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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,207 records · Page 67
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Electron Detachment as a Probe of Intrinsic Nucleobase Dynamics in Dianion-Nucleobase Clusters: Photoelectron Spectroscopy of the Platinum II Cyanide Dianion Bound to Uracil, Thymine, Cytosine and Adenine

We report the first low-temperature photodetachment photoelectron spectra of isolated gas-phase complexes of the platinum II cyanide dianion bound to nucleobases. These systems are model systems for understanding platinum-complex photodynamic therapies, and knowledge of the intrinsic photodetachment properties is crucial for understanding their broader photophysical properties. Well-resolved, distinct peaks are observed in the spectra consistent with the complexes where the Pt(CN)42- moiety is largely intact. The adiabatic electron detachment energies for the dianion-nucleobase complexes are measured to be between 2.39-2.46 eV. The magnitudes of the repulsive Coulomb barriers of the complexes are estimated to be between 1.9 and 2.1 eV, values that are lower than for the bare Pt(CN)42- dianion as a result of charge solvation by the nucleobases. In addition to the resolved spectral features, broad featureless bands indicative of delayed electron detachment are observed in the 193 nm photodetachment spectra of the four nucleobase-dianion complexes, and also in the 266 nm spectra of the Pt(CN)42-∙thymine and Pt(CN)42-∙adenine complexes. The selective excitation of these features in the 266 nm spectra is attributed to one-photon excitation of [Pt(CN)42-∙T]* and [Pt(CN)42-∙A]* long-lived excited states that can effectively couple to the electron detachment continuum, producing strong electron detachment signals. We attribute the resonant electron detachment bands observed here for Pt(CN)42-∙T and Pt(CN)42-∙A but not for Pt(CN)42-∙U and Pt(CN)42-∙C to fundamental differences in the individual nucleobase photophysics following 266 nm excitation. This indicates that the Pt(CN)42- dianion in the Pt(CN)42-∙M clusters can be viewed as a “dynamic tag” which has the propensity to emit electrons when the attached nucleobase disaplys a long-lived excited state.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2017

ZnO($10\bar 10$) Surface Hydroxylation under Ambient Water Vapor

The interaction of water vapor with a single crystal ZnO($10\bar 10$) surface was investigated using synchrotron-based ambient pressure X-ray photoelectron spectroscopy (APXPS). Two isobaric experiments were performed at 0.3 and 0.07 Torr water vapor pressure at sample temperatures ranging from 750 to 295 K up to a maximum of 2% relative humidity (RH). Below 10–4 % RH the ZnO($10\bar 10$) interface is covered with ~0.25 monolayers of OH groups attributed to dissociation at nonstoichiometric defect sites. At ~10–4 % RH there is a sharp onset in increased surface hydroxylation attributed to reaction at stoichiometric terrace sites. The surface saturates with an OH monolayer ~0.26 nm thick and occurs in the absence of any observable molecularly bound water, suggesting the formation of a 1 × 1 dissociated monolayer structure. This is in stark contrast to ultrahigh vacuum experiments and molecular simulations that show the optimum structure is a 2 × 1 partially dissociated H2O/OH monolayer. The sharp onset to terrace site hydroxylation at ~10–4 % RH for ZnO($10\bar 10$) contrasts with APXPS observations for MgO(100) which show a sharp onset at 10–2 % RH. A surface thermodynamic analysis reveals that this shift to lower RH for ZnO($10\bar 10$) compared to MgO(100) is due to a more favorable Gibbs free energy for terrace site hydroxylation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Aminopolymer Mobility and Support Interactions in Silica-PEI Composites for CO 2 Capture Applications: A Quasielastic Neutron Scattering Study

