Ionic Liquid-Induced Inversion of the Humidity-Dependent Conductivity of Thin PEDOT:PSS Films.

The humidity influence on the electronic and ionic resistance properties of thin post-treated poly(3,4-ethylene dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films is investigated. In particular, the resistance of these PEDOT:PSS films post-treated with three different concentrations (0, 0.05, and 0.35 M) of ethyl-3-methylimidazolium dicyanamide (EMIM DCA) is measured while being exposed to a defined humidity protocol. A resistance increase upon elevated humidity is observed for the 0 M reference sample, while the EMIM DCA post-treated samples demonstrate a reverse behavior. Simultaneously performed in situ grazing-incidence small-angle X-ray scattering (GISAXS) measurements evidence changes in the film morphology upon varying the humidity, namely, an increase in the PEDOT domain distances. This leads to a detriment in the interdomain hole transport, which causes a rise in the resistance, as observed for the 0 M reference sample. Finally, electrochemical impedance spectroscopy (EIS) measurements at different humidities reveal additional contributions of ionic charge carriers in the EMIM DCA post-treated PEDOT:PSS films. Therefrom, a model is proposed, which describes the hole and cation transport in different post-treated PEDOT:PSS films dependent on the ambient humidity.

Morphological Insights into the Degradation of Perovskite Solar Cells under Light and Humidity.

Perovskite solar cells (PSCs) have achieved competitive power conversion efficiencies compared with established solar cell technologies. However, their operational stability under different external stimuli is limited, and the underlying mechanisms are not fully understood. In particular, an understanding of degradation mechanisms from a morphology perspective during device operation is missing. Herein, we investigate the operational stability of PSCs with CsI bulk modification and a CsI-modified buried interface under AM 1.5G illumination and 75 ± 5% relative humidity, respectively, and concomitantly probe the morphology evolution with grazing-incidence small-angle X-ray scattering. We find that volume expansion within perovskite grains, induced by water incorporation, initiates the degradation of PSCs under light and humidity and leads to the degradation of device performance, in particular, the fill factor and short-circuit current. However, PSCs with modified buried interface degrade faster, which is ascribed to grain fragmentation and increased grain boundaries. In addition, we reveal a slight lattice expansion and PL redshifts in both PSCs after exposure to light and humidity. Our detailed insights from a buried microstructure perspective on the degradation mechanisms under light and humidity are essential for extending the operational stability of PSCs.

Squid Skin Cell-Inspired Refractive Index Mapping of Cells, Vesicles, and Nanostructures.

The fascination with the optical properties of naturally occurring systems has been driven in part by nature's ability to produce a diverse palette of vibrant colors from a relatively small number of common structural motifs. Within this context, some cephalopod species have evolved skin cells called iridophores and leucophores whose constituent ultrastructures reflect light in different ways but are composed of the same high refractive index material─a protein called reflectin. Although such natural optical systems have attracted much research interest, measuring the refractive indices of biomaterial-based structures across multiple different environments and establishing theoretical frameworks for accurately describing the obtained refractive index values has proven challenging. Herein, we employ a synergistic combination of experimental and computational methodologies to systematically map the three-dimensional refractive index distributions of model self-assembled reflectin-based structures both in vivo and in vitro. When considered together, our findings may improve understanding of squid skin cell functionality, augment existing methods for characterizing protein-based optical materials, and expand the utility of emerging holotomographic microscopy techniques.

Ge/Al and Ge/Si3N4/Al Core/Shell Quantum Dot Lattices in Alumina: Boosting the Spectral Response by Tensile Strain.

