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Novel and effective surface passivation for high efficiency n- and p-type Silicon solar cell

The project objective was to develop a novel Si surface passivation method using chalcogens, sulfur (S) and/or selenium (Se), as passivating elements, to withstand industry-standard high temperature contacting and metallization schemes for p-type Si based passivated emitter and rear contact (p-PERC) solar cells. The back surface passivation of PERC cells has been improved drastically with the invention and successful application of an Al 2 O 3 passivation layer. However, the front n + diffused junction surface is still poorly passivated by the standard amorphous silicon nitride (SiNx) anti-reflection coating (ARC) layer. This project sought to address the passivation challenges of both front n+ emitter and undiffused p-Si back surface. Improved p-PERC solar cell performance with open circuit voltage (V OC ) > 680 mV and efficiency of 22% were targeted to validate superior defect passivation properties as compared to standard SiO 2 / Al 2 O 3 passivation. During this project, we systematically investigated process-structure-properties-performance relationships of this novel advanced defect passivation approach. The S/Se passivation was carried out by reacting industrial Czochralski (Cz) Si wafers in H 2 S and H 2 Se gases in a chemical vapor deposition (CVD) reactor at temperatures up to 700°C. After an exhaustive optimization of the process parameters (temperature, time, and gas concentration), we established an optimized process and demonstrated extremely low surface recombination velocities (SRVs) of 1.5 cm/s and 8 cm/s on n-type and p-type Si, respectively, by S-passivation. In-depth surface and interface characterization were performed using soft x-ray and photoelectron spectroscopies (XPS, UPS, XES), combined with capacitance-voltage-frequency (C-V-f) measurements, to decipher the surface chemical/electronic structure and interface defect state densities. These measurements provided critical understanding of the defect passivation mechanism and elucidated the presence of surface S-Si bonds, a reduction of surface dipoles, and low interface state densities (D it ) < 10 11 cm -2 ev -1 . We also found that the Se-passivation is inferior to the S-passivation (by at least one order of magnitude in SRV). Application of the optimized S-passivation to the n+ diffused emitter surface led to a low surface recombination current density, J0 ≈ 40 fA/cm 2 (~ 1/4 of the industry-standard SiNx-passivation), and high implied V OC (686 mV) in p-PERC solar cell structures. The S-passivation process also was found to improve the bulk quality of the p-type Si, better than the SiO 2 or Al 2 O 3 passivation processes. After successful demonstration of efficient passivation of Si surface defects by S, we extensively studied the air, thermal, and illumination stability of the passivation structure. S-passivation itself degrades in air due to competing reactions with moisture and oxygen to form oxides, which can be eliminated by a SiNx capping layer (also acting as a anti-reflective coating). After SiNx process optimization, we demonstrated illumination and thermally stable S-passivation with SRV < 5 cm/s and J 0 < 80 fA/cm 2 . These enhancements in Si passivation, incorporated into p-PERC cells, achieved an efficiency of 19.93% with V OC = 649 mV, using manufacturing metallization and contacting schemes. The low cell performance (cell V OC is much less than the implied V OC = 686 mV, anticipated from surface passivation) was identified due to degradation of S-passivation during the metal firing step (out-diffusion of S from the Si interface to the SiNx surface). The S-passivation of Si surfaces shows significant promise with excellent passivation quality, essential for high performance (high V OC , high efficiency) solar cells. Integration of this innovative defect passivation into devices, however, demands further development of the capping layer, low temperature (<700°C) metallization process, and/or engineering of advanced device structures. Surface passivation-dominated advanced Si solar cells, such as tunnel oxide passivated contacts and Si heterojunctions, are increasingly of interest due to their high-performance potential and will have a growing photovoltaic market share in the near future.

14 SOLAR ENERGY↗

The Effect of Dopant Concentration and Annealing Treatments on N-Type Iodine Doped CdTe

We report properties of highly conducting n-type cadmium telluride single crystals doped with iodine (CdTe:I). These crystals were grown with dopant concentrations in the range of 10^17 cm-3 to 10^19 cm-3 by Modified Vertical Bridgman (MVB) melt growth. Post-growth dopant activation, including Cd annealing, Te annealing, and rapid thermal annealing (RTA), was applied to improve free carrier density. The structural, optical, and electrical properties were analyzed by Glow Discharge Mass Spectroscopy (GDMS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Photoluminescence Spectroscopy (PL), optical absorption, Hall measurements, Capacitance-Voltage (CV) measurements, and time-resolved photoluminescence (TRPL). The results indicate that Cd annealing is the most effective activation method to get 100% donor activation (n is approximately 2 x 10^18 cm-3), which is close to the room temperature solubility limit of iodine. This leads to the lowest resistivity and the highest mobility. Moreover, this data suggests a potential role of Cd vacancy-related defects on electrical self-compensation.

annealing↗

Flow and Heat Transfer Experimental Study for 3D-Printed Solar Receiving Tubes With Helical Fins at Internal Surface