Composite gas sorbents, formed from an active polymer phase and a porous support, are promising materials for the separation of acid gases from a variety of gas streams. Significant changes in sorption performance (capacity, rate, stability etc.) can be achieved by tuning the properties of the polymer and the nature of interactions between polymer and support. We utilize quasielastic neutron scattering (QENS) and coarse-grained molecular dynamics (MD) simulations to characterize the dynamic behavior of the most commonly reported polymer in such materials, poly(ethylenimine) (PEI), both in bulk form and when supported in a mesoporous silica framework. The polymer chain dynamics (rotational and translational diffusion) are characterized using two neutron backscattering spectrometers that have overlapping time scales, ranging from picoseconds to a few nanoseconds. Two modes of motion are detected for the PEI molecule in QENS. At low energy transfers, a “slow process” on the time scale of ~200 ps is found and attributed to jump-mediated, center-of-mass diffusion. Second, a “fast process” at ~20 ps scale is also found and is attributed to a locally confined, jump-diffusion. Characteristic data (time scale and spectral weight) of these processes are compared to those characterized by MD, and reasonable agreement is found. For the nanopore-confined PEI, we observe a significant reduction in the time scale of polymer motion as compared to the bulk. The impacts of silica surface functionalization and of polymer fill fraction in the silica pores (controlling the portion of polymer molecules in contact with the pore walls), are both studied in detail. Hydrophobic functionalization of the silica leads to an increase of the PEI mobility above that in native silanol-terminated silica, but the dynamics are still slower than those in bulk PEI. Sorbents with faster PEI dynamics are also found to be more efficient for CO 2 capture, possibly because sorption sites are more accessible than those in systems with slower PEI dynamics. Therefore, this work supports the existence of a link between the affinity of the support for PEI and the accessibility of active sorbent functional groups.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Simulating Fluorescence-Detected Two-Dimensional Electronic Spectroscopy of Multichromophoric Systems

Here, we present a theory for modeling fluorescence-detected two-dimensional electronic spectroscopy of multichromophoric systems. The theory is tested by comparison of the predicted spectra of the light-harvesting complex LH2 with experimental data. A qualitative explanation of the strong cross-peaks as compared to conventional two-dimensional electronic spectra is given. The strong cross-peaks are attributed to the clean ground-state signal that is revealed when the annihilation of exciton pairs created on the same LH2 complex cancels oppositely signed signals from the doubly excited state. This annihilation process occurs much faster than the nonradiative relaxation. Furthermore, the line shape difference is attributed to slow dynamics, exciton delocalization within the bands, and intraband exciton–exciton annihilation. This is in line with existing theories presented for model systems. We further propose the use of time-resolved fluorescence-detected two-dimensional spectroscopy to study state-resolved exciton–exciton annihilation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Resonance Raman Study of Shell Morphology in InP/ZnSe/ZnS Core/Shell/Shell Nanocrystals

Resonance Raman spectra and absolute cross sections of InP/ZnSe/ZnS core/shell/shell nanocrystals have been obtained at excitation wavelengths of 501.7, 457.9, and 410 nm. Eight different structures having nearly the same lowest excitonic absorption wavelength but significantly different stoichiometries are compared. The Raman spectra show phonon features attributable to both the InP core and the ZnSe shell. The largest differences among the structures are seen in the ZnSe phonon region by using excitation at 457.9 nm, on the low-energy edge of the absorption features having significant contributions from the ZnSe shell. Here, structures that are nearly stoichiometric (In:P ratio ≈1.0) show a sharp, strongly polarized peak near the bulk ZnSe phonon frequency (~250 cm –1 ) and a weak lower-frequency shoulder with a higher depolarization ratio. Structures having excess indium show a stronger low-frequency shoulder near 225 cm –1 and lower integrated Raman intensities throughout the ZnSe phonon region. These changes are attributed to the presence of indium atoms in the ZnSe shell. Furthermore, these results support a previous assignment of a slow rise component in the time-resolved photoluminescence spectra of nonstoichiometric structures to transient trapping of holes at indium defects in the shell.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Heavy Versus Light Lanthanide Selectivity for Graphene Oxide Films is Concentration Dependent

Rare earths are important materials in various technologies such as catalysis and optoelectronics. Graphene oxide (GO) is a promising material for separation applications, including the isolation of lanthanides from complex mixtures. Previous works using fatty acid monolayers have demonstrated preferential heavy versus light lanthanide adsorption, which has been attributed to differences in lanthanide ion size. In this work, we used interfacial X-ray fluorescence measurements to reveal that GO thin films at the air/water interface have no lanthanide selectivity for dilute subphases. However, at high subphase concentrations, ~8 times more Lu is adsorbed than La. By comparing the GO results with an ideal monolayer with a carboxylic acid headgroup, arachidic acid (AA), we demonstrate that the number of Lu ions adsorbed to GO is significantly higher than the number expected to compensate for the surface charge. Vibrational sum frequency generation (SFG) spectroscopy results on both GO thin films and AA monolayers reveal a red-shifted SFG signal in the OH region, which we attribute to partial dehydration of the adsorbed ions and carboxylic acid headgroups. Liquid surface X-ray reflectivity data show that the GO thin film structure does not significantly change between the very dilute and concentrated subphases. We speculate that the functional groups of both GO and AA facilitate cation dehydration, which is essential for ion adsorption. Heavy lanthanide Lu has stronger ion–ion correlations that can overcome the electrostatic repulsion between cations at higher concentrations compared to light lanthanide La, meaning GO and AA can exhibit apparent overcharge with Lu. Lastly, the layered structure of the GO films and reactive chemical nature of GO itself can accommodate ion adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