We investigated the production conditions and optoelectrical properties of thin film material consisting of regularly ordered core/shell Ge/Al and Ge/Si3N4/Al quantum dots (QDs) in an alumina matrix. The materials were produced by self-assembled growth achieved by means of multilayer magnetron sputtering deposition. We demonstrated the successful fabrication of well-ordered 3D lattices of Ge/Al and Ge/Si3N4/Al core/shell quantum dots with a body-centred tetragonal arrangement within the Al2O3 matrix. The addition of shells to the Ge core enables a strong tuning of the optical and electrical properties of the material. An Al shell induces a bandgap shift toward smaller energies, and, in addition, it prevents Ge oxidation. The addition of a thin Si3N4 shell induces huge changes in the material spectral response, i.e., in the number of extracted excitons produced by a single photon. It increases both the absolute value and the width of the spectral response. For the best sample, we achieved an enhancement of over 250% of the produced number of excitons in the measured energy range. The observed changes are, as it seems, the consequence of the large tensile strain in Ge QDs which is induced by the Si3N4 shell addition and which is measured to be about 3% for the most strained QDs. The tensile strain causes activation of the direct bandgap of germanium, which has a very strong effect on the spectral response of the material.

Multiple Exciton Generation in 3D-Ordered Networks of Ge Quantum Wires in Alumina Matrix.

Thin films containing 3D-ordered semiconductor quantum wires offer a great tool to improve the properties of photosensitive devices. In the present work, we investigate the photo-generated current in thin films consisting of an interconnected 3D-ordered network of Ge quantum wires in an alumina matrix. The films are prepared using nitrogen-assisted magnetron sputtering co-deposition of Ge and Al2O3. We demonstrate a strong photocurrent generation in the films, much stronger than in similar films containing Ge quantum dots. The enhanced photocurrent generation is the consequence of the multiple exciton generation and the films' specific structure that allows for efficient carrier transport. Thin film with the largest nitrogen content showed enhanced performance compared to other thin films with 1.6 excitons created after absorption of a single photon at an energy nearly equal to the double bandgap value. The bandgap value depends on the geometrical properties of the quantum wires, and it is close to the maximum of the solar irradiance in this case. In addition, we show that the multiple exciton generation is the most pronounced at the photon energy values equal to multiple values of the thin film bandgap.

Surface Morphology of Textured Transparent Conductive Oxide Thin Film Seen by Various Probes: Visible Light, X-rays, Electron Scattering and Contact Probe.

Fluorine-doped tin oxide thin films (SnO2:F) are widely used as transparent conductive oxide electrodes in thin-film solar cells because of their appropriate electrical and optical properties. The surface morphology of these films influences their optical properties and therefore plays an important role in the overall efficiencies of the solar cells in which they are implemented. At rough surfaces light is diffusely scattered, extending the optical path of light inside the active layer of the solar cell, which in term improves light absorption and solar cell conversion efficiency. In this work, we investigated the surface morphology of undoped and doped SnO2 thin films and their influence on the optical properties of the films. We have compared and analysed the results obtained by several complementary methods for thin-film surface morphology investigation: atomic force microscopy (AFM), transmission electron microscopy (TEM), and grazing-incidence small-angle X-ray scattering (GISAXS). Based on the AFM and TEM results we propose a theoretical model that reproduces well the GISAXS scattering patterns.

In Situ Observation of Morphological and Oxidation Level Degradation Processes within Ionic Liquid Post-treated PEDOT:PSS Thin Films upon Operation at High Temperatures.

Organic thermoelectric thin films are investigated in terms of their stability at elevated operating temperatures. Therefore, the electrical conductivity of ethyl-3-methylimidazolium dicyanamide (EMIM DCA) post-treated poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) thin films is measured over 4.5 h of heating at 50 or 100 °C for different EMIM DCA concentrations. The changes in the electrical performance are correlated with changes in the film morphology, as evidenced with in situ grazing-incidence small-angle X-ray scattering (GISAXS). Due to the overall increased PEDOT domain distances, the resulting impairment of the interdomain charge carrier transport directly correlates with the observed electrical conductivity decay. With in situ ultraviolet-visible (UV-Vis) measurements, a simultaneously occurring reduction of the PEDOT oxidation level is found to have an additional electrical conductivity lowering contribution due to the decrease of the charge carrier density. Finally, the observed morphology and oxidation level degradation is associated with the deterioration of the thermoelectric properties and hence a favorable operating temperature range is suggested for EMIM DCA post-treated PEDOT:PSS-based thermoelectrics.

