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This study describes the capabilities and limitations of carrying out total scattering experiments on the Powder Diffraction (PD) beamline at the Australian Synchrotron, ANSTO. A maximum instrument momentum transfer of 19 Å−1 can be achieved if the data are collected at 21 keV. The results detail how the pair distribution function (PDF) is affected by Q max, absorption and counting time duration at the PD beamline, and refined structural parameters exemplify how the PDF is affected by these parameters. There are considerations when performing total scattering experiments at the PD beamline, including (1) samples need to be stable during data collection, (2) highly absorbing samples with a μR > 1 always require dilution and (3) only correlation length differences >0.35 Å may be resolved. A case study comparing the PDF atom–atom correlation lengths with EXAFS-derived radial distances of Ni and Pt nanocrystals is also presented, which shows good agreement between the two techniques. The results here can be used as a guide for researchers considering total scattering experiments at the PD beamline or similarly setup beamlines.

A range of advanced imaging techniques are employed to study the micron- and nano-scale morphology of a polymer/non-fullerene acceptor blend. Cryo-electron microscopy in particular reveals nanoscale variations in molecular orientation and order.

This study is jointly supported by MOST (2017YFA0204702, 2018YFA0208504,) and NSFC (52073016, 51773207, 51973031, 21905018, 21905158) of China. This work was further supported by the Fundamental Research Funds for the Central Universities (buctrc201828, XK1802-2), Open Project of State Key Laboratory of Supramolecular Structure and Materials (sklssm202043), Jiangxi Provincial Department of Science and Technology (No. 20192ACB20009) and Hong Kong Scholars Program (Grant No. XJ2020051). The research reported in this publication was supported by funding from King Abdullah University of Science and Technology (KAUST). A.C.Y.L. acknowledges support from the Australian Research Council (FT180100594). The authors acknowledge the use of instruments and assistance at the Monash Ramaciotti Centre for Cryo-Electron Microscopy, a Node of Microscopy Australia, including the Titan Krios (Australian Research Council LE120100090). This work was performed in part at the SAXS/WAXS beamtline at the Australian Synchrotron, part of ANSTO. Z. T. acknowledges the Shanghai Pujiang Program (Grant No. 19PJ1400500).

Mixed halide perovskites with the ability to tune bandgaps exhibit attractive applications in tandem solar cells, building integrated photovoltaic and wavelength-tunable light-emitting devices. However, halide demixing under illumination or in the dark with a charge-carrier injection in both hybrid and inorganic perovskites results in bandgap instability and current-density-voltage (J-V) hysteresis, which can significantly hamper their application. Here, we demonstrate that halide segregation and J-V hysteresis in mixed halide inorganic CsPbIBr2 solar cells can be effectively mitigated by introducing an intermediate phase-enhanced Ostwald ripening through the control of the chemical composition in the CsPbIBr2 precursor solution. Excess amounts of either PbBr2 or CsI are incorporated into originally even molar amounts of PbBr2 and CsI precursor solutions. With the PbBr2-excess, we observed an enlarged perovskite grain size, no detectable halide phase segregation at the grain boundaries nor the perovskite/TiO2 interface, an increased minority carrier lifetime, a reduced J-V hysteresis, and an improved solar-cell performance. However, different CsI:PbBr2 stoichiometric ratios were found to have different effects on the performance of the perovskite solar cell. The excessive lead phase is reactive with the dimethyl sulfoxide (DMSO) in the precursor solution to form the Pb(I, Br)2-DMSO complex and the quasi-two-dimensional (2D) CsPb2(I, Br)5, which are conducive to Ostwald maturation and defect extinction. Finally, the CsPbIBr2 solar cell with a PbBr2-excess precursor composition reaches a power conversion efficiency (PCE) of 9.37% (stabilized PCE of 8.48%) and a maximum external quantum efficiency of over 90%.

Quasiperiodicity is a form of spatial order that has been observed in quasicrystalline matter but not light. We construct a quasicrystalline surface out of a light emitting diode. Using a nanoscale waveguide as a microscope (NSOM), we directly image the light field at the surface of the diode. Here we show, using reciprocal space representations of the images, that the light field is quasiperiodic. We explain the structure of the light field with wave superposition. Periodic ordering is limited to at most six-fold symmetry. The light field exhibits 12-fold quasisymmetry, showing order while disproving periodicity. This demonstrates that a new class, consisting of projections from hyperspace, exists in the taxonomy of light ordering.

The nanomorphology of bulk heterojunction (BHJ) blends based on poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediy...

The excitability of local surface plasmon modes in radial trimers composed of gold nanorods was mapped using hyperspectral cathodoluminescence (CL) in the scanning electron microscope. In symmetric trimers, the local plasmon resonances could be excited most effectively at the ends of individual rods. Introducing asymmetry into the structure breaks the degeneracy of the dipole modes and changes the excitability of transverse dipole modes in different directions. CL in the scanning electron microscope has great potential to interrogate individual nanophotonic structures and is a complement to electron energy loss spectroscopy and optical microscopy.

