271.8 for the Marcellus Shale to -51.9 for the Polish Shale. Higher molecular weight compounds like toluene (C7H8) have an average deltaD of -89.7 0/00, ranging from -156.0 for the Barnett Shale to -50.0 for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during formation within each basin. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas-water or oil-water interaction in resource plays, and further as a possible indicator of paleo-environmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analysis. More experiments are planned to discern these two or other possible scenarios.

Socki, Richard A.↗

NASA NTRS2014

Visible-Light-Responsive Catalysts Using Quantum Dot-Modified TiO2 for Air and Water Purification

Photocatalysis, the oxidation or reduction of contaminants by light-activated catalysts, utilizing titanium dioxide (TiO2) as the catalytic substrate has been widely studied for trace contaminant control in both air and water applications. The interest in this process is due primarily to its low energy consumption and capacity for catalyst regeneration. Titanium dioxide requires ultraviolet light for activation due to its relatively large band gap energy of 3.2 eV. Traditionally, Hg-vapor fluorescent light sources are used in PCO reactors; however, the use of mercury precludes the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure. The development of a visible-light responsive (VLR) TiO2-based catalyst would eliminate the concerns over mercury contamination. Further, VLR development would allow for the use of ambient visible solar radiation or highly efficient LEDs, both of which would make PCO approaches more efficient, flexible, economical, and safe. Though VLR catalyst development has been an active area of research for the past two decades, there are few commercially available VLR catalysts. Those VLR catalysts that are commercially available do not have adequate catalytic activity, in the visible region, to make them competitive with those operating under UV irradiation. This study was initiated to develop more effective VLR catalysts through a novel method in which quantum dots (QD) consisting of narrow band gap semiconductors (e.g., CdS, CdSe, PbS, ZnSe, etc.) are coupled to TiO2 via two preparation methods: 1) photodeposition and 2) mechanical alloying using a high-speed ball mill. A library of catalysts was developed and screened for gas and aqueous phase applications using ethanol and 4-chlorophenol as the target contaminants, respectively. Both target compounds are well studied in photocatalytic systems and served as model contaminants for this research. Synthesized catalysts were compared in terms of preparation method, nature of the quantum dots, and dosage of quantum dots.

visible light↗

NASA NTRS2014

Hydrogen (H) Isotope Composition of Type II Kerogen Extracted by Pyrolysis-GC-MS-IRMS: Terrestrial Shale Deposits as Martian Analogs

Described here is a technique for H isotope analysis of organic compounds pyrolyzed from kerogens isolated from gas‐ and liquids‐rich shales. Application of this technique will progress the understanding of the use of H isotopes not only in potential kerogen occurrences on Mars, but also in terrestrial oil and gas resource plays. H isotope extraction and analyses were carried out utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC interfaced with a Thermo MAT 253 IRMS. Also, a split of GC‐separated products was sent to a DSQ II quadrupole MS to make qualitative and semi‐quantitative compositional measurements of these products. Kerogen samples from five different basins (type II and II‐S) were dehydrated (heated to 80 C overnight under vacuum) and analyzed for their H isotope compositions by Pyrolysis‐GC‐MS‐TC‐IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C), which quantitatively forms H2. Samples ranging from ~0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. and separated on a Poraplot Q GC column. H isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight. H2O average delta D = ‐215.2 per mille (V‐SMOW), ranging from ‐ 271.8 per mille for the Marcellus Shale to ‐51.9 per mille for a Polish shale. Higher molecular weight compounds like toluene (C7H8) have an average delta D of ‐89.7 per mille, ranging from ‐156.0 per mille for the Barnett Shale to ‐50.0 per mille for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during basin formation. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas‐water or oil‐water interaction in resource plays, and further as a possible indicator of paleoenvironmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analyses. Understanding the role that these H‐bearing compounds play in terrestrial shale paleo‐environmental reconstruction may also prove useful as analogs for understanding the interactions of water and potential kerogen/organic compounds on the planet Mars.

Socki, Richard A.↗

NASA NTRS2014

Cascade Distillation System Development

NASA's Advanced Exploration Systems (AES) Life Support System (LSS) Project is chartered with de-veloping advanced life support systems that will ena-ble NASA human exploration beyond low Earth orbit (LEO). The goal of AES is to increase the affordabil-ity of long-duration life support missions, and to re-duce the risk associated with integrating and infusing new enabling technologies required to ensure mission success. Because of the robust nature of distillation systems, the AES LSS Project is pursuing develop-ment of the Cascade Distillation Subsystem (CDS) as part of its technology portfolio. Currently, the system is being developed into a flight forward Generation 2.0 design.