3D-printing technology was applied to fabricate novel solar thermal collection tubes that have internal heat transfer enhancement fins and external surfaces with high solar absorptivity and low emissivity due to the ability to use different materials in one tube. Helical fins were selected to introduce circumferential flow and thus minimize the circumferential temperature difference of the tube that receives sunlight on one side. The structures of the helical fins were previously optimized from computational fluid dynamics (CFD) analysis with the objective of low entropy production rate by looking for high heat transfer coefficient and relatively lower pressure loss. High-temperature alloy, Inconel-718, was used to 3D print the tubes, which can resist corrosion for the potential application of molten chloride salts as heat transfer fluid. Experimental tests were carried out using water as the heat transfer fluid with the high heat flux provided by a tubular furnace heater. The tested Reynolds number ranges from 3.9 × 10 3 to 6.1 × 10 4 . Heat transfer coefficients of up to 2.8 times that of the smooth tube could be obtained with the expense of increased pressure loss compared to that of the smooth tube. The total system entropy generation can be significantly reduced due to the benefit of heat transfer enhancement that is greater than the expenses of the increased pressure loss. The experimental results of the 3D-printed heat transfer tubes confirmed the CFD-based results of fin optimization. Furthermore, the novel heat transfer tube is recommended for application in concentrating solar power systems.

14 SOLAR ENERGY↗

Mechanical Properties of Aerogels

Aerogels are extremely low density solids that are characterized by a high porosity and pore sizes on the order of nanometers. Their low thermal conductivity and sometimes transparent appearance make them desirable for applications such as insulation in cryogenic vessels and between double paned glass in solar architecture. An understanding of the mechanical properties of aerogels is necessary before aerogels can be used in load bearing applications. In the present study, the mechanical behavior of various types of fiber-reinforced silica aerogels was investigated with hardness, compression, tension and shear tests. Particular attention was paid to the effects of processing parameters, testing conditions, storage environment, and age on the aerogels' mechanical response. The results indicate that the addition of fibers to the aerogel matrix generally resulted in softer, weaker materials with smaller elastic moduli. Furthermore, the testing environment significantly affected compression results. Tests in ethanol show an appreciable amount of scatter, and are not consistent with results for tests in air. In fact, the compression specimens appeared to crack and begin to dissolve upon exposure to the ethanol solution. This is consistent with the inherent hydrophobic nature of these aerogels. In addition, the aging process affected the aerogels' mechanical behavior by increasing their compressive strength and elastic moduli while decreasing their strain at fracture. However, desiccation of the specimens did not appreciably affect the mechanical properties, even though it reduced the aerogel density by removing trapped moisture. Finally, tension and shear test results indicate that the shear strength of the aerogels exceeds the tensile strength. This is consistent with the response of brittle materials. Future work should concentrate on mechanical testing at cryogenic temperatures, and should involve more extensive tensile tests. Moreover, before the mechanical response of reinforced aerogels can be fully understood, more tests of unreinforced aerogels are necessary. Unreinforced aerogels are of particular use because their birefringent nature allows for visual determination of stress fields during mechanical testing. The success of any future tests depends on the availability of a large supply of quality specimens with well-documented preparation and storage histories.

Parmenter, Kelly E.↗

A Modeling Study of the Latitudinal Variations in the Nighttime Plasma Temperatures of the Equatorial Topside Ionosphere During Northern Winter at Solar Maximum

Latitudinal variations in the nighttime plasma temperatures of the equatorial topside ionosphere during northern winter at solar maximum have been examined by using values modelled by SUPIM (Sheffield University Plasmasphere Ionosphere Model) and observations made by the DMSP F10 satellite at 21.00 LT near 800 km altitude. The modelled values confirm that the crests observed near 15 deg latitude in the winter hemisphere are due to adiabatic heating and the troughs observed near the magnetic equator are due to adiabatic cooling as plasma is transported along the magnetic field lines from the summer hemisphere to the winter hemisphere. The modelled values also confirm that the interhemispheric plasma transport needed to produce the required adiabatic heating/cooling can be induced by F-region neutral winds. It is shown that the longitudinal variations in the observed troughs and crests arise mainly from the longitudinal variations in the magnetic meridional wind. At longitudes where the magnetic declination angle is positive the eastward geographic zonal wind combines with the northward (summer hemisphere to winter hemisphere) geographic meridional wind to enhance the northward magnetic meridional wind. This leads to deeper troughs and enhanced crests. At longitudes where the magnetic declination angle is negative the eastward geographic zonal wind opposes the northward geographic meridional wind and the trough depth and crest values are reduced. The characteristic features of the troughs and crests depend, in a complicated manner, on the field-aligned flow of plasma, thermal conduction, and inter-gas heat transfer. At the latitudes of the troughs/crests, the low/high plasma temperatures lead to increased/decreased plasma concentrations.

Bailey, G. J.↗

Corrosion-Resistant Container for Molten-Material Processing

In a carbothermal process, gaseous methane is passed over molten regolith, which is heated past its melting point to a temperature in excess of 1,625 C. At this temperature, materials in contact with the molten regolith (or regolith simulant) corrode and lose their structural properties. As a result, fabricating a crucible to hold the molten material and providing a method of contact heating have been problematic. Alternative containment approaches use a large crucible and limit the heat zone of the material being processed, which is inefficient because of volume and mass constraints. Alternative heating approaches use non-contact heating, such as by laser or concentrated solar energy, which can be inefficient in transferring heat and thus require higher power heat sources to accomplish processing. The innovation is a combination of materials, with a substrate material having high structural strength and stiffness and high-temperature capability, and a coating material with a high corrosion resistance and high-temperature capability. The material developed is a molybdenum substrate with an iridium coating. Creating the containment crucible or heater jacket using this material combination requires only that the molybdenum, which is easily processed by conventional methods such as milling, electric discharge machining, or forming and brazing, be fabricated into an appropriate shape, and that the iridium coating be applied to any surfaces that may come in contact with the corrosive molten material. In one engineering application, the molybdenum was fashioned into a container for a heat pipe. Since only the end of the heat pipe is used to heat the regolith, the container has a narrowing end with a nipple in which the heat pipe is snugly fit, and the external area of this nipple, which contacts the regolith to transfer heat into it, is coated with iridium. At the time of this reporting, no single material has been found that can perform the functions of this combination of materials, and other combinations of materials have not proven to be survivable to the corrosiveness of this environment. High-temperature processing of materials with similar constituencies as lunar regolith is fairly common. The carbo-thermal process is commonly used to make metallurgical-grade silicon for the semiconductor and solar-cell industries.

