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DOE OSTI2022

Design Rules of the Mixing Phase and Impacts on Device Performance in High-Efficiency Organic Photovoltaics

In nonfullerene acceptor- (NFA-) based solar cells, the exciton splitting takes place at both domain interface and donor/acceptor mixture, which brings in the state of mixing phase into focus. The energetics and morphology are key parameters dictating the charge generation, diffusion, and recombination. It is revealed that tailoringthe electronic properties of the mixing region by doping with larger-bandgap components could reduce the density of state but elevate the filling state level, leading to improved open-circuit voltage ( V OC ) and reduced recombination. The monomolecular and bimolecular recombinations are shown to be intercorrelated, which show a Gaussian-like relationship with V OC and linear relationship with short-circuit current density ( J SC ) and fill factor (FF). The kinetics of hole transfer and exciton diffusion scale with J SC similarly, indicating the carrier generation in mixing region and crystalline domain are equally important. From the morphology perspective, the crystalline order could contribute to V OC improvement, and the fibrillar structure strongly affects the FF. These observations highlight the importance of the mixing region and its connection with crystalline domains and point out the design rules to optimize the mixing phase structure, which is an effective approach to further improve device performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1971

Chemical evidence relating to the origin of the returned lunar material.

The material returned on the Apollo 11 mission can be separated into four types on chemical as well as structural grounds. Two distinct crystalline rock types can be identified, which may have been formed during two separate magmatic events. The lunar soil and breccias (which are apparently impacted soil material) can be thought of as being composed of a crystalline rock component similar in composition to, but differing in detail from, the two types of Apollo 11 crystalline rocks, and anorthositic component amounting to about 20% in the lunar soil, and a meteoritic component resembling carbonaceous chondrites in composition. Data on Ga, Ge, In, Ir, and Au in Apollo 11 rocks reflect the high temperature history of the lunar surface material, and the presence of a meteoritic component in the soil and breccias.

Baedecker, P. A.↗

NASA NTRS1973

Laboratory and field observations of the growth of columnar and plate crystals from frozen droplets

A laboratory experiment was initiated to grow the banded columnar crystals found in cirrus clouds and to determine if they nucleated through a freezing nucleus. Banded columnar crystals were collected in cirrus clouds and also grown in a laboratory cold box over a temperature range of -20 to -46C. They were observed to grow from a frozen droplet through several distinct crystalline transitions. The first distinct crystalline form observed following the growth of a frozen droplet was a polyhedral crystal. With further growth, the polyhedral crystal developed end plates, and it appeared to be a 'double plate.' Then the separation between the plates nearly filled in to leave the characteristic band. Certain columns (-6 to -10C) and plates (-10 to -20C) were also observed to grow from a frozen droplet and showed similar crystalline transitions.

Heymsfield, A. J.↗

NASA NTRS1977

Apollo 14 revisited, or breccias aren't so bad after all

A study of large Apollo 14 samples suggests that they were formed by the same processes which formed the impactites found at Apollo 16 and 17 and in terrestrial craters, especially those in crystalline targets. The abundant crystalline matrix breccias of the Apollo 14 samples generally show higher clast contents and less refractory clast populations than the clast-laden impact melts abundant at the other Apollo nonmare landing sites. The Apollo 14 characteristics are attributed to the mixing of a greater amount of cold clastic debris into the superheated melt formed during impacts. The other major lithology at Apollo 14, the vitric matrix breccias, are made in part from agglutinate-bearing soil and cannot be the protolith of crystalline matrix breccias, because of differences in structure and composition. Variations among the breccias indicate the occurrence of several impact events.