Correlation of Thermoelectric Performance, Domain Morphology and Doping Level in PEDOT:PSS Thin Films Post-Treated with Ionic Liquids.

Ionic liquid (IL) post-treatment of poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) thin films with ethyl-3-methylimidazolium dicyanamide (EMIM DCA), allyl-3-methylimidazolium dicyanamide (AMIM DCA), and 1-ethyl-3-methylimidazolium tetracyanoborate (EMIM TCB) is compared. Doping level modifications of PEDOT are characterized using UV-Vis spectroscopy and directly correlate with the observed Seebeck coefficient enhancement. With conductive atomic force microscopy (c-AFM) the authors investigate changes in the topographic-current features of the PEDOT:PSS thin film surface due to IL treatment. Grazing incidence small-angle X-ray scattering (GISAXS) demonstrates the morphological rearrangement towards an optimized PEDOT domain distribution upon IL post-treatment, directly facilitating the interconductivity and causing an increased film conductivity. Based on these improvements in Seebeck coefficient and conductivity, the power factor is increased up to 236 µW m-1 K- 2 . Subsequently, a model is developed indicating that ILs, which contain small, sterically unhindered ions with a strong localized charge, appear beneficial to boost the thermoelectric performance of post-treated PEDOT:PSS films.

Structural, Optical and Electrical Properties of Al+MoO3 and Au+MoO3 Thin Films Prepared by Magnetron Codeposition.

Structural, optical and electrical properties of Al+MoO3 and Au+MoO3 thin films prepared by simultaneous magnetron sputtering deposition were investigated. The influence of MoO3 sputtering power on the Al and Au nanoparticle formation and spatial distribution was explored. We demonstrated the formation of spatially arranged Au nanoparticles in the MoO3 matrix, while Al incorporates in the MoO3 matrix without nanoparticle formation. The dependence of the Au nanoparticle size and arrangement on the MoO3 sputtering power was established. The Al-based films show a decrease of overall absorption with an Al content increase, while the Au-based films have the opposite trend. The transport properties of the investigated films also are completely different. The resistivity of the Al-based films increases with the Al content, while it decreases with the Au content increase. The reason is a different transport mechanism that occurs in the films due to their different structural properties. The choice of the incorporated material (Al or Au) and its volume percentage in the MoO3 matrix enables the design of materials with desirable optical and electrical characteristics for a variety of applications.

Lipid Nanosystems and Serum Protein as Biomimetic Interfaces: Predicting the Biodistribution of a Caffeic Acid-Based Antioxidant.

PURPOSE: AntiOxCIN3 is a novel mitochondriotropic antioxidant developed to minimize the effects of oxidative stress on neurodegenerative diseases. Prior to an investment in pre-clinical in vivo studies, it is important to apply in silico and biophysical cell-free in vitro studies to predict AntiOxCIN3 biodistribution profile, respecting the need to preserve animal health in accordance with the EU principles (Directive 2010/63/EU). Accordingly, we propose an innovative toolbox of biophysical studies and mimetic models of biological interfaces, such as nanosystems with different compositions mimicking distinct membrane barriers and human serum albumin (HSA). METHODS: Intestinal and cell membrane permeation of AntiOxCIN3 was predicted using derivative spectrophotometry. AntiOxCIN3 -HSA binding was evaluated by intrinsic fluorescence quenching, synchronous fluorescence, and dynamic/electrophoretic light scattering. Steady-state and time-resolved fluorescence quenching was used to predict AntiOxCIN3-membrane orientation. Fluorescence anisotropy, synchrotron small- and wide-angle X-ray scattering were used to predict lipid membrane biophysical impairment caused by AntiOxCIN3 distribution. RESULTS AND DISCUSSION: We found that AntiOxCIN3 has the potential to permeate the gastrointestinal tract. However, its biodistribution and elimination from the body might be affected by its affinity to HSA (>90%) and by its steady-state volume of distribution (VDSS =1.89± 0.48 L∙Kg-1). AntiOxCIN3 is expected to locate parallel to the membrane phospholipids, causing a bilayer stiffness effect. AntiOxCIN3 is also predicted to permeate through blood-brain barrier and reach its therapeutic target - the brain. CONCLUSION: Drug interactions with biological interfaces may be evaluated using membrane model systems and serum proteins. This knowledge is important for the characterization of drug partitioning, positioning and orientation of drugs in membranes, their effect on membrane biophysical properties and the study of serum protein binding. The analysis of these interactions makes it possible to collect valuable knowledge on the transport, distribution, accumulation and, eventually, therapeutic impact of drugs which may aid the drug development process.

