Quantification of Unsupported Thin-Film X-ray Spectra Using Bulk Standards.

A quantification model which uses standard X-ray spectra collected from bulk materials to determine the composition and mass thickness of single-layer and multilayer unsupported thin films is presented. The multivariate model can be iteratively solved for single layers in which each element produces at least one visible characteristic X-ray line. The model can be extended to multilayer thin films in which each element is associated with only one layer. The model may sometimes be solved when an element is present in multiple layers if additional information is added in the form of independent k-ratios or model assumptions. While the algorithm is suitable for any measured k-ratios, it is particularly well suited to energy-dispersive X-ray spectrometry where the bulk standard spectra can be used to deconvolve peak interferences in the thin-film spectra. The algorithm has been implemented and made available in the Open Source application National Institute of Standards and Technology DTSA-II. We present experimental data and Monte Carlo simulations supporting the quantification model.

Mapping Polar Distortions using Nanobeam Electron Diffraction and a Cepstral Approach.

Measuring local polar ordering is key to understanding ferroelectricity in thin films, especially for systems with small domains or significant disorder. Scanning nanobeam electron diffraction (NBED) provides an effective local probe of lattice parameters, local fields, polarization directions, and charge densities, which can be analyzed using a relatively low beam dose over large fields of view. However, quantitatively extracting the magnitudes and directions of polarization vectors from NBED remains challenging. Here, we use a cepstral approach, similar to a pair distribution function, to determine local polar displacements that drive ferroelectricity from NBED patterns. Because polar distortions generate asymmetry in the diffraction pattern intensity, we can efficiently recover the underlying displacements from the imaginary part of the cepstrum transform. We investigate the limits of this technique using analytical and simulated data and give experimental examples, achieving the order of 1.1 pm precision and mapping of polar displacements with nanometer resolution.

Steam-created grain boundaries for methane C-H activation in palladium catalysts.

Defects may display high reactivity because the specific arrangement of atoms differs from crystalline surfaces. We demonstrate that high-temperature steam pretreatment of palladium catalysts provides a 12-fold increase in the mass-specific reaction rate for carbon-hydrogen (C­H) activation in methane oxidation compared with conventional pretreatments. Through a combination of experimental and theoretical methods, we demonstrate that an increase in the grain boundary density through crystal twinning is achieved during the steam pretreatment and oxidation and is responsible for the increased reactivity. The grain boundaries are highly stable during reaction and show specific rates at least two orders of magnitude higher than other sites on the palladium on alumina (Pd/Al2O3) catalysts. Theoretical calculations show that strain introduced by the defective structure can enhance C­H bond activation. Introduction of grain boundaries through laser ablation led to further rate increases.

Nanoparticle size and 3D shape measurement by electron tomography: An Inter-Laboratory Comparison.

Electron tomography (ET) has been used for quantitative measurement of shape and size of objects in three dimensions (3D) for many years. However, systematic investigation of repeatability and reproducibility of ET has not been evaluated in detail. To assess the reproducibility and repeatability of a protocol for measuring size and three-dimensional (3D) shape parameters for nanoparticles (NPs) by ET, an inter-laboratory comparison (ILC) has been performed. The ILC included six laboratories and six instruments models from three instrument manufacturers following a standard measurement protocol. A technical specification describing the normative steps of the protocol is published by the International Standards Organization (ISO). Gold NPs with 30 nm nominal diameter contained within a rod-shaped carbon support were measured. The use of a rod-shaped sample support eliminated the missing wedge effect in the experimental tilt series of projected images for improved quantification. A total of 443 NPs were initially measured by NRC-NANO and then 115 out of the 443 NPs were measured by five other labs to compare measurands such as the Volume (V), maximum Feret diameter (Fmax), minimum Feret diameter (Fmin), volume-equivalent diameter (Deq) and aspect ratio (Frat) of the NPs. The results of the five labs were compared with the results obtained at NRC-NANO. The maximum disagreement in measurements of Fmin and Fmax obtained by the participating labs did not exceed 7 %. The measured Deq was between 27.5 nm and 30.3 nm in agreement with the NP manufacturer's specification (28 nm-32 nm). In addition to the above, the influence of the missing wedge effect and beam-induced NP movement was quantified based on the differences of the results between labs.

Influence of Polymer Aggregation and Liquid Immiscibility on Morphology Tuning by Varying Composition in PffBT4T-2DT/Non-Fullerene Organic Solar Cells.