The mechanical properties of crystals are controlled by the translational symmetry of their structures. But for glasses with a disordered structure, the link between the symmetry of local particle arrangements and stability is not well established. In this contribution, we provide experimental verification that the centrosymmetry of nearest-neighbor polyhedra in a glass strongly correlates with the local mechanical stability. We examine the distribution of local stability and local centrosymmetry in a glass during aging and deformation using microbeam x-ray scattering. These measurements reveal the underlying relationship between particle-level structure and larger-scale behavior and demonstrate that spatially connected, coordinated local transformations to lower symmetry structures are fundamental to these phenomena. While glassy structures lack obvious global symmetry breaking, local structural symmetry is a critical factor in predicting stability.

All-polymer solar cells have gained attention in recent years with a solar cell performance of over 11% power conversion efficiency (PCE) recently demonstrated. The n-type polymer PNDIT2, also known as N2200 or P(NDI2OD-T2), has been extensively used for both photovoltaic and field-effect transistor applications. When paired with donor materials that have appropriately aligned energy levels, PNDIT2 exhibited device efficiencies over 10% PCE, and organic field-effect transistors fabricated with PNDIT2 exhibited mobilities over 1 cm2/V s. Thionation of the naphthalene diimide (NDI) moiety, which is the substitution of imide oxygen with sulfur atoms, has been shown to improve the field-effect transistor performance of NDI-based small molecules. By applying this strategy to PNDIT2, we explored the effect that thionation, in a 2S-trans configuration, has on the performance of all-polymer solar cells fabricated with the donor polymer PTB7-Th. Solar cells were fabricated with the original polymer, PNDIT2, as a r...

The evolution of polygonal-shaped nanoholes on the (100) surface of germanium, aided by focused ion beam induced self-organization, is presented. The energetic beam of ions creates a viscous phase which, at a thermodynamical minimum, leads to surface self-organization. A directed viscous-flow along the predefined nanoholes provides well-ordered polygonal nanostructures, ranging from triangles to hexagons and octagons, as desired. The amorphization exhibiting a confined viscous-flow at the walls of nanoholes is attributed to the localized melting zones induced by site-specific thermal spikes during ion irradiation, as revealed by microscopy and molecular dynamics studies. This leads to a local self-organization in the vicinity of each circular nanohole via a viscous-fingering process at the nanoscale. Such controlled self-organization, with the help of a predefined scanning grid, transforms the circular holes into the desired polygonal shape. The present morphology manipulation promises to surmount the barriers concerning the size reduction efforts in the field of nanofabrication.

Crystallography employing conventional large-volume diffraction has enabled the firm connections between structure and properties and structure and function that have solved many of the most difficult problems in materials science and biology. Disordered materials possess a large variety of local structural arrangements and pose a special challenge for crystallography. Often the local structures and symmetries that are responsible for observed phenomena in structurally complex disordered materials cannot be distinguished from conventional diffraction alone. In this article, we review analytical approaches for understanding local structure and symmetry from angular correlations in limited-volume diffraction patterns of amorphous materials, with a special focus on electron nano-diffraction. We discuss how these angular correlations can be interpreted in the context of dense, disordered, three-dimensional materials probed in a projection geometry and highlight the experimental challenges and considerations. New developments in this field are described whereby these angular correlations are statistically analyzed to probe the symmetry and variety of local structures, transformed to a real-space function that contains the 2-, 3- and 4-body particle correlations, and employed to develop reverse Monte Carlo models with more realistic higher-order correlations.

Nanoparticle dimers composed of different metals or metal oxides, as well as different shapes and sizes, are of wide interest for applications ranging from nanoplasmonic sensing to nanooptics to biomedical engineering. Shaped nanoparticles, like triangles and nanorods, can be particularly useful in applications due to the strong localized plasmonic hot-spot that forms at the tips or corners. By placing catalytic, but traditionally weakly- or non-plasmonic nanoparticles, such as metal oxides and metals like palladium, in these hot-spots, an enhanced function for sensing, photocatalysis or optical use is predicted. Here, we present an electrostatic colloidal assembly strategy for nanoparticles, incorporating different sizes, shapes and metal or metal oxide compositions into heterodimers with smaller gaps than are achievable using nanofabrication techniques. This versatile method is demonstrated on 14 combinations, including a variety of shaped gold nanoparticles as well as palladium, iron oxide, and titanium oxide nanoparticles. These colloidal nanoparticles are stabilized with traditional surfactants, such as citrate, CTAB, PVP and oleic acid/oleylamines, indicating the wide applicability of our approach. Heterodimers of gold and palladium are further analyzed using cathodoluminescence to demonstrate the tunability of these "plasmonic molecules". Since systematically altering the absorption and emission of the plasmonic nanoparticles dimers is crucial to extending their functionality, and small gap sizes produce the strongest hot-spots, this method indicates that the electrostatic approach to heterodimer assembly can be useful in creating new nanoparticle dimers for many applications.

