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Porous materials are widely used in applications such as adsorption, catalysis and separation. The use of expander molecules is a versatile route to enlarge the mesopore size in micellar templated mesoporous silica materials. Typical expanders used for this purpose are fossil-based organic molecules such as trimethylbenzene (TMB). In the course of making such syntheses greener and more sustainable, it is highly desirable to substitute such fossil-based chemicals with renewable ones. Here, we show that bio-based limonene can be used as an alternative expander molecule for the synthesis of large-pore templated silica. On the basis of electron microscopy, nitrogen physisorption and small angle X-ray scattering we show that the substitution of TMB by limonene leads to very similar material characteristics, reaching mean mesopore diameters of 17-19 nm. A comparative life-cycle assessment demonstrates the reduced environmental impact of limonene production from citrus peel waste compared to TMB production, supporting the call for more applications of renewable chemicals, ideally from waste-streams, also for the production of porous materials.

Some studies have speculated that the concentration of bromide ions plays a crucial role in the surfactant density surrounding gold nanorods (AuNR). Small-angle X-ray and neutron scattering (SAXS and SANS) experiments were conducted to analyze any influence the bromide ions might have on the stabilization layer and the aggregation behavior of the ligand CTAB molecules in general. The AuNR were immersed in solutions containing a fixed CTA

Herein we systematically investigate the influence of hydrogenation time and temperature on defects formation, structural changes, and co-catalyst free photocatalytic activity for epitaxially grown anatase thin films on strontium titanate single crystals. The photocatalytic activity trend of the anatase epi layers is similar to that of anatase powders and brookite single crystals in reported recent literature, that is, the H2 evolution rate exhibits a typical maximum upon hydrogenation under moderate annealing temperatures (500 °C). By combining surface sensitive X-ray diffraction methods and analytical high-resolution electron microscopy techniques we reveal quantitatively the oxygen loss from the epi-layer ascribed to the hydrogenation (H2 reduction) treatment. We observe specific physicochemical changes associated with the introduction of oxygen vacancies: (i) the formation of a nanoscale strained crystal surface, (ii) the agglomeration of point defects in the bulk of the anatase epi layer, and (iii) a transition towards a Ti2O3 like symmetry at the film surface, i.e. an evident oxygen deficiency at the epi layer surface in particular prominent for the most active sample as a function of the hydrogenation parameters. These extensive experimental findings allow us to propose an empirical model, which links detrimental and beneficial effects of Ti3+ centers and oxygen vacancies in the bulk and at the surface and their abundance to an optimum point defect configuration for water splitting via “grey” anatase.

Herein we introduce for the first time a reduced “grey” brookite TiO2 photocatalyst, produced by thermal hydrogenation of brookite nanoparticles, that shows a remarkable noble metal free photocatalytic H2 evolution. Its activity is substantially higher than that of other TiO2 polymorphs, i.e. anatase or rutile, comparably sized and activated by hydrogenation under optimized conditions. Along with brookite powders, an oriented brookite single crystal was investigated as a defined surface to confirm the effects of the hydrogenation treatment. By a combination of electron paramagnetic resonance (EPR), electron and X-ray characterization techniques applied to the powders and single crystal, we find that hydrogenation forms in brookite a defective crystalline surface layer rich in Ti3+ states. Amorphization effects, i.e. forming the so called “amorphous shell” as reported in previous work for black anatase TiO2, were not detected. Overall, we provide experimental evidence that hydrogenation forms in brookite a surface strained zone with point defects that are mediators for electron transfer to H2O, leading to a significantly enhanced noble metal free photocatalytic H2 evolution in comparison to anatase.

The thermally induced stereochemical interconversion between the trans and cis isomers of [Co(acac)2(N3)(py)] in liquid solution is investigated with time-resolved Fourier-transform infrared spectroscopy. The complex is synthesized stereo-selectively in its trans-form. Upon dissolution of the trans-form, the kinetic build-up of the cis-form is evidenced by the spectro-temporal evolution of the FTIR-spectrum. The individual isomer-specific component spectra are in good agreement with calculated spectra obtained from density functional theory. The rate constants of the forward and backward reactions responsible for the trans-cis isomerization equilibrium are derived from the kinetic traces in combination with existing thermochemical data from the literature. Moreover, the temperature-dependence of the rate constants are in line with Arrhenius activation energies of (122 ± 8) kJ/mol and (109 ± 8) kJ/mol for the forward and backward reactions, respectively. DFT-calculations suggest that the stereochemical rearrangement is caused by a pyridine rebound mechanism involving penta-coordinated square-pyramidal [Co(acac)2(N3)]-intermediates.

