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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 163 records · Page 9

Measurement of Poly-Si Film Thickness on Textured Surfaces by X-Ray Diffraction in Poly-Si/SiOx Passivating Contacts for Monocrystalline Si Solar Cells

Polycrystalline Silicon on tunneling silicon oxide (poly-Si/SiOx) passivating contacts have shown great potential for the next-generation monocrystalline Si (c-Si) industrial photovoltaic technology. However, these cells typically suffer from strong parasitic absorption in the thick front poly-Si layer, which is designed to reduce metal-induced recombination. In previous work, we demonstrated an improved short-circuit current density, Jsc, by thinning the front poly-Si film in an SF6 plasma using the front metal grids as a self-aligned mask, but the sub - 100 nm thick poly-Si film is difficult to measure on an alkaline textured surface. Conventional optical techniques such as spectroscopic ellipsometry cannot be used due to the high scattering nature of the random pyramids. At poly-Si thicknesses below 50 nm, secondary electron microscopy (SEM) has difficulty distinguishing the poly-Si from the underlying c-Si substrate. Here, we demonstrate X-ray diffraction as an effective method to quantitatively measure the front poly-Si thickness. The thickness calculated from the diffraction peak height of the Si(111) crystallographic plane agrees well with the cross-section SEM analysis and simulations using SunSolve. We show that by thinning the front poly-Si from 200 to 60 nm, Jsc increased by 2.4 mA/cm2, while maintaining the same Voc. This led to an absolute efficiency gain of 1.73%. In addition, we also discuss possible reasons for the premature loss of passivation before the removal of all poly-Si, which prevented an even higher gain in Jsc.

light/electron beam induced current↗

Short-Range Order Tunes Optical Properties in Long-Range Disordered ZnSnN2-ZnO Alloy

Local site ordering offers a new paradigm for property control in functional materials. However, systems that exhibit a propensity for local order and global disorder are often challenging to characterize, and demonstrations of ordering-induced property tuning are few and far between. Here, we demonstrate that short-range ordering tunes the optical absorption edge in the long-range disordered alloy system (ZnSnN2)1-x(ZnO)2x at x = 0.25. We use combinatorial cosputtering to synthesize a set of thin-film samples spanning this alloy space. X-ray diffraction demonstrates lattice contraction as a function of alloy composition, confirming that a mixed-anion and -cation alloy has been synthesized. Using N and O K-edge X-ray absorption near-edge structure in conjunction with simulations of cation-disordered supercell structures, we find that samples exhibit octet-rule-breaking motifs around both anions. Upon annealing at an alloy composition of x = 0.25, X-ray absorption analysis suggests that local motif structure shifts toward octet-rule-conserving while long-range disorder is maintained. Spectroscopic ellipsometry reveals that local ordering increases the absorption edge energy at constant composition. Additionally, alloy-induced optical absorption edge tuning is demonstrated. This work paves the way toward property tuning with short-range ordering in (ZnSnN2)1-x(ZnO)2x and beyond.

36 MATERIALS SCIENCE↗

Site-Selective Atomic Layer Deposition at Thermally Generated Surface Oxygen Vacancies on Rutile TiO 2

Unique atomic arrangements (i.e., defects) on material surfaces may exhibit distinctive reactivity that affords opportunities for selective surface chemistry exclusively at those sites. While theoretically appealing, site-selective atomic layer deposition (ALD) processes remain largely unrealized experimentally. Here we provide evidence for site-selective ALD that exclusively targets oxygen vacancies thermally generated at the surface of TiO 2 single crystals. High-resolution in situ ellipsometry reveals the nucleation behavior of dimethylaluminum isopropoxide (DMAI) and water at process conditions precisely tuned for selective hydroxylation of surface defects. An island growth model for nucleation and atomic force microscopy (AFM) imaging are consistent with a site-selective growth mechanism that depends on the surface oxygen vacancy density. This approach to direct ALD reactions at defective surface sites may provide future opportunities for targeted remediation of electronically imperfect interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Generic Behavior of Ultrastability and Anisotropic Molecular Packing in Codeposited Organic Semiconductor Glass Mixtures