Site-specific ion-irradiation is a promising tool fostering strain-engineering of freestanding nanostructures to realize 3D-configurations towards various functionalities. We first develop a novel approach of fabricating freestanding 3D silicon nanostructures by low dose ion-implantation followed by chemical-etching. The fabricated nanostructures can then be deformed bidirectionally by varying the local irradiation of kiloelectronvolt gallium ions. By further tuning the ion-dose and energy, various nanostructure configurations can be realized, thus extending its horizon to new functional 3D-nanostructures. It has been revealed that at higher-energies (∼30 kV), the nanostructures can exhibit two-stage bidirectional-bending in contrast to the bending towards the incident-ions at lower-energies (∼16), implying an effective transfer of kinetic-energy. Computational studies show that the spatial-distribution of implanted-ions, dislocated silicon atoms, has potentially contributed to the local development of stresses. Nanocharacterization confirms the formation of two distinguishable ion-irradiated and un-irradiated regions, while the smoothened morphology of the irradiated-surface suggested that the bending is also coupled with sputtering at higher ion-doses. The bending effects associated with local ion irradiation in contrast to global ion irradiation are presented, with the mechanism elucidated. Finally, weaving of nanostructures is demonstrated through strain-engineering for new nanoscale artefacts such as ultra-long fully-bent nanowires, nano-hooks, and nano-meshes. The aligned growth of bacterial-cells is observed on the fabricated nanowires, and a mesh based "bacterial-trap" for site-specific capture of bacterial cells is demonstrated emphasizing the versatile nature of the current approach.

The coercivity of Fe-based nanocrystalline soft magnetic materials depends critically on the grain size of bcc-Fe grains. Accurately estimating the volume-weighted mean grain size is extremely important to develop new Fe-based nanocrystalline soft magnetic materials with low coercivity. This article shows that autocorrelation analysis of dark-field transmission electron microscope (TEM) images provides a very good estimation of bcc-Fe grain size in nanocrystalline soft magnetic materials. This method can be used to efficiently estimate the volume-weighted average grain size from multiple TEM images with much less inherent bias than manual measurement techniques. The estimated grain sizes show good consistency to the grain sizes estimated by X-ray diffraction (XRD) and manual measurement. In contrast to XRD, this method can also reveal the differences in grain size from different micron-sized regions of a sample.

Here, we systematically study the effect of fluorination on the performance of all-polymer solar cells by employing a naphthalene diimide (NDI)-based polymer acceptor with thiophene-flanked phenyl co-monomer. Fluorination of the phenyl co-monomer with either two or four fluorine units is used to create a series of acceptor polymers with either no fluorination (PNDITPhT), bifluorination (PNDITF2T), or tetrafluorination (PNDITF4T). In blends with the donor polymer PTB7-Th, fluorination results in an increase in power conversion efficiency from 3.1 to 4.6% despite a decrease in open-circuit voltage from 0.86 V (unfluorinated) to 0.78 V (tetrafluorinated). Countering this decrease in open-circuit voltage is an increase in short-circuit current from 7.7 to 11.7 mA/cm2 as well as an increase in fill factor from 0.45 to 0.53. The origin of the improvement in performance with fluorination is explored using a combination of morphological, photophysical, and charge-transport studies. Interestingly, fluorination is ...

Local structure and symmetry are keys to understanding how a material is formed and the properties it subsequently exhibits. This applies to both crystals and amorphous and glassy materials. In the case of amorphous materials, strong links between processing and history, structure and properties have yet to be made because measuring amorphous structure remains a significant challenge. Here, we demonstrate a method to quantify proportions of the bond-orientational order of nearest neighbor clusters [Steinhardt, et al. (1983) Phys Rev B 28:784-805] in colloidal packings by statistically analyzing the angular correlations in an ensemble of scanning transmission microbeam small-angle X-ray scattering (μSAXS) patterns. We show that local order can be modulated by tuning the potential between monodisperse, spherical colloidal silica particles using salt and surfactant additives and that more pronounced order is obtained by centrifugation than sedimentation. The order in the centrifuged glasses reflects the ground state order in the dispersion at lower packing fractions. This diffraction-based method can be applied to amorphous systems across decades in length scale to connect structure to behavior in disordered systems with a range of particle interactions.

The structural and magnetic properties of amorphous Fe87 − yB13Cuy (y = 0 to 1.5) annealed with a range of heating rates (α) up to 150 K/s were investigated. The lowest coercivity (Hc) for Fe87B13 after crystallization shows a dramatic decrease from 174 A/m to 6.7 A/m when α is increased from 1.7 K/s to 150 K/s. The coercivity of Fe87 − yB13Cuy annealed at 150 K/s is reduced by Cu addition and Hc = 3.0 A/m is obtained at y = 1.5. Nanostructures with a grain size of 15 to 20 nm were evident in transmission electron micrographs from these rapidly annealed alloys.

Asymmetric nanoparticle trimers composed of particles with increasing diameter act as "plasmonic lenses" and have been predicted to exhibit ultrahigh confinement of electromagnetic energy in the space between the two smallest particles. Here we present an electrostatic self-assembly approach for creating gold nanoparticle trimers with an assembly yield of over 60%. We demonstrate that the trimer assembly leads to characteristic red-shifts and show the localization of the relevant plasmon modes by means of cathodoluminescence and electron energy loss spectroscopy. The results are analyzed in terms of surface plasmon hybridization.