Adding to the versatile class of ionic liquids, we report the detailed structure and property analysis of a new class of asymmetrically substituted imidazolium salts, offering interesting thermal characteristics, such as liquid crystalline behavior, polymorphism or glass transitions. A scalable general synthetic procedure for N-polyaryl-N’-alkyl-functionalized imidazolium salts with para-substituted linker (L) moieties at the aryl chain, namely [LPhmImHR]+ (L=Br, CN, SMe, CO2Et, OH; m=2, 3; R=C12, PEGn; n=2, 3, 4), was developed. These imidazolium salts were studied by single-crystal X-ray diffraction (SC-XRD), NMR spectroscopy and thermochemical methods (DSC, TGA). Furthermore, these imidazolium salts were used as N-heterocyclic carbene (NHC) ligand precursors for mononuclear, first-row transition metal complexes (MnII, FeII, CoII, NiII, ZnII, CuI, AgI, AuI) and for the dinuclear Ti-supported Fe-NHC complex [(OPy)2Ti(OPh2ImC12)2(FeI2)] (OPy=pyridin-2-ylmethanolate). The complexes were studied concerning their structural and magnetic behavior via multi-nuclear NMR spectroscopy, SC-XRD analyses, variable temperature and field-dependent (VT-VF) SQUID magnetization methods, X-band EPR spectroscopy and, where appropriate, zero-field 57Fe Mössbauer spectroscopy.

Bulk heterojunction organic solar cells (BHJ‐OSCs) are designed to overcome inefficient charge generation and limited exciton diffusion of organic semiconductors. However, there are some disadvantages involving inherent voltage losses, microstructure control, and operational instability. Bilayer solar cells (BL‐OSCs) without mixed regions are free from these problems and offer a platform to explore the photophysical processes at the donor–acceptor interface. Here, a breakthrough for n‐i‐p BL‐OSCs in charge generation efficiency is reported. A gradual adjustment of the molecular interface orientation of the polymer donor (PM6) is accompanied by the evolution of charge‐transfer states and Forster energy transfer. Besides, less recombination losses and superior morphological stability of BL‐OSCs are achieved at a PCE comparable to that of BHJ‐OSCs with similar layer thickness. This investigation confirms the feasibility of manufacturing BL‐OSCs by a transfer printing method and provides a versatile architecture to study fundamental interface phenomena in OSCs independent from microstructure disorder.

Identification and investigation of strain at buried interfaces in halide perovskite photovoltaics are crucial for directing research on the performance and stability of perovskite solar cells. In this work, we find a gradual shift in the bandgap of up to 60 meV over a perovskite layer thickness of 300 nm caused by interfacial strain. This graded bandgap is desired from the aspect of device engineering. However, in parallel, the increased defect density causes charge recombination at the buried interface. These two effects compensate each other, resulting in an overall performance improvement under standard one sun illumination. Nevertheless, the disadvantage of enhanced defect density is clearly observed at low light intensities, where the device performance becomes dominated by charge recombination and ion migration. Moreover, the strained interfaces are proven to induce enhanced defect densities, causing significantly accelerated device degradation under illumination as well as in the dark.

We studied structure and dynamics in liquid Ge and ${\text{Si}}_{20}{\text{Ge}}_{80}$. Quasielastic neutron scattering (QNS) was employed to accurately determine the Ge self-diffusion coefficient. Static structure factors were measured using neutron and x-ray diffraction. Containerless processing via electromagnetic levitation (EML) enabled to obtain structure factors over a broad temperature range from the metastable regime of the undercooled melt to several hundred Kelvin above the melting point. Moreover, isotopic substitution and combination with x-ray diffraction allowed to determine the partial structure factors ${S}_{\mathrm{NN}}(q), {S}_{\mathrm{NC}}(q), {S}_{\mathrm{GeGe}}(q)$, and ${S}_{\mathrm{GeSi}}(q)$ for liquid ${\text{Si}}_{20}{\text{Ge}}_{80}$. The topological structures of liquid Ge and ${\text{Si}}_{20}{\text{Ge}}_{80}$ are very similar. In addition, the Ge self-diffusion coefficients in liquid Ge and ${\text{Si}}_{20}{\text{Ge}}_{80}$ are equal within error limits.