Vapor-deposited glass mixtures of organic semiconductors commonly serve as active layers in organic electronic devices, whose lifetime and performance are strongly influenced by the stability and structure of these mixed glasses. Here, we study the stability and anisotropic molecular packing of six co-deposited organic semiconductor glass mixtures with 50:50 weight ratio, by differential scanning calorimetry and spectroscopic ellipsometry. We also find that all six binary systems exhibit high kinetic stability and significantly reduced enthalpy relative to the corresponding liquid-cooled glassy mixtures (ultrastable behavior), even for systems where the glass transition temperatures of the components differ by more than 90 K. Furthermore, we demonstrate that the birefringence of a co-deposited glass mixture, a measure of its anisotropic packing, can be predicted from the birefringence of glasses of the two pure components. These results for stability and structure are expected to be applicable to other co-deposited organic semiconductor glass mixtures, so long as the two components mix well in the glass and individually can form ultrastable glasses. Therefore, our findings are significant for designing novel electronic devices with enhanced device lifetime and increased operational efficiency.

36 MATERIALS SCIENCE↗

Tailoring the Interfacial Interactions of Porous Polymer Membranes to Accelerate Atomic Layer Deposition: The Latent Path to Antifouling Membranes

Atomic layer deposition (ALD) is a powerful strategy to engineer hybrid organic-inorganic membranes with emergent functionalities. The combination of atomic-level thickness control, a wide materials palette, and unprecedented conformality allows the physiochemical properties (e.g., hydrophilicity) of mesoporous polymer membranes to be precisely tuned. The nucleation of ALD material growth on polymer surfaces relies on Lewis acid-base interactions and remains an overlooked motif with tremendous potential to accelerate ALD nucleation and growth. Strategies to enhance these interactions could enable desirable properties such as antifouling behavior to be imparted on inert polymer surfaces that lack the necessary functional groups for ALD nucleation. Here, in this study, we demonstrate that the reactivity of polyacrylonitrile (PAN) membranes toward ALD metal oxide (MO) precursors with Lewis acid characteristics is enhanced by introducing strong Lewis base functional groups (amidoxime: Am) on the PAN backbone (Am-PAN). The resulting Lewis acid-base interactions accelerate the MO nucleation in Am-PAN and reduce the number of deposition cycles required to achieve hydrophilicity compared with the untreated PAN membrane. Unveiling the reaction mechanism, in situ Fourier transform infrared (FTIR) spectroscopy measurements established enhanced interaction dynamics between the ALD MO precursors and the Am-PAN membrane, unlike the PAN membrane. Spectroscopic ellipsometry and thermogravimetric analysis measurements revealed higher MO loadings in Am-PAN membranes compared to PAN membranes for the same number of ALD cycles. We found that strong Lewis acid-base interactions accelerated the ALD for a range of materials including Al 2 O 3 , TiO 2 , SnO 2 , and ZnO. More broadly, our work demonstrates that tailoring metal-precursor-polymer interactions is a powerful strategy to accelerate and modulate the ALD. We used this design strategy to fabricate Al 2 O 3 -Am-PAN hybrid membranes that showed 2-fold higher antifouling capability compared to pristine PAN membranes prepared with an equivalent number of Al 2 O 3 ALD cycles. Our approach expands the scope of design options for fouling-resistant porous hybrid inorganic-organic membranes and may ultimately reduce the operational costs of water treatment.

36 MATERIALS SCIENCE↗

Sequential Infiltration Synthesis of Multinary Metal Oxides: The Role of Precursor Diffusion and Reactivity

