Molecular packing analysis of the crystal smectic E phase of a benzothieno-benzothiophene derivative by a combined experimental / computational approach

The molecule 2-decyl-7-phenyl[1]benzothieno[3,2-b][1]benzothiophene has gained a lot of attention since high charge carrier mobility was observed in thin film transistors. Its thermotropic liquid crystalline states may play an important role in the thin film formation since the smectic A and the crystal smectic E phase (SmE) are claimed to be pre-stages of the final bulk structure. To understand the phase diversity, structural characterisation of solution processed thin films is performed by X-ray diffraction in the complete temperature range up to the isotropic state at 240°C. The diffraction pattern of the SmE phase is analysed in detail. Peak broadening analysis reveals that the crystallographic order across the smectic layers is larger than the order along the smectic layers. A combined experimental and computational approach is used to determine the molecular packing within the SmE phase. It leads to a number of different packing motifs. A comparison of the calculated diffraction pattern with the experimental results reveals that nano-segregation is present within the SmE phase. Energy consideration clearly favours a herringbone arrangement of the aromatic units. The nano-segregation within the SmE phase with herringbone packing of the aromatic units is accompanied with interdigitation of side chains from neighbouringherringbone layers

Electrochromic Polymer Ink Derived from a Sidechain-Modified EDOT for Electrochromic Devices with Colorless Bright State

AbstractPrintable organic electrochromic materials are the key component of flexible low power and low weight displays and dynamic shading systems. A vast number of more or less well‐performing materials is reported in the literature, but only a very limited number of them have been tested in an industrially‐relevant environment so far. Upscaling requires simplicity of synthesis, overall sustainability, low cost and compatibility with simple and high throughput wet‐chemical deposition techniques, such as slot‐die coating or inkjet printing. In the present paper, an original process is described that enables the controlled oxidative polymerization of a water insoluble, functionalized 3,4‐ethylene dioxythiophene (EDOT) derivative. This process leads to the formation of an ink that consists solely of active polymeric material (no dispersing agents) and has suitable rheological properties for use in roll‐to‐roll slot‐die coating or ink‐jet printing. The straightforward deposition, followed by a simple thermal treatment, directly yields stable and homogeneous thin films with state‐of‐the‐art electrochromic performance

Controlled recrystallization from the melt of the organic n-type small molecule semiconductor 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene S,S,S′,S′-tetraoxide

Abstract Recrystallization from the melt of the n-type BTBT derivative 2-dectyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene S,S,S',S'-tetraoxide (Ph-BTBTOx2-10) reveals a defined crystal structure of the molecule. It leads to the formation of alternating nano-segregated layers consisting of parallelly stacked aromatic units and alkyl units. This polymorph appears to be the thermodynamic stable phase. Charge carrier mobility measurements indicate an electron mobility of 4*10−6 cm2 V−1 s−1 for this phase

An Integrated Theoretical/Experimental Study of Quinolinic-Isoquinolinic Derivatives Acting as Reversible Electrochromes

A series of compounds, featuring an ethenylic bridge and quinoline and isoquinoline end capping units possessing systematically varied substitution patterns, were prepared as molecular materials for electrochromic applications. The different structures were optimized in order to maximize the electrochromic contrast in the visible region, mostly by achieving a completely UV-absorbing oxidized state. Density functional theory (DFT) calculations are exploited in order to rationalize the correlation between the molecular structure, the functional groups' electronic properties, and the electrochemical behavior. It is shown that the molecular planarity (i.e. ring/ring pi conjugation) plays a major role in defining the mechanism of the electrochemical charge transfer reaction, while the substituent's nature has an influence on the LUMO energy. Among the compounds here studied, the (E)-10-methyl-9-(2-(2-methylisoquinolinium1- yl)-vinyl)-1,2,3,4-tetrahydroacri-dinium trifluoromethanesulfonate derivative shows the most interesting properties as an electrochromophore

New Roll‐to‐Roll Processable PEDOT‐Based Polymer with Colorless Bleached State for Flexible Electrochromic Devices

Conjugated electrochromic (EC) polymers for flexible EC devices (ECDs) generally lack a fully colorless bleached state. A strategy to overcome this drawback is the implementation of a new sidechain-modified poly(3,4-ethylene dioxythiophene) derivative that can be deposited in thin-film form in a customized high-throughput and large-area roll-to-roll polymerization process. The sidechain modification provides enhanced EC properties in terms of visible light transmittance change, Δτv = 59% (ΔL* = 54.1), contrast ratio (CR = 15.8), coloration efficiency (η = 530 cm² C−1), and color neutrality (L* = 83.8, a* = −4.3, b* = −4.1) in the bleached state. The intense blue-colored polymer thin films exhibit high cycle stability (10 000 cycles) and fast response times. The design, synthesis, and polymerization of the modified 3,4-ethylene dioxythiophene derivative are discussed along with a detailed optical, electrochemical, and spectroelectrochemical characterization of the resulting EC thin films. Finally, a flexible see-through ECD with a visible light transmittance change of Δτv = 47% (ΔL* = 51.9) and a neutral-colored bleached state is developed

Chitosan gated organic transistors printed on ethyl cellulose as a versatile platform for edible electronics and bioelectronics

Edible electronics is an emerging research field targeting electronic devices that can be safely ingested and directly digested or metabolized by the human body. As such, it paves the way to a whole new family of applications, ranging from ingestible medical devices and biosensors, to smart labelling for food quality monitoring and anti-counterfeiting. Being a newborn research field, many challenges need to be addressed to realize fully edible electronic components. In particular, an extended library of edible electronic materials is required, with suitable electronic properties depending on the target device and compatible with large-area printing processes, to allow scalable and cost-effective manufacturing. In this work, we propose a platform for future low-voltage edible transistors and circuits that comprises an edible chitosan gating medium and inkjet printed inert gold electrodes, compatible with low thermal budget edible substrates, such as ethylcellulose. We report the compatibility of the platform, characterized by critical channel features as low as 10 µm, with different inkjet printed carbon-based semiconductors, including biocompatible polymers present in the picograms range per device. A complementary organic inverter is also demonstrated with the same platform as a proof-of-principle logic gate. The presented results offer a promising approach to future low-voltage edible active circuitry, as well as a testbed for non-toxic printable semiconductors

State of the Art in Flexible Electrochromic Devices for Shading Applications

Electrochromic devices based on inorganic materials are a consolidate market reality with applications ranging from smart windows, automotive, sunglasses to displays. Recent years witnessed an intense interest in the development of alternative all-solid-state devices, mostly on flexible substrates, featuring organic and hybrid electrochromic materials. Amongst the main advantages of such new technological solutions are: reduction in production cost, lightweight, color tunability and switching speed. The literature already reports a good selection of book chapters and review articles giving the state of the art for organic electrochromic materials, both polymeric and molecular, yet there is a lack of contributions including the implementation of the most performing materials in fully assembled devices. The latter is a task at least as important as the development of performing materials. Given the multilayer nature of solid state electrochromic devices, the correct assembly of all different materials in a suitable sandwich structure, proper sealing and contacting as well as a final integration in the working environment, all represent the next challenge for commercialization of this technology. In this contribution we will focus our attention on shading applications, where devices have to fulfill the most demanding set of performances in order to compete with well-established inorganic technologies