Harnessing 2D Ruddlesden-Popper Perovskite with Polar Organic Cation for Ultrasensitive Multibit Nonvolatile Transistor-Type Photomemristors.

Photomemristors have been regarded as one of the most promising candidates for next-generation hardware-based neuromorphic computing due to their potentials of fast data transmission and low power consumption. However, intriguingly, so far, photomemristors seldom display truly nonvolatile memory characteristics with high light sensitivity. Herein, we demonstrate ultrasensitive photomemristors utilizing two-dimensional (2D) Ruddlesden-Popper (RP) perovskites with a highly polar donor-acceptor-type push-pull organic cation, 4-(5-(2-aminoethyl)thiophen-2-yl)benzonitrile+ (EATPCN+), as charge-trapping layers. High linearity and almost zero-decay retention are observed in (EATPCN)2PbI4 devices, which are very distinct from that of the traditional 2D RP perovskite devices consisting of nonpolar organic cations, such as phenethylamine+ (PEA+) and octylamine+ (OA+), and traditional 3D perovskite devices consisting of methylamine+ (MA+). The 2-fold advantages, including desirable spatial crystal arrangement and engineered energetic band alignment, clarify the mechanism of superior performance in (EATPCN)2PbI4 devices. The optimized (EATPCN)2PbI4 photomemristor also shows a memory window of 87.9 V and an on/off ratio of 106 with a retention time of at least 2.4 × 105 s and remains unchanged after >105 writing-reading-erasing-reading endurance cycles. Very low energy consumptions of 1.12 and 6 fJ for both light stimulation and the reading process of each status update are also demonstrated. The extremely low power consumption and high photoresponsivity were simultaneously achieved. The high photosensitivity surpasses that of a state-of-the-art commercial pulse energy meter by several orders of magnitude. With their outstanding linearity and retention, rabbit images have been rebuilt by (EATPCN)2PbI4 photomemristors, which truthfully render the image without fading over time. Finally, by utilizing the powerful ∼8 bits of nonvolatile potentiation and depression levels of (EATPCN)2PbI4 photomemristors, the accuracies of the recognition tasks of CIFAR-10 image classification and MNIST handwritten digit classification have reached 89% and 94.8%, respectively. This study represents the first report of utilizing a functional donor-acceptor type of organic cation in 2D RP perovskites for high-performance photomemristors with characteristics that are not found in current halide perovskites.

Ultrafast Proton Conduction in an Aqueous Electrolyte Confined in Adamantane-like Micropores of a Sulfonated, Aromatic Framework.

Sulfonated, cross-linked porous polymers are promising frameworks for aqueous high-performance electrolyte-host systems for electrochemical energy storage and conversion. The systems offer high proton conductivities, excellent chemical and mechanical stabilities, and straightforward water management. However, little is known about mass transport mechanisms in such nanostructured hosts. We report on the synthesis and postsynthetic sulfonation of an aromatic framework (SPAF-2) with a 3D-interconnected nanoporosity and varying sulfonation degrees. Water adsorption produces the system SPAF-2H20. It features proton exchange capacities up to 6 mequiv g-1 and exceptional proton conductivities of about 1 S cm-1. Two contributions are essential for the highly efficient transport. First, the nanometer-sized pores link the charge transport to the diffusion of adsorbed water molecules, which is almost as fast as bulk water. Second, continuous exchange between interface-bound and mobile species enhances the conductivities at elevated temperatures. SPAF-2H20 showcases how to tailor nanostructured electrolyte-host systems with liquid-like conductivities.

Effects of the Grazing Incidence Geometry on X-ray Photon Correlation Spectroscopy Measurements.

X-ray photon correlation spectroscopy (XPCS) is a versatile tool to measure dynamics on the nanometer to micrometer scale in bulk samples. XPCS has also been applied in grazing incidence (GI) geometry to examine the dynamics of surface layers. However, considering GI scattering experiments more universally, the GI geometry leads to a superposition of signals due to reflection and refraction effects, also known from the distorted-wave Born approximation (DWBA). In this paper, the impact of these reflection and refraction effects on the correlation analysis is determined experimentally by measuring grazing incidence transmission XPCS (GT-XPCS) and grazing incidence XPCS (GI-XPCS) simultaneously for a thin film sample, showing non-equilibrium dynamics. The results of the GI and GT geometry comparisons are combined within the framework of the standardly applied, simplified DWBA. These calculations allow identifying the main contributions of the detected signal from the leading scattering terms along the out-of-plane direction qz, which dominate the measured intensity pattern on the detector. In combination with the calculation of the non-linear effect of refraction in GTSAXS and GISAXS, it is possible to identify experimental conditions that can be chosen to run experiments and data analysis as close as possible to transmission XPCS and to explain which limitations for data interpretations are observed. Consequently, the beam exposure can be significantly reduced by using GI geometry only. Calculations of experimental settings prior to experiments are detailed to determine suitable qz regions for a variety of material systems measured in bulk-sensitive GI-XPCS experiments, allowing us to determine the scaling behavior of typical decay times as a function of q that is comparable to the scaling behavior obtained in distortion-free GT-XPCS or transmission XPCS experiments.