Understanding volatile metal–organic precursor transport in polymer matrices during sequential infiltration synthesis (SIS) is critical to the design of hybrid materials of tailored composition and uniform structure. Here, we investigate the diffusion and reaction behavior of diethylzinc (DEZ) in poly(methyl methacrylate) (PMMA) matrices with variable indium and zinc incorporation. Unlike conventional SIS where precursors adduct or react directly with the polymer backbone, DEZ shows minimal interaction with PMMA. However, DEZ may interact strongly with In–OH or Zn–OH moieties that are previously incorporated into a PMMA thick film. Using spectroscopic ellipsometry, X-ray photoelectron spectroscopy depth profiling, and EDX line scans, we quantify Zn incorporation as a function of exposure time, polymer thickness, and previous infiltration steps. The Zn distribution evolves from surface-localized to deep within the ∼1 μm thick film with increasing DEZ exposures up to 30 min. A reaction-diffusion model incorporating a hindering factor to capture diffusivity decay due to product accumulation reproduces the Zn depth profile and yields physically meaningful parameters to guide future growth. Furthermore, this study provides a framework for interpreting metal–organic precursor infiltration behavior and highlights the utility of model-guided SIS process design.

diethylzinc↗

Sequential Infiltration Synthesis of Electronic Materials: Group 13 Oxides via Metal Alkyl Precursors

The sequential infiltration synthesis (SIS) of group 13 indium and gallium oxides (In 2 O 3 and Ga 2 O 3 ) into poly(methyl methacrylate) (PMMA) thin films is demonstrated using trimethylindium (TMIn) and trimethylgallium (TMGa), respectively, with water. In situ Fourier transform infrared (FTIR) spectroscopy reveals that these metal alkyl precursors reversibly associate with the carbonyl groups of PMMA in analogy to trimethylaluminum (TMAl), however, with significantly lower affinity. This is demonstrated to have important kinetic consequences that dramatically alter the synthetic parameters required to achieve material growth. Ab initio density functional theory simulations of the methyl methacrylate monomer with group 13 metal alkyls corroborate association energy that is 3X greater for TMAl than for either TMIn or TMGa. As a consequence, the kinetics of activated diffusion within the film is observed to be far more rapid for TMIn and TMGa than for TMAI. Spectroscopic ellipsometry and scanning electron microscopy, in combination with Hall effect measurements of SIS-derived In 2 O 3 films, demonstrate that SIS enables rapid growth of thin films with continuous electrically conductive pathways after postannealing. Notably, SIS with TMIn and water enables the growth of In 2 O 3 at 80°C, well below the onset temperature of atomic layer deposition (ALD) using these precursors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Orientation for Vapor-Deposited Organic Glasses Follows Rate-Temperature Superposition: The Case of Posaconazole

The anisotropic properties of organic glasses produced by physical vapor deposition (PVD) depend upon substrate temperature and deposition rate. In recent work, it was shown for a liquid crystalline system that the anisotropic structure of the glass was controlled by a single combined variable as indicated by the observation of deposition rate-substrate temperature superposition (RTS). Here we test the utility of RTS for posaconazole, a molecule that does not form liquid crystals. We prepare glasses of posaconazole utilizing a range of deposition rates covering 2 orders of magnitude and an 18 K range in substrate temperature. We characterize the glasses using ellipsometry and X-ray scattering. Consistent with RTS, we find that decreasing the deposition rate has the same effect upon molecular orientation as increasing the substrate temperature during deposition. Thus, RTS can be used to predict and control the structure of glasses prepared at a wide range of deposition conditions. We use RTS to infer a characteristic time for molecular reorientation at the surface of posaconazole.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantifying Charge Carrier Localization in PBTTT Using Thermoelectric and Spectroscopic Techniques

Chemically doped poly[2,5-bis(3-alkylthiophen-2-yl)thieno[3,2- b ]thiophene] (PBTTT) shows promise for many organic electronic applications, but rationalizing its charge transport properties is challenging because conjugated polymers are inhomogeneous, with convoluted optical and solid-state transport properties. Herein, we use the semilocalized transport (SLoT) model to quantify how the charge transport properties of PBTTT change as a function of iron(III) chloride (FeCl 3 ) doping level. We use the SLoT model to calculate fundamental transport parameters, including the carrier density needed for metal-like electrical conductivities and the position of the Fermi energy level with respect to the transport edge. We then contextualize these parameters with other polymer-dopant systems and previous PBTTT reports. Additionally, we use grazing incidence wide-angle X-ray scattering and spectroscopic ellipsometry techniques to better characterize inhomogeneity in PBTTT. Our analyses indicate that PBTTT obtains high electrical conductivities due to its quickly rising reduced Fermi energy level, and this rise is afforded by its locally high carrier densities in highly ordered microdomains. Ultimately, this report sets a benchmark for comparing transport properties across polymer-dopant-processing systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modular Assembly of FTO|Chromophore-Catalyst Hierarchical Films Based on Strong Dipole Interactions

