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At least 1,405 records · Page 78

Corrosion of carbon steel and the passivating properties of corrosion films formed under high-PT geothermal conditions

Corrosion is a major obstacle to a safe implementation of geotechnical applications. Here, using a novel approach that includes vertical scanning interferometry (VSI) and electrochemical impedance spectroscopy (EIS) we discuss time-dependent carbon steel corrosion and film formation at geothermally relevant temperatures (80-160 °C) in CO 2 -saturated mildly acidic Na—Cl brine. Iron dissolution kinetics follows a logarithmic rate at 80 and 160 °C and a linear rate at 120 °C. At 80 °C, high initial corrosion rates (first 24 h) generate H 2 at a minimum rate of 12 μmol h -1 cm -2 and lead to the formation of a continuous ~100 μm thick porous corrosion film. It exhibits a duplex structure with a crystalline outer FeCO 3 layer and an inner layer composed of a skeletal network of Fe 3 C impregnated with FeCO 3 . Being an electrical conductor we hypothesize the Fe 3 C to strongly enhance corrosion rates by providing additional cathodic sites. Pseudo-passivity due to an anodic film-forming reaction (presumably Fe-oxide) was observed at 120 and 160 °C, soon followed by the initiation of pitting at 120 °C. Steady-state corrosion rates at 160 °C are at least one order of magnitude lower than for 120 °C. Lastly, our experimental approach demonstrated potential for general applicability in studying corrosion-related phenomena.

36 MATERIALS SCIENCE↗

Suspension systems for ground testing large space structures

A research program is documented for the development of improved suspension techniques for ground vibration testing of large, flexible space structures. The suspension system must support the weight of the structure and simultaneously allow simulation of the unconstrained rigid-body movement as in the space environment. Exploratory analytical and experimental studies were conducted for suspension systems designed to provide minimum vertical, horizontal, and rotational degrees of freedom. The effects of active feedback control added to the passive system were also investigated. An experimental suspension apparatus was designed, fabricated, and tested. This test apparatus included a zero spring rate mechanism (ZSRM) designed to support a range of weights from 50 to 300 lbs and provide vertical suspension mode frequencies less than 0.1 Hz. The lateral suspension consisted of a pendulum suspended from a moving cart (linear bearing) which served to increase the effective length of the pendulum. The torsion suspension concept involved dual pendulum cables attached from above to a pivoting support (bicycle wheel). A simple test structure having variable weight and stiffness characteristics was used to simulate the vibration characteristics of a large space structure. The suspension hardware for the individual degrees of freedom was analyzed and tested separately and then combined to achieve a 3 degree of freedom suspension system. Results from the exploratory studies should provide useful guidelines for the development of future suspension systems for ground vibration testing of large space structures.

Gold, Ronald R.↗

Amphilic Water-Lean Carbon Capture Solvent Wetting Behavior through Decomposition by Stainless-Steel Interfaces

In this work, we report on a combined experimental and theoretical study of the wetting and reactivity of water-lean carbon capture solvents on the surface of common column packing materials. Paradoxically, we find that these solvents are equally able to wet hydrophobic and hydrophilic surfaces. The solvents are amphiphilic and are able to adapt to any interfacial environment due to their inherent heterogeneous molecular structure. Ab initio molecular dynamics indicates that these structures enable the formation of a strong adlayer on the surface of hydrophilic surfaces like oxidized steel which promotes solvent decomposition akin to hydrolysis from surface oxides and hydroxides. This decomposition passivates the surface, making it effectively hydrophobic, and the decomposed solvent promotes leaching of the iron into the bulk fluid. This study links the wetting behavior to the observed corrosion of the steels via decomposition of solvent at steel interfaces. The overall affect is strongly dependent on the chemical composition of the solvent, in that amines are stable, whereas imines and alcohols are not. We also observed that plastic packing shows little to no solvent degradation, but an equal degree of wetting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Characterization and Optimization of GaN Cap Layers and SiN Cap Layers on AlGaN/GaN HEMT Structures Grown on 200 mm GaN on Silicon