Simonds, C. H.↗

NASA NTRS1981

The radiolysis and radioracemization of amino acids on silica surfaces

Results are presented of experiments on the radioracemization of amino acids in the presence of silica surfaces such as may have been found on the prebiotic earth. L-leucine and a DL-leucine mixture deposited on samples of 1-quartz and an amorphous silica preparation (Syloid 63) was subjected to Co-60 gamma-ray irradiation, then analyzed by gas chromatography to determine the radiolysis and racemization rates. The quartz surface is found to have a marginal efficacy in enhancing radiolysis when compared with a crystalline L-leucine control, although enhancing radioracemization symmetrically by a factor of two. Both the radiolysis and radioracemization of L-leucine and DL-leucine on a Syloid-63 silica surface are observed to increase with increasing radiation dose, and to be substantially greater than in the crystalline controls. Additional experiments with the nonprotein amino acid isovaline deposited on Syloid 63 confirm the greater radiolysis susceptibility of amino acids deposited on silica with respect to the crystalline state, although racemization is not observed. The observations suggest that the presence of a silica surface would have a deleterious effect on any mechanism for the origin of molecular chirality relying on stereoselective beta-radiolysis.

Bonner, W. A.↗

NASA NTRS1984

Investigation of accelerated stress factors and failure/degradation mechanisms in terrestrial solar cells

Research on the reliability of terrestrial solar cells was performed to identify failure/degradation modes affecting solar cells and to relate these to basic physical, chemical, and metallurgical phenomena. Particular concerns addressed were the reliability attributes of individual single crystalline, polycrystalline, and amorphous thin film silicon cells. Results of subjecting different types of crystalline cells to the Clemson accelerated test schedule are given. Preliminary step stress results on one type of thin film amorphous silicon (a:Si) cell indicated that extraneous degradation modes were introduced above 140 C. Also described is development of measurement procedures which are applicable to the reliability testing of a:Si solar cells as well as an approach to achieving the necessary repeatability of fabricating a simulated a:Si reference cell from crystalline silicon photodiodes.

Lathrop, J. W.↗

NASA NTRS1985

Surface Passivation and Junction Formation Using Low Energy Hydrogen Implants

New applications for high current, low energy hydrogen ion implants on single crystal and polycrystal silicon grain boundaries are discussed. The effects of low energy hydrogen ion beams on crystalline Si surfaces are considered. The effect of these beams on bulk defects in crystalline Si is addressed. Specific applications of H+ implants to crystalline Si processing are discussed. In all of the situations reported on, the hydrogen beams were produced using a high current Kaufman ion source.

Fonash, S. J.↗

NASA NTRS1986

Laboratory studies of the infrared small-particle extinction of amorphous silicates

The broad interstellar IR extinction features located at 9.7 and 18 microns wavelength are believed to originate from silicate dust grains. Cosmic abundances suggest that the silicate should have a chemical composition similar to that of olivine, (Mg,Fe)2 SiO4. Olivine is a very common terrestrial silicate mineral of crystalline structure. However, crystalline olivine grains do not fit the interstellar features well. Based on spectroscopic data obtained in laboratory studies and astronomical observations it was concluded that the interstellar silicate grains consist of a material with amorphous rather than crystalline structure. The astronomical arguments and the results obtained in our laboratory experiments which support this view are reviewed.

Kraetschmer, W.↗

NASA NTRS1986

Determination of solid mass fraction in partially frozen hydrocarbon fuels

Filtration procedures alone are insufficient to determine the amounts of crystalline solid in a partially frozen hydrocarbon distillate fraction. This is due to the nature of the solidification process by which a large amount of liquid becomes entrapped within an interconnected crystalline structure. A technique has been developed to supplement filtration methods with an independent determination of the amount of liquid in the precipitate thereby revealing the actual value of mass percent crystalline solid, %S. A non-crystallizing dye is injected into the fuel and used as a tracer during the filtration. The relative concentrations of the dye in the filtrate and precipitate fractions is subsequently detected by a spectrophotometric comparison. The filtration apparatus was assembled so that the temperature of the sample is recorded immediately above the filter. Also, a second method of calculation has been established which allows significant reduction in test time while retaining acceptable accuracy of results. Data have been obtained for eight different kerosene range hydrocarbon fuels.