Stern, Theodore G.↗

Comparative Magma Oceanography

The question of whether the Earth ever passed through a magma ocean stage is of considerable interest. Geochemical evidence strongly suggests that the Moon had a magma ocean and the evidence is mounting that the same was true for Mars. Analyses of martian (SNC) meteorites have yielded insights into the differentiation history of Mars, and consequently, it is interesting to compare that planet to the Earth. Three primary features of Mars contrast strongly to those of the Earth: (i) the extremely ancient ages of the martian core, mantle, and crust (about 4.55 b.y.); (ii) the highly depleted nature of the martian mantle; and (iii) the extreme ranges of Nd isotopic compositions that arise within the crust and depleted mantle. The easiest way to explain the ages and diverse isotopic compositions of martian basalts is to postulate that Mars had an early magma ocean. Cumulates of this magma ocean were later remelted to form the SNC meteorite suite and some of these melts assimilated crustal materials enriched in incompatible elements. The REE pattern of the crust assimilated by these SNC magmas was LREE enriched. If this pattern is typical of the crust as a whole, the martian crust is probably similar in composition to melts generated by small degrees of partial melting (about 5%) of a primitive source. Higher degrees of partial melting would cause the crustal LREE pattern to be essentially flat. In the context of a magma ocean model, where large degrees of partial melting presumably prevailed, the crust would have to be dominated by late-stage, LREE-enriched residual liquids. Regardless of the exact physical setting, Nd and W isotopic evidence indicates that martian geochemical reservoirs must have formed early and that they have not been efficiently remixed since. The important point is that in both the Moon and Mars we see evidence of a magma ocean phase and that we recognize it as such. Several lines of theoretical inference point to an early Earth that was also hot and, perhaps, mostly molten. The Giant Impact hypothesis for the origin of the Moon offers a tremendous input of thermal energy and the same could be true for core formation. And current solar system models favor the formation of a limited number of large (about 1000 km) planetesimals that, upon accreting to Earth, would cause great heating, being lesser versions of the Giant Impact. Several lines of geochemical evidence do not favor this hot early Earth scenario. (i) Terrestrial man-tle xenoliths are sometimes nearly chondritic in their major element compositions, suggesting that these rocks have never been much molten. Large degrees of partial melting probably promote differentiation rather than homogenization. (ii) Unlike the case of Mars, the continental crust probably did not form as a highly fractionated residual liquid from a magma ocean (about 99% crystallization), but, rather, formed in multiple steps. [The simplest model for the formation of continental crust is complicated: (a) about 10% melting of a primitive mantle, making basalt; (b) hydrothermal alteration of that basalt, converting it to greenstone; and (c) 10% partial melting of that greenstone, producing tonalite.] This model is reinforced by the recent observation from old (about 4.1 b.y.) zircons that the early crust formed from an undepleted mantle having a chondritic Lu/Hf ratio. (iii) If the mantle were once differentiated by a magma ocean, the mantle xenolith suite requires that it subsequently be homogenized. The Os isotopic compositions of fertile spinel lherzolites place constraints on the timing of that homogenization. The Os isotopic composition of spinel lherzolites approaches that of chondrites and correlates with elements such as Lu and Al. As Lu and Al concentrations approach those of the primitive mantle, Os isotopic compositions approach chondritic. The Re and Os in these xenoliths were probably added as a late veneer. Thus, the mantle that received the late veneer must have been nearly chondritic in terms of its major elements (excluding Fe). If the mantle that the veneer was mixed into was not al-ready homogenized, then Os isotopes should not correlate with incompatible elements such as Al. Consequently, either early differentiation of the mantle did not occur or the homogenization of this differentiation must have occurred before the late veneer was added. The timing of the late veneer is itself uncertain but presumably postdated core formation at about 4.45 b.y. and did not postdate the 3.8-3.9 b.y. late bombardment of the Moon. This timing based on siderophile elements is consistent with the Hf isotopic evidence cited above. If the Earth, Moon and Mars had magma oceans, the Earth subsequently rehomogenized whereas the Moon and Mars did not. The simplest solution to this observation is that homogenization of igneous differentiates was never necessary on Earth, either because the hypothetical magma ocean never occurred or because this event did not produce mantle differentiation.