X-ray Photoelectron Spectroscopy Analysis of Nafion-Containing Samples: Pitfalls, Protocols, and Perceptions of Physicochemical Properties

X-ray photoelectron spectroscopy (XPS) is one of the most common techniques used to analyze the surface composition of catalysts and support materials used in polymer electrolyte membrane (PEM) fuel cells and electrolyzers, providing important insights for further improvement of their properties. Characterization of catalyst layers (CLs) is more challenging, which can be at least partially attributed to the instability of ionomer materials such as Nafion during measurements. This work explores the stability of Nafion during XPS measurements, illuminating and addressing Nafion degradation concerns. The extent of Nafion damage as a function of XPS instrumentation, measurement conditions, and sample properties was evaluated across multiple instruments. Results revealed that significant Nafion damage to the ion-conducting sulfonic acid species (>50% loss in sulfur signal) may occur in a relatively short time frame (tens of minutes) depending on the exact nature of the sample and XPS instrument. This motivated the development and validation of a multipoint XPS data acquisition protocol that minimizes Nafion damage, resulting in reliable data acquisition by avoiding significant artifacts from Nafion instability. The developed protocol was then used to analyze both thin film ionomer samples and Pt/C-based CLs. Comparison of PEM fuel cell CLs to Nafion thin films revealed several changes in Nafion spectral features attributed to charge transfer due to interaction with conductive catalyst and support species. This study provides a method to reliably characterize ionomer-containing samples, facilitating fundamental studies of the catalyst-ionomer interface and more applied investigations of structure-processing-performance correlations in PEM fuel cell and electrolyzer CLs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Resistance of Boron Nitride Nanotubes to Radiation-Induced Oxidation

We present unprecedented results on the damage thresholds and pathways for boron nitride nanotubes (BNNT) under the influence of energetic electrons in an oxidative gas environment, using an environmental aberration-corrected electron microscope over a range of oxygen pressures. We observe a damage cascade process that resists damage until a higher electron dose, compared with carbon nanotubes, initiating at defect-free BNNT sidewalls and proceeding through the conversion from crystalline nanotubes to amorphous boron nitride (BN), resisting oxidation throughout. We compare with prior results on the oxidation of carbon nanotubes and present a model that attributes the onset of damage in both cases to a physisorbed oxygen layer that reduces the threshold for damage onset. Surprisingly, increased temperatures offer protection against damage, as do electron dose rates that significantly exceed the oxygen dose rates, and our model attributes both effects to a physisorbed oxygen population.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Effect of Cation Rotation on Charge Dynamics in Hybrid Lead Halide Perovskites

Organic-inorganic hybrid halide perovskites are a promising class of materials for photovoltaic application with reported power efficiencies over similar to 22%. However, not much is known about the influence of the organic dipole rotation and phase transitions on charge carrier dynamics. Here, we report substantial changes in mobility and lifetime of charge carriers in CH 3 NH 3 PbI 3 after the low-temperature tetragonal (beta) to orthorhombic (gamma) phase transition. By using microwave conductivity measurements, we observed that the mobility and lifetime of ionized charge carriers increase as the temperature decreases and a sudden increment is seen after the beta-gamma phase transition. For CH 3 NH 3 PbI 3 , the mobility and the half-lifetime increase by a factor of 36 compared with the values before the beta-gamma phase transition. We attribute the considerable change in the dynamics at low temperature to the decrease of the inherent dynamic disorder of the organic cation (CH 3 NH 3+ ) inside the perovskite crystal structure.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Ultrafast excited-state dynamics in shape- and composition-controlled gold–silver bimetallic nanostructures