The solar cell performance and microstructure of DPP-based polymers with different degrees of fluorination are reported. DPP-based polymers with thiophene–phenyl–thiophene comonomer and thiophene flanking units are studied, with the degree of fluorination of the phenyl unit varied. With bifluorination of the phenyl ring, a higher open circuit voltage is achieved whilst maintaining or even improving the overall solar cell efficiency. While tetrafluorination leads to a further 0.1 V increase in VOC, reaching a high photo voltage of 0.81 V, overall solar cell performance significantly drops. Microstructural studies using AFM, TEM, Grazing incidence wide-angle X-ray scattering (GIWAXS), and Resonant soft X-ray scattering (R-SoXS) reveal that bifluorination largely preserves the microstructure of the nonfluorinated system, whereas tetrafluorination results in coarse phase separation between the polymer donor and the fullerene acceptor. Our results demonstrate that the use of an extended comonomer is a promising strategy for optimizing the beneficial effects of fluorination for DPP-based polymer solar cells, especially in improving the open circuit voltage. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 49–59

In response to concerns about the world’s generation of greenhouse gases, there are incentives to develop lower energy alternatives to cryogenic air separation. Oxygen sorbents are one such alternative in which high oxygen uptakes are achieved through engineering materials with a high number of oxygen vacancy defects. For a series of Tb–CeO2 mixed oxides, the oxygen uptake was determined using thermogravimetric analysis (TGA). Electron energy loss spectroscopy (EELS) was used to investigate the relative oxygen vacancy concentration and complement those findings obtained using TGA. Gas switching experiments conducted at 700 °C show that a higher oxygen uptake was obtained when 30% Tb was incorporated into the lattice (76 μmol·g–1) in comparison to when 10% Tb was introduced (21 μmol·g–1). The O IB/IC ratio, indicative of oxygen vacancies, was found to increase with increasing Tb content, and Raman spectroscopy demonstrated that these defects were introduced with the addition of Tb. The increase in oxygen u...

The optoelectronic properties of asymmetric metal nanostructures are of current interest for applications in photonics, sensing, and catalysis. Here, we break the symmetry of the localized surface plasmon resonance of gold nanorods by selective overgrowth of a single tip via a high-yield ( > 80 % ) wet-chemical method. While optical spectroscopy exhibits a bathochromic shift of the nanoparticle plasmon resonance, cathodoluminescence and electron energy loss spectroscopy measurements reveal a breaking of the symmetry of the associated localized surface plasmon resonance mode, which results in the subwavelength concentration of electromagnetic energy. The simple, one-step postsynthetic modification allows control of nanoparticle structural parameters, and we demonstrate how the asymmetric energy redistribution leads to increases in the surface-enhanced Raman scattering of a model analyte attached to the surface of the nanostructures. The spatial localization of energy in these nanostructures may find applications in nanofocusing, nanoimaging, and light harvesting.

How the structure of disordered porous carbons evolves during their activation is particularly poorly understood. This problem endures primarily because of a lack of high-resolution 3D techniques for the characterization of amorphous and highly disordered structure. To address this, the measurement of the 3D pair-angle distribution function using nanodiffraction patterns from high-energy electrons is demonstrated. These rich multiatom correlations are measured for a disordered carbon and they clearly show the structural evolution during activation. They provide previously inaccessible bond-angle information and direct evidence for the presence of ring and adatom defects. An increase in the short-range order and the number of fivefold ring defects with activation are observed, indicating stress relaxation by increasing curvature. These observations support models of disordered porous carbons based on curved graphene networks and explain how large amounts of free volume can be created with surprisingly small changes in the average ratios of tetrahedral to graphitic bonding.

The photovoltaic properties of a series of diketopyrrolo[3,4-c]pyrrole (DPP) copolymers containing 3,4-ethylenedioxythiophene (EDOT) as a comonomer are reported. With use of different aryl flanking units on the DPP core, namely thiophene, pyridine or phenyl, optical gaps ranging from 1.91 eV to 1.13 eV are achieved. When blended with the fullerene derivative [6,6]-phenyl C71-butyric acid methyl ester (PC71BM), the thiophene-flanked copolymer PDPP[T]2-EDOT with an optical gap of 1.13 eV was found to have the best photovoltaic performance, with an efficiency of 2.5% in an inverted device architecture. Despite having the lowest open circuit voltage of the three polymers studied, PDPP[T]2-EDOT-based devices were able to achieve superior efficiencies due to the high short circuit current of up to ∼15 mA cm−2. PDPP[T]2-EDOT-based devices also exhibit higher external quantum efficiencies which are associated with a superior microstructure – as revealed by transmission electron microscopy (TEM) and grazing incidence wide-angle X-ray scattering (GIWAXS) – which is associated with the enhanced aggregation tendency of PDPP[T]2-EDOT chains. In particular PDPP[T]2-EDOT : PC71BM blends were found to have a finer phase separated morphology with superior thin-film crystallinity. Surface morphology was also investigated with atomic force microscopy and near-edge X-ray absorption fine-structure spectroscopy.