Jones, J. H.↗

Measurements of Ice Particles in Tropical Cirrus Anvils: Importance in Radiation Balance

Cirrus is important in the radiation balance of the global atmosphere, both at solar and thermal infrared (IR) wavelengths. In particular cirrus produced by deep convection over the oceans in the tropics may be critical in controlling processes whereby energy from warm tropical oceans is injected to different levels in the tropical atmosphere to subsequently influence not only tropical but mid latitude climate. Details of the cloud composition may differentiate between a net cooling or warming at these levels. The cloud composition may change depending on the input of nuclei from volcanic or other sources. Observations of cirrus during the FIRE-2 Project over Coffeyville, Kansas and by satellite demonstrate that cirrus, on occasion, is composed not only of larger particles with significant fall velocity (few hundred micrometers, 0.5 m/s) but much more numerous small particles, size 10-20 micrometers, with small fall velocity (cm/s), which may sometimes dominate the radiation field. This is consistent with emissivity measurements. In the thermal IR, ice absorption is strong, so that ice particles only 10 micrometers thick are opaque, at some wavelengths; on the other hand at other wavelengths and in the visible, ice is only moderately to weakly absorbing. It follows that for strongly absorbing wavelengths the average projected area of the ice particles is the important parameter, in weakly absorbing regions it is the volume (mass) of ice which is important. The shape of particles and also their internal structure may also have significant effect on their radiative properties. In order to access the role of cirrus in the radiation budget it is necessary to measure the distribution of ice particles sizes, shapes and concentrations in the regions of interest. A casual observation of any cirrus cloud shows that there is variability down to a scale of at least a few 100 m; this is confirmed by radar and lidar remote sensing. Thus aircraft measurements designed to give insight into the spatial distribution of radiation properties of ice crystals must be capable of examination of concentration, size and shape over a distance ideally of 100 m or less and to detect particles down to a size below which radiative effects are no longer significant.

Foster, Theodore↗

Origin, Bulk Chemical Composition and Physical Structure of the Galilean Satellites of Jupiter: A Post-Galileo Analysis

The origin of Jupiter and the Galilean satellite system is examined in the light of the new data that has been obtained by the NASA Galileo Project. In particular, special attention is given to a theory of satellite origin which was put forward at the start of the Galileo Mission and on the basis of which several predictions have now been proven successful. These predictions concern the chemical composition of Jupiter's atmosphere and the physical structure of the satellites. According to the proposed theory of satellite origin, each of the Galilean satellites formed by chemical condensation and gravitational accumulation of solid grains within a concentric family of orbiting gas rings. These rings were cast off equatorially by the rotating proto-Jovian cloud (PJC which contracted gravitationally to form Jupiter some 4 1/2 billion years ago. The PJC formed from the gas and grains left over from the gas ring that had been shed at Jupiter's orbit by the contracting proto-solar cloud (PSC Supersonic turbulent convection provides the means for shedding discrete gas rings. The temperatures T (sub n) of the system of gas rings shed by the PSC and PJC vary with their respective mean orbital radii R (sub n) (n = 0, 1,2,...) according as T (sub n) proportional to R (sub n) (exp -0.9). If the planet Mercury condenses at 1640 K, so accounting for the high density of that planet via a process of chemical fractionation between iron and silicates, then T (sub n) at Jupiter's orbit is 158 K. Only 35% of the water vapour condenses out. Thus fractionation between rock and ice, together with an enhancement in the abundance of solids relative to gas which takes place through gravitational sedimentation of solids onto the mean orbit of the gas ring, ensures nearly equal proportions of rock and ice in each of Ganymede and Callisto. Io and Europa condense above the H20 ice point and consist solely of hydrated rock (h-rock). The Ganymedan condensate consists of h-rock and H20 ice. For Callisto, NH3 ice makes up -5% of the condensate mass next to h-rock (approximately 50%) and H2O ice (approximately 45%). Detailed thermal and structural models for each of Europa, Ganymede and Callisto are constructed on the basis of the above initial bulk chemical compositions. For Europa (E), a predicted 2-zone model consisting of a dehydrated rock core of mass 0.912 M (sub E) and a 150 km thick frozen mantle of salty H2O yields a moment-of-inertia coefficient which matches the Galileo Orbiter gravity measurement. For Ganymede (G), a 3-zone model possessing an inner core of solid FeS and mass approximately 0.116 M (sub G), and an outer H2O ice mantle of mass approximately 0.502 M (sub G) is needed to explain the gravity data. Ganymede's native magnetic field was formed by thermoremanent magnetization of Fe3O4. A new Callisto (C) model is proposed consisting of a core of mass 0.826 M (sub C) containing a uniform mixture of h-rock (60% by mass) and H2O and NH3 ices, and capped by a mantle of pure ice. This model may have the capacity to yield a thin layer of liquid NH3 (raised dot) 2H2O at the core boundary, in line with Galileo's discovery of an induced magnetic field.

Prentice, A. J. R.↗

Electron- and Photon-stimulated Desorption of Alkali Atoms from Lunar Sample and a Model Mineral Surface