It is demonstrated by a detailed structural analysis that the crystallinity and the efficiency of small molecule based organic photovoltaics can be tuned by solvent vapor annealing (SVA). Blends made of the small molecule donor 2,2′-[(3,3′″,3″″,4′-tetraoctyl[2,2′:5′,2″:5″,2′″:5′″,2″″-quinquethiophene]-5,5″″-diyl)bis[(Z)-methylidyne(3-ethyl-4-oxo-5,2-thiazolidinediylidene)]]bis-propanedinitrile (DRCN5T) and the acceptor [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) were annealed using solvent vapors with either a high solubility for the donor (tetrahydrofuran), the acceptor (carbon disulfide) or both (chloroform). The samples were analyzed by grazing-incidence wide-angle X-ray scattering (GIWAXS), electron diffraction, X-ray pole figures, and time-of-flight secondary ion mass spectrometry (ToF-SIMS). A phase separation of DRCN5T and PC71BM is induced by SVA leading to a crystallization of DRCN5T and the formation of a DRCN5T enriched layer. The DRCN5T crystallites possess the two dimensional oblique crystal system with the lattice parameters a = 19.2 Å, c = 27.1 Å, and β = 111.1° for the chloroform case. No major differences in the crystal structure for the other solvent vapors were observed. However, the solvent choice strongly influences the size of the DRCN5T enriched layer. Missing periodicity in the [010]-direction leads to the extinction of all Bragg reflections with k ≠ 0. The annealed samples are randomly orientated with respect to the normal of the substrate (fiber texture).

The magnetism of the mixed-valence high-spin cluster [Mn18SrO8(N3)7Cl(MedhmpH)12(MeCN)6]Cl2 (1) exhibiting intramolecular ferromagnetic interactions was studied using inelastic neutron scattering (INS), and reliable values for the exchange coupling constants were determined based on the quality of simultaneous fits to the INS and magnetic data. The challenge of the huge size of the Hilbert space (3 375 000) and many exchange coupling constants (7 assuming a C3 symmetry) generally encountered in large spin clusters was resolved as follows: (a) The results of the restricted Hilbert space ferromagnetic cluster spin wave theory were compared to the experimental spectroscopic data. The observed INS transitions were thus assigned to spin wave excitations in a bounded ferromagnetic spin cluster and moreover could be visualized in a straightforward way based on this theory. (b) Simultaneously, Quantum Monte Carlo (QMC) calculations of the temperature-dependent magnetic susceptibility with the same parameter set were compared to the experimental data. Application of state-of-the-art QMC algorithms, as available in the open source ALPS package, in ferromagnetic clusters avoids the full Hamiltonian diagonalization without sacrificing calculation accuracy of the magnetic susceptibility down to the lowest temperatures, which was crucial for the successful analysis. The combined fits revealed two exchange-coupling models with equally good overall agreement to the data. Our preferred model was inspired by magnetostructural correlations and is consistent with them. The model involves three different exchange interactions, one describing the interaction between the core MnIII spins Ja = 14.3(1.0) K and two interactions linking the core and the peripheral MnII spins: Jb = 8.3(4) K and J6 = 3.6(4) K. The use of open-source QMC software and our systematic approach to fitting multiple sets of data obtained by different experimental techniques are described in detail and are generally applicable for understanding large ferromagnetically coupled clusters.

Gold nanorods (AuNRs) are of interest for many applications, since their absorption in the regime of visible light can easily be tuned by their exact shape. To produce these AuNRs, a two-step synthesis that starts from small seed particles is used. These seed particles are stabilized by cetyltrimethylammonium bromide (CTAB), which forms micelles at the used concentration (0.1 mol/L). In this work, the influence of the micelle morphology on the stabilization of these seed particles and the consequences on the formation of AuNRs is reported. The elongation of CTAB micelles by the addition of n-hexanol leads to much more stable seed particle dispersions and thus less polydisperse AuNRs. In contrast, a higher number of micelles compared to pure CTAB dispersions result from the addition of n-pentanol. This promotes the formation of larger seed particles and leads to lower yields of AuNRs. The gold nanoparticles are characterized by UV–vis–NIR absorption spectroscopy, transmission electron microscopy, and small...