Cotterell, E. M.↗

NASA NTRS1985

Preparation and analysis of particulate metal deposits

Small particles and clusters of palladium were grown by deposition from the vapor phase under ultrahigh vacuum conditions. Amorphous and crystalline support films of Al2O3 and ultrathin amorphous carbon films were used as substrate materials. The growth of the metal deposit was monitored in situ by scanning transmission diffraction of energy-filtered 100 kV electrons and high resolution transmission electron microscopy (TEM) analysis was performed in a separate instrument. It was established by in situ TEM, however, that the transfer of specimens in this case did not unduly affect the size and distribution of deposit particles. It was found that the cleanness, stoichiometry, crystallinity and structural perfection of the support surface play an essential role in determining the crystalline perfection and structure of the particles. The smallest palladium clusters reproducibly prepared contained not more than six atoms but size determinations below 1 nm average particle diameter are very problematic with conventional TEM. Palladium particles grown on carbon supports feature an impurity-stabilized mosaic structure.

Poppa, H.↗

NASA NTRS1986

The vapor pressures of solid and liquid ozone

Vapor pressures of solid and liquid ozone have been measured over a temperature range 87 to below 66 K. The experiment was performed under flow conditions, and the gas was analyzed by a precision mass spectrometer system. In the range of solid ozone two forms, supercooled and crystalline ozone, were found. A least-square fit of the data for crystalline ozone resulted in the equation log P(torr) = A + B/T, where A = 10.460 and B = -1021.6. The estimated uncertainty of the data is + or - 1.0 percent. A triple-point temperature of 79.6 + or - 0.3 K was found where supercooled and crystalline ozone data intersect.

Hanson, David↗

NASA NTRS1987

Mechanical properties and morphology of poly(etheretherKetone)

Mechanical properties and morphology of poly(etheretherketone) (PEEK) were studied for samples having different thermal histories. Isothermal and rate-dependent crystallization were studied to ascertain the relationship between crystallinity/morphology and processing condition. Degree of crystallinity and microstructure were controlled by cooling the melt at different rates, ranging from quenching to slowly cooling, and by annealing amorphous material above the glass transition temperature Tg. It is found that degree of crystallinity was not as important as processing history in determining the room temperature mechanical properties. Samples with the same degree of crystallinity had very different tensile properties, depending on rate of cooling from the melt. All samples yielded by shear band formation and necked down. Quenched films had the largest breaking strains, drawing to 270 percent. Slowly cooled films exhibited ductile failure at relatively low strains. Best combined mechanical properties were obtained from semicrystalline films cooled at intermediate rates from the melt.

Cebe, Peggy↗

NASA NTRS1988

A compilation of information and data on the Manson impact structure

A problem for the impact hypothesis for the Cretaceous-Tertiary (K-T) mass extinction is the apparent absence of an identifiable impact site. The Manson Impact Structure is a candidate because it is the largest recognized in the U.S.; it is relatively close to the largest and most abundant shocked quartz grains found at the K-T boundary; and its age is indistinguishable from that of the K-T boundary based on paleontological evidence, fission track dates, and preliminary Ar-40/Ar-39 measurements. The region of northwest central Iowa containing the Manson Impact Structure is covered by Quaternary glacial deposits underlain by Phanerozoic sedimentary rocks (mostly flat-lying carbonates) and Proterozoic red clastic, metamorphic, volcanic, and plutonic rocks. In a circular area about 22 miles (35 km) in diameter around Manson, Iowa, this normal sequence is absent or disturbed and near the center of the disturbed area granitic basement rocks have been uplifted some 20,000 ft (6000m). Attention was drawn to Manson initially by the unusual quality of the groundwater there. Within the structure three roughly concentric zones of rock associations have been identified: (1) displaced strata; (2) completely disrupted strata, and igneous and metamorphic rocks. Manson was established as an impact structure based on its circular shape, its central uplift, and the presence of shocked quartz within the granitic central uplift. A gravity survey identified locations of low-density brecciated rocks and high-density uplifted crystalline rocks, but the outer boundary of the structure could not be established. Aeromagnetic and ground magnetic surveys showed locations and depths of shallowly buried crystalline rock and the locations of faults. A refraction seismic survey identified the crystalline central uplift, determined that the average elevation of bedrock is 70 ft (20 m) higher outside the structure than within, and was used to map the bedrock topography within the structure. A connection between the Manson impact and the K-T boundary may be established or refuted through study of the impact energy, the impact time, and composition of host rock, possible impactors, and impact melts.

