Blade Coating Poly(3-hexylthiophene): The Importance of Molecular Weight on Thin-Film Microstructures.

Poly(3-hexylthiophene) is one of the most prevalent and promising conjugated polymers for use in organic electronics. However, the deposition of this material in thin films is highly dependent on the process, such as blade coating versus spin coating and material properties such as molecular weight. Typically, large polymer dispersity makes it difficult to isolate the effect of molecular weight without considering a distribution. In this study, we characterize oligothiophenes of exactly 8, 11, and 14 repeat units, which were deposited into thin films by varying blade coating conditions and postdeposition annealing. From synchrotron-based grazing incidence wide-angle X-ray scattering (GIWAXS), scanning transmission X-ray microscopy (STXM) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS), Raman microscopy, optical microscopy, and X-ray diffraction (XRD), it was suggested that higher molecular weight polymers exhibit a fast-forming crystalline polymorph (form-1) while low molecular weight polymers exhibit a slow forming polymorph (form-2) with large domain boundaries. As molecular weight is gradually increased, the polymorph formed transitions from form-1 and form-2, where 11 repeat unit oligomers display both polymorphs. We also found that processing conditions can increase the formation of the form-2 polymorph. We also report improved organic thin film transistor (OTFT) performance when form-1 is present. Overall, oligothiophene polymorph formation is highly dependent on the molecular weight and processing conditions, providing critical insight into the importance of polymer weight control in the development of thin-film electronics based on conjugated polymers.

Resonant Energy Transfer-Mediated Efficient Hole Transfer in the Ternary Blend Organic Solar Cells.

The ternary blend approach accomplished improved spectral coverage and enhanced the power conversion efficiency (PCE) of organic solar cells (OSCs). However, the role of the third component in improving the photovoltaic parameters needs critical analysis. Here, we introduced a wide band gap n-type twisted perylene diimide (TPDI) into the PM6:Y6 blend as a third component that improves spectral coverage and morphology, resulting in an overall increase in the efficiency of the OSCs. TPDI acts as an antenna for efficient energy- and charge-transfer processes. A systematic study compared charge- and energy-transfer dynamics and the orientational dependence nanomorphology of ternary blends with those of their binary counterparts. Femtosecond transient absorption measurements reveal enhanced hole-transfer efficiency in finely tuned ternary mixtures. This study provides a rational approach to identifying a third component to improve light management and morphology. These parameters enhance the energy and charge-transfer processes, improving the PCE of OSCs.

Soft X-ray spectro-ptychography of boron nitride nanobamboos, carbon nanotubes and permalloy nanorods.

Spectro-ptychography offers improved spatial resolution and additional phase spectral information relative to that provided by scanning transmission X-ray microscopes. However, carrying out ptychography at the lower range of soft X-ray energies (e.g. below 200 eV to 600 eV) on samples with weakly scattering signals can be challenging. Here, results of soft X-ray spectro-ptychography at energies as low as 180 eV are presented, and its capabilities are illustrated with results from permalloy nanorods (Fe 2p), carbon nanotubes (C 1s) and boron nitride bamboo nanostructures (B 1s, N 1s). The optimization of low-energy X-ray spectro-ptychography is described and important challenges associated with measurement approaches, reconstruction algorithms and their effects on the reconstructed images are discussed. A method for evaluating the increase in radiation dose when using overlapping sampling is presented.

Metal halide perovskite layers studied by scanning transmission X-ray microscopy.

We describe the investigation of metal halide perovskite layers, particularly CH3NH3PbI3 used in photovoltaic applications, by soft X-ray scanning transmission X-ray microscopy (STXM). Relevant reference spectra were used to fit the experimental data using singular value decomposition. The distribution of key elements Pb, I, and O was determined throughout the layer stack of two samples prepared by wet process. One sample was chosen to undergo electrical biasing. Spectral data shows the ability of STXM to provide relevant chemical information for these samples. We found the results to be in good agreement with the sample history, both regarding the deposition sequence and the degradation of the perovskite material.

Soft X-ray characterization of halide perovskite film by scanning transmission X-ray microscopy.

Organic-inorganic metal halide perovskites (MHPs) have recently been receiving a lot of attention due to their newfound application in optoelectronic devices, including perovskite solar cells (PSCs) which have reached power conversion efficiencies as high as 25.5%. However, the fundamental mechanisms in PSCs, including the correlation of degradation with the excellent optoelectrical properties of the perovskite absorbers, are poorly understood. In this paper, we have explored synchrotron-based soft X-ray characterization as an effective technique for the compositional analysis of MHP thin films. Most synchrotron-based studies used for investigating MHPs so far are based on hard X-rays (5-10 keV) which include various absorption edges (Pb L-edge, I L-edge, Br K-edge, etc.) but are not suited for the analysis of the organic component in these materials. In order to be sensitive to a maximum number of elements, we have employed soft X-ray-based scanning transmission X-ray microscopy (STXM) as a spectro-microscopy technique for the characterization of MHPs. We examined its sensitivity to iodine and organic components, aging, or oxidation by-products in MHPs to make sure that our suggested method is suitable for studying MHPs. Furthermore, methylammonium triiodide with different deposition ratios of PbI2 and CH3NH3I (MAI), and different thicknesses, were characterized for chemical inhomogeneity at the nanoscale by STXM. Through these measurements, we demonstrate that STXM is very sensitive to chemical composition and homogeneity in MHPs. Thus, we highlight the utility of STXM for an in-depth analysis of physical and chemical phenomena in PSCs.