The elementary light-triggered dynamics of the transition metal complex, trans-[CoIII(acac)2(N3)(py)] (trans-[1]), was investigated using femtosecond mid-infrared (mIR) and UV-Vis spectroscopies following ultrafast acetylacetonate-to-cobalt charge-transfer excitation at 266 nm. The spectro-temporal response is indicative of an ultrafast return to the electronic ground state via a sequential intramolecular electron transfer. The locally excited ligand-to-metal charge transfer state, 1LMCTacac, decays within 200 fs via azide-to-acac electron transfer to another charge-transfer state, 1LMCTazide, that features an azidyl radical ligand attached to a cobalt(II) center. A subsequent cobalt-to azidyl electron transfer occurring within 1.8 ps generates an excited metal centered state, 1MC, thereby re-establishing the fully closed-shell character of the anionic azido and acac ligands. The fully relaxed electronic ground state of trans-[1] is then recovered via internal conversion and vibrational energy relaxation on a 10 ps-time scale.

Semiconducting self-assembled monolayers (SAMs) represent highly relevant components for the fabrication of organic thin-film electronics because they enable the precise formation of active it-conjugates in terms of orientation and layer thickness. In this work, we demonstrate self-assembled monolayer field-effect transistors (SAMFETs) composed of phosphonic acid oligomers of 3-hexylthiophene (oligothiophenes-OT) with systematic variations of thiophene repeating units (5, 10, and 20). The devices exhibit stable lateral charge transport with increased mobility as a function of thiophene unit counts. Importantly, our work reveals the packing and intermolecular order of varied-chain-length SAMs at the molecular scale via X-ray reflectivity (XRR) and quantitative X-ray photoelectron spectroscopy (XPS). Short oligomers (OT5-PA and OT10-PA) arrange almost perpendicular to the substrate, forming highly ordered SAMs, whereas the long-chain OT20-PA exhibits a folded structure. By tuning the molecular order in the monolayers via the SAM substitution reaction, the OT20-PA devices show a tripling in mobility.

Outer-sphere radical hydrogenation of olefins proceeds via stepwise hydrogen atom transfer (HAT) from transition metal hydride species to the substrate. Typical catalysts exhibit M-H bonds that are either too weak to efficiently activate H2 or too strong to reduce unactivated olefins. This contribution evaluates an alternative approach, that starts from a square-planar cobalt(II) hydride complex. Photoactivation results in Co-H bond homolysis. The three-coordinate cobalt(I) photoproduct binds H2 to give a dihydrogen complex, which is a strong hydrogen atom donor, enabling the stepwise hydrogenation of both styrenes and unactivated aliphatic olefins with H2 via HAT.

The preparation of a highly ordered nanostructured transparent electrode based on a combination of nanosphere lithography and anodization is presented. The size of perfectly ordered pore domains is improved by an order of magnitude with respect to the state of the art. The concomitantly reduced density of defect pores increases the fraction of pores that are in good electrical contact with the underlying transparent conductive substrate. This improvement in structural quality translates directly and linearly into an improved performance of energy conversion devices built from such electrodes in a linear manner.

Ambient conditions sorption isotherms of dihydrogen in a series of various levels of Cu-exchanged ZSM-5 zeolites, with two different Si/Al ratios, namely 11.5 and 25, show the presence of different amount of Cu centres able to strongly bind H2. Although the isosteric heats of adsorption derived from these isotherms are rather similar, of the order of 30 kJ/mol H2, Inelastic Neutron Scattering (INS) of adsorbed dihydrogen and Fourier-Transformed Infra-Red (FTIR) spectroscopy measurements of adsorbed CO and NO reveal that copper is encountered in two oxidation states. At least two types of Cu(I) ions are clearly detected as well as some heterogeneity of the Cu(II) species. The number of these Cu species is different in the two investigated ZSM-5 materials and depends on the Cu exchange level. With the aid of DFT model cluster calculations we find that under different coordination environments, determined by the Al distribution, both mono- and divalent Cu ions could bind H2 with a different strength. Unprecedentedly, we found that Cu-ions compensating two Al atoms, i.e. formally Cu(II) species, relatively far apart from each other, may behave very similarly to the monovalent Cu-species or alternatively viewed – as Cu(I) species that compensate for two framework Al-atoms. Such Cu-species also form stable η2 dihydrogen complexes.

The transition-metal dichalcogenide HfS2 is a promising alternative semiconductor with adequate band gap and high carrier mobility. However, a controllable growth of continuous HfS2 films with selectivity for specific surfaces at a low temperature on a large scale has not been demonstrated yet. Herein, HfS2 films are grown at 100 °C by atomic layer deposition (ALD) based on the precursors tetrakis(dimethylamido)hafnium and H2S. In situ vibrational spectroscopy allows for the definition of the temperature range over which (Me2N)4Hf chemisorbs as one monolayer. In that range, sequential exposures of the solid surface with (Me2N)4Hf and H2S result in self-limiting reactions that yield alternating surface termination with dimethylamide and thiol. Repeating the cycle grows smooth, continuous, stoichiometric films of thicknesses adjustable from angstroms to >100 nm, as demonstrated by spectroscopic ellipsometry, XRR, AFM, UV–vis and Raman spectroscopy, XPS, and TEM. The well-defined surface chemistry enables one to deposit HfS2 selectively using, for example, patterns generated in molecular selfassembled monolayers. This novel ALD reaction combines several attractive features necessary for integrating HfS2 into devices.