In this paper, we have examined the ultrafast dynamics of shape- and composition-controlled bimetallic Au/Ag core/shell nanostructures with transient absorption spectroscopy (TAS) as a function of Ag layer thickness (0–15 nm) and pump excitation fluence (50–500 nJ/pulse). Our synthesis approach generated both bimetallic nanocubes and nanopyramids with distinct dipolar plasmon resonances and plasmon dephasing behavior at the resonance. Lifetimes obtained from TAS at low powers (50 nJ/pulse) demonstrated minimal dependence on the Ag layer thickness, whereas at high power (500 nJ/pulse) a rise in electron–phonon coupling lifetime (τ 1 ) was observed with increasing Ag shell thickness for both nanocubes and nanopyramids. This is attributable to the stronger absorption of the 400 nm pump pulse with higher Ag content, which induced higher electron temperatures. The phonon–phonon scattering lifetime (τ 2 ) also rises with increasing Ag layer, contributed both by the increasing size of the Au/Ag nanostructures as well as by surface chemistry effects. Further, we observed that even the thinnest, 2 nm, Ag shell strongly impacts both τ 1 and τ 2 at high power despite minimal change in overall size, indicating that the nanostructure composition also strongly impacts the thermalization temperature following absorption of 400 nm light. We also observed a shape-dependent trend at high power, where τ 2 increased for the nanopyramids with increasing Ag shell thickness and nanostructure size, but bimetallic nanocubes demonstrated an unexpected decrease in τ 2 for the thickest, 15 nm, Ag shell. This was attributed to the larger number of corners and edges in the nanocubes relative to the nanopyramids.

36 MATERIALS SCIENCE↗
DOE OSTI2020

The Role of Exciton Binding Energy on LO phonon Broadening and Polaron Formation in (BA) 2 PbI 4 Ruddlesden-Popper Films

The effect of carrier–carrier and carrier–phonon interactions is presented in n = 1 (2D) (BA) 2 PbI 4 Ruddlesden–Popper thin films, and their effect is compared to that of conventional MAPbI 3 . While temperature-dependent photoluminescence shows the well-studied structural phase transitions and evidence of longitudinal optical (LO) phonon scattering in MPbI 3 , the 2D (BA) 2 PbI 4 films produce subtler properties. At low temperatures, evidence of two competing intrinsic exciton transitions is observed (P1 and P3), in addition to several extrinsic transitions attributed to the impurities in the (BA) 2 PbI 4 film. At higher temperatures, (BA) 2 PbI 4 is dominated by the two intrinsic excitons that are attributed to varying degrees of localization caused by deformations of the PbI 4 framework mediated by structural relaxation. Although both exciton complexes are well separated from the continuum (490 meV or greater), their interaction with phonons is quite different. In the case of the more strongly bound complex (P3), the strong excitonic nature and short-range interaction are mediated by the emission of LO phonon replicas. In the case of the exciton with the smaller binding energy (P1), the more extended wavefunction manifests itself in strong carrier–phonon scattering and evidence of large, stable polarons.

2D perovskites↗
DOE OSTI2020

Understanding and Controlling the Performance-Limiting Steps of Catalyst-Modified Semiconductors

Understanding and controlling factors that restrict the rates of fuel-forming reactions are essential to designing effective catalyst-modified semiconductors for applications in solar-to-fuel technologies. Herein, we describe GaAs semiconductors featuring a polymeric coating that contains cobaloxime-type catalysts for photoelectrochemically powering hydrogen production. The activities of these electrodes (limiting current densities >20 mA cm –2 under 1-sun illumination) enable identification of fundamental performance-limiting bottlenecks encountered at relatively high rates of fuel formation. Experiments conducted under varying bias potential, pH, illumination intensity, and scan rate reveal two distinct mechanisms of photoelectrochemical hydrogen production. At relatively low polarization and pH, the limiting photoactivity is independent of illumination conditions and is attributed to a mechanism involving reduction of substrate protons. At relatively high polarization or pH, the limiting photoactivity shows a linear response to increasing photon flux and is attributed to a mechanism involving reduction of substrate water. Furthermore, this work illustrates the complex interplay between transport of photons, electrons, and chemical substrates in photoelectrosynthetic reactions and highlights diagnostic tools for better understanding these processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Effect of tert -Butyl Substitution on the Interactions of Cobalt Phthalocyanine with a Carbon Monoxide-Functionalized Tip