Intracellular amorphous Ca-carbonate and magnetite biomineralization by a magnetotactic bacterium affiliated to the Alphaproteobacteria.

Bacteria synthesize a wide range of intracellular submicrometer-sized inorganic precipitates of diverse chemical compositions and structures, called biominerals. Their occurrences, functions and ultrastructures are not yet fully described despite great advances in our knowledge of microbial diversity. Here, we report bacteria inhabiting the sediments and water column of the permanently stratified ferruginous Lake Pavin, that have the peculiarity to biomineralize both intracellular magnetic particles and calcium carbonate granules. Based on an ultrastructural characterization using transmission electron microscopy (TEM) and synchrotron-based scanning transmission X-ray microscopy (STXM), we showed that the calcium carbonate granules are amorphous and contained within membrane-delimited vesicles. Single-cell sorting, correlative fluorescent in situ hybridization (FISH), scanning electron microscopy (SEM) and molecular typing of populations inhabiting sediments affiliated these bacteria to a new genus of the Alphaproteobacteria. The partially assembled genome sequence of a representative isolate revealed an atypical structure of the magnetosome gene cluster while geochemical analyses indicate that calcium carbonate production is an active process that costs energy to the cell to maintain an environment suitable for their formation. This discovery further expands the diversity of organisms capable of intracellular Ca-carbonate biomineralization. If the role of such biomineralization is still unclear, cell behaviour suggests that it may participate to cell motility in aquatic habitats as magnetite biomineralization does.

Backside-illuminated scientific CMOS detector for soft X-ray resonant scattering and ptychography.

The impressive progress in the performance of synchrotron radiation sources is nowadays driven by the so-called `ultimate storage ring' projects which promise an unprecedented improvement in brightness. Progress on the detector side has not always been at the same pace, especially as far as soft X-ray 2D detectors are concerned. While the most commonly used detectors are still based on microchannel plates or CCD technology, recent developments of CMOS (complementary metal oxide semiconductor)-type detectors will play an ever more important role as 2D detectors in the soft X-ray range. This paper describes the capabilities and performance of a camera equipped with a newly commercialized backside-illuminated scientific CMOS (sCMOS-BSI) sensor, integrated in a vacuum environment, for soft X-ray experiments at synchrotron sources. The 4 Mpixel sensor reaches a frame rate of up to 48 frames s-1 while matching the requirements for X-ray experiments in terms of high-intensity linearity (>98%), good spatial homogeneity (<1%), high charge capacity (up to 80 ke-), and low readout noise (down to 2 e- r.m.s.) and dark current (3 e- per second per pixel). Performance evaluations in the soft X-ray range have been carried out at the METROLOGIE beamline of the SOLEIL synchrotron. The quantum efficiency, spatial resolution (24 line-pairs mm-1), energy resolution (<100 eV) and radiation damage versus the X-ray dose (<600 Gy) have been measured in the energy range from 40 to 2000 eV. In order to illustrate the capabilities of this new sCMOS-BSI sensor, several experiments have been performed at the SEXTANTS and HERMES soft X-ray beamlines of the SOLEIL synchrotron: acquisition of a coherent diffraction pattern from a pinhole at 186 eV, a scattering experiment from a nanostructured Co/Cu multilayer at 767 eV and ptychographic imaging in transmission at 706 eV.

A pressure-actuated flow cell for soft X-ray spectromicroscopy in liquid media.

We present and fully characterize a flow cell dedicated to imaging in liquid at the nanoscale. Its use as a routine sample environment for soft X-ray spectromicroscopy is demonstrated, in particular through the spectral analysis of inorganic particles in water. The care taken in delineating the fluidic pathways and the precision associated with pressure actuation ensure the efficiency of fluid renewal under the beam, which in turn guarantees a successful utilization of this microfluidic tool for in situ kinetic studies. The assembly of the described flow cell necessitates no sophisticated microfabrication and can be easily implemented in any laboratory. Furthermore, the design principles we relied on are transposable to all microscopies involving strongly absorbed radiation (e.g. X-ray, electron), as well as to all kinds of X-ray diffraction/scattering techniques.

Lignans in Knotwood of Norway Spruce: Localisation with Soft X-ray Microscopy and Scanning Transmission Electron Microscopy with Energy Dispersive X-ray Spectroscopy.