Here, we have designed and characterized modular self-assembled hierarchical films containing a molecular catalyst tethered to an anchoring molecule by means of dipole-induced dipole interactions. In order to do so, two new Co III -based molecular catalyst candidates were designed, namely, [Co III L 1 (pyrr) 2 ]ClO 4 (Co1) and [Co III L 2 (pyrr) 2 ]ClO 4 (Co2), where L 1 and L 2 are the respective deprotonated forms of N,N′-[4,5-bis(dodecyloxy)-1,2-phenylene]dipicolinamide and N,N′-[4,5-bis(methoxyethoxy)-1,2-phenylene]dipicolinamide and were characterized by electrochemical, electronic, and film formation properties. Species Co1 and Co2 were deposited onto an anchor molecule such as octylphosphonic acid (OPA) or the chromophoric [Ru II (bpy PO3H ) 2 (bpy C7 )]Cl 2 (Ru) previously attached onto conductive fluorine-doped tin oxide (FTO). Four hierarchical films of the form substrate|anchor-catalyst were obtained, namely, FTO|OPA-Co1, FTO|OPA-Co2, FTO|Ru-Co1, and FTO|Ru-Co2, and the role of dipole-dipole interactions between anchor and catalyst modules was assessed. These newly synthesized hierarchical films were characterized by a host of surface-specific methods that include X-ray photoelectron spectroscopy, ellipsometry, X-ray fluorescence, and water contact angle, thus enabling an unprecedented level of analysis. Compared to the weak C-H van der Waals interactions exhibited by Co1, the presence of alkoxy chains in Co2 ensures stronger dipole-dipole interactions with the alkyl chain of the anchors due to O···H formation. The persistence of their redox properties, which include metal oxidation, and directionality of electron transport were probed suggesting direct relevance to catalytic processes such as water oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Super-Resolved Single-Molecule Tracking Studies of Rhodamine B Accumulation on Fresh and Aged Polyethylene Terephthalate

It is well-known that toxic organic micropollutants (OMs) accumulate on the surfaces of microplastics. However, much remains to be learned about the exact molecular level mechanisms of OM accumulation and how these evolve as the plastics age. In this work, super-resolved single-molecule tracking (SMT) is used for the first time to investigate the accumulation of Rhodamine B (RhB) dye on fresh and artificially aged polyethylene terephthalate (PET) surfaces. PET thin films serve as models for microplastics, while RhB serves as a proxy for the OMs they accumulate. Artificial aging of the films is accomplished by exposing them in a UV-ozone chamber. Water contact angle, spectroscopic ellipsometry, and carbonyl index measurements reveal a gradual decrease in film hydrophobicity, thickness, and carbonyl content with age. Atomic force microscopy (AFM) data reveal an increase in surface roughness and confirm that the films remain largely intact and continuous across the aging times explored. In SMT experiments, wide-field fluorescence videos acquired from the water/PET interface under 7.5 pM RhB reveal both mobile and immobile dye molecules. Measurements of the frame-to-frame displacements of the dye show that diffusion occurs by a desorption-mediated mechanism and that the diffusion rate varies with PET film age. The surface density of mobile dye molecules decreases with increasing PET age, while the population of immobile molecules becomes relatively larger, suggesting an age-dependent transformation of the mechanism(s) by which the dye is accumulated. SMT data reveal that both mobile and immobile molecules repeatedly adsorb over the same surface sites, consistent with the emergence of nanoscale PET surface heterogeneity also revealed by AFM. Estimates of the adsorption coefficients are obtained using a nearest-neighbor analysis, giving values from 9.9 × 10 5 to 2.1 × 10 6 M –1 for immobile molecules and from 1.8 × 10 5 to 2.5 × 10 5 M –1 for mobile molecules on fresh and 5 min aged PET, respectively. Here, anomalous age-dependent variations in the velocity of molecular motion on the PET surface and in the population of immobile molecules are shown to correlate with changes in the strength of RhB adsorption.

