Detection of X‐Rays by Solution‐Processed Cesium‐Containing Mixed Triple Cation Perovskite Thin Films

Materials and technology development for designing innovative and efficient X‐ray radiation detectors is of utmost importance for a wide range of applications ranging from security to medical imaging. Here, highly sensitive direct X‐ray detectors based on novel cesium (Cs)‐based triple cation mixed halide perovskite thin films are reported. Despite being in a thin film form, the devices exhibit a remarkably high X‐ray sensitivity of (3.7 ± 0.1) µC Gy^?1 cm^?2 under short‐circuit conditions. At a small reverse bias of 0.4 V, the sensitivity further increases by orders of magnitude reaching a record value of (97 ± 1) µC Gy^?1 cm^?2 which surpasses state‐of‐the‐art inorganic large‐area detectors (a‐Se and poly‐CZT). Based on detailed structural, electrical, and spectroscopic investigations, the exceptional sensitivity of the triple cation Cs perovskite is attributed to its high ambipolar mobility‐lifetime product as well as to the formation of a pure stable perovskite phase with a low degree of energetic disorder, due to an efficient solution‐based alloying of individual n‐ and p‐type perovskite semiconductors.     

Electric‐Field‐Induced Pattern Morphologies in Thin Liquid Films

Liquid‐polymer films sandwiched between two electrodes develop a surface instability caused by the electric field, giving rise to polymer structures that span the two plates. This study investigates the development of the resulting polymer morphologies as a function of time. The initial phase of the structure formation process is a sinusoidal surface undulation, irrespective of the sample parameters. The later stages of pattern formation depend on the relative amount of polymer in the capacitor gap (filling ratio). For high enough filling ratios, the final morphology of the pattern is determined by the partial coalescence of the initial pattern. The introduction of lateral‐field heterogeneities influences the initial pattern formation, with columns nucleated at locations of highest electric field (isolated points or edges). The subsequently formed secondary columns have higher degree of lateral symmetry compared to the pattern formed in a homogeneous field. The nucleation of individual columns or plugs also dominates the pattern formation in the presence of an electrode consisting of an array of lines. The results of this study therefore allow us to draw the conclusion that the accurate replication of structured electrodes typically proceeds by the initial nucleation of individual columns, followed by a coalescence process that yields the polymer replica.     

Microscopical Investigations of PEDOT:PSS Thin Films

Electron microscopy studies are used to explore the morphology of thin poly(3,4‐ethylenedioxythiophene) and polystyrene sulfonate acid (PEDOT:PSS) films. The figures show that the films are composed of grains with diameters in the range of about 50 nm. Energy dispersive X‐ray spectroscopy analysis reveals that individual grains have a PEDOT‐rich core and a PSS‐rich shell with a thickness of about 5–10 nm. Atomic force microscopy (AFM) is then used to analyze the topography of fracture surfaces of ruptured PEDOT:PSS tensile specimens. These AFM scans also show that the films are composed of grains dispersed in a matrix. The investigations presented herein yield a picture of PEDOT:PSS morphology with unprecedented clarity.     

Periodically Ordered Meso‐ and Macroporous SiO2 Thin Films and Their Induced Electrochemical Activity as a Function of Pore Hierarchy

Silica thin films with variable pore hierarchy (different combinations of small meso‐, large meso‐, and macropores) were produced via evaporation induced self‐assembly in a one‐pot synthesis. A suitable block copolymer and an ionic liquid served as porogens for the generation of different types of mesopores whereas polymethylmethacrylate particles were used as macrotemplate. The silica architectures were characterized by various state‐of‐the‐art techniques, such as 2D‐SAXS, TEM, SEM, AFM, krypton and nitrogen sorption. Moreover, electrochemical functionalization was utilized as a tool to study the hierarchy‐property relationship. Thus, hierarchically porous films prepared on FTO‐coated glass were post‐synthetically silylated and electrochemically active ferrocene groups subsequently grafted onto the pore walls. Cyclic voltammetry was used to monitor the induced electrochemical activity as a function of variations in the pore hierarchy. It turned out that multimodal pore systems possess a relatively higher electrochemical response due to better connection between the pores and higher surface area.     