Lignans are bioactive compounds that are especially abundant in the Norway spruce (Picea abies L. Karst.) knotwood. By combining a variety of chromatographic, spectroscopic and imaging techniques, we were able to quantify, qualify and localise the easily extractable lignans in the xylem tissue. The knotwood samples contained 15 different lignans according to the gas chromatography-mass spectrometry analysis. They comprised 16% of the knotwood dry weight and 82% of the acetone extract. The main lignans were found to be hydroxymatairesinols HMR1 and HMR2. Cryosectioned and resin-embedded ultrathin sections of the knotwood were analysed with scanning transmission X-ray microscopy (STXM). Cryosectioning was found to retain only lignan residues inside the cell lumina. In the resin-embedded samples, lignan was interpreted to be unevenly distributed inside the cell lumina, and partially confined in deposits which were either readily present in the lumina or formed when OsO4 used in staining reacted with the lignans. Furthermore, the multi-technique characterisation enabled us to obtain information on the chemical composition of the structural components of knotwood. A simple spectral analysis of the STXM data gave consistent results with the gas chromatographic methods about the relative amounts of cell wall components (lignin and polysaccharides). The STXM analysis also indicated that a torus of a bordered pit contained aromatic compounds, possibly lignin.

X-ray spectromicroscopy of nanoparticulate iron oxide phases.

Soft x-ray spectromicroscopy techniques have seen great amount of development in the recent years, and with the development of new diffraction limited synchrotron source, many new nanoscale and mesoscale characterization opportunities of applied materials are foreseen. In this perspective, the authors present some examples that illustrate the capabilities of spectromicroscopy techniques, namely, 2D and 3D spatially resolved chemical quantification, surface and bulk sensitive measurements, and polarization dependent measurements as applied to iron oxide nanoparticulate materials of biological, geological, and other origins.

HERMES: a soft X-ray beamline dedicated to X-ray microscopy.

The HERMES beamline (High Efficiency and Resolution beamline dedicated to X-ray Microscopy and Electron Spectroscopy), built at Synchrotron SOLEIL (Saint-Auban, France), is dedicated to soft X-ray microscopy. The beamline combines two complementary microscopy methods: XPEEM (X-ray Photo Emitted Electron Microscopy) and STXM (Scanning Transmission X-ray Microscopy) with an aim to reach spatial resolution below 20 nm and to fully exploit the local spectroscopic capabilities of the two microscopes. The availability of the two methods within the same beamline enables the users to select the appropriate approach to study their specific case in terms of sample environment, spectroscopy methods, probing depth etc. In this paper a general description of the beamline and its design are presented. The performance and specifications of the beamline will be reviewed in detail. Moreover, the article is aiming to demonstrate how the beamline performances have been specifically optimized to fulfill the specific requirements of a soft X-ray microscopy beamline in terms of flux, resolution, beam size etc. Special attention has been dedicated to overcome some limiting and hindering problems that are usually encountered on soft X-ray beamlines such as carbon contamination, thermal stability and spectral purity.

Effect of Chalcogens on Electronic and Photophysical Properties of Vinylene-Based Diketopyrrolopyrrole Copolymers.

Three vinylene linked diketopyrrolopyrrole based donor-acceptor (D-A) copolymers have been synthesized with phenyl, thienyl, and selenyl units as donors. Optical and electronic properties were investigated with UV-vis absorption spectroscopy, cyclic voltammetry, near edge X-ray absorption spectroscopy, organic field effect transistor (OFET) measurements, and density functional theory (DFT) calculations. Optical and electrochemical band gaps decrease in the order phenyl, thienyl, and selenyl. Only phenyl-based polymers are nonplanar, but the main contributor to the larger band gap is electronic, not structural effects. Thienyl and selenyl polymers exhibit ambipolar charge transport but with higher hole than electron mobility. Experimental and theoretical results predict the selenyl system to have the best transport properties, but OFET measurements prove the thienyl system to be superior with p-channel mobility as high as 0.1 cm(2) V(-1) s(-1).

Nanomorphology of bulk heterojunction photovoltaic thin films probed with resonant soft X-ray scattering.

The bulk nanomorphology of organic bulk heterojunction devices, particularly of all-polymer devices, is difficult to characterize due to limited electron density contrast between constituent materials. Resonant soft X-ray scattering can overcome this problem and is used to show that the morphologies in chloroform cast and subsequently annealed polyfluorene copolymer poly(9,9'-dioctylfluorene-co-bis(N,N'-(4,butylphenyl))bis(N,N'-phenyl-1,4-phenylene)diamine) (PFB) and poly(9,9'-dioctylfluorene-co-benzothiadiazole) (F8BT) blends exhibit a hierarchy of length scales with impure domains in as-cast films. With annealing, these domains first become purer at the smallest length scale and only then evolve in size with annealing. Even optimized cells using present fabrication methods are found to have a dominant domain size much larger than the exciton diffusion length. The observed morphology is far from ideal for efficient solar cell operation and very different from those achieved in high-efficiency fullerene-based devices. This strongly implies that lack of morphological control contributes to the relatively poor performance of the all-polymer PFB/F8BT devices and may be problematic for all-polymer devices in general. Novel processing strategies will have to be employed to harness the full potential these high open circuit voltage devices offer.