The temperature dependent aggregation behavior of PffBT4T polymers used in organic solar cells plays a critical role in the formation of a favorable morphology in fullerene-based devices. However, there has been little investigation into the impact of donor/acceptor ratio on morphology tuning, especially for non-fullerene acceptors (NFAs). Herein, the influence of composition on morphology is reported for blends of PffBT4T-2DT with two NFAs, O-IDTBR and O-IDFBR. The monotectic phase behavior inferred from differential scanning calorimetry provides qualitative insight into the interplay between solid-liquid and liquid-liquid demixing. Transient absorption spectroscopy suggests that geminate recombination dominates charge decay and that the decay rate is insensitive to composition, corroborated by negligible changes in open-circuit voltage. Exciton lifetimes are also insensitive to composition, which is attributed to the signal being dominated by acceptor excitons which are formed and decay in domains of similar size and purity irrespective of composition. A hierarchical morphology is observed, where the composition dependence of size scales and scattering intensity from resonant soft X-ray scattering (R-SoXS) is dominated by variations in volume fractions of polymer/polymer rich domains. Results suggest an optimal morphology where polymer crystallite size and connectivity are balanced, ensuring a high probability of hole extraction via such domains.

Crystallography, Morphology, Electronic Structure, and Transport in Non-Fullerene/Non-Indacenodithienothiophene Polymer:Y6 Solar Cells.

Emerging nonfullerene acceptors (NFAs) with crystalline domains enable high-performance bulk heterojunction (BHJ) solar cells. Thermal annealing is known to enhance the BHJ photoactive layer morphology and performance. However, the microscopic mechanism of annealing-induced performance enhancement is poorly understood in emerging NFAs, especially regarding competing factors. Here, optimized thermal annealing of model system PBDB-TF:Y6 (Y6 = 2,2'-((2Z,2'Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]-thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) decreases the open circuit voltage (VOC) but increases the short circuit current (JSC) and fill factor (FF) such that the resulting power conversion efficiency (PCE) increases from 14 to 15% in the ambient environment. Here we systematically investigate these thermal annealing effects through in-depth characterizations of carrier mobility, film morphology, charge photogeneration, and recombination using SCLC, GIXRD, AFM, XPS, NEXAFS, R-SoXS, TEM, STEM, fs/ns TA spectroscopy, 2DES, and impedance spectroscopy. Surprisingly, thermal annealing does not alter the film crystallinity, R-SoXS characteristic size scale, relative average phase purity, or TEM-imaged phase separation but rather facilitates Y6 migration to the BHJ film top surface, changes the PBDB-TF/Y6 vertical phase separation and intermixing, and reduces the bottom surface roughness. While these morphology changes increase bimolecular recombination (BR) and lower the free charge (FC) yield, they also increase the average electron and hole mobility by at least 2-fold. Importantly, the increased µh dominates and underlies the increased FF and PCE. Single-crystal X-ray diffraction reveals that Y6 molecules cofacially pack via their end groups/cores, with the shortest π-π distance as close as 3.34 Å, clarifying out-of-plane π-face-on molecular orientation in the nanocrystalline BHJ domains. DFT analysis of Y6 crystals reveals hole/electron reorganization energies of as low as 160/150 meV, large intermolecular electronic coupling integrals of 12.1-37.9 meV rationalizing the 3D electron transport, and relatively high µe of 10-4 cm2 V-1 s-1. Taken together, this work clarifies the richness of thermal annealing effects in high-efficiency NFA solar cells and tasks for future materials design.

Cosolvent Effects When Blade-Coating a Low-Solubility Conjugated Polymer for Bulk Heterojunction Organic Photovoltaics.