Hartung, Jack B.↗

NASA NTRS1990

On diamond, graphitic and amorphous carbons in primitive extraterrestrial solar system materials

Carbon is among the most abundant elements in the universe and carbon chemistry in meteorites and comets is an important key to understanding many Solar System and interstellar processes. Yet, the mineralogical properties and interrelations between various structural forms of elemental carbon remain ambiguous. Crystalline elemental carbons include rhombohedral graphite, hexagonal graphite, cubic diamond, hexagonal diamond (i.e., lonsdaleite or carbon-2H) and chaoite. Elemental carbon also occurs as amorphous carbon and poorly graphitized (or turbostratic) carbon but of all the forms of elemental carbon only graphite is stable under physical conditions that prevail in small Solar System bodies and in the interstellar medium. The recent discovery of cubic diamond in carbonaceous chondrites and hexagonal diamond in chondritic interplanetary dust particles (IDPs) have created a renewed interest in the crystalline elemental carbons that were not formed by shock processes on a parent body. Another technique, Raman spectroscopy, confirms a widespread occurrence of disordered graphite in the Allende carbonaceous chondrite and in chondritic IDPs. Elemental carbons have also been identified by their characteristic K-edge features in electron energy loss spectra (EELS). However, the spectroscopic data do not necessarily coincide with those obtained by selected area electron diffraction (SAED). In order to interpret these data in terms of rational crystalline structures, it may be useful to consider the principles underlying electron diffraction and spectroscopic analyses. Electron diffraction depends on electron scattering, on the type of atom and the distance between atoms in a crystal lattice. Spectroscopic data are a function of the type of atom and the energy of bonds between atoms. Also, SAED is a bulk sampling technique when compared to techniques such as Raman spectroscopy or EELS. Thus, it appears that combined analyses provide contradictory results and that amorphous, or short-range ordered, carbon identified by conventional TEM imaging and SAED may show evidence for sp(3) bonds in EELS spectra. It is suggested that complex, nanometer-scale, mineralogical interrelations are common to all elemental carbons irrespective of their origin. The subsequent thermal history, or energy balance, will determine the ultimate microstructure.

Rietmeijer, Frans J. M.↗

NASA NTRS1992

The study of the thermal behavior of a new semicrystalline polyimide

Thermal properties of a new semicrystalline polyimide synthesized from 3,3',4,4' benzophenone tetracarboxylic dianhydride (BTDA) and 2,2 dimethyl 1,2-(4 aminophenoxy) propane (DMDA) were studied. Heat capacities in the solid and liquid states of BTDA-DMDA were measured. The heat capacity increase at the glass transition temperature (T sub g = 230 C) is 145 J/(C mol) for amorphous BTDA-DMDA. The equilibrium heat of fusion of the BTDA-DMDA crystals was obtained using wide angle X ray diffraction and differential scanning calorimetry measurements, and it is 75.8 kJ/mol. Based on the information of crystallinity and the heat capacity increase at T sub g, a rigid amorphous fraction is identified in semicrystalline BTDA-DMDA samples. The rigid amorphous fraction represents an interfacial region between the crystalline and amorphous states. In particular, this fraction increases with the crystallinity of the sample which should be associated with crystal sizes, and therefore, with crystal morphology. It was also found that this polymer has a high temperature crystal phase upon annealing above its original melting temperature. The thermal degradation activation energies are determined to be 154 and 150 kJ/mol in nitrogen and air, respectively.