We have studied capping layers for AlGaN‐based high electron mobility transistor (HEMT) structures, looking at different thicknesses of GaN, SiN, and GaN + SiN caps. SiN capping has no effect on the sheet resistance of the layers, as expected from a high quality amorphous passivation layer. GaN cap layers increase the sheet resistance whether combined with a SiN cap or not, a consequence of the polarisation charge present at the GaN/AlGaN interface. For both GaN and SiN caps on their own, we get excellent morphology from only 2 nm thickness, with no degradation for layers up to 10 nm thick. For GaN + SiN caps, we have a speckled morphology with lots of small holes, which transmission electron microscopy (TEM) analysis showed to be linked to holes created in the GaN layers before the deposition of SiN layers. We attribute this to the roughening effect of silane on GaN layers, known in the literature. Upon processing SiN capped and GaN + SiN capped layers into HEMT based heterojunction diode devices, the two have equivalent forward current, but GaN + SiN capping has greatly increased reverse current. We conclude that GaN + SiN is not an appropriate capping layer for AlGaN HEMT based diodes, compared with high quality in situ SiN passivation directly grown on the AlGaN.

Charles, Matthew↗

Decimeter-scale mapping of carbonate-controlled trace element distribution in Neoarchean cuspate stromatolites

We present that ancient stromatolites can provide key insights into the early evolution of life on Earth. Neoarchean fenestrate stromatolites from the ~2520 Ma Upper Nauga Formation (Transvaal Supergroup, South Africa) preserve cuspate morphologies. They possess clearly delineated support and drape structures interpreted as dolomitized microbial mat material. Petrographic observations show that the biogenic structures are composed of planar-s to non-planar ferroan dolomite, encased in ferroan calcite, including herringbone calcite textures. The cuspate stromatolites were analyzed using Synchrotron Rapid Scanning X-Ray Fluorescence (SRS-XRF) and more conventional techniques to determine: (i) whether element distributions could be distinguished in ancient stromatolites at both cm to dm scales, (ii) whether element distributions show variation between biogenic and abiogenic textures, and (iii) the sample’s paragenesis. The distributions of Ca, Fe, Mn, Pb, Cu, As, Br, Al, Si, P, and S directly correspond to dolomitized stromatolitic structures and show trace element distributions are principally controlled by calcite and dolomite occurrence. Dolomite formation was mainly driven by seawater-derived fluids given the high concentrations of Fe and retention of marine shale-normalized rare earth element and yttrium (REY SN ) patterns, however the spatial association of dolomite to stromatolite structures may reflect microbially-influenced mineral nucleation. Lastly, given the complexity of this sample’s paragenetic evolution, trace metal distributions cannot be conclusively tied to specific metabolic pathways, bioaccumulation or passive binding, however, the results show SRS-XRF can be used for quantifiable, spatial, in-situ investigation of ancient microbialites.

58 GEOSCIENCES↗

Anomalous lattice expansion of bcc Ta in helium-loaded diamond anvil cells

Anomalous lattice expansion of bcc Ta is observed in helium-loaded diamond anvil cell (DAC) experiments near 6 GPa and above 400 K, while co-loaded W, Mo, and Au exhibit normal thermal expansion. The Ta volume expansion increases with temperature, reaching ~14% near 650 K before plateauing, and is largely retained after recovery to ambient conditions. Time-resolved measurements at 500 K reveal progressive expansion over several hours, consistent with gradual, thermally activated He incorporation. The largely retained expansion during subsequent cooling and holding at 400 K indicates that the incorporated He is predominantly kinetically trapped. The data reveal two distinct regimes: below ~550 K, modest and spatially uniform expansion consistent with interstitial He trapping at isolated, randomly distributed vacancies; above ~550 K, He-vacancy cluster growth producing dramatically larger expansion, peak broadening, and a core–shell microstructure revealed by micron-resolution X-ray diffraction mapping. These results demonstrate that He is not always a passive pressure medium in DAC experiments and reveal a previously unrecognized regime of He-mediated lattice modification in Ta, complementing conventional ion-implantation studies relevant to nuclear and fusion structural materials.

Diamond anvil cell↗

Passive wireless surface acoustic wave sensors for monitoring sequestration sites CO 2 emission