Spark Discharge Doping-Achieving Unprecedented Control over Aggregate Fraction and Backbone Ordering in Poly(3-hexylthiophene) Solutions.

The properties of semiconducting polymers are strongly influenced by their aggregation behavior, that is, their aggregate fraction and backbone planarity. However, tuning these properties, particularly the backbone planarity, is challenging. This work introduces a novel solution treatment to precisely control the aggregation of semiconducting polymers, namely current-induced doping (CID). It utilizes spark discharges between two electrodes immersed in a polymer solution to create strong electrical currents resulting in temporary doping of the polymer. Rapid doping-induced aggregation occurs upon every treatment step for the semiconducting model-polymer poly(3-hexylthiophene). Therefore, the aggregate fraction in solution can be precisely tuned up to a maximum value determined by the solubility of the doped state. A qualitative model for the dependences of the achievable aggregate fraction on the CID treatment strength and various solution parameters is presented. Moreover, the CID treatment can yield an extraordinarily high quality of backbone order and planarization, expressed in UV-vis absorption spectroscopy and differential scanning calorimetry measurements. Depending on the selected parameters, an arbitrarily lower backbone order can be chosen using the CID treatment, allowing for maximum control of aggregation. This method may become an elegant pathway to finely tune aggregation and solid-state morphology for thin-films of semiconducting polymers.

Effects of the diphenyl ether additive in halogen-free processed non-fullerene acceptor organic solar cells.

The development of an environmentally friendly fabrication process for non-fullerene acceptor organic solar cells is an essential condition for their commercialization. However, devices fabricated by processing the active layer with green solvents still struggle to reach, in terms of efficiency, the same performance as those fabricated with halogenated solvents. The reason behind this is the non-optimal nanostructure of the active layer obtained with green solvents. Additives in solution have been used to fine-tune the nanostructure and improve the performance of organic solar cells. Therefore, the identification of non-halogenated additives and the study of their effects on the device performance and stability are of primary importance. In this work, we propose the use of diphenyl ether (DPE) as additive, in combination with the non-halogenated solvent o-xylene, to fabricate organic solar cells with a completely halogen-free process. Thanks to the addition of DPE, a best efficiency of 11.7% have been obtained for the system TPD-3F:IT-4F, an increase over 15% with respect to the efficiency of devices fabricated without additive. Remarkably, the stability under illumination of the solar cells is also improved when DPE is used. The addition of DPE has effects on the molecular organization in the active layer, with an enhancement in the donor polymer ordering, showing a higher domain purity. The resulting structure improves the charge carrier collection, leading to a superior short-circuit current and fill factor. Furthermore, a reduction of the non-radiative recombination losses and an improved exciton diffusion, are the results of the superior molecular ordering. With a comprehensive insight of the effects of DPE when used in combination with a non-halogenated solvent, our study provides an approach to make the fabrication of organic solar cell environmentally friendlier and more suitable for large scale production.

Microstructural and Thermal Transport Properties of Regioregular Poly(3-hexylthiophene-2,5-diyl) Thin Films.

Polymeric thin films offer a wide range of exciting properties and applications, with several advantages compared to inorganic counterparts. The thermal conductivity of such thin films ranges typically between 0.1-1 W m-1 K-1. This low thermal conductivity can cause problems with heat dissipation in various applications. Detailed knowledge about thermal transport in polymeric thin films is desired to overcome these shortcomings, especially in light of the multitude of possible microstructures for semi-crystalline thin films. Therefore, poly(3-hexylthiophene-2,5-diyl) (P3HT) is chosen as a model system to analyze the microstructure and optoelectronic properties using X-ray scattering and absorption spectra along with the thermal transport properties using the photoacoustic technique. This combination of analysis methods allows for determining the optoelectronic and thermal transport properties on the same specimen, supplemented by structural information. The effect of different molecular weights and solvents during film preparation is systematically examined. A variation of the optoelectronic properties, mainly regarding molecular weight, is apparent, while no direct influence of the solvent during preparation is discernible. In contrast, the thermal conductivities of all films examined fall within a similar range. Therefore, the microstructural properties in the ordered regions do not significantly affect the resulting thermal properties in the sample space investigated in this work. We conclude that it is mainly the amorphous regions that determine the thermal transport properties, as these represent a bottleneck for thermal transport.