Electric Field Tuning Molecular Packing and Electrical Properties of Solution‐Shearing Coated Organic Semiconducting Thin Films

Recent improvements in solution‐coated organic semiconductors (OSCs) evidence their high potential for cost‐efficient organic electronics and sensors. Molecular packing structure determines the charge transport property of molecular solids. However, it remains challenging to control the molecular packing structure for a given OSC. Here, the application of alternating electric fields is reported to fine‐tune the crystal packing of OSC solution‐shearing coated at ambient conditions. First, a theoretical model based on dielectrophoresis is developed to guide the selection of the optimal conditions (frequency and amplitude) of the electric field applied through the solution‐shearing blade during coating of OSC thin films. Next, electric field‐induced polymorphism is demonstrated for OSCs with both herringbone and 2D brick‐wall packing motifs in 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene and 6,13‐bis(triisopropylsilylethynyl) pentacene, respectively. Favorable molecular packing can be accessible in some cases, resulting in higher charge carrier mobilities. This work provides a new approach to tune the properties of solution‐coated OSCs in functional devices for high‐performance printed electronics.     

A Morphological Model for the Solvent‐Enhanced Conductivity of PEDOT:PSS Thin Films

The well‐known enhanced conductivity of poly(3,4‐ethylenedioxythiophene):poly(4‐styrenesulfonate) (PEDOT:PSS) thin films that is obtained by addition of high‐boiling solvents like sorbitol to the aqueous dispersion used for film deposition is shown to be associated with a rearrangement of PEDOT‐rich clusters into elongated domains, as evidenced from STM and AFM. Consistently, temperature dependent conductivity measurements for sorbitol‐treated films reveal that charge transport occurs via quasi 1D variable range hopping (VRH), in contrast to 3D VRH for untreated PEDOT:PSS films. The typical hopping distance of 60–90 nm, extracted from the conductivity measurements is consistent with hopping between the 30–40 nm sized grains observed with scanning probe microscopy.     

n‐Type Doping of Organic Thin Films Using Cationic Dyes

We present an approach to stable n‐type doping of organic matrices using organic dopants. In order to circumvent stability limitations inherent to strong organic donors, we produce the donor from a stable precursor compound in situ. As an example, the cationic dye pyronin B chloride is studied as a dopant in a 1,4,5,8‐naphthalene tetracarboxylic dianhydride (NTCDA) matrix. Conductivities of up to 1.9 × 10^–4 S cm^–1 are obtained for doped NTCDA, two orders of magnitude higher than the conductivity of NTCDA doped with bis(ethylenedithio)‐tetrathiafulvalene as investigated previously, and four orders of magnitude higher than nominally undoped NTCDA films. Field‐effect measurements are used to prove n‐type conduction and to study the doping effect further. The findings are interpreted using a model of transport in disordered solids using a recently published model. Combined FTIR, UV‐vis, and mass spectroscopy investigations suggest the formation of leuco pyronin B during sublimation of pyronin B chloride.     

Structural Evolution of Self‐Assembling Nanohybrid Thin Films from Functionalized Urea Precursors

Hybrid organic‐inorganic thin films exhibiting patterned structuring on the nanometer scale have been prepared through the controlled hydrolysis‐condensation of enantiomerically pure chiral urea‐based silyl compounds. The thin films are obtained by spin‐coating of sols obtained via acid‐ or base‐catalyzed hydrolytic condensation of these molecular precursors. A self‐templating process is demonstrated via atomic force and transmission electron microscopy, showing the formation of nanometer size aggregates consisting of interconnected spherulates under acidic condition and of assembled fibers under basic conditions.     