Variability in the short-intermediate range order of pure amorphous Si synthesized by different experimental and computational techniques is probed by measuring mass density, atomic coordination, bond-angle deviation, and dihedral angle deviation. It is found that there is significant variability in order parameters at these length scales in this archetypal covalently bonded, monoatomic system. This diversity strongly reflects preparation method and thermal history in both experimental and simulated systems. Where experiment and simulation do not quantitatively agree, this is partly due to inherent differences in analysis and time scales. Relaxed forms of amorphous Si quantitatively match continuous random networks generated by a hybrid method of bond-switching Monte Carlo and molecular dynamics simulation. Qualitative trends were identified in other experimental and computed forms of a-Si. Ion-implanted a-Si′s are less ordered than the relaxed forms. Preparation methods which narrowly avoid crystallization such as experimental pressure-induced amorphization or simulated melt-quenching result in the most disordered structures. As no unique form of amorphous Si exists, there can be no single model for the material.

Atomic networks of as-implanted and relaxed amorphous silicon solids were simulated using a Hybrid Reverse Monte Carlo algorithm constrained by high-resolution electron diffraction data. No signifi...

The microstructure and photophysics of low-band gap, all-polymer photovoltaic blends are presented. Blends are based on the donor polymer BFS4 (a dithienyl-benzo[1,2-b:4,5-b]dithiophene/5-fluoro-2,1,3-benzothiadiazole co-polymer) paired with the naphthalene diimide-based acceptor polymer P(NDI2OD-T2). Efficiencies of over 4% are demonstrated, with an open circuit voltage of greater than 0.9 V achieved. Transmission electron microscopy reveals a relatively coarse phase-separated morphology, with elongated domains up to 200 nm in width. Near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy and atomic force microscopy (AFM) measurements reveal that the top surface of BFS4:P(NDI2OD-T2) blends is covered with a pure BFS4 capping layer. Depth profiling measurements confirm this vertical phase separation with a surface-directed spinodal decomposition wave observed. Grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements confirm that BFS4 and P(NDI2OD-T2) are semicrystalline with both polymers retaining their semicrystalline nature when blended. Photoluminescence spectroscopy reveals incomplete photoluminescence quenching with as much as 30% of excitons failing to reach a donor/acceptor interface. Transient absorption spectroscopy measurements also find evidence for rapid geminate recombination.

Although the equilibrium phase diagram predicts that alloys in the central part of the V–Zr system should consist of V2Zr Laves phase with partial segregation of one element, it is known that under non-equilibrium conditions these materials can form amorphous structures. Here we examine the structures and stabilities of thin film V–Zr alloys deposited at room temperature by magnetron sputtering. The films were characterized by X-ray diffraction, transmission electron microscopy and computational methods. Atomic-scale modelling was used to investigate the enthalpies of formation of the various competing structures. The calculations confirmed that an amorphous solid solution would be significantly more stable than a random body-centred solid solution of the elements, in agreement with the experimental results. In addition, the modelling effort provided insight into the probable atomic configurations of the amorphous structures allowing predictions of the average distance to the first and second nearest neighbours in the system.

Single-walled carbon nanotubes (SWCNNT) and single-walled boron nitride nanotubes (SWBNNT) were irradiated with 30 keV Kr + ions at room temperature. The structural changes during irradiation were monitored in situ using transmission electron microscopy (TEM) and ex situ at certain dose points using Raman spectroscopy. Our measurements demonstrate that metallic/semiconducting SWCNNT and insulating SWBNNT undergo similar structural modifications due to keV-ion irradiation. Point defects due to primary knock-on events accumulate and lead to the formation of defect complexes and eventual amorphization. The loss of atoms due to sputtering reduces the nanotube diameter and leads to shrinkage. Time resolved footage of the ion irradiation of a particular area demonstrated that NT scission and subsequent shortening can take place with some probability, possibly due to collision cascade events.

The structures of four types of amorphous silicon are examined by an experimentally constrained structural relaxation method (ECSR). Experimental selected area electron diffraction data and fluctuation electron microscopy normalized diffraction variance data were used as constraints to guide a Monte Carlo relaxation procedure towards best fit models. A Tersoff potential was also used to further restrict the space of possible solutions. The materials examined were self-ion-implanted silicon and pressure-amorphized silicon, both in their as-prepared and thermally annealed states. In the fitted models for these materials regions containing two types of medium-range order were identified. One type involves formation of paracrystallites with cubic and hexagonal structures, where both short-range crystalline and medium-range order are present. The other type of medium-range order appears in the form of extended crystalline planes without associated short-range crystalline order. These two types can coexist. It is observed that the best fit models for both as-prepared samples contain approximately 10–15% paracrystalline ordered regions, reducing to about 5–10% in the annealed materials. None of the models are true continuous random networks. We conclude that, with long computational times and with a suitable potential function, the ECSR procedure provides a powerful, although at present semi-quantitative, tool for determining the structural form of medium-range order in thin amorphous materials.