University of Pittsburgh’s Transducer lab has teamed with the U.S. Department of Energy’s National Energy Technology Laboratory (DOE NETL) to conduct a comprehensive study to develop/evaluate low-cost, efficient CO 2 measuring technologies for geological sequestration sites leakage monitoring. A passive wireless CO 2 sensing system based on surface acoustic wave technology and carbon nanotube nanocomposite was developed. Surface acoustic wave device was studied to determine the optimum parameters. Delay line structure was adopted as basic sensor structure. CNT polymer nanocomposite was fabricated and tested under different temperature and strain condition for natural environment impact evaluation. Nanocomposite resistance increased for 5 times under pure strain, while the temperature dependence of resistance for CNT solely was -1375ppm/°C. The overall effect of temperature on nanocomposite resistance was -1000ppm/°C. The gas response of the nanocomposite was about 10% resistance increase under pure CO 2 . The sensor frequency change was around 300ppm for pure CO 2 . With paralyne packaging, the sensor frequency change from relative humidity of 0% to 100% at room temperature decreased from over 1000ppm to less than 100ppm. The lowest detection limit of the sensor is 1% gas concentration, with 36ppm frequency change. Wireless module was tested and showed over one foot transmission distance at preferred parallel orientation.

47 OTHER INSTRUMENTATION↗

Retrieval of the HEAO-C spacecraft with Space Shuttle

A plan has been developed to retrieve the HEAO-C spacecraft from orbit with the Space Shuttle in the early 1980s. The initial HEAO-C orbit altitude must be increased to provide additional lifetime. A simple passive stabilization mode, using gravity gradient and aerodynamic torques, is used for long-term storage. Most of the modifications required for Orbiter compatibility result from manned safety requirements and the structural mounting. There is a positive disconnect of all power before entering the Orbiter bay, and pressure vessels are monitored continuously. Structural equipment is added in the Orbiter bay to receive and stow the Observatory.

Mitchell, D. H.↗

The Space Station as a Construction Base for Large Space Structures

The feasibility of using the Space Station as a construction site for large space structures is examined. An overview is presented of the results of a program entitled Definition of Technology Development Missions (TDM's) for Early Space Stations - Large Space Structures. The definition of LSS technology development missions must be responsive to the needs of future space missions which require large space structures. Long range plans for space were assembled by reviewing Space System Technology Models (SSTM) and other published sources. Those missions which will use large space structures were reviewed to determine the objectives which must be demonstrated by technology development missions. The three TDM's defined during this study are: (1) a construction storage/hangar facility; (2) a passive microwave radiometer; and (3) a precision optical system.

Gates, R. M.↗

System concept for a moderate cost Large Deployable Reflector (LDR)

A study was carried out at JPL during the first quarter of 1985 to develop a system concept for NASA's LDR. Major features of the concept are a four-mirror, two-stage optical system; a lightweight structural composite segmented primary reflector; and a deployable truss backup structure with integral thermal shield. The two-stage optics uses active figure control at the quaternary reflector located at the primary reflector exit pupil, allowing the large primary to be passive. The lightweight composite reflector panels limit the short-wavelength operation to approximately 30 microns but reduce the total primary reflector weight by a factor of 3 to 4 over competing technologies. On-orbit thermal analysis indicates a primary reflector equilibrium temperature of less than 200 K with a maximum gradient of about 5 C across the 20-m aperture. Weight and volume estimates are consistent with a single Shuttle launch, and are based on Space Station assembly and checkout.

Swanson, P. N.↗

Microwave radiative transfer studies of precipitation

Since the deployment of the DMSP SSM/I microwave imagers in 1987, increased utilization of passive microwave radiometry throughout the 10 - 100 GHz spectrum has occurred for measurement of atmospheric constituents and terrestrial surfaces. Our efforts have focused on observations and analysis of the microwave radiative transfer behavior of precipitating clouds. We have focused particular attention on combining both aircraft and SSM/I radiometer imagery with ground-based multiparameter radar observations. As part of this and the past NASA contract, we have developed a multi-stream, polarized radiative transfer model which incorporates scattering. The model has the capability to be initialized with cloud model output or multiparameter radar products. This model provides the necessary 'link' between the passive microwave radiometer and active microwave radar observations. This unique arrangement has allowed the brightness temperatures (TB) to be compared against quantities such as rainfall, liquid/ice water paths, and the vertical structure of the cloud. Quantification of the amounts of ice and water in precipitating clouds is required for understanding of the global energy balance.