Solvent‐Induced Morphology in Polymer‐Based Systems for Organic Photovoltaics

Studies on the influence of four different solvents on the morphology and photovoltaic performance of bulk‐heterojunction films made of poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁ butyric acid methyl ester (PCBM) via spin‐coating for photovoltaic applications are reported. Solvent‐dependent PCBM cluster formation and P3HT crystallization during thermal annealing are investigated with optical microscopy and grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) and are found to be insufficient to explain the differences in device performance. A combination of atomic force microscopy (AFM), X‐ray reflectivity (XRR), and grazing‐incidence small‐angle X‐ray scattering (GISAXS) investigations results in detailed knowledge of the inner film morphology of P3HT:PCBM films. Vertical and lateral phase separation occurs during spin‐coating and annealing, depending on the solvent used. The findings are summarized in schematics and compared with the IV characteristics. The main influence on the photovoltaic performance arises from the vertical material composition and the existence of lateral phase separation fitting to the exciton diffusion length. Absorption and photoluminescence measurements complement the structural analysis.     

Nanostructured Titanium Oxynitride Porous Thin Films as Efficient Visible‐Active Photocatalysts

Nanocrystalline mesoporous N‐doped titania films have been prepared for the first time. The introduction of nitrogen into the anatase structure starts at 500 °C, with N bonding to titanium via oxygen substitution. Increasing the treatment temperature leads to the formation of TiN (TiN_1–xO_x) and N‐doped rutile showing mixed‐valence Ti states. Microstructural characterization shows that the ordered mesoporosity is maintained until 700 °C, where TiN (TiN_1–xO_x) begins to form. Optical characterization shows that the discrete introduction of N is able to shift the titania absorption edge. The photocatalytic tests give the best results under visible light excitation for the film nitrided at 500 °C. At this temperature the concentration of nitrogen in the structure is optimal since oxygen vacancies are still not important enough to promote the recombination of the photogenerated electrons and holes.     

Effect of Molecular Weight on the Structure and Morphology of Oriented Thin Films of Regioregular Poly(3‐hexylthiophene) Grown by Directional Epitaxial Solidification

Regioregular head‐to‐tail (HT)‐coupled poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) with a weight‐average molecular weight (M_w) in the 7.3–69.6 kDa range is crystallized by directional epitaxial solidification in 1,3,5‐trichlorobenzene (TCB) to yield highly oriented thin films. An oriented and periodic lamellar structure consisting of crystalline lamellae separated by amorphous interlamellar zones is evidenced by atomic force microscopy (AFM) and transmission electron microscopy (TEM). Both the overall crystallinity as well as the orientation of the crystalline lamellae decrease significantly with increasing M_w. The total lamellar periodicity is close to the length of “fully extended” chains for M_w = 7.3 kDa (polystyrene‐equivalent molecular weight, eq. PS) and it saturates to a value of ca. (25–28) ± 2 nm for M_w ≥ 18.8 kDa (eq. PS). This behavior is attributed to a transition from an oligomeric‐like system, for which P3HT chains are essentially in a fully extended all‐trans conformation and do not fold, to a semicrystalline system that involves a periodic alternation of crystalline lamellae separated by extended amorphous interlamellar zones, which harbor chain folds, chain ends, and tie molecules. For P3HT with M_w of ca. 7.3 kDa (eq. PS), epitaxial crystallization on TCB allows for the growth of both “edge‐on” and “flat‐on” oriented crystalline lamellae on the TCB substrate. The orientation of the lamellae is attributed to 1D epitaxy. Because of the large size of the “flat‐on” crystalline lamellae, a characteristic single‐crystal electron diffraction pattern corresponding to the [001] zone was obtained by selected area electron diffraction (SAED), indicating that P3HT crystallizes in a monoclinic unit cell with a = 16.0 Å, b = 7.8 Å, c = 7.8 Å, and γ = 93.5°.     