The adoption of solution-processed active layers in the production of thin-film photovoltaics is hampered by the transition from research fabrication techniques to scalable processing. We report a detailed study of the role of processing in determining the morphology and performance of organic photovoltaic devices using a commercially available, low-solubility, high-molar mass diketopyrrolopyrrole-based polymer donor. Ambient blade coating of thick layers in an inverted architecture was performed to best model scalable processing. Device performance was strongly dependent on the introduction of either o-dichlorobenzene (DCB), 1,8-diiodooctane, or diphenyl ether cosolvent into the chloroform (CHCl3) solution, which were all shown to drastically improve the morphology. To understand the origin of these morphological changes as a result of the addition of the cosolvent, in situ studies with grazing-incidence X-ray scattering and optical reflection interferometry were performed. Use of any of the cosolvents decreases the domain size relative to the single solvent system and moved the drying mechanism away from what is likely liquid-liquid phase separation to solid-liquid phase separation driven by polymer aggregation. Comparing the CHCl3 + DCB cast films to the CHCl3-only cast films, we observed both the formation of small domains and an increase in crystallinity during the evaporation of DCB due to a high nucleation rate from supersaturation. This resulted in percolated bulk heterojunction networks that performed similarly well with a wide range of film thicknesses from 180 to 440 nm, making this system amenable to continuous roll-to-roll processing methods.

In situ oxidation and reduction of cerium dioxide nanoparticles studied by scanning transmission electron microscopy.

Cerium dioxide nanocubes and truncated octahedra were reduced and oxidized in the scanning transmission electron microscope. The reduction process was stimulated by the electron beam and oxidation was supported by background gases in the microscope environment. High-angle annular dark field imaging is sensitive to local lattice distortions that arise as oxygen vacancies are created and cerium cations reduce enabling high spatial resolution characterization of this process with temporal resolution on the order of seconds. Such measurements enable us to differentiate and infer that the observed behavior between the nanocubes and truncated octahedra may be due to the difference in crystallographic termination of surfaces. In situ measurements taken with different partial pressures of oxygen reveal the cerium oxidation state and the dose rate threshold for the onset of beam reduction are influenced by the environment. Increasing oxygen partial pressure reduces the Ce3+ content and decreases susceptibility to electron beam driven reduction.

Formation of the Conducting Filament in TaO x-Resistive Switching Devices by Thermal-Gradient-Induced Cation Accumulation.

The distribution of tantalum and oxygen ions in electroformed and/or switched TaO x-based resistive switching devices has been assessed by high-angle annular dark-field microscopy, X-ray energy-dispersive spectroscopy, and electron energy-loss spectroscopy. The experiments have been performed in the plan-view geometry on the cross-bar devices producing elemental distribution maps in the direction perpendicular to the electric field. The maps revealed an accumulation of +20% Ta in the inner part of the filament with a 3.5% Ta-depleted ring around it. The diameter of the entire structure was approximately 100 nm. The distribution of oxygen was uniform with changes, if any, below the detection limit of 5%. We interpret the elemental segregation as due to diffusion driven by the temperature gradient, which in turn is induced by the spontaneous current constriction associated with the negative differential resistance-type I- V characteristics of the as-fabricated metal/oxide/metal structures. A finite-element model was used to evaluate the distribution of temperature in the devices and correlated with the elemental maps. In addition, a fine-scale (∼5 nm) intensity contrast was observed within the filament and interpreted as due phase separation of the functional oxide in the two-phase composition region. Understanding the temperature-gradient-induced phenomena is central to the engineering of oxide memory cells.

Local degradation pathways in lithium-rich manganese-nickel-cobalt-oxide epitaxial thin films.

The electrochemical performance and microstructure of positive electrodes are intimately linked. As such, developing batteries resistance to capacity and voltage fade requires understanding these underlying structure-properties relationships and their evolution with operation. Epitaxial films of a Li-rich manganese-nickel- cobalt oxide cathode material were deposited on (100) and (111) orientated SrRuO3/SrTiO3 substrates. Cyclic voltammetry and impedance spectroscopy tracked the response of these positive electrode materials, while the microstructure of the pristine and cycled films was characterized using transmission electron microscopy. Energy-dispersive X-ray spectroscopy identifies compositional fluctuations in as-deposited films. Phase transformations and dissolution were observed after electrochemical testing. There is a correlation between both local composition and substrate orientation (i.e., surface faceting) and what degradation pathways are active. Regions with comparatively higher concentrations of Ni and Co were more resistant to dissolution and unfavorable phase transformations than those with relatively more Mn. As such, a global composition metric may not be an accurate predictor of degradation and performance. Rather possessing the synthetic ability to engineer the chemical profile as well as characterizing it, pose a challenge and opportunity.

Domain Formation in Lithium-Rich Manganese-Nickel-Cobalt-Oxide Epitaxial Thin Films and Implications for Interpretation of Electrochemical Behavior.