Adsorption↗

Surface Equilibration Mechanism Controls the Stability of a Model Codeposited Glass Mixture of Organic Semiconductors

While previous work has identified the conditions for preparing ultrastable single-component organic glasses by physical vapor deposition (PVD), little is known about the stability of codeposited mixtures. Here, we prepared binary PVD glasses of organic semiconductors, TPD (N,N'-Bis(3-methylphenyl)-N,N'-diphenylbenzidine) and m-MTDATA (4,4',4"-Tris[phenyl(m-tolyl)amino]triphenylamine), with a 50:50 mass concentration over a wide range of substrate temperatures (T sub ). The enthalpy and kinetic stability are evaluated with differential scanning calorimetry and spectroscopic ellipsometry. Binary organic semiconductor glasses with exceptional thermodynamic and kinetic stability comparable to the most stable single-component organic glasses are obtained when deposited at T sub = 0.78–0.90T g (where T g is the conventional glass transition temperature). When deposited at 0.94T g , the enthalpy of the m-MTDATA/TPD glass equals that expected for the equilibrium liquid at that temperature. Thus, the surface equilibration mechanism previously advanced for single-component PVD glasses is also applicable for these codeposited glasses. Furthermore, these results provide an avenue for designing high-performance organic electronic devices.

36 MATERIALS SCIENCE↗

High Density Two-Component Glasses of Organic Semiconductors Prepared by Physical Vapor Deposition

Physical Vapor Deposition (PVD) is widely utilized for the production of organic semiconductor devices due to its ability to form thin layers with exceptional properties. Although the layers in the device usually consist of two or more components, there is limited understanding about the fundamental characteristics of such multi-component vapor-deposited glasses. Here, spectroscopic ellipsometry was employed to characterize the densities, thermal stabilities and optical properties of co-vapor deposited NPD and TPD glasses across the entire range of composition. We find that co-deposited NPD and TPD form high density glasses with enhanced thermal stability. The dependences of density and stability upon substrate temperature are correlated, and the birefringence of the co-deposited glasses is determined by the reduced substrate temperature of mixtures. Additionally, we observe that the transformation of a highly stable and dense two-component glass into its supercooled liquid initiates from the free surface and propagates into the bulk at constant velocity, like single component PVD glasses. As a result, all these features are consistent with the surface equilibration mechanism.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Origin of Anisotropic Molecular Packing in Vapor-Deposited Alq 3 Glasses

Anisotropic molecular packing is a key feature that makes glasses prepared by physical vapor deposition (PVD) unique materials, warranting a mechanistic understanding of how a PVD glass attains its structure. To this end, we use X-ray scattering and ellipsometry to characterize the structure of PVD glasses of tris(8-hydroxyquinoline) aluminum (Alq 3 ), a molecule used in organic electronics, and compare our results to simulations of its supercooled liquid. X-ray scattering reveals a tendency for molecular layering in Alq 3 glasses that depends upon the substrate temperature during deposition and the deposition rate. Simulations reveal that the Alq 3 supercooled liquid, like liquid metals, exhibits surface layering. We propose that the layering in Alq 3 glasses observed here as well as the previously reported bulk dipole orientation are inherited from the surface structure of the supercooled liquid. This work significantly advances our understanding of the mechanism governing the formation of anisotropic structure in PVD glasses.