We report recent results on an investigation of source mechanisms for the origin of alkali atoms in the tenuous planetary atmospheres, with focus on non-thermal processes (photon stimulated desorption (PSD), electron stimulated desorption (ESD), and ion sputtering). Whereas alkaline earth oxides (MgO, CaO) are far more abundant in lunar samples than alkali oxides (Na2O, K2O), the atmosphere of the Moon contains easily measurable concentrations of Na and K, while Ca and Mg are undetected there; traces of Ca have recently been seen in the Moon's atmosphere (10-3 of Na). The experiments have included ESD, PSD and ion sputtering of alkali atoms from model mineral surface (amorphous SiO2) and from a lunar basalt sample obtained from NASA. The comparison is made between ESD and PSD efficiency of monovalent alkalis (Na, K) and divalent alkaline earths (Ba, Ca).The ultrahigh vacuum measurement scheme for ESD and PSD of Na atoms includes a highly sensitive alkali metal detector based on surface ionization, and a time-of-flight technique. For PSD measurements, a mercury arc light source (filtered and chopped) is used. We find that bombardment of the alkali covered surfaces by ultraviolet photons or by low energy electrons (E>4 eV) causes desorption of hot alkali atoms. This results are consistent with the model developed to explain our previous measurements of sodium desorption from a silica surface and from water ice: electron- or photon-induced charge transfer from the substrate to the ionic adsorbate causes formation of a neutral alkali atom in a repulsive configuration, from which desorption occurs. The two-electron charge transfer to cause desorption of divalent alkaline eath ions is a less likely process.The data support the suggestion that PSD by UV solar photons is a dominant source process for alkalis in the tenuous lunar atmosphere.

Yakshinskiy, B. V.↗

Magnetic shaping of planetary nebulae and other stellar wind bubbles

As in the case of the solar wind, the magnetic field in the wind from a magnetized, rotating star becomes increasingly toroidal with distance from the star. The strength of the magnetic field can be characterized by sigma, the ratio of toroidal magnetic energy density to kinetic energy density in the equatorial plane of the wind. A fast wind shocks against the external medium and creates a bubble whose volume is dominated by shocked gas. The toroidal magnetic field increases in the shocked bubble and can dominate the thermal pressure. Because of the low velocities in the bubble, hydrostatic equilibrium is a good approximation and allows the calculation of the thermal and magnetic pressure in the bubble, as in the model of Begelman and Li (1992) for the Crab Nebula. The structure, which is axisymmetric and extended in the polar direction, depends on two parameters: sigma nu(sub w)/w(sub 0), where nu(sub w) is the wind velocity and w(sub 0) is the shell velocity in the polar direction, and lambda = nu(sub a)/w(sub 0), where nu(sub a) is the velocity of the slow wind. For small values of lambda, there is a cusp in the shell in the equatorial plane, i.e., there is an equatorial ring. For larger values of lambda, the maximum of the surface density moves away from the equator i.e., a double ring structure. Our models should apply to planetary nebulae, if their central stars are sufficiently magnetized; the calculated shapes do resemble the observed shapes of planetaries. In all cases, our model predicts that X-ray emission from the bubble is concentrated toward the polar axis. Finally, we briefly discuss the asymmetry of the Crab Nebula and 3C 58.

Chevalier, Roger A.↗

Production of hydrogen peroxide in an intra-meander hyporheic zone at East River, Colorado.

The traditionally held assumption that photo-dependent processes are the predominant source of H 2 O 2 in natural waters has been recently questioned by an increasing body of evidence showing the ubiquitiousness of H 2 O 2 in dark water bodies and in groundwater. In this study, we conducted field measurement of H 2 O 2 in an intra-meander hyporheic zone and in surface water at East River, CO. On-site detection using a sensitive chemiluminescence method suggests H 2 O 2 concentrations in groundwater ranging from 6 nM (at the most reduced region) to ~ 80 nM (in a locally oxygen-rich area) along the intra-meander transect with a maxima of 186 nM detected in the surface water in an early afternoon, lagging the maximum solar irradiance by ~1.5 h. Our results suggest that the dark profile of H 2 O 2 in the hyporheic zone is closely correlated to local redox gradients, indicating that interactions between various redox sensitive elements could play an essential role. Due to its transient nature, the widespread presence of H 2 O 2 in the hyporheic zone indicates the existence of a sustained balance between H 2 O 2 production and consumption, which potentially involves a relatively rapid succession of various biogeochemically important processes (such as organic matter turnover, metal cycling and contaminant mobilization). More importantly, this study confirmed the occurrence of reactive oxygen species at a subsurface redox transition zone and further support our understanding of redox boundaries on reactive oxygen species generation and as key locations of biogeochemical activity.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

Nanometer-Scale Imaging of Inhomogeneous Active Charge Carriers in Arsenic-Doped CdTe Thin Films

We report nanometer-scale imaging of active carrier distribution of As-doped CdTe films by scanning capacitance microscopy (SCM). We developed SCM sample preparation for CdTe by ion-milling followed by thermal processing. The nanometer-resolution carrier delineation for CdTe was validated by imaging on a CdTe cross-section sample made by a molecular beam epitaxy layer stack with As-doping concentrations of 10^15 ~10^18 /cm 3 . We found that the carrier distribution in As-doped films was significantly nonuniform, with inhomogeneity ranging from sub-um to a few um and concentration variation of one order of magnitude (low 10^16 to low 10^17 /cm 3 ). This nonuniformity is distributed randomly, independent of grain structure and grain boundary (GB). We used Kelvin probe force microscopy (KPFM) and cathodoluminescence (CL) to further map the surface potential and radiative illumination on the same area as the SCM image. Higher potential and lower CL intensity were found on GBs but not on SCM contrast, illustrating positive GB charging and GB recombination but not GB-distinguished doping. The overall KPFM potential image is in rough agreement with the SCM carrier distribution, in terms of Fermi-level position relative to the bandgap edge - thus resulting in the band-edge potential fluctuation. Nonuniform carrier concentration, potential fluctuation, and defect recombination can all together cause the Voc deficit of the As-doped CdTe device.