Due to the directional dependence of physical properties, it is advantageous to grow and then study materials in specific orientations. Films of battery materials grown in epitaxy offers the possibility to gain new insight into the role of physical structure on electrochemical behaviors. Here we demonstrate the growth, testing, and characterization of monoclinic-phase (space group C2/m) Li-Mn-Ni-Co-O epitaxial films. The monoclinic phase is a layered structure and as such lithium diffusion is favored along specific crystallographic directions. Films were grown by pulsed laser deposition onto SrRuO3/SrTiO3 substrates with (001) and (111) orientations. Cyclic voltammetry measured the response of these positive electrode materials, while the film structure was characterized using scanning transmission electron microscopy. A combination of imaging and diffraction identifies the presence of orientational variants. Variants disrupt the orientation anisotropy expected of these layered materials when grown in epitaxy, thereby masking differences in electrochemical behavior as a function of substrate orientation. Learning to control the domain structure now presents itself as a challenge to realize the potential of low symmetry battery materials grown in epitaxy on high symmetry substrates.

Van der Waals interfaces in epitaxial vertical metal/2D/3D semiconductor heterojunctions of monolayer MoS2 and GaN.

A promising approach for high speed and high power electronics is to integrate two-dimensional (2D) materials with conventional electronic components such as bulk (3D) semiconductors and metals. In this study we explore a basic integration step of inserting a single monolayer MoS2 (1L-MoS2) inside a Au/p-GaN junction and elucidate how it impacts the structural and electrical properties of the junction. Epitaxial 1L-MoS2 in the form of 1-2 µm triangle domains are grown by powder vaporization on a p-doped GaN substrate, and the Au capping layer is deposited by evaporation. Transmission electron microscopy (TEM) of the van der Waals interface indicates that 1L-MoS2 remained distinct and intact between the Au and GaN and that the Au is epitaxial to GaN only when the 1L-MoS2 is present. Quantitative TEM analyses of the van der Waals interfaces are performed and yielded the atomic plane spacings in the heterojunction. Electrical characterization of the all-epitaxial, vertical Au/1L-MoS2/p-GaN heterojunctions enables the derivations of Schottky barrier heights (SBH) and drawing of the band alignment diagram. Notably, 1L-MoS2 appears to be electronically semi-transparent, and thus can be considered as a modifier to the Au contact rather than an independent semiconductor component forming a pn-junction. The I-V analysis and our first principles calculation indicated Fermi level pinning and substantial band bending in GaN at the interface. Lastly, we illustrate how the depletion regions are formed in a bipolar junction with an ultrathin monolayer component using the calculated distribution of the charge density across the Au/1L-MoS2/GaN junction.

Reduced Bimolecular Recombination in Blade-Coated, High-Efficiency, Small-Molecule Solar Cells.

To realize the full promise of solution deposited photovoltaic devices requires processes compatible with high-speed manufacturing. We report the performance and morphology of blade-coated bulk heterojunction devices based on the small molecule donor p-DTS(FBTTh2)2 when treated with a post-deposition solvent vapor annealing (SVA) process. SVA with tetrahydrofuran improves the device performance of blade-coated films more than solvent additive processing (SA) with 1,8-diiodooctane. In spin-coating, SA and SVA achieve similar device performance. Our optimized, blade coated, SVA devices achieve power conversion efficiencies over 8 % and maintain high efficiencies in films up to ≈ 250 nm thickness, providing valuable resilience to small process variations in high-speed manufacturing. Using impedance spectroscopy, we show that this advantageous behavior originates from highly suppressed bimolecular recombination in the SVA-treated films. Electron microscopy and grazing-incidence X-ray scattering experiments show that SA and SVA both produce highly crystalline donor domains, but SVA films have a radically smaller domain size compared to SA films. We attribute the different behavior to variations in initial nucleation density and relative ability of SVA and SA to control subsequent crystal growth.

Multimodal Characterization of the Morphology and Functional Interfaces in Composite Electrodes for Li-S Batteries by Li Ion and Electron Beams.