Cheng, Stephen Z. D.↗

NASA NTRS1992

Research core drilling in the Manson impact structure, Iowa

The Manson impact structure (MIS) has a diameter of 35 km and is the largest confirmed impact structure in the United States. The MIS has yielded a Ar-40/Ar-39 age of 65.7 Ma on microcline from its central peak, an age that is indistinguishable from the age of the Cretaceous-Tertiary boundary. In the summer of 1991 the Iowa Geological Survey Bureau and U.S. Geological Survey initiated a research core drilling project on the MIS. The first core was beneath 55 m of glacial drift. The core penetrated a 6-m layered sequence of shale and siltstone and 42 m of Cretaceous shale-dominated sedimentary clast breccia. Below this breccia, the core encountered two crystalline rock clast breccia units. The upper unit is 53 m thick, with a glassy matrix displaying various degrees of devitrification. The upper half of this unit is dominated by the glassy matrix, with shock-deformed mineral grains (especially quartz) the most common clast. The glassy-matrix unit grades downward into the basal unit in the core, a crystalline rock breccia with a sandy matrix, the matrix dominated by igneous and metamorphic rock fragments or disaggregated grains from those rocks. The unit is about 45 m thick, and grains display abundant shock deformation features. Preliminary interpretations suggest that the crystalline rock breccias are the transient crater floor, lifted up with the central peak. The sedimentary clast breccia probably represents a postimpact debris flow from the crater rim, and the uppermost layered unit probably represents a large block associated with the flow. The second core (M-2) was drilled near the center of the crater moat in an area where an early crater model suggested the presence of postimpact lake sediments. The core encountered 39 m of sedimentary clast breccia, similar to that in the M-1 core. Beneath the breccia, 120 m of poorly consolidated, mildly deformed, and sheared siltstone, shale, and sandstone was encountered. The basal unit in the core was another sequence of sedimentary clast breccia. The two sedimentary clast units, like the lithologically similar unit in the M-1 core, probably formed as debris flows from the crater rim. The middle, nonbrecciated interval is probably a large, intact block of Upper Cretaceous strata transported from the crater rim with the debris flow. Alternatively, the sequence may represent the elusive postimpact lake sequence.

Anderson, R. R.↗

NASA NTRS1992

Far-infrared spectral studies of phase changes in water ice induced by proton irradiation

Changes in the FIR spectrum of crystalline and amorphous water ice as a function of temperature are reported. The dramatic differences between the spectra of these ices in the FIR are used to examine the effect of proton irradiation on the stability of the crystalline and amorphous ice phases from 13 to 77 K. In particular, the spectra near 13 K show interconversion between the amorphous and crystalline ice phases beginning at doses near 2 eV/molecule and continuing cyclically with increased dose. The results are used to estimate the stability of irradiated ices in astronomical environments.

Moore, Marla H.↗

NASA NTRS1993

Thermal processing of omicron-terphenyl - A Raman study

Raman spectra from omicron-terphenyl sealed in glass capillary tubes were acquired over temperatures ranging from 233 to 343 K. Over this temperature range, omicron-terphenyl can exist in the solid-crystalline, molten, supercooled-liquid, and amorphous-glassy states. Representative structure-sensitive spectra are presented along with a qualitative description. The lattice spectral feature occurring at a Raman shift of 123/cm displays abrupt changes in profile and intensity as melting and glass transition occur. The intensity ratio of the C-C stretching 996/cm line and C-H stretching line at 1008/cm displays a change related to the transformation of the ordered-crystalline phase to the disordered-liquid or glassy state. At a Raman shift of 1162/cm the solid-crystalline state shows a splitting due to the effect of the crystal field. The possibility of using these structure-sensitive Raman characteristics for in situ diagnostics during materials processing is discussed.

Biswas, A.↗