Structure, self-assembly, and properties of a truncated reflectin variant.

Naturally occurring and recombinant protein-based materials are frequently employed for the study of fundamental biological processes and are often leveraged for applications in areas as diverse as electronics, optics, bioengineering, medicine, and even fashion. Within this context, unique structural proteins known as reflectins have recently attracted substantial attention due to their key roles in the fascinating color-changing capabilities of cephalopods and their technological potential as biophotonic and bioelectronic materials. However, progress toward understanding reflectins has been hindered by their atypical aromatic and charged residue-enriched sequences, extreme sensitivities to subtle changes in environmental conditions, and well-known propensities for aggregation. Herein, we elucidate the structure of a reflectin variant at the molecular level, demonstrate a straightforward mechanical agitation-based methodology for controlling this variant's hierarchical assembly, and establish a direct correlation between the protein's structural characteristics and intrinsic optical properties. Altogether, our findings address multiple challenges associated with the development of reflectins as materials, furnish molecular-level insight into the mechanistic underpinnings of cephalopod skin cells' color-changing functionalities, and may inform new research directions across biochemistry, cellular biology, bioengineering, and optics.

In Operando GISAXS and GIWAXS Stability Study of Organic Solar Cells Based on PffBT4T-2OD:PC71BM with and without Solvent Additive.

Solvent additives are known to modify the morphology of bulk heterojunction active layers to achieve high efficiency organic solar cells. However, the knowledge about the influence of solvent additives on the morphology degradation is limited. Hence, in operando grazing-incidence small and wide angle X-ray scattering (GISAXS and GIWAXS) measurements are applied on a series of PffBT4T-2OD:PC71BM-based solar cells prepared without and with solvent additives. The solar cells fabricated without a solvent additive, with 1,8-diiodoctane (DIO), and with o-chlorobenzaldehyde (CBA) additive show differences in the device degradation and changes in the morphology and crystallinity of the active layers. The mesoscale morphology changes are correlated with the decay of the short-circuit current J sc and the evolution of crystalline grain sizes is codependent with the decay of open-circuit voltage V oc. Without additive, the loss in J sc dominates the degradation, whereas with solvent additive (DIO and CBA) the loss in V oc rules the degradation. CBA addition increases the overall device stability as compared to DIO or absence of additive.

Deposition of Thin Alumina Films Containing 3D Ordered Network of Nanopores on Porous Substrates.

Self-supporting thin films containing nanopores are very promising materials for use for multiple applications, especially in nanofiltration. Here, we present a method for the production of nanomembranes containing a 3D ordered network of nanopores in an alumina matrix, with a diameter of about 1 nm and a body centered tetragonal structure of the network nodes. The material is produced by the magnetron sputtering deposition of a 3D ordered network of Ge nanowires in an alumina matrix, followed by a specific annealing process resulting in the evaporation of Ge. We demonstrate that the films can be easily grown on commercially available alumina substrates containing larger pores with diameters between 20 and 400 nm. We have determined the minimal film thickness needed to entirely cover the larger pores. We believe that these films have the potential for applications in the fields of filtration, separation and sensing.

Prediction of paclitaxel pharmacokinetic based on in vitro studies: Interaction with membrane models and human serum albumin.