Organic-inorganic hybrid perovskites, such as CH3 NH3 PbI3, have shown highly promising photovoltaic performance. Electron microscopy (EM) is a powerful tool for studying the crystallography, morphology, interfaces, lattice defects, composition, and charge carrier collection and recombination properties at the nanoscale. Here, the sensitivity of CH3 NH3 PbI3 to electron beam irradiation is examined. CH3 NH3 PbI3 undergoes continuous structural and compositional changes with increasing electron dose, with the total dose, rather than dose rate, being the key operative parameter. Importantly, the first structural change is subtle and easily missed and occurs after an electron dose significantly smaller than that typically applied in conventional EM techniques. The electron dose conditions under which these structural changes occur are identified. With appropriate dose-minimization techniques, electron diffraction patterns can be obtained from pristine material consistent with the tetragonal CH3 NH3 PbI3 phases determined by X-ray diffraction. Radiation damage incurred at liquid nitrogen temperatures and using Ga+ irradiation in a focused ion beam instrument are also examined. Finally, some simple guidelines for how to minimize electron-beam-induced artifacts when using EM to study hybrid perovskite materials are provided.

The structure of hyper-eutectic ZrxPt100−x (73 ≤ x ≤ 77) metallic glasses produced by melt spinning was examined with high-energy synchrotron X-ray diffraction (HEXRD) and fluctuation electron microscopy. In addition, details of the amorphous structure were studied by combining ab initio molecular dynamics and reverse Monte Carlo simulations. Crystallization pathways in these glasses have been reported to vary dramatically with small changes in compositions; however, in the current study, the structures of the different glasses were also observed to vary with composition, particularly the prepeak in the total structure factor that occurs at a Q value of around 17 nm−1. Results from simulations and fluctuation electron microscopy suggest that the medium-range order of the amorphous structure is characterized by extended groups of Pt-centered clusters that increase in frequency, structural order, or spatial organization at higher Pt contents. These clusters may be related to the Zr5Pt3 structure, which contains Pt-centered clusters coordinated by 9Zr and 2Pt atoms.

The design, synthesis, and characterization of a hierarchically ordered composite whose structure and optical properties can be reversibly switched by adjustment of solvent conditions are described. Solvent-induced swelling and de-swelling is shown to provide control over the internal packing arrangement and hence, optical properties of in situ synthesized metal nanoparticles. Specifically, a gold-nanoparticle-containing ionic-liquid-derived polymer is synthesized in a single step by UV irradiation of a metal-ion-precursor-doped, self-assembled ionic liquid gel, 1-decyl-3-vinylimidazolium chloride. Small-angle X-ray scattering (SAXS) studies indicate that in the de-swollen state, the freestanding polymer adopts a perforated lamellar structure. Optical spectroscopy of the dried composite reveals plasmon resonances positioned in the near-IR. Strong particle-particle interactions arise from matrix-promoted formation of aggregated 1D clusters or chains of gold nanoparticles. Upon swelling in alcohol, the composite undergoes a structural conversion to a disordered structure, which is accompanied by a color change from purple to pale pink and a shift in the surface plasmon resonance to 527 nm, consistent with isolated, non-interacting particles. These results demonstrate the far-field tuning of the plasmonic spectrum of gold nanoparticles by solvent-mediated changes in its encapsulating matrix, offering a straightforward, low-cost strategy for the fabrication of nanophotonic materials.

The refinement of gold in crystallising amorphous silicon volumes was tested as a means of creating a conducting element embedded in the crystalline matrix. Amorphous silicon volumes were created by self-ion-implantation through a mask. Five hundred kiloelectronvolt Au+ was then implanted into the volumes. The amorphous volumes were crystallised on a hot stage in air, and the crystallisation was characterised using cross sectional transmission electron microscopy. It was found that the amorphous silicon volumes crystallised via solid phase epitaxy at all the lateral and vertical interfaces. The interplay of the effects of the gold and also the hydrogen that infilitrated from the surface oxide resulted in a plug of amorphous material at the surface. Further annealing at this temperature demonstrated that the gold, once it had reached a certain critical concentration nucleated poly-crystalline growth instead of solid phase epitaxy. Time resolved reflectivity and Rutherford backscattering and channeling measurements were performed on large area samples that had been subject to the same implantation regime to investigate this system further. It was discovered that the crystallisation dynamics and zone refinement of the gold were complicated functions of both gold concentration and temperature. These findings do not encourage the use of this method to obtain conducting elements embedded in the crystalline silicon substrate.

Deep amorphous silicon wells were created in a crystalline substrate by MeV ion-implantation. The sides of the rectangular amorphous volume were aligned normal to fast growth directions. Upon heating at elevated temperatures crystallisation proceeded inwards at both lateral and vertical interfaces. The progress of the epitaxy and the number and nature of the secondary structures formed were investigated through both plan-view and cross-sectional transmission electron microscopy analyses. The number of spanning dislocations was significantly reduced in this aligned configuration compared with the situation where the sides of the well were not coincident with crystallographic directions. The reduction in the number of spanning dislocations allowed a more complete characterisation of other defects which arise uniquely from the crystallisation of volumes in this geometry.