The mechanism behind the stability of organic nanoparticles prepared by liquid antisolvent (LAS) precipitation without a specific stabilizing agent is poorly understood. In this work, we propose that the organic solvent used in the LAS process rapidly forms a molecular stabilizing layer at the interface of the nanoparticles with the aqueous dispersion medium. To confirm this hypothesis, n-octadecyltrichlorosilane (OTS)-functionalized silicon wafers in contact with water-solvent mixtures were used as a flat model system mimicking the solid-liquid interface of the organic nanoparticles. We studied the equilibrium structure of the interface by X-ray reflectometry (XRR) for water-solvent mixtures (methanol, ethanol, 1-propanol, 2-propanol, acetone, and tetrahydrofuran). The formation of an organic solvent-rich layer at the solid-liquid interface was observed. The layer thickness increases with the organic solvent concentration and correlates with the polar and hydrogen bond fraction of Hansen solubility parameters. We developed a self-consistent adsorption model via complementing adsorption isotherms obtained from XRR data with molecular dynamics simulations.

Summary Organic solar cells (OSCs) based on non-fullerene acceptors (NFAs) have developed very fast in recent years. A proper balance among power conversion efficiency (PCE), stability, and production cost needs further elaboration. Here we investigate the industrial viability of highly efficient OSCs based on several representative NFAs. The most stable OSCs exhibit PCE of ∼8% along with extrapolated T80 lifetime (80% of the initial PCE) of over 11,000 hr under equivalent 1 sun illumination, which would lead to a very impressive operational lifetime approaching 10 years. Photo-stability is strongly dependent on the end-group and side-chain engineering of the NFAs. Breaking of conjugation during photo-aging leads to increased energetic traps. Fluorination of the end-group stabilizes molecules against light soaking, while adding methyl groups shows an opposite trend. Side-chain modification can significantly influence the morphological stability. Reducing synthetic complexity of this class of NFAs will ultimately push the organic photovoltaics technology into real-life applications.

The operational stability of organic solar cells (OSCs) is the essential barrier to commercialization. Compared to thermally-induced degradation, photo-stability of OSCs is far away from being resolved. Here, we demonstrate that the thermal- and photo-degradation of metastable bulk-heterojunction OSCs are governed by the same mechanism. Understanding the fundamental principles behind this mechanism is of significant importance to fully address the instability issues. Structural incompatibilities between the donor and acceptor molecules are identified as the main origin of the instability. Further, we introduce a top-down approach mainly based on their melting temperature and interaction parameters to rationally screen molecular phase stabilizers from a database with more than 10 000 small molecules. Eventually, five chemicals were selected to validate our concept and tested in unstable organic solar cells. 1,4-Piperazine, which possesses a high melting point, good miscibility with polymers and the capability of forming inter-molecular hydrogen bonding, can indeed stabilize the mixed amorphous phases, leading to significantly improved stability of otherwise metastable OSCs.

High-quality epitaxial growth of oriented microcrystallites on a semiconductor substrate is demonstrated here for formamidinium lead bromide perovskite, by drop casting of precursor solutions in air. The microcrystallites exhibit green photoluminescence at room temperature, as well as lasing with low thresholds. Lasing is observed even though the substrate is fully opaque at the lasing wavelengths, and even though it has a higher refractive index as the perovskite active material. Moreover, the lasing is stable for more than 109 excitation pulses, which is more than what is previously achieved for devices kept in the air. Such highly stable lasing under pulsed excitation represents an important step towards continuous mode operation or even electrical excitation in future perovskite-based devices.