Interactions of paclitaxel (PTX) with models mimicking biological interfaces (lipid membranes and serum albumin, HSA) were investigated to test the hypothesis that the set of in vitro assays proposed can be used to predict some aspects of drug pharmacokinetics (PK). PTX membrane partitioning was studied by derivative spectrophotometry; PTX effect on membrane biophysics was evaluated by dynamic light scattering, fluorescence anisotropy, atomic force microscopy and synchrotron small/wide-angle X-ray scattering; PTX distribution/molecular orientation in membranes was assessed by steady-state/time-resolved fluorescence and computer simulations. PTX binding to HSA was studied by fluorescence quenching, derivative spectrophotometry and dynamic/electrophoretic light scattering. PTX high membrane partitioning is consistent with its efficacy crossing cellular membranes and its off-target distribution. PTX is closely located in the membrane phospholipids headgroups, also interacting with the hydrophobic chains, and causes a major distortion of the alignment of the membrane phospholipids, which, together with its fluidizing effect, justifies some of its cellular toxic effects. PTX binds strongly to HSA, which is consistent with its reduced distribution in target tissues and toxicity by bioaccumulation. In conclusion, the described set of biomimetic models and techniques has the potential for early prediction of PK issues, alerting for the required drug optimizations, potentially minimizing the number of animal tests used in the drug development process.

Self-Assembly in ultrahigh molecular weight sphere-forming diblock copolymer thin films under strong confinement.

Ultrahigh molecular weight (UHMW) diblock copolymers (DBCs) have emerged as a promising template for fabricating large-sized nanostructures. Therefore, it is of high significance to systematically study the influence of film thickness and solvent vapor annealing (SVA) on the structure evolution of UHMW DBC thin films. In this work, spin coating of an asymmetric linear UHMW polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) DBC is used to fabricate thin films, which are spherically structured with an inter-domain distance larger than 150 nm. To enhance the polymer chain mobility and facilitate approaching equilibrium nanostructures, SVA is utilized as a post-treatment of the spin coated films. With increasing film thickness, a local hexagonal packing of PMMA half-spheres on the surface can be obtained, and the order is improved at larger thickness, as determined by grazing incidence small angle X-ray scattering (GISAXS). Additionally, the films with locally hexagonal packed half-spherical morphology show a poor order-order-poor order transition upon SVA, indicating the realization of ordered structure using suitable SVA parameters.

Insight into the nanostructure of anisotropic cellulose aerogels upon compression.

Cellulose II aerogels are a highly porous class of biobased ultra-light-weight materials. They consist of interlinked networks of loosely aggregated cellulose fibrils. The latter typically have random orientation due to spontaneous phase separation triggered by addition of antisolvent to moleculardisperse cellulose solutions. Deceleration of phase separation has been recently proposed as a novel approach towards aerogels featuring preferred cellulose orientation. Here, we investigate the mechanical response of such oriented cellulose aerogels towards load up to 80% compression. Stress-strain curves were recorded and in situ small angle X-ray scattering (SAXS) was performed during compression test to obtain information about the structural alterations of the aerogel fibril networks on the nano-scale related to deformation. Using SAXS in addition, structural changes can be followed in much more detail than by recording stress-strain curves alone. Buckling and coalescence of fibers and a change in fibril orientation can be related to certain regimes in the stress-strain curve. If the loading axis is oriented parallel to the network orientation the aerogels show higher resilience towards the compression.

Structure-Function Correlations in Sputter Deposited Gold/Fluorocarbon Multilayers for Tuning Optical Response.