Callahan, Michael R.↗

NASA NTRS2016

Demonstrating the Error Budget for the Climate Absolute Radiance and Refractivity Observatory Through Solar Irradiance Measurements

The Climate Absolute Radiance and Refractivity Observatory (CLARREO) mission addresses the need to observe highaccuracy, long-term climate change trends and to use decadal change observations as a method to determine the accuracy of climate change. A CLARREO objective is to improve the accuracy of SI-traceable, absolute calibration at infrared and reflected solar wavelengths to reach on-orbit accuracies required to allow climate change observations to survive data gaps and observe climate change at the limit of natural variability. Such an effort will also demonstrate National Institute of Standards and Technology (NIST) approaches for use in future spaceborne instruments. The current work describes the results of laboratory and field measurements with the Solar, Lunar for Absolute Reflectance Imaging Spectroradiometer (SOLARIS) which is the calibration demonstration system (CDS) for the reflected solar portion of CLARREO. SOLARIS allows testing and evaluation of calibration approaches, alternate design and/or implementation approaches and components for the CLARREO mission. SOLARIS also provides a test-bed for detector technologies, non-linearity determination and uncertainties, and application of future technology developments and suggested spacecraft instrument design modifications. Results of laboratory calibration measurements are provided to demonstrate key assumptions about instrument behavior that are needed to achieve CLARREO's climate measurement requirements. Absolute radiometric response is determined using laser-based calibration sources and applied to direct solar views for comparison with accepted solar irradiance models to demonstrate accuracy values giving confidence in the error budget for the CLARREO reflectance retrieval.

CLARREO↗

NASA NTRS2016

Solar Powered CO.Sub.2 Conversion

Methods and devices for reducing CO.sub.2 to produce hydrocarbons are disclosed. A device comprises a photoanode capable of splitting H.sub.2O into electrons, protons, and oxygen; an electrochemical cell cathode comprising an electro-catalyst capable of reducing CO.sub.2; H.sub.2O in contact with the surface of the photoanode; CO.sub.2 in contact with the surface of the cathode; and a proton-conducting medium positioned between the photoanode and the cathode. Electrical charges associated with the protons and the electrons move from the photoanode to the cathode, driven in part by a chemical potential difference sufficient to drive the electrochemical reduction of CO.sub.2 at the cathode. A light beam is the sole source of energy used to drive chemical reactions. The photoanode can comprise TiO.sub.2 nanowires or nanotubes, and can also include WO.sub.3 nanowires or nanotubes, quantum dots of CdS or PbS, and Ag or Au nanostructures. The cathode can comprise a conductive gas diffusion layer with nanostructures of an electro-catalyst such as Cu or Co.

Chen, Bin↗

NASA NTRS2013

MERRA/AS: The MERRA Analytic Services Project Interim Report

MERRA AS is a cyberinfrastructure resource that will combine iRODS-based Climate Data Server (CDS) capabilities with Coudera MapReduce to serve MERRA analytic products, store the MERRA reanalysis data collection in an HDFS to enable parallel, high-performance, storage-side data reductions, manage storage-side driver, mapper, reducer code sets and realized objects for users, and provide a library of commonly used spatiotemporal operations that can be composed to enable higher-order analyses.

MapReduce↗

NASA NTRS2016

Deep HST/STIS Visible-Light Imaging of Debris Systems Around Solar Analog Hosts

We present new Hubble Space Telescope observations of three a priori known starlight-scattering circumstellar debris systems (CDSs) viewed at intermediate inclinations around nearby close-solar analog stars: HD 207129, HD202628, and HD 202917. Each of these CDSs possesses ring-like components that are more massive analogs of our solar systems Edgeworth Kuiper Belt. These systems were chosen for follow-up observations to provide imaging with higher fidelity and better sensitivity for the sparse sample of solar-analog CDSs that range over two decades in systemic ages, with HD 202628 and HD 207129 (both approx. 2.3 Gyr) currently the oldest CDSs imaged in visible or near-IR light. These deep (10-14 ks) observations, made with six-roll point-spread-function template visible-light coronagraphy using the Space Telescope Imaging Spectrograph, were designed to better reveal their angularly large debris rings of diffuse low surface brightness, and for all targets probe their exo-ring environments for starlight-scattering materials that present observational challenges for current ground-based facilities and instruments. Contemporaneously also observing with a narrower occulter position, these observations additionally probe the CDS endo-ring environments that are seen to be relatively devoid of scatterers. We discuss the morphological, geometrical, and photometric properties of these CDSs also in the context of other CDSs hosted by FGK stars that we have previously imaged as a homogeneously observed ensemble. From this combined sample we report a general decay in quiescent-disk F disk /F star optical brightness approx. t( exp.-0.8), similar to what is seen at thermal IR wavelengths, and CDSs with a significant diversity in scattering phase asymmetries, and spatial distributions of their starlight-scattering grains.