14 SOLAR ENERGY↗

The Distribution, Composition, and Particle Properties of Mars Mesospheric Aerosols: an Analysis of CRISM Visible/near-IR Limb Spectra with Context from Near-Coincident MCS and MARCI Observations

The Compact Reconnaissance Imaging Spectral Mapper (CRISM) onboard the Mars Reconnaissance Orbiter (MRO) obtains pole-to-pole observations (i.e., full MRO orbits) of vertical profiles for visible/near-IR spectra (λ=0.4–4.0 μm), which are ideally suited to identifying the composition and particle sizes of Mars ice and dust aerosols over 50–100 km altitudes in the Mars mesosphere. Within the coverage limitations of the CRISM limb data set, a distinct compositional dichotomy is found in Mars mesospheric ice aerosols. CO2 ice clouds appear during the aphelion period of Mars orbit (Solar Longitudes, Ls∼0–160°) at low latitudes (∼20S–10N) over specific longitude regions (Meridiani, Valles Marineris) and at typical altitudes of 55–75 km. Apart from faint water ice hazes below 55 km, mesospheric H2O ice clouds are primarily restricted to the perihelion orbital range (Ls∼160 – 350°) at northern and southern mid-to-low latitudes with less apparent longitudinal dependences. Mars mesospheric CO2 clouds are presented in CRISM spectra with a surprisingly large range of particle sizes (cross section weighted radii, Reff=0.3 to 2.2 μm). The smaller particle sizes (Reff ≤1 μm) appear concentrated near the spatial (latitude and altitude) boundaries of their global occurrences. CRISM spectra of mesospheric CO2 clouds also show evidence of iridescence, indicating very narrow particle size distributions (effective variance, Veff∼0.03) and so very abrupt CO2 cloud nucleation. Furthermore, these clouds are sometimes accompanied by altitude coincident peaks in 1.27 μm O2 dayglow, which indicates very dry, cold regions of formation. Mesospheric water ice clouds generally exhibit small particle sizes (Reff=0.1–0.3 μm), although larger particle sizes (Reff=0.4–0.7 μm) appear infrequently. On average, water ice cloud particle sizes decrease with altitude over 50–80 km in the perihelion mesosphere. Water ice mass appears similar in clouds over a large range of observed cloud particle sizes, with particle number densities increasing to ∼10 cm−3 for Reff=0.2 μm. Near coincident Mars Climate Sounder (MCS) temperature and aerosol profile measurements for a subset of CRISM mesospheric aerosol measurements indicate near saturation (H2O and CO2) conditions for ice clouds and distinct mesospheric temperature increases associated with mesospheric dust loading. Dayside (3 pm) mesospheric CO2 clouds with larger particle sizes (Reff ≥0.5 μm) scatter surface infrared emission in MCS limb infrared radiances, as well as solar irradiance in the MCS solar band channel. Scattering of surface infrared emission is most strikingly presented in nighttime (3 am) MCS observations at 55–60 km altitudes, indicating extensive mesospheric nighttime CO2 clouds with considerably larger particle sizes (Reff∼7 μm). Mesospheric CO2 ice clouds present cirrus-like waveforms over extensive latitude and longitude regions (10°×10°), as revealed in coincident Mars Color Imager (MARCI) nadir imaging. Solar tides, gravity waves, and the large orbital variation of the extended thermal structure of the Mars atmosphere influence all of these behaviors. Mesospheric dust aerosols appear infrequently over the non-global (planet encircling) dust storm era of the CRISM limb data set (2009–2016), and exhibit smaller particle sizes (Reff=0.2–0.7 μm) relative to dust in the lower atmosphere. One isolated case of an aphelion (Ls=96°) mesospheric dust layer with large dust particle sizes (Reff ∼2 μm) over Syria Planum may reflect high altitude, non-local transport of dust over elevated regions.

Clancy, Todd R.↗

High-Temperature Particle Heat Exchanger for sCO2 Power Cycles [Award 30342]

This report describes the design, development, and testing of a prototype 100 kWt particle-to-supercritical CO 2 (sCO2) heat exchanger. An analytic hierarchy process was implemented to compare and evaluate alternative heat-exchanger designs (fluidized bed, shell-and-plate moving packed bed, and shell-and-tube moving packed bed) that could meet the high pressure (≥ 20 MPa) and high temperature (≥ 700 °C) operational requirements associated with sCO2 power cycles. Cost, heat-transfer coefficient, structural reliability, manufacturability, parasitics and heat losses, scalability, compatibility, erosion and corrosion, transient operation, and inspection ease were considered in the evaluation. A 100 kWt shell-and-plate design was selected for construction and integration with Sandia’s falling particle receiver system that heats the particles using concentrated sunlight. Sandia worked with industry to design and construct the moving packed-bed shell-and-plate heat exchanger. Tests were performed to evaluate its performance using both electrical heating and concentrated sunlight to heat the particles. Overall heat transfer coefficients at off-design conditions (reduced operating temperatures and only three stainless steel banks in the counter-crossflow heat exchanger) were measured to be approximately ~25 - 70 W/m 2 -K, significantly lower than simulated values of >100 W/m 2 -K. Tests using the falling particle receiver to heat the particles with concentrated sunlight yielded overall heat transfer coefficients of ~35 – 80 W/m 2 -K with four banks (including a nickel-alloy bank above the three stainless steel banks). The overall heat transfer coefficient was observed to decrease with increasing particle inlet temperatures, which contrasted the results of simulations that showed an increase in heat transfer coefficient with temperature due to increased effective particle-bed thermal conductivity from radiation. The likely cause of the discrepancy was particle-flow maldistributions and funnel flow within the heat exchanger caused by internal ledges and cross-bracing, which could have been exacerbated by increased particle-wall friction at higher temperatures. Additional heat loss at higher temperatures may also contribute to a lower overall heat-transfer coefficient. Design challenges including pressure drop, particle and sCO2 flow maldistribution, and reduced heat transfer coefficient are discussed with approaches for mitigation in future designs. Lessons learned regarding instrumentation, performance characterization, and operation of particle components and sCO2 flow loops are also discussed. Finally, a 200 MWt commercial-scale shell-and-plate heat-exchanger design based on the concepts investigated in this report is proposed.

