Transiently delocalized states enhance hole mobility in organic molecular semiconductors.

Evidence shows that charge carriers in organic semiconductors self-localize because of dynamic disorder. Nevertheless, some organic semiconductors feature reduced mobility at increasing temperature, a hallmark for delocalized band transport. Here we present the temperature-dependent mobility in two record-mobility organic semiconductors: dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]-thiophene (DNTT) and its alkylated derivative, C8-DNTT-C8. By combining terahertz photoconductivity measurements with atomistic non-adiabatic molecular dynamics simulations, we show that while both crystals display a power-law decrease of the mobility (µ) with temperature (T) following µ ∝ T -n, the exponent n differs substantially. Modelling reveals that the differences between the two chemically similar semiconductors can be traced to the delocalization of the different states that are thermally accessible by charge carriers, which in turn depends on their specific electronic band structure. The emerging picture is that of holes surfing on a dynamic manifold of vibrationally dressed extended states with a temperature-dependent mobility that provides a sensitive fingerprint for the underlying density of states.

Enantiopure Dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophenes: Reaching High Magnetoresistance Effect in OFETs.

Chiral molecules are known to behave as spin filters due to the chiral induced spin selectivity (CISS) effect. Chirality can be implemented in molecular semiconductors in order to study the role of the CISS effect in charge transport and to find new materials for spintronic applications. In this study, the design and synthesis of a new class of enantiopure chiral organic semiconductors based on the well-known dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophene (DNTT) core functionalized with chiral alkyl side chains is presented. When introduced in an organic field-effect transistor (OFET) with magnetic contacts, the two enantiomers, (R)-DNTT and (S)-DNTT, show an opposite behavior with respect to the relative direction of the magnetization of the contacts, oriented by an external magnetic field. Each enantiomer displays an unexpectedly high magnetoresistance over one preferred orientation of the spin current injected from the magnetic contacts. The result is the first reported OFET in which the current can be switched on and off upon inversion of the direction of the applied external magnetic field. This work contributes to the general understanding of the CISS effect and opens new avenues for the introduction of organic materials in spintronic devices.

High throughput processing of dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) organic semiconductors.

The deposition of organic semiconductors (OSCs) using solution shearing deposition techniques is highly appealing for device implementation. However, when using high deposition speeds, it is necessary to use very concentrated OSC solutions. The OSCs based on the family of dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) have been shown to be excellent OSCs due to their high mobility and stability. However, their limited solubility hinders the processing of these materials at high speed. Here, we report the conditions to process alkylated DNTT and the S-shaped π-core derivative S-DNTT by bar-assisted meniscus shearing (BAMS) at high speed (i.e., 10 mm s-1). In all the cases, homogeneous thin films were successfully prepared, although we found that the gain in solubility achieved with the S-DNTT derivative strongly facilitated solution processing, achieving a field-effect mobility of 2.1 cm2 V-1 s-1, which is two orders of magnitude higher than the mobility found for the less soluble linear derivatives.

Temperature-induced polymorphism of a benzothiophene derivative: reversibility and impact on the thin film morphology.

The identification of polymorphs in organic semiconductors allows for establishing structure-property relationships and gaining understanding of microscopic charge transport physics. Thin films of 2,7-bis(octyloxy)[1]benzothieno[3,2-b]-benzothiophene (C8O-BTBT-OC8) exhibit a substrate-induced phase (SIP) that differs from the bulk structure, with important implications for the electrical performance in organic field effect transistors (OFETs). Here we combine grazing incidence wide-angle X-ray scattering (GIWAXS) and atomic force microscopy (AFM) to study how temperature affects the morphology and structure of C8O-BTBT-OC8 films grown by physical vapor deposition on SiO2. We report a structural transition for C8O-BTBT-OC8 films, from the SIP encountered at room temperature (RT) to a high temperature phase (HTP) when the films are annealed at a temperature T ≥ 90 °C. In this HTP structure, the molecules are packed with a tilt angle (≈39° respect to the surface normal) and an enlarged in-plane unit cell. Although the structural transition is reversible on cooling at RT, AFM reveals that molecular layers at the SiO2 interface can remain with the HTP structure, buried under the film ordered in the SIP. For annealing temperatures close to 150 °C, dewetting occurs leading to a more complex morphological and structural scenario upon cooling, with coexistence of different molecular tilts. Because the molecular packing at the interface has direct impact in the charge carrier mobility of OFETs, identifying the different polymorphs of a material in the thin film form and determining their stability at the interfaces are key factors for device optimization.

Dinaphthotetrathienoacenes: Synthesis, Characterization, and Applications in Organic Field-Effect Transistors.