Bringi, V. N.↗

Classification of Tropical Oceanic Precipitation using High Altitude Aircraft: Microwave and Electric Field Measurements

During the 1998 and 2001 hurricane seasons of the western Atlantic Ocean and Gulf of Mexico, the Advanced Microwave Precipitation Radiometer (AMPR), the ER-2 Doppler (EDOP) radar, and the Lightning Instrument Package (LIP) were flown aboard the National Aeronautics and Space Administration ER-2 high altitude aircraft as part of the Third Convection and Moisture Experiment (CAMEX-3) and the Fourth Convection and Moisture Experiment (CAMEX-4). Several hurricanes, tropical storms, and other precipitation systems were sampled during these experiments. An oceanic rainfall screening technique has been developed using AMPR passive microwave observations of these systems collected at frequencies of 10.7, 19.35,37.1, and 85.5 GHz. This technique combines the information content of the four AMPR frequencies regarding the gross vertical structure of hydrometeors into an intuitive and easily executable precipitation mapping format. The results have been verified using vertical profiles of EDOP reflectivity and lower altitude horizontal reflectivity scans collected by the National Oceanic and Atmospheric Administration WP-3D Orion radar. Matching the rainfall classification results with coincident electric field information collected by the LIP readily identifies convective rain regions within the precipitation fields. This technique shows promise as a real-time research and analysis tool for monitoring vertical updraft strength and convective intensity from airborne platforms such as remotely operated or uninhabited aerial vehicles. The technique is analyzed and discussed for a wide variety of precipitation types using the 26 August 1998 observations of Hurricane Bonnie near landfall.

Hood, Robbie E.↗

Classification of Tropical Oceanic Precipitation using High-Altitude Aircraft Microwave and Electric Field Measurements

During the 1998 and 2001 hurricane seasons of the western Atlantic Ocean and Gulf of Mexico, the Advanced Microwave Precipitation Radiometer (AMPR), the ER-2 Doppler (EDOP) radar, and the Lightning Instrument Package (LIP) were flown aboard the NASA ER-2 high-altitude aircraft as part of the Third Convection and Moisture Experiment (CAMEX-3) and the Fourth Convection and Moisture Experiment (CAMEX-4). Several hurricanes, tropical storms, and other precipitation systems were sampled during these experiments. An oceanic rainfall screening technique has been developed using AMPR passive microwave observations of these systems collected at frequencies of 10.7, 19.35, 37.1, and 85.5 GHz. This technique combines the information content of the four AMPR frequencies regarding the gross vertical structure of hydrometeors into an intuitive and easily executable precipitation mapping format. The results have been verified using vertical profiles of EDOP reflectivity and lower-altitude horizontal reflectivity scans collected by the NOAA WP3D Orion radar. Matching the rainfall classification results with coincident electric field information collected by the LIP readily identifies convective rain regions within the precipitation fields. This technique shows promise as a real-time research and analysis tool for monitoring vertical updraft strength and convective intensity from airborne platforms such as remotely operated or uninhabited aerial vehicles. The technique is analyzed and discussed for a wide variety of precipitation types using the 26 August 1998 observations of Hurricane Bonnie near landfall.

Hood, Robbie E.↗

Tropical Cyclone Diurnal Cycle as Observed by TRMM

Using infrared satellite data, previous work has shown a consistent diurnal cycle in the pattern of cold cloud tops around mature tropical cyclones. In particular, an increase in the coverage by cold cloud tops often occurs in the inner core of the storm around the time of sunset and subsequently propagates outward to several hundred kilometers over the course of the following day. This consistent cycle may have important implications for structure and intensity changes of tropical cyclones and the forecasting of such changes. Because infrared satellite measurements are primarily sensitive to cloud top, the goal of this study is to use passive and active microwave measurements from the Tropical Rainfall Measurement Mission (TRMM) Microwave Imager (TMI) and Precipitation Radar (PR), respectively, to examine and better understand the tropical cyclone diurnal cycle throughout a larger depth of the storm's clouds. The National Hurricane Center's best track dataset was used to extract all PR and TMI pixels within 1000 km of each tropical cyclone that occurred in the Atlantic basin between 1998-2011. Then the data was composited according to radius (100-km bins from 0-1000 km) and local standard time (LST; 3-hr bins). Specifically, PR composites involved finding the percentage of pixels with reflectivity greater than or equal to 20 dBZ at various heights (i.e., 2-14 km in increments of 2 km) as a function of radius and time. The 37- and 85- GHz TMI channels are especially sensitive to scattering by precipitation-sized ice in the mid to upper portions of clouds. Hence, the percentage of 37- and 85-GHz polarization corrected temperatures less than various thresholds were calculated using data from all storms as a function of radius and time. For 37 GHz, thresholds of 260 K, 265 K, 270 K, and 275 K were used, and for 85 GHz, thresholds of 200-270 K in increments of 10 K were utilized. Note that convection forced by the interactions of a tropical cyclone with land (e.g., due to frictional convergence) may disrupt the natural convective cycle of a cyclone. Hence, only data pertaining to storms whose centers were greater than 300 km from land were included in the composites. Early results suggest the presence of a diurnal cycle in the PR composites of all Atlantic basin tropical cyclones from a height of 2-12 km from approximately 0-400 km radius, but the cycle is most apparent above 6 km. At a height of 8 km, there is a peak (minimum) in the percentage of PR pixels greater than or equal to 20 dBZ near 0 (21) LST in the inner core with some indication that this signal propagates outward with time. In contrast, the 37- and 85-GHz composites show little indication of a diurnal cycle at any radii, regardless of the threshold used. Ongoing work with this project will involve sub-setting the composites according to storm intensity to see if the diurnal cycle varies with storm strength. Moderate to strong vertical wind shear often leads to asymmetries in tropical cyclone convection and may disrupt the cyclone's natural diurnal cycle. Therefore, wind shear thresholds will be applied to the composites to determine if the diurnal cycle becomes more apparent in a low shear environment. Finally, other work to be completed will involve developing composites for other tropical cyclone basins, including the East Pacific, Northwest Pacific, South Pacific, and Indian Ocean.