Tuning Local Molecular Orientation–Composition Correlations in Binary Organic Thin Films by Solution Shearing

A general impact of solution shearing on molecular orientation correlation is observed in polymer:fullerene organic solar cells in which one of the components forms fibrils or aggregates. Further investigation with polarized soft X‐ray scattering reveals that solution shearing induces more face‐to‐face orientation relative to the interface of two components compared to spin‐coating. This impact is shearing speed dependent, that is, slow shearing speed can induce more face‐to‐face orientation than a fast shearing speed. These results demonstrate that solution shearing is an effective method to control the relative molecular orientation. Solution shearing can also modify the domain size and average composition variations.     

Morphology and Field‐Effect‐Transistor Mobility in Tetracene Thin Films

The growth of vacuum‐sublimed tetracene thin films on silicon dioxide has been investigated from the early stages of the process. The effects of deposition flux and substrate silanization on film morphology and electrical properties have been explored. Tetracene shows an island growth, resulting in films with a granular structure. Both an increase in the deposition flux and the substrate silanization determine a decrease of the grain size and an improvement of the connectivity of the film in direct contact with the substrate. The hole mobility in field‐effect transistors based on tetracene thin films, which also generate electroluminescence, increases with the deposition flux and values as high as 0.15 cm² V^–1 s^–1 are obtained.     

Role of Side‐Chain Branching on Thin‐Film Structure and Electronic Properties of Polythiophenes

Side‐chain engineering is increasingly being utilized as a technique to impact the structural order and enhance the electronic properties of semiconducting polymers. However, the correlations drawn between structural changes and the resulting charge transport properties are typically indirect and qualitative in nature. In the present work, a combination of grazing incidence X‐ray diffraction and crystallographic refinement calculations is used to determine the precise molecular packing structure of two thiophene‐based semiconducting polymers to study the impact of side‐chain modifications. The optimized structures provide high‐quality fits to the experimental data and demonstrate that in addition to a large difference in interchain spacing between the two materials, there exists a significant disparity in backbone orientation as well. The calculated structures are utilized in density functional theory calculations to determine the band structure of the two materials and are shown to exhibit a dramatic disparity in interchain dispersion which accounts for the large observed difference in charge carrier mobility. The techniques presented here are meant to be general and are therefore applicable to many other highly diffracting semicrystalline polymers.     

Boosting Direct X‐Ray Detection in Organic Thin Films by Small Molecules Tailoring

The attention focused on the application of organic electronics for the detection of ionizing radiation is rapidly growing among the international scientific community, due to the great potential of organic technology to enable large‐area conformable sensor panels. However, high‐energy photon absorption is challenging as organic materials are constituted of atoms with low atomic numbers. Here it is reported how, by synthesizing new solution‐processable organic molecules derived from 6,13‐bis(triisopropylsilylethynyl)pentacene (TIPS‐pentacene) and 2,8‐difluoro‐5,11‐bis(triethylsilylethynyl)anthradithiophene, with Ge‐substitution in place of the Si atoms to increase the material atomic number, it is possible to boost the X‐ray detection performance of organic thin films on flexible plastic substrates. Bis(triisopropylgermylethynyl)‐pentacene based flexible organic thin film transistors show high electrical performance with higher mobility (0.4 cm² V^?1 s^?1) and enhanced X‐ray sensitivity, up to 9.0 × 10⁵ µC Gy^?1 cm^?3, with respect to TIPS‐pentacene‐based detectors. Moreover, similar results are obtained for 5,11‐bis(triethylgermylethynyl)anthradithiophene devices, confirming that the proposed strategy, that is, increasing the atomic number of organic molecules by chemical tailoring to improve X‐ray sensitivity, can be generalized to organic thin film detectors, combining high X‐ray absorption, mechanical flexibility, and large‐area processing.     