We report the characterization of multiscale 3D structural architectures of novel poly[sulfur-random-(1,3-diisopropenylbenzene)] copolymer-based cathodes for high-energy-density Li-S batteries capable of realizing discharge capacities >1000 mAh/g and long cycling lifetimes >500 cycles. Hierarchical morphologies and interfacial structures have been investigated by a combination of focused Li ion beam (LiFIB) and analytical electron microscopy in relation to the electrochemical performance and physicomechanical stability of the cathodes. Charge-free surface topography and composition-sensitive imaging of the electrodes was performed using recently introduced low-energy scanning LiFIB with Li+ probe sizes of a few tens of nanometers at 5 keV energy and 1 pA probe current. Furthermore, we demonstrate that LiFIB has the ability to inject a certain number of Li cations into the material with nanoscale precision, potentially enabling control of the state of discharge in the selected area. We show that chemical modification of the cathodes by replacing the elemental sulfur with organosulfur copolymers significantly improves its structural integrity and compositional homogeneity down to the sub-5-nm length scale, resulting in the creation of (a) robust functional interfaces and percolated conductive pathways involving graphitic-like outer shells of aggregated nanocarbons and (b) extended micro- and mesoscale porosities required for effective ion transport.

Optical Asymmetry and Nonlinear Light Scattering from Colloidal Gold Nanorods.

A systematic study is presented of the intensity-dependent nonlinear light scattering spectra of gold nanorods under resonant excitation of the longitudinal surface plasmon resonance (SPR). The spectra exhibit features due to coherent second and third harmonic generation as well as a broadband feature that has been previously attributed to multiphoton photoluminescence arising primarily from interband optical transitions in the gold. A detailed study of the spectral dependence of the scaling of the scattered light with excitation intensity shows unexpected scaling behavior of the coherent signals, which is quantitatively accounted for by optically induced damping of the SPR mode through a Fermi liquid model of the electronic scattering. The broadband feature is shown to arise not from luminescence, but from scattering of the second-order longitudinal SPR mode with the electron gas, where efficient excitation of the second order mode arises from an optical asymmetry of the nanorod. The electronic-temperature-dependent plasmon damping and the Fermi-Dirac distribution together determine the intensity dependence of the broadband emission, and the structure-dependent absorption spectrum determines the spectral shape through the fluctuation-dissipation theorem. Hence a complete self-consistent picture of both coherent and incoherent light scattering is obtained with a single set of physical parameters.

Origins and demonstrations of electrons with orbital angular momentum.

The surprising message of Allen et al. (Allen et al. 1992 Phys. Rev. A 45, 8185 (doi:10.1103/PhysRevA.45.8185)) was that photons could possess orbital angular momentum in free space, which subsequently launched advancements in optical manipulation, microscopy, quantum optics, communications, many more fields. It has recently been shown that this result also applies to quantum mechanical wave functions describing massive particles (matter waves). This article discusses how electron wave functions can be imprinted with quantized phase vortices in analogous ways to twisted light, demonstrating that charged particles with non-zero rest mass can possess orbital angular momentum in free space. With Allen et al. as a bridge, connections are made between this recent work in electron vortex wave functions and much earlier works, extending a 175 year old tradition in matter wave vortices.This article is part of the themed issue 'Optical orbital angular momentum'.

Analytical Multimode Scanning and Transmission Electron Imaging and Tomography of Multiscale Structural Architectures of Sulfur Copolymer-Based Composite Cathodes for Next-Generation High-Energy Density Li-S Batteries.

Poly[sulfur-random-(1,3-diisopropenylbenzene)] copolymers synthesized via inverse vulcanization represent an emerging class of electrochemically active polymers recently used in cathodes for Li-S batteries, capable of realizing enhanced capacity retention (1,005 mAh/g at 100 cycles) and lifetimes of over 500 cycles. The composite cathodes are organized in complex hierarchical three-dimensional (3D) architectures, which contain several components and are challenging to understand and characterize using any single technique. Here, multimode analytical scanning and transmission electron microscopies and energy-dispersive X-ray/electron energy-loss spectroscopies coupled with multivariate statistical analysis and tomography were applied to explore origins of the cathode-enhanced capacity retention. The surface topography, morphology, bonding, and compositions of the cathodes created by combining sulfur copolymers with varying 1,3-diisopropenylbenzene content and conductive carbons have been investigated at multiple scales in relation to the electrochemical performance and physico-mechanical stability. We demonstrate that replacing the elemental sulfur with organosulfur copolymers improves the compositional homogeneity and compatibility between carbons and sulfur-containing domains down to sub-5 nm length scales resulting in (a) intimate wetting of nanocarbons by the copolymers at interfaces; (b) the creation of 3D percolation networks of conductive pathways involving graphitic-like outer shells of aggregated carbons;