There is a strong market driven need for processing organic photovoltaics from eco-friendly solvents. Water-dispersed organic semiconducting nanoparticles (NPs) satisfy these premises convincingly. However, the necessity of surfactants, which are inevitable for stabilizing NPs, is a major obstacle towards realizing competitive power conversion efficiencies for water-processed devices. Here, we report on a concept for minimizing the adverse impact of surfactants on solar cell performance. A poloxamer facilitates the purification of organic semiconducting NPs through stripping excess surfactants from aqueous dispersion. The use of surfactant-stripped NPs based on poly(3-hexylthiophene) / non-fullerene acceptor leads to a device efficiency and stability comparable to the one from devices processed by halogenated solvents. A record efficiency of 7.5% is achieved for NP devices based on a low-band gap polymer system. This elegant approach opens an avenue that future organic photovoltaics processing may be indeed based on non-toxic water-based nanoparticle inks., Water-based semiconducting polymer nanoparticles are eco-friendly and non-toxic but their performance suffers from the surfactants. Here Xie et al. design an approach to minimize the amount of residual surfactant in these nanoparticles and make high-efficiency and stability solar cells.

The growth of silver shells on gold nanorods is investigated by in situ liquid cell transmission electron microscopy using an advanced liquid cell architecture. The design is based on microwells in which the liquid is confined between a thin Si3N4 membrane on one side and a few-layer graphene cap on the other side. A well-defined specimen thickness and an ultraflat cell top allow for the application of high-resolution TEM and the application of analytical TEM techniques on the same sample. The combination of high-resolution data with chemical information is validated by radically new insights into the growth of silver shells on cetrimonium bromide stabilized gold nanorods. It is shown that silver bromide particles already formed in the stock solution play an important role in the exchange of silver ions. The Ag shell growth can be directly correlated with the layer-by-layer dissolution of AgBr nanocrystals, which can be controlled by the electron flux density via distinctly generated chemical species in t...

Development of high-quality organic nanoparticle inks is a significant scientific challenge for the industrial production of solution-processed organic photovoltaics (OPVs) with eco-friendly processing methods. In this work, we demonstrate a novel, robot-based, high-throughput procedure performing automatic poly(3-hexylthio-phene-2,5-diyl) and indene-C60 bisadduct nanoparticle ink synthesis in nontoxic alcohols. A novel methodology to prepare particle dispersions for fully functional OPVs by manipulating the particle size and solvent system was studied in detail. The ethanol dispersion with a particle diameter of around 80–100 nm exhibits reduced degradation, yielding a power conversion efficiency of 4.52%, which is the highest performance reported so far for water/alcohol-processed OPV devices. By successfully deploying the high-throughput robot-based approach for an organic nanoparticle ink preparation, we believe that the findings demonstrated in this work will trigger more research interest and effort...

The effect of the addition of n-hexanol as co-surfactant on the structure of cetyltrimethylammonium bromide (CTAB) micelles has been studied using small-angle X-ray and neutron scattering (SAXS, SANS). Contrast variation neutron scattering experiments were performed to determine the structure of both pure CTAB and n-hexanol modified CTAB micelles. The incorporation of n-hexanol leads to an elongation of the ellipsoidal CTAB micelles. The scattering length density of the micellar shell linearly depends on the degree of deuteration of the dispersion medium water and revealed the existence of substantial amounts of water in the micellar shell. The water content in the shell increased from 20 vol-% observed for pure CTAB micelles to 44 vol-% found for n-hexanol modified CTAB micelles. The amount of n-hexanol in the micellar shell was determined by varying the amount of fully deuterated and protonated n-hexanol. These experiments revealed a volume fraction of 26 vol-% of n-hexanol molecules in the micellar core which equals a molar fraction of 50 % n-hexanol within the CTAB micelles. The total composition of micellar core and shell was estimated. The packing density of headgroups, water molecules and bromide ions turned out to drastically increase in n-hexanol modified CTAB micelles. These findings contribute to a fundamental understanding of the stabilization mechanism of micelles by alcoholic co-surfactants and the resulting alteration of the morphology and interface composition. These results will facilitate the optimization of processes where CTAB and other comparable surfactants are used as phase transfer catalysts, structure directing agents or stabilizers in colloidal dispersions or emulsions.

In this work, we present and support the positive influence of 1,8-diiodooctane (DIO) as processing additive for the fabrication of solution processed near infrared (NIR) organic photodiodes (OPDs) based on the spray-coated blend of [6,6]phenyl-C70-butyric acid methyl ester (PC70BM) and poly[(2,5-bis(2-hexyldecyl)-2,3,5,6-tetrahydro-3,6-diox-opyrrolo[3,4-c]pyrrole-1,4-diyl)-alt-([2,2’:5′,2″-terthioph-ene]-5,5″-diyl)] (PDPP3T). Transmission electron microscopy (TEM) analysis show that the use of DIO improves donor–acceptor interfaces in the bulk heterojunction (BHJ) layer. Besides the enhancement of electron/hole transport pathways that leads to higher efficiencies, it reduces significantly the roughness of spray coated layers. The External Quantum Efficiency (EQE) is increased up to 35% at 900 nm and the dark current is decreased one order of magnitude in comparison to the reference down to 20 nA/cm2 at -5 V. The OPD's detectivity is increased from 1.66 × 1011 Jones to 3.34 × 1012 Jones and the linearity response is improved. A comprehensive morphological and electro-optical characterization of the generated layers and devices is the main focus of this work.