14 SOLAR ENERGY↗

The distribution, composition, and particle properties of Mars mesospheric aerosols: An analysis of CRISM visible/near-IR limb spectra with context from near-coincident MCS and MARCI observations

The Compact Reconnaissance Imaging Spectral Mapper (CRISM) onboard the Mars Reconnaissance Orbiter (MRO) obtains pole-to-pole observations (i.e., full MRO orbits) of vertical profiles for visible/near-IR spectra (λ= 0.4–4.0 μm), which are ideally suited to identifying the composition and particle sizes of Mars ice and dust aerosols over 50–100 km altitudes in the Mars mesosphere. Within the coverage limitations of the CRISM limb data set, a distinct compositional dichotomy is found in Mars mesospheric ice aerosols. CO2 ice clouds appear during the aphelion period of Mars orbit (Solar Longitudes, L(s )∼ 0–160°) at low latitudes (∼20S–10N) over specific longitude regions (Meridiani, Valles Marineris) and at typical altitudes of 55–75 km. Apart from faint water ice hazes below 55 km, mesospheric H2O ice clouds are primarily restricted to the perihelion orbital range (L(s)∼160 – 350°) at northern and southern mid-to-low latitudes with less apparent longitudinal dependences. Mars mesospheric CO2 clouds are presented in CRISM spectra with a surprisingly large range of particle sizes (cross section weighted radii, R(eff) = 0.3 to 2.2 μm). The smaller particle sizes (R(eff) ≤1 μm) appear concentrated near the spatial (latitude and altitude) boundaries of their global occurrences. CRISM spectra of mesospheric CO2 clouds also show evidence of iridescence, indicating very narrow particle size distributions (effective variance, V(eff) ∼ 0.03) and so very abrupt CO2 cloud nucleation. Furthermore, these clouds are sometimes accompanied by altitude coincident peaks in 1.27 μm O2 dayglow, which indicates very dry, cold regions of formation. Mesospheric water ice clouds generally exhibit small particle sizes (R(eff) = 0.1–0.3 μm), although larger particle sizes (R(eff) = 0.4–0.7 μm) appear infrequently. On average, water ice cloud particle sizes decrease with altitude over 50–80 km in the perihelion mesosphere. Water ice mass appears similar in clouds over a large range of observed cloud particle sizes, with particle number densities increasing to ∼10 per cu. cm for R(eff) = 0.2 μm. Near coincident Mars Climate Sounder (MCS) temperature and aerosol profile measurements for a subset of CRISM mesospheric aerosol measurements indicate near saturation (H2O and CO2) conditions for ice clouds and distinct mesospheric temperature increases associated with mesospheric dust loading. Dayside (3 pm) mesospheric CO2 clouds with larger particle sizes (R(eff) ≥0.5 μm) scatter surface infrared emission in MCS limb infrared radiances, as well as solar irradiance in the MCS solar band channel. Scattering of surface infrared emission is most strikingly presented in nighttime (3 am) MCS observations at 55–60 km altitudes, indicating extensive mesospheric nighttime CO2 clouds with considerably larger particle sizes (R(eff)∼7 μm). Mesospheric CO2 ice clouds present cirrus-like waveforms over extensive latitude and longitude regions (10°×10°), as revealed in coincident Mars Color Imager (MARCI) nadir imaging. Solar tides, gravity waves, and the large orbital variation of the extended thermal structure of the Mars atmosphere influence all of these behaviors. Mesospheric dust aerosols appear infrequently over the non-global (planet encircling) dust storm era of the CRISM limb data set (2009–2016), and exhibit smaller particle sizes (R(eff) = 0.2–0.7 μm) relative to dust in the lower atmosphere. One isolated case of an aphelion (L(s) = 96°) mesospheric dust layer with large dust particle sizes (R(eff) ∼2 μm) over Syria Planum may reflect high altitude, non-local transport of dust over elevated regions.