A new strategy to nanoengineer gold/fluorocarbon multilayer (ML) nanostructures is reported. We have investigated the morphological changes occurring at the metal-polymer interface in ML structures with varying volume fraction of gold (Au) and the kinetic growth aspect of the microscale properties of nano-sized Au in plasma polymer fluorocarbon (PPFC). Investigations were carried out at various temperatures and annealing times by means of grazing incidence small-angle and wide-angle X-ray scattering (GISAXS and GIWAXS). We have fabricated a series of MLs with varying volume fraction (0.12, 0.27, 0.38) of Au and bilayer periodicity in ML structure. They show an interesting granular structure consisting of nearly spherical nanoparticles within the polymer layer. The nanoparticle (NP) morphology changes due to the collective effects of NPs diffusion within ensembles in the in-plane vicinity and interlayer with increasing temperature. The in-plane NPs size distinctly increases with increasing temperature. The NPs become more spherical, thus reducing the surface energy. Linear growth of NPs with temperature and time shows diffusion-controlled growth of NPs in the ML structure. The structural stability of the multilayer is controlled by the volume ratio of the metal in polymer. At room temperature, UV-Vis shows a blue shift of the plasmon peak from 560 nm in ML Au/PTFE_1 to 437 nm in Au/PTFE_3. We have identified the fabrication and postdeposition annealing conditions to limit the local surface plasmon resonance (LSPR) shift from Δ λ L S P R = 180 nm (Au/PTFE_1) to Δ λ L S P R = 67 nm (Au/PTFE_3 ML)) and their optical response over a wide visible wavelength range. A variation in the dielectric constant of the polymer in presence of varying Au inclusion is found to be a possible factor affecting the LSPR frequency. Our findings may provide insights in nanoengineering of ML structure that can be useful to systematically control the growth of NPs in polymer matrix.

Preparation of non-oxidized Ge quantum dot lattices in amorphous Al2O3, Si3N4 and SiC matrices.

The preparation of non-oxidized Ge quantum dot (QD) lattices embedded in Al2O3, Si3N4, SiC matrices by self-assembled growth was studied. The materials were produced by magnetron sputtering deposition, using different substrate temperatures. The deposition regimes leading to the self-assembled growth type and the formation of three-dimensionally ordered Ge QD lattices in different matrices were investigated and determined. The oxidation of the Ge QDs in different matrices was monitored and the best conditions for the production of non-oxidized Ge QDs were found. The optical properties of the Ge QD lattices in different matrices show a strong dependence on the Ge oxidation and the matrix type.

Influence of Structure on Electronic Charge Transport in 3D Ge Nanowire Networks in an Alumina Matrix.

We demonstrate formation of material consisting of three-dimensional Germanium nanowire network embedded in an insulating alumina matrix. A wide range of such nanowire networks is produced using a simple magnetron sputtering deposition process. We are able to vary the network parameters including its geometry as well as the length and width of the nanowires. The charge transport in these materials is shown to be related to the nanowire surface per unit volume of the material, α. For low values of α, transport is characterized by space charge limited conduction and a drift of carriers in the extended states with intermittent trapping-detrapping in the localized states. For large values of α, charge transport occurs through hopping between localized electronic states, similar to observations in disorder-dominated arrays of quantum dots. A crossover between these two mechanisms is observed for the intermediate values of α. Our results are understood in terms of an almost linear scaling of the characteristic trap energy with changes in the nanowire network parameters.

Ionic Liquids as Post-Treatment Agents for Simultaneous Improvement of Seebeck Coefficient and Electrical Conductivity in PEDOT:PSS Films.

Ionic liquid (IL) post-treatment for thin films of poly(3,4-ethylene dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is employed for the simultaneous enhancement of Seebeck coefficients and electrical conductivities. Through systematic variation of the ILs, by changing the anions while keeping the cation unchanged, changes in thermoelectric, spectroscopic, and morphological properties are investigated by means of UV-vis spectroscopy and grazing-incidence wide-angle X-ray scattering (GIWAXS) as a function of the IL concentration. The simultaneous enhancement in the two important thermoelectric properties is ascribed to the binary nature of the ILs, which complements that of PEDOT:PSS. The anions of the ILs primarily interact with the positively charged, conducting PEDOT, while the cations interact with negatively charged insulating PSS. Therefore, post-treatment with ILs allows for primary and secondary doping of PEDOT:PSS at the same time. Differences in the obtained Seebeck coefficients for the investigated ILs are ascribed to the chemical properties of the anions. Additionally, the choice of the latter has implications on the morphology of the treated PEDOT:PSS films regarding average π-π-stacking distances of PEDOT chains, PEDOT-to-PSS ratios, and edge-on-to-face-on ratios, influencing charge transport properties macroscopically. A morphological model is presented, highlighting the influence of each IL in comparison with pristine PEDOT:PSS films.