ZnO nanoparticles (NPs) are highly relevant for various industrial applications, however, after synthesis of the NPs residual chemicals need to be removed from the colloidal raw product by washing, as they may influence the performance of the final device. In the present study we focus on the effect of washing by antisolvent flocculation with subsequent redispersion of the NPs on the stabilizing acetate shell. Purification of the ZnO nanoparticles is reported to be optimal with respect to zeta potential that has a maximum after one washing cycle. In this work, we will shed light on this observation using small angle X-ray and neutron scattering (SAXS, SANS) by demonstrating that after the first washing cycle the content of acetate in the ligand shell around the ZnO NPs increases. In detail, it was observed that the diffuse acetate shell shrinks to the size of a monolayer upon washing but the acetate content of this monolayer is higher than within the diffuse shell of the particles of the native dispersion. A second washing cycle reduces the acetate concentration within the stabilizing shell and the stability of the dispersion drops accordingly. After another (third) washing cycle strong agglomeration was observed for all investigated samples.

Nanosized materials are expected to play a unique role in the development of future catalytic processes. Herein, pre-prepared and geometrically well-defined amorphous silica spheres are densified into silica-rich zeolites with nanosized dimensions. After the densification, the obtained nanosized zeolites exhibit the same spherical morphology like the starting precursor but characterized by a drastically reduced size, higher density, and high crystallinity. The phase transformation into crystalline zeolite material and the densification effect are achieved through a well-controlled steam-assisted treatment of the larger precursor particles so that the transformation process proceeds always towards the center of the spheres, just like a shrinking process. Furthermore, this procedure is applicable also to commercially available silica particles, as well as aluminum-containing systems (precursors) leading to acidic nano-catalysts with improved catalytic performance.

Kagome lattice types have been of intense interest as idealized examples of extended frustrated spin systems. Here we demonstrate how the use of neutron diffraction and inelastic neutron scattering coupled with spin wave theory calculations can be used to elucidate the complex magnetic interactions of extended spin networks. We show that the magnetic properties of the coordination polymer Mn3(1,2,4-(O2C)3C6H3)2, a highly distorted kagome lattice, have been erroneously characterized as a canted antiferromagnet in previous works. Our results demonstrate that, although the magnetic structure is ferrimagnetic, with a net magnetic moment, frustration persists in the system. We conclude by showing that the conventions of the Goodenough–Kanamori rules, which are often applied to similar magnetic exchange interactions, are not relevant in this case.

We present quasielastic neutron scattering results on hydrous silica, sodium aluminosilicate, and sodium trisilicate melts with 10 mol% total water content, studied at high temperature under high pressure. Combining neutron time-of-flight spectrometry with neutron backscattering, intrinsic, microscopic proton dynamics is investigated on a time scale from 0.2 ps up to 1 ns between 850 K and 1250 K. All three hydrous silicate melts exhibit a relatively slow proton dynamics, although the melt viscosity is drastically reduced upon water dissolution. The self-diffusion coefficient of proton in the hydrous sodium trisilicate melt is on the order of 10 −11 m 2 s −1 , two orders of magnitude slower than the sodium dynamics in the corresponding anhydrous melt. The proton dynamics in hydrous silica and albite is not faster than that time scale. We show that the transport mechanism involves not only –OH but also molecular water species. All protons are mobile during the transport of the water instead of diffusion of a specific water speciation. These characteristics of the proton structural relaxation in the melt can be attributed to a transport in a complex H-bonding environment.

Recently, in situ characterization methods have attracted increasing attention, especially in organic photovoltaics (OPV) field, since they provide greater insight into the mechanism of film formation, thus help to identify optimized processing conditions used to process the most efficient organic bulk-heterojunction thin films. In combination with various powerful X-ray-based characterization methods, several studies observed the morphological changes under the influence of different processing conditions. In this review, we summarize the fundamentals and implementation of X-ray-based and optical characterization methods, utilized in in situ mode and introduce the reader a better overview of the information acquired from a given technique in terms of microstructure formation in OPV. While we give a chronological development of in situ characterization methods in the field of OPV, we discuss the interplay between thermodynamics of solutions and drying kinetics of different types of organic blends.