Traps and transport resistance are the next frontiers for stable non-fullerene acceptor solar cells.

Stability is one of the most important challenges facing material research for organic solar cells (OSC) on their path to further commercialization. In the high-performance material system PM6:Y6 studied here, we investigate degradation mechanisms of inverted photovoltaic devices. We have identified two distinct degradation pathways: one requires the presence of both illumination and oxygen and features a short-circuit current reduction, the other one is induced thermally and marked by severe losses of open-circuit voltage and fill factor. We focus our investigation on the thermally accelerated degradation. Our findings show that bulk material properties and interfaces remain remarkably stable, however, aging-induced defect state formation in the active layer remains the primary cause of thermal degradation. The increased trap density leads to higher non-radiative recombination, which limits the open-circuit voltage and lowers the charge carrier mobility in the photoactive layer. Furthermore, we find the trap-induced transport resistance to be the major reason for the drop in fill factor. Our results suggest that device lifetimes could be significantly increased by marginally suppressing trap formation, leading to a bright future for OSC.

Degradation of low-density polyethylene to nanoplastic particles by accelerated weathering.

When plastics enter the environment, they are exposed to abiotic and biotic impacts, resulting in degradation and the formation of micro- and nanoplastic. Microplastic is ubiquitous in every environmental compartment. Nevertheless, the underlying degradation processes are not yet fully understood. Here, we studied the abiotic degradation of commonly used semi-crystalline, low-density polyethylene (LDPE) in a long-term accelerated weathering experiment combining several macro- and microscopic methods. Based on our observations, the degradation of LDPE proceeds in three stages. Initially, LDPE objects are prone to abrasion, followed by a period of surface cracking. A large number of secondary particles with a high degree of crystallinity are formed, with sizes down to the nanometer scale. These particles consist of highly polar oligomers leading to agglomeration in the final stage. We therefore suppose that weathered microplastic and nanoplastic particles will attach to colloidal environmental matter. This offers an explanation for the absence of free nanoplastic particles in natural samples.

The Impact of Solvent Vapor on the Film Morphology and Crystallization Kinetics of Lead Halide Perovskites during Annealing.

One of the key factors for the remarkable improvements of halide perovskite solar cells over the last few years is the increased control over perovskite crystallinity and its thin film morphology. Among various processing methods, solvent vapor-assisted annealing (SVAA) has proven to be promising in achieving high-quality perovskite films. However, a comprehensive understanding of the perovskite crystallization process during SVAA is still lacking. In this work, we use a home-built setup to precisely control the SVAA conditions to investigate in detail the perovskite crystallization kinetics. By changing the solvent vapor concentration during annealing, the perovskite grain size can be tuned from 200 nm to several micrometers. We monitor the crystallization kinetics during solvent-free annealing and SVAA using in situ grazing incidence wide-angle X-ray scattering, where we find a diminished perovskite growth rate and the formation of low dimensional perovskite at the top of the perovskite layer during SVAA. Scanning electron microscopy images of the final films further suggest that the perovskite growth follows an Ostwald ripening process at higher solvent concentrations. Thus, our results will contribute to achieve a more targeted processing of perovskite films.

Electrophoresis Assisted Printing: A Method To Control the Morphology in Organic Thin Films.

A major advantage of organic solar cells (OSC) is the processability out of solution allowing for advanced printing methods toward large-scale production. Controlling the blend morphology of solution coated active layers is a key challenge to optimize their power conversion efficiency. We have derived a printing procedure from an industrial coating process that facilitates tuning the nanomorphology of a blend of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as model system for OSCs. Applying an electric field during printing and the film drying process modifies the vertical film composition of the photoactive layer and optimizes the polymer crystal orientation. The choice of chloroform as solvent allows us to obtain material transport within the wet film, due to an induced electrophoretic mobility. Tailoring the morphology improves the power conversion efficiency of the OSCs by up to 25%. Our findings indicate that electrophoresis assisted printing provides an efficient approach to optimize the active layer for various material and solvent combinations that exhibit an electrophoretic mobility.