Supported cobalt phthalocyanines (CoPc) are promising catalysts for CO 2 reduction, a critical process for mitigating greenhouse gas emissions. Enhancing the catalytic performance of CoPc involves modifying the interaction between the cobalt center and intermediate species. This study focuses on the effects of tert-butyl substitution on CoPc using (tert-butyl) 4 CoPc, where the substitution can both directly alter the molecule’s intramolecular electronic structure and indirectly alter it by the bulky group weakening the interaction with the support. Toward this end, we investigated the structural and chemical properties of (tert-butyl) 4 CoPc on a Ag(111) surface at the single-molecule level using three-dimensional atomic force microscopy (AFM) with a CO-terminated tip and discussed them in comparison with data for unmodified CoPc and amino-substituted CoPc. Notably, distance-dependent force measurements revealed anomalies in the tert-butyl groups’ force curves, attributed to their rotational flexibility. The tert-butyl (t-butyl) groups were also observed to increase the attraction of the central Co atom to CO, but this effect was attributed largely to enhanced interactions of the back of the tip with the peripheral t-butyl groups. In conclusion, while this longer-range interaction would not be expected to impact the interaction of small molecules with the catalytic center, the results reveal the ability of AFM to characterize longer range environmental interactions that can enhance adsorption and subsequent reactions of larger molecules, as well as the role side chains that offer configurational adaptability may play in these interactions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

INBOUND APPOINTEE PUBLICATION Importance of Substrate-Particle Repulsion for Protein-Templated Assembly of Metal Nanoparticles

We study the protein-directed assembly of colloidal gold nanoparticles on de novo designed protein nanofiber templates. Using sequential assembly on glass substrates, we attach of positively-charged gold nanoparticles to protein nanofibers engineered to have a high density of negatively-charged surface residues. Using a combination of electron and optical microscopy, we measure the density of particle attachment and characterize binding specificity. By varying nanoparticle size and pH of the solution, we explore the importance of charge-dependent particle-fiber and particle-substrate interactions. We find an inverse correlation between particle size and attachment density to the protein nanofibers, attributed to the balance between size-dependent electrostatic particle-fiber attraction and particle-substrate repulsion. We show pH-dependent particle attachment density and binding specificity in relation to the protonation fraction of each assembly layer. Finally, we employ hyperspectral scattering microscopy to draw conclusions about particle density and interparticle spacings of optically-observable particle assemblies.

Guye, Kathryn N.↗
DOE OSTI2024

Self-Assembled Bolaamphiphile-Based Organic Nanotubes as Efficient Cu(II) Ion Adsorbents

Self-assembled organic nanotubes (ONTs) have been actively examined for various applications such as chemical separations and catalysis owing to their well-defined tubular nanostructures with distinct chemical environments at the wall and internal/external surfaces. Adsorption of heavy metal ions onto ONTs plays an essential role in many of these applications, but it has rarely been assessed quantitatively. Herein, we investigated interactions between Cu 2+ and single-/quadruple-wall bolaamphiphile-based ONTs having inner carboxyl groups with different inner diameters, COOH-ONT 10nm and COOH-ONT 20nm . We first examined the effects of Cu 2+ on their nanotubular structures using SAXS, STEM, and AFM. COOH-ONT 10nm was stable in aqueous Cu 2+ solution in contrast to COOH-ONT 20nm owing to the presence of polyglycine-II-type hydrogen bonding networks within its wall. Subsequently, we studied the Cu 2+ adsorption behavior of COOH-ONT 10nm by monitoring the concentration of unbound Cu 2+ using linear sweep anodic stripping voltammetry. The Cu 2+ adsorption was quick, attributable to efficient Cu 2+ partitioning through the open ends of the ONT, followed by fast Cu 2+ diffusion in the uniform, relatively large nanochannel. More importantly, the Cu 2+ adsorption capacity and affinity of COOH-ONT 10nm were measured at different pH using the Langmuir adsorption model. The adsorption capacity was similar at the pH range examined, showing the participation of approximately 25% of the inner carboxyl groups in the adsorption. The adsorption affinity increased with pH, indicating the essential role of the deprotonated carboxyl groups in the Cu 2+ adsorption. Most interestingly, the Langmuir adsorption constant was significantly higher than those of previously reported synthetic adsorbents and planar monolayer based on carboxyl binding sites. The high Cu 2+ affinity of the ONT was attributable to the highly dense binding sites on the well-defined nanoscale concave structure of the inner channel. Furthermore, these results provide a valuable guideline to designing self-assembled nanomaterials for efficient chemical separations, detection, and catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Surface Interactions and Confinement of Methane: A High Pressure Magic Angle Spinning NMR and Computational Chemistry Study