starlight-scattering circumstellar debris systems ↗

NASA NTRS2016

Results from Source-Based and Detector-Based Calibrations of a CLARREO Calibration Demonstration System

The Climate Absolute Radiance and Refractivity Observatory (CLARREO) mission is formulated to determine long-term climate trends using SI-traceable measurements. The CLARREO mission will include instruments operating in the reflected solar (RS) wavelength region from 320 nm to 2300 nm. The Solar, Lunar for Absolute Reflectance Imaging Spectroradiometer (SOLARIS) is the calibration demonstration system (CDS) for the reflected solar portion of CLARREO and facilitates testing and evaluation of calibration approaches. The basis of CLARREO and SOLARIS calibration is the Goddard Laser for Absolute Measurement of Response (GLAMR) that provides a radiance-based calibration at reflective solar wavelengths using continuously tunable lasers. SI-traceability is achieved via detector-based standards that, in GLAMRs case, are a set of NIST-calibrated transfer radiometers. A portable version of the SOLARIS, Suitcase SOLARIS is used to evaluate GLAMRs calibration accuracies. The calibration of Suitcase SOLARIS using GLAMR agrees with that obtained from source-based results of the Remote Sensing Group (RSG) at the University of Arizona to better than 5 (k2) in the 720-860 nm spectral range. The differences are within the uncertainties of the NIST-calibrated FEL lamp-based approach of RSG and give confidence that GLAMR is operating at 5 (k2) absolute uncertainties. Limitations of the Suitcase SOLARIS instrument also discussed and the next edition of the SOLARIS instrument (Suitcase SOLARIS- 2) is expected to provide an improved mechanism to further assess GLAMR and CLARREO calibration approaches. (2016) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE).

Angal, Amit↗

DOE OSTI2011

Influence of Damp Heat on the Electrical, Optical, and Morphological Properties of Encapsulated CuInGaSe2 Devices: Preprint

CuInGaSe2 (CIGS) devices, encapsulated with different backsheets having different water vapor transmission rates (WVTR), were exposed to damp heat (DH) at 85C and 85% relative humidity (RH) and characterized periodically to understand junction degradation induced by moisture ingress. Performance degradation of the devices was primarily driven by an increase in series resistance within first 50 h of exposure, resulting in a decrease in fill factor and, accompanied loss in carrier concentration and widening of depletion width. Surface analysis of the devices after 700-h DH exposure showed the formation of Zn(OH)2 from hydrolysis of the Al-doped ZnO (AZO) window layer by the moisture, which was detrimental to the collection of minority carriers. Minority carrier lifetimes observed for the CIGS devices using time resolved photoluminescence (TRPL) remained relatively long after DH exposure. By etching the DH-exposed devices and re-fabricating with new component layers, the performance of reworked devices improved significantly, further indicating that DH-induced degradation of the AZO layer and/or the CdS buffer was the primary performance-degrading factor.

14 SOLAR ENERGY↗

DOE OSTI2011

US Veteran Gets a Facelift

Idaho National Laboratory's Advanced Test Reactor (ATR) has received replacement instrumentation and control systems - the process distributed control system (DCS) and the console display system (CDS), which included a replacement annunciator subsystem. The new systems offer the latest software and technology advancements, ensuring the availability of the reactor for future energy research. ATR, a pressurized, light water moderated 250 MW materials test reactor, became operational in 1965. In the early 1990s, after nearly thirty years of analogue/pneumatic controls, the laboratory upgraded ATR to digital-based instrumentation and control systems. By 2007, the equipment and technology used in these digital systems were reaching the end of their lifecycle. The systems component failure rates were on a rise, while vendor support and parts availability were declining. With current projections and plans for operating ATR into 2040, modernization of the reactor's infrastructure is necessary to maintain reliability and efficiency. As a result, the Idaho National Laboratory and the U.S. Department of Energy (DOE) invested more than $13 million in a four-year project to replace ATR's instrumentation and control systems.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2012

Bandgap Engineering of InP QDs Through Shell Thickness and Composition

Fields as diverse as biological imaging and telecommunications utilize the unique photophysical and electronic properties of nanocrystal quantum dots (NQDs). The development of new NQD compositions promises material properties optimized for specific applications, while addressing material toxicity. Indium phosphide (InP) offers a 'green' alternative to the traditional cadmium-based NQDs, but suffers from extreme susceptibility to oxidation. Coating InP cores with more stable shell materials significantly improves nanocrystal resistance to oxidation and photostability. We have investigated several new InP-based core-shell compositions, correlating our results with theoretical predictions of their optical and electronic properties. Specifically, we can tailor the InP core-shell QDs to a type-I, quasi-type-II, or type-II bandgap structure with emission wavelengths ranging from 500-1300 nm depending on the shell material used (ZnS, ZnSe, CdS, or CdSe) and the thickness of the shell. Single molecule microscopy assessments of photobleaching and blinking are used to correlate NQD properties with shell thickness.