Ionic-Liquid Doping Enables High Transconductance, Fast Response Time, and High Ion Sensitivity in Organic Electrochemical Transistors.

Organic electrochemical transistors (OECTs) are highly attractive for applications ranging from circuit elements and neuromorphic devices to transducers for biological sensing, and the archetypal channel material is poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), PEDOT:PSS. The operation of OECTs involves the doping and dedoping of a conjugated polymer due to ion intercalation under the application of a gate voltage. However, the challenge is the trade-off in morphology for mixed conduction since good electronic charge transport requires a high degree of ordering among PEDOT chains, while efficient ion uptake and volumetric doping necessitates open and loose packing of the polymer chains. Ionic-liquid-doped PEDOT:PSS that overcomes this limitation is demonstrated. Ionic-liquid-doped OECTs show high transconductance, fast transient response, and high device stability over 3600 switching cycles. The OECTs are further capable of having good ion sensitivity and robust toward physical deformation. These findings pave the way for higher performance bioelectronics and flexible/wearable electronics.

Resonant Grazing-Incidence Small-Angle X-ray Scattering at the Sulfur K-Edge for Material-Specific Investigation of Thin-Film Nanostructures.

Scattering techniques are a powerful tool for probing thin-film nanomorphologies but often require additional characterization by other methods. We applied the well-established grazing-incidence small-angle X-ray scattering (GISAXS) technique for a selection of energies around the absorption edge of sulfur to exploit the resonance effect (grazing incidence resonant tender X-ray scattering, GIR-TeXS) of the sulfur atoms within a poly(3-hexylthiophene-2,5-diyl):phenyl-C61-butyric acid methyl ester (P3HT:PC61BM) sample to gain information about the composition of the film morphology. With this approach, it is possible not only to identify structures within the investigated thin film but also to link them to a particular material combination.

Directing the Aggregation of Native Polythiophene during in Situ Polymerization.

The performance of semiconducting polymers strongly depends on their intra- and intermolecular electronic interactions. Therefore, the morphology and particularly crystallinity and crystal structure play a crucial role in enabling a sufficient overlap between the orbitals of neighboring polymers. A new solution-based in situ polymerization for the fabrication of native polythiophene thin films is presented, which exploits the film formation process to influence the polymer crystal structure in the resulting thin films. The synthesis of the insoluble polythiophene is based on an oxidative reaction in which the oxidizing agent, iron(III) p-toluenesulfonate (FeTos), initially oxidizes the monomers to enable the polymer chain growth and secondly the final polymers, thereby chemically doping the polythiophene. To exploit the fact that the doped polythiophene has a different crystal packing structure compared to the undoped polythiophene, we investigate the structural effect of this inherent doping process by varying the amounts of FeTos in the reaction mixture, creating polythiophene thin films with different degrees of doping. The structural investigation performed by means of grazing incidence wide-angle X-ray scattering (GIWAXS) suggests that the strongly doped polymer chains aggregate in a π-stacked manner in the film formation process. Moreover, this π-stacking can be maintained after the removal of the dopant molecules. GIWAXS measurements, molecular dynamics simulations, and spectroscopic analysis suggest the presence of polythiophene in a novel and stable crystal structure with an enhanced intermolecular interaction.

Printed Thin Magnetic Films Based on Diblock Copolymer and Magnetic Nanoparticles.

Printing techniques have been well established for large-scale production and have developed to be effective in controlling the morphology and thickness of the film. In this work, printing is employed to fabricate magnetic thin films composed of polystyrene coated maghemite nanoparticles (γ-Fe2O3 NPs) and polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer. By applying an external magnetic field during the print coating step, oriented structures with a high content of nanoscale magnetic particles are created. The morphology of the magnetic films and the arrangement of NPs within the polymer matrix are characterized with real and reciprocal space techniques. Due to the applied magnetic field, the magnetic NPs self-assemble into microscale sized wires with controlled widths and separation distances, endowing hybrid films with a characteristic magnetic anisotropy. At the nanoscale level, due to the PS coating, the NPs disperse as single particles at low NP concentrations. The NPs self-assemble into nanosized clusters inside the PS domains when the NP concentration increases. Due to a high loading of uniformly dispersed magnetic NPs across the whole printed film, a strong sensitivity to an external magnetic field is achieved. The enhanced superparamagnetic property of the printed films renders them promising candidate materials for future magnetic sensor applications.

Note: Setup for chemical atmospheric control during in situ grazing incidence X-ray scattering of printed thin films.