tropical cyclones↗

Satellite Optical Remote Sensing of Clouds and Aerosols: From Particle Single-Scattering and Gaseous Absorption Through Radiative Transfer to Retrieval Products

Clouds and aerosols are fundamental regulators of Earth’s radiation budget and climate system, influencing both solar and terrestrial radiation through scattering, absorption, and emission processes. Accurate characterization of their physical and radiative properties from space requires a rigorous understanding of particle single-scattering, gaseous absorption, and radiative transfer in the atmosphere, as well as reliable inversion methods. This review synthesizes the physical foundations and algorithmic implementations of satellite-based passive optical remote sensing of clouds and aerosols, spanning the ultraviolet to thermal infrared spectral range. Beginning with electromagnetic scattering theory and state-of-the-art methods for computing single-scattering by nonspherical particles and computationally efficient methods for accounting for atmospheric absorption, we discuss the radiative transfer framework underpinning cloud and aerosol retrievals. The connection between single-scattering and multiple-scattering is rigorously formulated. We then summarize operational and research-grade retrieval techniques, including cloud masking and thermodynamic phase determination, CO₂ slicing for cloud-top pressure, the Nakajima-King shortwave bi-spectral, and infrared split-window approaches for cloud optical thickness and effective particle size, inversion algorithms for determining aerosol properties from multi-spectral and/or multi-angle radiometric and polarimetric measurements, and active-passive sensing synergy. Examples of the global cloud and aerosol climatologies are illustrated using observations from the Moderate Resolution Imaging Spectroradiometer (MODIS) and the Multi-angle Imaging SpectroRadiometer (MISR). Furthermore, the unique strengths of active remote sensing techniques based on spaceborne lidar observations are briefly elaborated in the context of studying ice clouds composed of randomly and horizontally oriented ice crystals, which is a significant challenge for conventional passive remote sensing techniques. By connecting physical theory to practical retrievals, this review highlights both the maturity of current methodologies and the remaining challenges in reducing uncertainties in particle morphology, vertical structure, absorption, and aerosol-cloud interactions. Furthermore, the impact of artificial intelligence (AI) on atmospheric remote sensing is briefly addressed.