Characterization and modeling of the molecular-level behavior of simple hydrocarbon gases, such as methane, in the presence of both nonporous and nano-porous mineral matrices allows for predictive understanding of important processes in engineered and natural systems. In this study, changes in local electromagnetic environments of the carbon atoms in methane under conditions of high pressure (up to 130 bar) and moderate temperature (up to 346 K) were observed with 13C magic-angle spinning (MAS) NMR spectroscopy while the methane gas was mixed with two model solid substrates: a fumed non-porous, 12 nm particle size silica and a mesoporous silica with 200 nm particle size and 4 nm average pore diameter. Examination of the interactions between methane and the silica systems over temperatures and pressures that include the supercritical regime was allowed by a novel high pressure MAS sample containment system, which provided high resolution spectra collected under in situ conditions. For pure methane, no significant thermal effects were found for the observed 13C chemical shifts at all pressures studied here (28.2 bar, 32.6 bar, 56.4 bar, 65.1 bar, 112.7 bar, and 130.3 bar). However, the 13C chemical shifts of resonances arising from confined methane changed slightly with changes in temperature in mixtures with mesoporous silica. The chemical shift values of 13C nuclides in methane change measurably as a function of pressure both in the pure state and in mixtures with both silica matrices, with a more pronounced shift when meso-porous silica is present. Molecular-level simulations utilizing GCMC, MD and DFT confirm qualitatively that the experimentally measured changes are attributed to interactions of methane with the hydroxylated silica surfaces as well as densification of methane within nanopores and on pore surfaces.

confinement↗
DOE OSTI2018

Crystallization Modes of Poly(3-dodecylthiophene)-Based Block Copolymers Depend on Regioregularity and Morphology

Conjugated block copolymers (BCPs) can self-assemble into highly ordered nanostructures in a melt state. Yet, when cooled below the melting temperature, crystal growth can disrupt the self-assembled structure and produce a poorly ordered fibrillar texture. We determine that crystallization modes of conjugated BCPs based on poly(3-dodecylthiophene) (P3DDT) and poly(2-vinylpyridine) (P2VP) can be tuned through P3DDT regioregularity (RR), as this attribute controls the melting temperature and crystallization rates of P3DDT. When RR is low (7080%), crystallization is observed at temperatures near or below the glass transition of P2VP, so crystal growth is largely confined by the glassy cylindrical or lamellar BCP structure. When RR is high (94%), crystallization occurs at 40 K above the glass transition of P2VP, so there is no longer a restriction of glassy domains. Importantly, crystal growth remains confined by the rubbery P2VP lamellae, but breaks through the rubbery P2VP cylinders. This morphology-dependent behavior is attributed to geometric compatibility of P3DDT crystal growth and the self-assembled symmetry. In a lamellar phase, the P3DDT chain orientations at the P3DDT- block -P2VP interface are compatible with crystal growth, and both the alkyl-stacking and $\pi\pi$ growth directions are unrestricted within a lamellar sheet. In a cylindrical phase, the radial orientation of P3DDT chains at the P3DDT- block -P2VP interface is not compatible with crystal growth, and the hexagonal close-packed symmetry only allows for one direction of unrestricted crystal growth. Significantly, these studies demonstrate that tuning RR of polyalkylthiophenes can open up multiple crystallization modes with the same monomer chemistries and block lengths, thereby decoupling the parameters that govern classical BCP self-assembly and crystal growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

High Photoluminescence Quantum Yield in Band Gap Tunable Bromide Containing Mixed Halide Perovskites

Hybrid organic-inorganic halide perovskite based semiconductor materials are attractive for use in a wide range of optoelectronic devices because they combine the advantages of suitable optoelectronic attributes and simultaneously low-cost solution processability. Here, we present a two-step low-pressure vapor-assisted solution process to grow high quality homogeneous CH 3 NH 3 PbI 3-x Br x perovskite films over the full band gap range of 1.6-2.3 eV. Photoluminescence light-in versus light-out characterization techniques are used to provide new insights into the optoelectronic properties of Br-containing hybrid organic-inorganic perovskites as a function of optical carrier injection by employing pump-powers over a 6 orders of magnitude dynamic range. The internal luminescence quantum yield of wide band gap perovskites reaches impressive values up to 30%. This high quantum yield translates into substantial quasi-Fermi level splitting and high "luminescence or optically implied" open-circuit voltage. Most importantly, both attributes, high internal quantum yield and high optically implied open-circuit voltage, are demonstrated over the entire band gap range (1.6 eV ≤ E g ≤ 2.3 eV). These results establish the versatility of Br-containing perovskite semiconductors for a variety of applications and especially for the use as high-quality top cell in tandem photovoltaic devices in combination with industry dominant Si bottom cells. (Figure Presented).

36 MATERIALS SCIENCE↗