In order to tailor the assembling of polymers and organic molecules, a deeper understanding of the kinetics involved in thin film production is necessary. While post-production characterization only provides insight on the final film structure, more sophisticated experimental setups are needed to probe the structure formation processes in situ during deposition. The drying kinetics of a deposited organic thin film strongly influences the assembling process on the nanometer scale. This work presents an experimental setup that enables fine control of the atmosphere composition surrounding the sample during slot die coating, while simultaneously probing the film formation kinetics using in situ grazing incidence X-ray scattering and spectroscopy.

Solvent-Morphology-Property Relationship of PTB7:PC71BM Polymer Solar Cells.

The influence of three different solvents and a solvent additive on the morphology and photovoltaic performance of bulk heterojunction films made of the copolymer based on thieno[3,4-b]thiophene-alt-benzodithiophene unit PTB7-F40 blended with [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) is investigated. Optical microscopy and atomic force microscopy are combined with X-ray reflectivity and grazing incidence small and wide-angle X-ray scattering (GISAXS and GIWAXS, respectively), enabling the characterization of the morphology of the whole photoactive film. The detailed study reveals that different length scales of PCBM clusters are observed using different solvents, while adding a solvent additive results in the PCBM clusters being selectively dissolved. Vertical and lateral phase separation occurs during spin coating and depends on the solvent used. A hierarchical morphology is detected within the bulk film through GISAXS measurements. Furthermore, GIWAXS shows that a rather amorphous film with low crystallinity was probed, which substantiates that high crystallinity is not necessarily required for high performance organic solar cells. Different models for the morphology are proposed through the combination of all the findings and correlated with the corresponding device properties. Consequently, the solvent-induced different device performance is mainly ascribed to the varied lateral structure sizes, whereas the highest device performance is a result of the smallest average multilength scale lateral structure sizes with the smallest length scale matching the exciton diffusion length.

Codependence between Crystalline and Photovoltage Evolutions in P3HT:PCBM Solar Cells Probed with in-Operando GIWAXS.

We address the correlation between the crystalline state of photoactive materials in a model organic solar cell based on poly(3-hexylthiophene-2,5-diyl):phenyl-C60-butyric acid methyl ester (P3HT:PCBM) and the photovoltage in an in-operando investigation. I-V curves are simultaneously measured together with grazing incidence wide-angle X-ray scattering probing the crystalline state of the device active layer as a function of the operation time. The results show a high degree of correlation between open-circuit voltage VOC and the crystalline state of P3HT.

Substituted Septithiophenes with End Groups of Different Size: Packing and Frustration in Bulk and Thin Films.

We report on three different liquid crystalline compounds with a central septithiophene core and alkylated end groups of strongly increasing bulkiness. In principle, the thiophene cores prefer to pack parallel to optimize their π-π interactions, which becomes sterically impossible for the bulkier end groups. Using X-ray diffraction, we find that the way out of this packing dilemma is toward liquid-crystal phases of higher dimensionality in the order smectic → columnar ↔ bicontinuous cubic. For the smectic phase, packing in a monolayer is no problem; for the other ones packing considerations become more stringent in films due to the boundaries. Surface X-ray techniques and atomic force microscopy indicate an appreciable difference between monolayer and three-layer films, in which the monolayers appear to escape from packing frustration by generating superstructures. We propose a basic structure of columns parallel to the substrate that provides a compromise between preserving some π-π interactions and packing the bulky alkyl groups.

Effect of Methanol Addition on the Resistivity and Morphology of PEDOT:PSS Layers on Top of Carbon Nanotubes for Use as Flexible Electrodes.

Overcoating carbon nanotube (CNT) films on flexible poly(ethylene terephthalate) (PET) foils with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) ( PEDOT: PSS) layers reduces the surface roughness, which is interesting for use in organic electronics. Adding methanol to the PEDOT: PSS aqueous solution used for spin coating of the PEDOT: PSS layer improves the wetting behavior of the CNT/PET surface. Samples with different volume fractions of methanol (0, 33, 50, 67, and 75 vol %) are compared with respect to the transmission, horizontal, and vertical resistivity. With grazing-incidence small-angle X-ray scattering, the film morphologies are probed, which is challenging because of the substrate flexibility. At 50 vol %, methanol optimum conditions are achieved with the resistivity close to that of the bare CNT/PET substrates because of the best contact between the PEDOT: PSS film and CNT surface. At lower methanol ratios, the PEDOT: PSS films cannot adapt the CNT morphology, and at higher methanol ratios, they rupture into domains and no continuous PEDOT: PSS layers are formed.