Compartmentalized Thin Films with Customized Functionality via Interfacial Cross‐linking of Protein Cages

Hybrid thin films with a high loading and homogeneous dispersion of functional nanoparticles (and/or molecules) find applications in (bio)‐sensors and electronic devices. The fabrication of such hybrid thin films, however, suffers from the complex and diverse surface and physicochemical properties of individual nanoparticles. To address this challenge, a facile and general strategy toward compartmentalized thin films through the interfacial cross‐linking of viral protein cages is reported. Employing these protein cages, gold nanoparticles, as well as enzyme horseradish peroxidase, are encapsulated into virus‐like particles and then cross‐linked into thin films with a thickness varying from monolayer to submicron dimensions. These compartmentalized thin films not only ensure that the cargo is homogeneously dispersed, but also display good catalytic activity. This strategy is, in principle, applicable for a wide range of (bio)‐organic nanocontainers, enabling the versatile fabrication of 2D thin films with extensive application prospects.     

High‐Resolution Near‐Field Optical Investigation of Crystalline Domains in Oligomeric PQT‐12 Thin Films

The structure and morphology on different length scales dictate both the electrical and optical properties of organic semiconductor thin films. Using a combination of spectroscopic methods, including scanning near‐field optical microscopy, we study the domain structure and packing quality of highly crystalline thin films of oligomeric PQT‐12 with 100 nanometer spatial resolution. The pronounced optical anisotropy of these layers measured by polarized light microscopy facilitates the identification of regions with uniform molecular orientation. We find that a hierarchical order on three different length scales exists in these layers, made up of distinct well‐ordered dichroic areas at the ten‐micrometer‐scale, which are sub‐divided into domains with different molecular in‐plane orientation. These serve as a template for the formation of smaller needle‐like crystallites at the layer surface. A high degree of crystalline order is believed to be the cause of the rather high field‐effect mobility of these layers of 10^?3 cm² V^?1 s^?1, whereas it is limited by the presence of domain boundaries at macroscopic distances.     

Sub‐Micrometer Zeolite Films on Gold‐Coated Silicon Wafers with Single‐Crystal‐Like Dielectric Constant and Elastic Modulus

A low‐temperature synthesis coupled with mild activation produces zeolite films exhibiting low dielectric constant (low‐k) matching the theoretically predicted and experimentally measured values for single crystals. This synthesis and activation method allows for the fabrication of a device consisting of a b‐oriented film of the pure‐silica zeolite MFI (silicalite‐1) supported on a gold‐coated silicon wafer. The zeolite seeds are assembled by a manual assembly process and subjected to optimized secondary growth conditions that do not cause corrosion of the gold underlayer, while strongly promoting in‐plane growth. The traditional calcination process is replaced with a nonthermal photochemical activation to ensure preservation of an intact gold layer. The dielectric constant (k), obtained through measurement of electrical capacitance in a metal–insulator–metal configuration, highlights the ultralow k ≈ 1.7 of the synthetized films, which is among the lowest values reported for an MFI film. There is large improvement in elastic modulus of the film (E ≈ 54 GPa) over previous reports, potentially allowing for integration into silicon wafer processing technology.     

Amphiphilic Poly(p‐phenylene)s for Self‐Organized Porous Blue‐Light‐Emitting Thin Films

Micro‐ and nanostructuring of conjugated polymers are of critical importance in the fabrication of molecular electronic devices as well as photonic and bandgap materials. The present report delineates the single‐step self‐organization of highly ordered structures of functionalized poly(p‐phenylene)s without the aid of either a controlled environment or expensive fabrication methodologies. Microporous films of these polymers, with a honeycomb pattern, were prepared by direct spreading of the dilute polymer solution on various substrates, such as glass, quartz, silicon wafer, indium tin oxide, gold‐coated mica, and water, under ambient conditions. The polymeric film obtained from C₁₂PPPOH comprises highly periodic, defect‐free structures with blue‐light‐emitting properties. It is expected that such microstructured, conjugated polymeric films will have interesting applications in photonic and optoelectronic devices. The ability of the polymer to template the facile micropatterning of nanomaterials gives rise to hybrid films with very good spatial dispersion of the carbon nanotubes.