Aerosols↗

ADEPT for Secondary Payloads

Deployable entry vehicles provide an enabling capability for large payloads at destinations across the solar system. The primary advantage of such systems derives from the fundamental limitation of available launch vehicle shroads preventing tried-and-true rigid aeroshell technology from being applied. However, little mission-pull exists for deployable entry vehicle technology for missions where the entry vehicle is the primary payload and can fit within available shrouds. The propensity toward applying rigid aeroshell technology is logical given that deployable concepts are higher risk and provide no marginal scientific benefit for missions where a rigid aeroshell is an option. A movement toward flying smaller spacecraft has emerged in recent years and is revealing novel applications for deployable entry vehicles as secondary payloads. Secondary payloads must minimize interference with the primary payload in order to ease accomodation. Advancements in small spacecraft technology have caught the attention of government entities who are now recognizing the high value proposition of small spacecraft for frequent, incremental technology development and science return rather than the traditional high cost and infrequent big-bang approaches. Worldwide, well over 200 small satellites (mass < 180 kg) have launched in recent years for such purposes as eduation, technology development, science, commerce, and defense. The Adaptable Deployable Entry and Placement Technology (ADEPT), a mechanically-deployable entry vehicle technology, has been under development at NASA since 2011. An Ames Center Innovation Fund (CIF) proposal was recently awarded to study ADEPT for EDL of small payloads. The unique capability of ADEPT for small science payloads comes from its ability to stow within a slender volume and deploy passively to achieve a mass-efficient drag surface with a high heat rate capability. The low ballistic coefficient results in entry heating and mechanical loads that can be met by a revolutionary three-dimensionally woven carbon fabric supported with rib structures. This carbon fabric has test-proven capability as both primary structure and payload thermal protection. This presentation will inform the EDL community of the capability of ADEPT for delivery of small secondary payloads as well as provide status of on-going technology development activities. Results of a mission applications study for secondary payloads to Mars and Venus will be presented. A primary goal of these mission design activities is to integrate high-value verification approaches wherever possible. For example, for some mission applications it is possible to test in NASA arc jet facilities at full-scale. This enables endto- end thermostructural requirement verification with a single test. Another important challenge that needs to be solved is the reliability of the decelerator to achieve the desired shape using simple passive mechanical actuators (such as springs) that do not require power from the primary payload for deployment. A configuration of ADEPT is being prototyped and used to evaluate the functionality and reliability of the deployment mechanism through bench-top testing. The prototype will then be tested in a low speed wind tunnel in late 2014 to evaluate aerodynamic load-carrying capability and deflected shape. Results of the deployment testing and status of wind tunnel test plans will be discussed.

Smith, B.↗

Investigation of methanol oxidation on a highly active and stable Pt–Sn electrocatalyst supported on carbon–polyaniline composite for application in a passive direct methanol fuel cell

Highlights: • PtSn/C-PANI performed superior in the MOR compared with a commercial PtRu/C. • Catalytic activity of PtRu/C was highly reduced during the accelerated durability test. • Anode of the PtSn/C-PANI in a passive DMFC lowered methanol crossover by 30%. - Abstract: Polyaniline fiber (PANI) was synthesized and utilized to fabricate a vulcan–polyaniline (C-PANI) composite. Pt/C-PANI and PtSn/C-PANI electro-catalysts with different Pt:Sn atomic ratios were prepared by the impregnation method. These electro-catalysts, along with commercial PtRu/C (Electrochem), were characterized with respect to their structural and electrochemical properties in methanol oxidation reaction (MOR). PtSn(70:30)/C-PANI showed excellent performance in MOR, the obtained maximum current density being about 40% and 50% higher than that for PtRu/C and Pt/C-PANI, respectively. It was also found that the CO tolerance and stability of PtSn(70:30)/C-PANI was considerably higher than that of PtRu/C. Finally, the performance of these two materials was compared in a passive direct methanol fuel cell (DMFC). The DMFC test results demonstrated that the membrane electrode assembly (MEA) prepared using PtSn(70:30)/C-PANI anode catalyst performed more satisfactorily in terms of maximum power density and lower methanol crossover.

36 MATERIALS SCIENCE↗

Enhanced Luminescent Stability through Particle Interactions in Silicon Nanocrystal Aggregates

Close-packed assemblies of ligand-passivated colloidal nanocrystals can exhibit enhanced photoluminescent stability, but the origin of this effect is unclear. Here, we use experiment, simulation, and ab initio computation to examine the influence of interparticle interactions on the photoluminescent stability of silicon nanocrystal aggregates. The time-dependent photoluminescence emitted by structures ranging in size from a single quantum dot to agglomerates of more than a thousand is compared with Monte Carlo simulations of noninteracting ensembles using measured single-particle blinking data as input. In contrast to the behavior typically exhibited by the metal chalcogenides, the measured photoluminescent stability shows an enhancement with respect to the noninteracting scenario with increasing aggregate size. We model this behavior using time-dependent density functional theory calculations of energy transfer between neighboring nanocrystals as a function of nanocrystal size, separation, and the presence of charge and/or surface-passivation defects. In conclusion, our results suggest that rapid exciton transfer from “bright” nanocrystals to surface trap states in nearest-neighbors can efficiently fill such traps and enhance the stability of emission by promoting the radiative recombination of slowly diffusing excited electrons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