36 MATERIALS SCIENCE↗

DOE OSTI2014

Back contact buffer layer for thin-film solar cells

A photovoltaic cell structure is disclosed that includes a buffer/passivation layer at a CdTe/Back contact interface. The buffer/passivation layer is formed from the same material that forms the n-type semiconductor active layer. In one embodiment, the buffer layer and the n-type semiconductor active layer are formed from cadmium sulfide (CdS). A method of forming a photovoltaic cell includes the step of forming the semiconductor active layers and the buffer/passivation layer within the same deposition chamber and using the same material source.

14 SOLAR ENERGY↗

DOE OSTI2015

Designing Passivating, Carrier-Selective Contacts for Photovoltaic Devices

"The first step towards building a high-efficiency solar cell is to develop an absorber with few recombination-active defects. Many photovoltaic technologies have already achieved this (monocrystalline Si, III-V materials grown on lattice-matched substrates, perovskites, polycrystalline CdTe and CIGS); those that have not (a-Si:H, organics) have been limited to low open-circuit voltage. The second step is to develop contacts that both inhibit surface recombination and allow for low-resistance collection of either only electrons or only holes. For most photovoltaic technologies, this step is both more difficult and less explored than the first, and we are unaware of a prescribed methodology for selecting materials for contacts to solar cells. We elucidate a unified, conceptual understanding of contacts within which existing contacting schemes can be interpreted and future contacting schemes can be imagined. Whereas a split of the quasi-Fermi levels of holes and electrons is required in the absorber of any solar cell to generate a voltage, carriers are eventually collected through a metallic wire in which no such quasi-Fermi-level split exists. We define a contact to be all layers between the bulk of the absorber and the recombination-active interface through which carriers are extracted. The quasi-Fermi levels must necessarily collapse at this interface, and thus the transition between maximal quasi-Fermi-level splitting (in the absorber) and no splitting occurs entirely in the contact. Depending on the solar cell architecture, the contact will usually extend from the surface of the absorber to the surface of a metal or transparent conductive oxide layer, and may include deposited or diffused doped layers (e.g., as in crystalline and thin-film Si cells) and heterostructure buffer layers (e.g., the CdS layer in a CdTe device). We further define a passivating contact as one that enables high quasi-Fermi-level splitting in the absorber (large “internal” voltage), where “high” is relative to the splitting dictated by bulk recombination. Finally, we define a carrier-selective contact as one that enables a high “external” voltage measured across the contacts, where “high” is relative to the internal voltage. With these definitions, passivating contacts are those that allow only electrons, only holes, or neither electrons or holes to transport from the absorber to any position in the contact that has recombination-active defects. An excellent example of this is a SiNx layer on a Si wafer: the layer removes dangling bonds at the wafer surface (where there are both electrons and holes) and does not allow either carrier type to travel to its outermost surface, where there are undoubtedly defects. Carrier-selective contacts are then passivating contacts that also allow for low-impedance flow of either electrons or holes (but not both) to the recombination-active, extracting interface. The most common example is a heavily doped layer that establishes an electric field at the absorber surface, which then “filters” the carriers that may pass to the contact according to the sign of their charge.

14 SOLAR ENERGY↗

DOE OSTI2019

Mechanisms of local stress sensing in multifunctional polymer films using fluorescent tetrapod nanocrystals

Nanoscale stress-sensing can be used across fields ranging from detection of incipient cracks in structural mechanics to monitoring forces in biological tissues. We demonstrate how tetrapod quantum dots (tQDs) embedded in block-copolymers act as sensors of tensile/compressive stress. Remarkably, tQDs can detect their own composite dispersion and mechanical properties, with a switch in optomechanical response when tQDs are in direct contact. Using experimental characterizations, atomistic simulations and finite-element analyses, we show that under tensile stress, densely-packed tQDs exhibit a photoluminescence peak shifted to higher energies (“blue-shift”) due to volumetric compressive stress in their core; loosely-packed tQDs exhibit a peak shifted to lower energies (“red-shift”) from tensile stress in the core. The stress-shifts result from the tQD's unique branched morphology in which the CdS arms act as antennas that amplify the stress in the CdSe core. Our nanocomposites exhibit excellent cyclability and scalability with no degraded properties of the host polymer. Colloidal tQDs allow sensing in many materials to potentially enable auto-responsive, smart structural nanocomposites that self-predict impending fracture.

36 MATERIALS SCIENCE↗