36 MATERIALS SCIENCE↗

Vapor-Deposited Glass Structure Determined by Deposition Rate–Substrate Temperature Superposition Principle

In this article, we show that deposition rate substantially affects the anisotropic structure of thin glassy films produced by physical vapor deposition. Itraconazole, a glass-forming liquid crystal, was deposited at rates spanning 3 orders of magnitude over a 25 K range of substrate temperatures, and structure was characterized by ellipsometry and X-ray scattering. Both the molecular orientation and the spacing of the smectic layers obey deposition rate–substrate temperature superposition, such that lowering the deposition rate is equivalent to raising the substrate temperature. We identify two different surface relaxations that are responsible for structural order in the vapor-deposited glasses and find that the process controlling molecular orientation is accelerated by more than 3 orders of magnitude at the surface relative to the bulk. Finally, the identification of distinct surface processes responsible for anisotropic structural features in vapor-deposited glasses will enable more precise control over the structure of glassy materials used in organic electronics.

36 MATERIALS SCIENCE↗

Spontaneous Formation of >90% Optically Transmissive, Electrochemically Active CoP Films for Photoelectrochemical Hydrogen Evolution

Earth-abundant catalysts for the hydrogen-evolution reaction need increased mass loadings, relative to Pt films, to achieve comparable activity and stability in acidic electrolytes. We report herein that spontaneous nanostructuring of opaque, electrodeposited CoP films, 40–120 nm in thickness, leads to transparent electrocatalyst films that exhibit up to 90% optical transmission in the visible spectrum. The photocurrent density under simulated sunlight at a representative n + p-Si(100)/CoP photocathode increases by 200% after exposure to 0.50 M H 2 SO 4 (aq) and remains stable for 12 h of continuous operation. Atomic force microscopy and scanning electron microscopy of the film before and after exposure to 0.50 M H 2 SO 4 (aq) validate an optical model for transparent CoP films as probed with spectroscopic ellipsometry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Defect Repair of Polyelectrolyte Bilayers Using SDS: The Action of Micelles Versus Monomers

Defects within single, double, and triple polyelectrolyte bilayers derived from poly(sodium 4-styrenesulfonate) (PSS) and poly(diallyldimethyammonium chloride) (PDDA) have been repaired using aqueous solutions of sodium dodecyl sulfate (SDS), as evidenced by a reduction in their permeability and an increase in their permeation selectivity. In contrast to the use of monomer solutions of SDS, which were moderately effective in repairing only double and triple bilayers, micellar solutions proved highly effective for all three assemblies. Here, evidence for intact micelles or micellar fragments being deposited on the surface of single bilayers of PSS/PDDA has been obtained from a combination of atomic force microscopy, X-ray photoelectron spectroscopy, ellipsometry, and contact angle measurements. Observed CO 2 permeances of ca. 200 GPU and CO 2 /N 2 selectivities of ca. 30 for SDS-repaired, single bilayers of PSS/PDDA suggest that further development of such assemblies could have the practical potential for the separation of CO 2 from N 2 in the flue gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single Molecule Spectroscopy Studies of Acid–Base Chemical Gradients Using Nile Red as a Probe of Local Surface Acidity

Single molecule spectroscopy studies of local acidity along bifunctional acid-base gradients are reported. Gradients are prepared by directional vapor phase diffusion and subsequent reaction of 3-aminopropyl-trimethoxysilane with a uniform silica film. Gradient formation is confirmed by spectroscopic ellipsometry and by static water contact angle measurements. X-ray photoelectron spectroscopy is used to characterize the nitrogen content and degree of nitrogen protonation along the gradient. Nile Red is employed as the probe dye in single molecule spectroscopy studies of these gradients. While Nile Red is well-known for its solvent sensitivity, it is used here, for the first time, to sense the acid/base properties of the film in two-color wide-field fluorescence imaging experiments. The data reveal broad bimodal distributions of Nile Red emission spectra that vary along the gradient direction. The single-molecule results are consistent with solution-phase ensemble acid/base studies of the dye. The former reveal a gradual transition from a surface dominated by basic aminosilane sites at the high-amine end of the gradient to one dominated by acidic silanol sites at the low-amine end. The sub-diffraction-limited spatial resolution afforded by superlocalization of the single molecules reveals spatial correlations in the acid/base properties of the gradient over ~ 200 nm distances. Furthermore, these studies provide data relevant to the use of aminosilane-modified silica in bifunctional, cooperative chemical catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