Molecular weight is an important factor determining the morphology and performance of all-polymer solar cells. Through the application of direct arylation polycondention, a series of batches of a fluorinated naphthalene diimide-based acceptor polymer are prepared with molecular weight varying from M-n = 20 to 167 kDa. Used in conjunction with a common low bandgap donor polymer, the effect of acceptor molecular weight on solar cell performance, morphology, charge generation, and transport is explored. Increasing the molecular weight of the acceptor from M-n = 20 to 87 kDa is found to increase cell efficiency from 2.3% to 5.4% due to improved charge separation and transport. Further increasing the molecular weight to M-n = 167 kDa however is found to produce a drop in performance to 3% due to liquid-liquid phase separation which produces coarse domains, poor charge generation, and collection. In addition to device studies, a systematic investigation of the microstructure and photophysics of this system is presented using a combination of transmission electron microscopy, grazing-incidence wide-angle X-ray scattering, near-edge X-ray absorption fine-structure spectroscopy, photoluminescence quenching, and transient absorption spectroscopy to provide a comprehensive understanding of the interplay between morphology, photophysics, and photovoltaic performance.

The interpretation of angular symmetries in electron nanodiffraction patterns from thin amorphous specimens is examined. It is found that in general there are odd symmetries in experimental electron nanodiffraction patterns. Using simulation, it is demonstrated that this effect can be attributed to dynamical scattering, rather than other divergences from the ideal experimental conditions such as probe-forming lens aberrations and camera noise. The departure of opposing diffracted intensities from Friedel's law in the phase grating formalism is calculated using a general structure factor for disordered materials. On the basis of this, a simple correction procedure is suggested to recover the kinematical angular symmetries, and thus readily interpretable information that reflects the symmetries of the original projected object. This correction is numerically tested using both the phase object and multislice calculations, and is demonstrated to fully recover all the kinematical diffracted symmetries from a simulated atomic model of a metallic glass.

The change in the carbonaceous skeleton of nanoporous carbons during their activation has received limited attention, unlike its counterpart process in the presence of an inert atmosphere. Here we adopt a multi-method approach to elucidate this change in a poly(furfuryl alcohol)-derived carbon activated using cyclic application of oxygen saturation at 250 °C before its removal (with carbon) at 800 °C in argon. The methods used include helium pycnometry, synchrotron-based X-ray diffraction (XRD) and associated radial distribution function (RDF) analysis, transmission electron microscopy (TEM) and, uniquely, electron energy-loss spectroscopy spectrum-imaging (EELS-SI), electron nanodiffraction and fluctuation electron microscopy (FEM). Helium pycnometry indicates the solid skeleton of the carbon densifies during activation from 78% to 93% of graphite. RDF analysis, EELS-SI, and FEM all suggest this densification comes through an in-plane growth of sp2 carbon out to the medium range without commensurate increase in order normal to the plane. This process could be termed ‘graphenization’. The exact way in which this process occurs is not clear, but TEM images of the carbon before and after activation suggest it may come through removal of the more reactive carbon, breaking constraining cross-links and creating space that allows the remaining carbon material to migrate in an annealing-like process. C.H. acknowledges a joint scholarship provided by China Scholarship Council (CSC) and the University of Adelaide. The support of the Australian Research Council Discovery Program (DP110101293) is also gratefully acknowledged. ACYL gratefully acknowledges the support of the Science Faculty and the Monash Centre for Electron Microscopy (MCEM), Monash University. The electron microscopy was performed in the MCEM. The FEI Titan3 80-300 FEGTEM was funded by the Australian Research Council (LE0454166). S.H.M. acknowledges the award of a President’s Scholarship from the University of South Australia.

Rutherford backscattering spectroscopy and ion channeling and secondary ion mass spectroscopy have been used to study the evolution of a potassium profile in amorphous silicon during solid phase epitaxial crystallisation. The potassium profile exhibits some propensity for refinement in front of the crystallising interface for the concentrations used in this experiment. Also, the potassium is partially substitutional in the crystallised layer. Preliminary studies on the influence of potassium on the rate of solid phase epitaxy (SPE) in silicon are presented. Surface amorphous films doped with potassium were crystallised and the rate of epitaxy was monitored using time resolved reflectivity. The inclusion of potassium was found to retard the rate of SPE. These results indicate that potassium doped amorphous films may be helpful in efforts to further refine present models of SPE in silicon.