Great attention has been paid to developing low bandgap non-fullerene acceptors (NFAs) for matching wide bandgap donor polymers to increase the photocurrent and therefore the power conversion efficiencies (PCEs) of NFA organic solar cells, while pyrene-core based acceptor–donor–acceptor (A–D–A) NFAs have been mainly reported via the 2,9-position connection due to their bisthieno[30,20-b']thienyl[a,h]pyrene fused via a five-membered ring bridge at the ortho-position of pyrene as the representative one named FPIC5, which has prohibited further narrowing their energy gap. Herein, an acceptor FPIC6 was exploited by creating the 1,8-position connection through fusing as bisthieno[30,20-b0]thienyl[f-g,m-n]pyrene linked at the bay-position via a six-membered bridge, with enhanced push–pull characteristics within such A–D–A structure. As a structural isomer of FPIC5, FPIC6 exhibited a much lower bandgap of 1.42 eV (1.63 eV for FPIC5). Therefore, the photocurrent and PCE of PTB7-Th:FPIC6 cells were improved to 21.50 mA cm2 and 11.55%, respectively, due to the balanced mobilities, better photoluminescence quenching efficiency and optimized morphology, which are both40% better than those of PTB7-Th:FPIC5 cells. Our results clearly proved that a pyrene fused core with 1,8-position connection with electron-withdrawing end groups instead of 2,9-position connection is an efficient molecular design strategy to narrow the optical bandgap and improve the photovoltaic performance of NFA based OSCs.

AlN single crystals grown by physical vapor transport have been analyzed by X-ray methods to evaluate dislocation types, densities and spatial distribution within the crystal. Potential changes of the AlN crystal quality during growth, both within the axial growth direction and within lateral expansion areas, have been investigated., AlN slices from bulk crystals grown under low thermomechanical stress conditions via the physical vapor transport (PVT) method were analyzed by X-ray methods to study the influence of the growth mode on the crystal quality. Defect types and densities were analyzed along axial [0001] as well as lateral growth directions. X-ray diffraction (0110) rocking-curve mappings of representative wafer cuts reveal a low mean FWHM of 13.4 arcsec, indicating the generally high crystal quality. The total dislocation density of 2 × 103 cm−2 as determined by X-ray topography is low and dislocations are largely threading edge dislocations of b = 1/3〈1120〉 type. The absence of basal plane dislocations in homogeneous crystal regions void of macroscopic defects can be linked to the low-stress growth conditions. Under the investigated growth conditions this high crystal quality can be maintained both along the axial [0001] direction and within lateral growth directions. Exceptions to this are some locally confined, misoriented grains and defect clusters, most of which are directly inherited from the seed or are formed due to the employed seed fixation technique on the outer periphery of the crystals. Seed-shaping experiments indicate no apparent kinetic limitations for an enhanced lateral expansion rate and the resulting crystal quality, specifically with regard to the growth mode on a-face facets.

A portable small-angle X-ray scattering instrument with geometrical dimensions suitable for installation at the D22 instrument was designed and constructed for simultaneous small-angle X-ray and neutron scattering experiments at ILL., Exploiting small-angle X-ray and neutron scattering (SAXS/SANS) on the same sample volume at the same time provides complementary nanoscale structural information in two different contrast situations. Unlike an independent experimental approach, the truly combined SAXS/SANS experimental approach ensures the exactness of the probed samples, particularly for in situ studies. Here, an advanced portable SAXS system that is dimensionally suitable for installation in the D22 zone of ILL is introduced. The SAXS apparatus is based on a Rigaku switchable copper/molybdenum microfocus rotating-anode X-ray generator and a DECTRIS detector with a changeable sample-to-detector distance of up to 1.6 m in a vacuum chamber. A case study is presented to demonstrate the uniqueness of the newly established method. Temporal structural rearrangements of both the organic stabilizing agent and organically capped gold colloidal particles during gold nanoparticle growth are simultaneously probed, enabling the immediate acquisition of correlated structural information. The new nano-analytical method will open the way for real-time investigations of a wide range of innovative nanomaterials and will enable comprehensive in situ studies on biological systems. The potential development of a fully automated SAXS/SANS system with a common control environment and additional sample environments, permitting a continual and efficient operation of the system by ILL users, is also introduced.