R. Todd Clancy↗

Secondary Fragmentation of Comet Shoemaker-Levy 9 and the Ramifications for the Progenitor's Breakup in July 1992

Comprehensive analysis of discrete events of secondary fragmentation leads to a conceptually new understanding of the process of disintegration of comet Shoemaker-Levy 9. We submit that the jovian tidal forces inflicted extensive cracks throughout the interior of the original nucleus but did not split it apart. The initial disruption was apparently accomplished by stresses exerted on the cracked object by its fast rotation during the early post-perijove period of time. We argue that this disruption was in fact a rapid sequence of episodes during July 1992 that gave birth to the 12 on-train, or primary, fragments: A, C, D, E, G, H, K, L, Q (later Q(sub 1)), R, S, and W. The discrete events of secondary fragmentation, which gave birth to the off-train fragments, are understood in this scenario as stochastic manifestations of the continuing process of progressive disintegration. Of the 13 off-train fragments considered, nine were secondary--B, F, G(sub 2), M, N, P (later P(sub 2) or P(sub 2a)), Q(sub 2), U, and V--and four tertiary (J, P(sub 1), P(sub 2b), and T). The separation parameters of 11 off-train fragments were determined. The vectorial distribution of separation velocities of these fragments shows a strong concentration toward a great circle, unquestionably an effect of the approximately conserved angular momentum of the progenitor comet since the time of its initial disruption. Also apparent is their clumping (except for P(sub 1)) to a segment along the great circle, implying that the fragments were consistently released from one side of their parents, thus explaining for the first time why the off-train fragments preferentially appeared on one side of the nuclear train. In order to obtain a consistent solution, our model requires that the points of separation be on the antisolar side of the parent fragments, where thermal stresses are likely to enhance the effect of rotation. The episodes of secondary fragmentation are found to have nine months after the close encounter with Jupiter in early July 1992, and the separation velocities ranged between 0.36 and 1.7 m/s. The spin-axis position is determined to have been nearly in the jovicentric orbit plane, which rules out the Asphaug-Benz-Solem strengthless aggregate model as a plausible breakup hypothesis. Since the separation velocities are rotational in nature, they cannot substantially exceed the critical limit for centrifugal breakup and offer an estimate for the original nuclear dimensions. The comet's nucleus is found to have been approximately 10 km in diameter and spinning rapidly. With the exception of P(sub 1) and apparently also P(sub 2) and F, no nongravitational deceleration was detected in the motions of the off-train fragments. Serious doubts are cast on continuing appreciable activity of any of these fragments. Indeed, when it was necessary to introduce a deceleration into the equations of motion, the effect appears to have been due to the action of solar radiation pressure on the centroid of centimeter-sized particulates in the disintegrating condensations.

Sekanina, Z.↗

Radiation Shielding Materials Containing Hydrogen, Boron, and Nitrogen: Systematic Computational and Experimental Study

The key objectives of this study are to investigate, both computationally and experimentally, which forms, compositions, and layerings of hydrogen, boron, and nitrogen containing materials will offer the greatest shielding in the most structurally robust combination against galactic cosmic radiation (GCR), secondary neutrons, and solar energetic particles (SEP). The objectives and expected significance of this research are to develop a space radiation shielding materials system that has high efficacy for shielding radiation and that also has high strength for load bearing primary structures. Such a materials system does not yet exist. The boron nitride nanotube (BNNT) can theoretically be processed into structural BNNT and used for load bearing structures. Furthermore, the BNNT can be incorporated into high hydrogen polymers and the combination used as matrix reinforcement for structural composites. BNNT's molecular structure is attractive for hydrogen storage and hydrogenation. There are two methods or techniques for introducing hydrogen into BNNT: (1) hydrogen storage in BNNT, and (2) hydrogenation of BNNT (hydrogenated BNNT). In the hydrogen storage method, nanotubes are favored to store hydrogen over particles and sheets because they have much larger surface areas and higher hydrogen binding energy. The carbon nanotube (CNT) and BNNT have been studied as potentially outstanding hydrogen storage materials since 1997. Our study of hydrogen storage in BNNT - as a function of temperature, pressure, and hydrogen gas concentration - will be performed with a hydrogen storage chamber equipped with a hydrogen generator. The second method of introducing hydrogen into BNNT is hydrogenation of BNNT, where hydrogen is covalently bonded onto boron, nitrogen, or both. Hydrogenation of BN and BNNT has been studied theoretically. Hyper-hydrogenated BNNT has been theoretically predicted with hydrogen coverage up to 100% of the individual atoms. This is a higher hydrogen content than possible with hydrogen storage; however, a systematic experimental hydrogenation study has not been reported. A combination of the two approaches may be explored to provide yet higher hydrogen content. The hydrogen containing BNNT produced in our study will be characterized for hydrogen content and thermal stability in simulated space service environments. These new materials systems will be tested for their radiation shielding effectiveness against high energy protons and high energy heavy ions at the HIMAC facility in Japan, or a comparable facility. These high energy particles simulate exposure to SEP and GCR environments. They will also be tested in the LaRC Neutron Exposure Laboratory for their neutron shielding effectiveness, an attribute that determines their capability to shield against the secondary neutrons found inside structures and on lunar and planetary surfaces. The potential significance is to produce a radiation protection enabling technology for future exploration missions. Crew on deep space human exploration missions greater than approximately 90 days cannot remain below current crew Permissible Exposure Limits without shielding and/or biological countermeasures. The intent of this research is to bring the Agency closer to extending space missions beyond the 90-day limit, with 1 year as a long-term goal. We are advocating a systems solution with a structural materials component. Our intent is to develop the best materials system for that materials component. In this Phase I study, we have shown, computationally, that hydrogen containing BNNT is effective for shielding against GCR, SEP, and neutrons over a wide range of energies. This is why we are focusing on hydrogen containing BNNT as an innovative advanced concept. In our future work, we plan to demonstrate, experimentally, that hydrogen, boron, and nitrogen based materials can provide mechanically strong, thermally stable, structural materials with effective radiation shielding against GCR, SEP, and neutrons.

Radiation↗