The effect of polymer regioregularity on the charge transport properties and bimolecular recombination rates of polymer-based solar cells is studied in detail using transient photovoltaic techniques. We compare organic solar cells fabricated with an ITO/ZnO/PEIE/P3HT:PCBM/MoO3/Ag structure using either 100% regioregular poly(3-hexylthiophene) (DF-P3HT) yielding an average power conversion efficiency (PCE) of 3.8 ± 0.3% or 92% regioregular P3HT (rr-P3HT) that yields an average PCE of 3.28 ± 0.4%. Transient photocurrent measurements reveal the presence of less mobile photoinduced charges in rr-P3HT:PCBM cells when compared to DF-P3HT:PCBM solar cells. Transient photovoltage measurements are used to establish the relationship between regioregularity and bimolecular recombination rate constant (k) finding that under 1 Sun, devices with high regioregularity have a longer τ despite having a higher k. The high value of k for the DF-P3HT:PCBM system as compared to the rr-P3HT:PCBM system is attributed to enhanced mobility and better charge transport of mobile charges in the DF-P3HT:PCBM system, consistent with enhanced fibrillar order in DF-P3HT films observed with transmission electron microscopy. We also note a slight decrease in cell open circuit voltage with increase in polymer regioregularity, which is due to the increase in k. Other recombination mechanisms such as trap-assisted recombination are found to be important in the lower regioregular P3HT device compounded by the reduced mobility and poor inter-chain ordering.

Organic–inorganic hybrid perovskite solar cells with mixed cations and mixed halides have achieved impressive power conversion efficiency of up to 22.1%. Phase segregation due to the mixed compositions has attracted wide concerns, and their nature and origin are still unclear. Some very useful analytical techniques are controversial in microstructural and chemical analyses due to electron beam-induced damage to the “soft” hybrid perovskite materials. In this study photoluminescence, cathodoluminescence, and transmission electron microscopy are used to study charge carrier recombination and retrieve crystallographic and compositional information for all-inorganic CsPbIBr2 films on the nanoscale. It is found that under light and electron beam illumination, “iodide-rich” CsPbI(1+x)Br(2−x) phases form at grain boundaries as well as segregate as clusters inside the film. Phase segregation generates a high density of mobile ions moving along grain boundaries as ion migration “highways.” Finally, these mobile ions can pile up at the perovskite/TiO2 interface resulting in formation of larger injection barriers, hampering electron extraction and leading to strong current density–voltage hysteresis in the polycrystalline perovskite solar cells. This explains why the planar CsPbIBr2 solar cells exhibit significant hysteresis in efficiency measurements, showing an efficiency of up to 8.02% in the reverse scan and a reduced efficiency of 4.02% in the forward scan, and giving a stabilized efficiency of 6.07%.

Porosity loss, also known as physical aging, in glassy polymers hampers their long term use in gas separations. Unprecedented interactions of porous aromatic frameworks (PAFs) with these polymers offer the potential to control and exploit physical aging for drastically enhanced separation efficiency. PAF-1 is used in the archetypal polymer of intrinsic microporosity (PIM), PIM-1, to achieve three significant outcomes. 1) hydrogen permeability is drastically enhanced by 375% to 5500 Barrer. 2) Physical aging is controlled causing the selectivity for H2 over N2 to increase from 4.5 to 13 over 400 days of aging. 3) The improvement with age of the membrane is exploited to recover up to 98% of H2 from gas mixtures with N2 . This process is critical for the use of ammonia as a H2 storage medium. The tethering of polymer side chains within PAF-1 pores is responsible for maintaining H2 transport pathways, whilst the larger N2 pathways gradually collapse.

Solid-phase epitaxy was examined in deep amorphous volumes formed in silicon wafers by multi-energy self-implantation through a mask. Crystallization was effected at elevated temperatures with the amorphous volume being transformed at both lateral and vertical interfaces. Sample topology was mapped using an atomic force microscope. Details of the process were clarified with both plan-view and cross-sectional transmission electron microscopy analyses. Crystallization of the amorphous volumes resulted in the incorporation of a surprisingly large number of dislocations. These arose from a variety of sources. Some of the secondary structures were identified to occur uniquely from the crystallization of volumes in this particular geometry.

Aging in super glassy polymers such as poly(trimethylsilylpropyne) (PTMSP), poly(4-methyl-2-pentyne) (PMP), and polymers with intrinsic microporosity (PIM-1) reduces gas permeabilities and limits their application as gas-separation membranes. While super glassy polymers are initially very porous, and ultra-permeable, they quickly pack into a denser phase becoming less porous and permeable. This age-old problem has been solved by adding an ultraporous additive that maintains the low density, porous, initial stage of super glassy polymers through absorbing a portion of the polymer chains within its pores thereby holding the chains in their open position. This result is the first time that aging in super glassy polymers is inhibited whilst maintaining enhanced CO2 permeability for one year and improving CO2/N2 selectivity. This approach could allow super glassy polymers to be revisited for commercial application in gas separations.

High-resolution radial distribution functions of as-implanted and thermally relaxed amorphous silicon created by ion implantation were measured using tilted-illumination selected area electron diffraction at room temperature. The diffracted intensities were measured out to a maximum scattering vector 2 sin(θ)/λ of 3.3–3.7 Å−1. The volume-averaged pair-correlation statistics of as-implanted and relaxed ion-implanted amorphous silicon are virtually indistinguishable with coordination numbers of 3.7 ± 0.3 and 3.9 ± 0.3 (for neighbors closer than 3 Å) and average bond angles of 109 ± 0.5° and 110 ± 0.6°, respectively. The atomic rearrangements in ion-implanted amorphous silicon due to a low temperature anneal are subtle.