The charge transport of crystalline organic semiconductors is limited by dynamic disorder that tends to localize charges. It is the main hurdle to overcome in order to significantly increase charge carrier mobility. An innovative design that combines a chemical structure based on sulfur-rich thienoacene with a solid-state herringbone (HB) packing is proposed and the synthesis, physicochemical characterization, and charge transport properties of two new thienoacenes bearing a central tetrathienyl core fused with two external naphthyl rings: naphtho[2,3-b]thieno-[2''',3''':4'',5'']thieno[2″,3″:4',5']thieno[3',2'-b]naphtho[2,3-b]thiophene (DN4T) and naphtho[1,2-b]thieno-[2''',3''':4'',5'']thieno[2'',3'':4',5']thieno[3',2'-b]naphtho[1,2-b]thiophene are presented. Both compounds crystallize with a HB pattern structure and present transfer integrals ranging from 33 to 99 meV (for the former) within the HB plane of charge transport. Molecular dynamics simulations point toward an efficient resilience of the transfer integrals to the intermolecular sliding motion commonly responsible for strong variations of the electronic coupling in the crystal. Best device performances are reached with DN4T with hole mobility up to µ = 2.1 cm2 V-1 s-1 in polycrystalline organic field effect transistors, showing the effectiveness of the electronic coupling enabled by the new aromatic core. These promising results pave the way to the design of high-performing materials based on this new thienoacene, notably through the introduction of alkyl side-chains.

High-Performance Humidity Sensing in π-Conjugated Molecular Assemblies through the Engineering of Electron/Proton Transport and Device Interfaces.

The development of systems capable of responding to environmental changes, such as humidity, requires the design and assembly of highly sensitive and efficiently transducing elements. Such a challenge can be mastered only by disentangling the role played by each component of the responsive system, thus ultimately achieving high performance by optimizing the synergistic contribution of all functional elements. Here, we designed and synthesized a novel [1]benzothieno[3,2-b][1]benzothiophene derivative equipped with hydrophilic oligoethylene glycol lateral chains (OEG-BTBT) that can electrically transduce subtle changes in ambient humidity with high current ratios (>104) at low voltages (2 V), reaching state-of-the-art performance. Multiscale structural, spectroscopical, and electrical characterizations were employed to elucidate the role of each device constituent, viz., the active material's BTBT core and OEG side chains, and the device interfaces. While the BTBT molecular core promotes the self-assembly of (semi)conducting crystalline films, its OEG side chains are prone to adsorb ambient moisture. These chains act as hotspots for hydrogen bonding with atmospheric water molecules that locally dissociate when a bias voltage is applied, resulting in a mixed electronic/protonic long-range conduction throughout the film. Due to the OEG-BTBT molecules' orientation with respect to the surface and structural defects within the film, water molecules can access the humidity-sensitive sites of the SiO2 substrate surface, whose hydrophilicity can be tuned for an improved device response. The synergistic chemical engineering of materials and interfaces is thus key for designing highly sensitive humidity-responsive electrical devices whose mechanism relies on the interplay of electron and proton transport.

1D-Confinement Inhibits the Anomaly in Secondary Relaxation of a Fluorinated Polymer.

We present an experimental study of the dynamics of a well-pronounced secondary relaxation observed in bulk and ultrathin films of the fluorinated copolymer poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP). In proximity to the glass transition, an anomalous phenomenon is observed: the ß-relaxation slows down upon heating. Measurements as a function of the film thickness show that this exceptional behavior gradually vanishes upon confinement at the nanoscale level. Regardless of sample size, the relaxation dynamics could be described in terms of the Minimal Model via an asymmetric double well potential. Supported by a structural investigation of surfaces and interfaces, our results reveal that the presence of adsorbing walls induces an increase in glass transition temperature, which counterbalances the asymmetry in the double well potential responsible for molecular motion.

Effect of the Organic Semiconductor Side Groups on the Structural and Electronic Properties of Their Interface with Dopants.

Two derivatives of [1]benzothieno[3,2-b][1]benzothiophene (BTBT), namely, 2,7-dioctyl-BTBT (C8-BTBT) and 2,7-diphenyl-BTBT (DPh-BTBT), belonging to one of the best performing organic semiconductor (OSC) families, have been employed to investigate the influence of the substitutional side groups on the properties of the interface created when they are in contact with dopant molecules. As a molecular p-dopant, the fluorinated fullerene C60F48 is used because of its adequate electronic levels and its bulky molecular structure. Despite the dissimilarity introduced by the OSC film termination, dopant thin films grown on top adopt the same (111)-oriented FCC crystalline structure in the two cases. However, the early stage distribution of the dopant on each OSC film surface is dramatically influenced by the group side, leading to distinct host-dopant interfacial morphologies that strongly affect the nanoscale local work function. In this context, Kelvin probe force microscopy and photoelectron emission spectroscopy provide a comprehensive picture of the interfacial electronic properties. The extent of charge transfer and energy level alignment between OSCs and dopant are debated in light of the differences in the ionization potential of the OSC in the films, the interface nanomorphology, and the electronic coupling with the substrate.

Tuning Spin Current Injection at Ferromagnet-Nonmagnet Interfaces by Molecular Design.

There is a growing interest in utilizing the distinctive material properties of organic semiconductors for spintronic applications. Here, we explore the injection of pure spin current from Permalloy into a small molecule system based on dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophene (DNTT) at ferromagnetic resonance. The unique tunability of organic materials by molecular design allows us to study the impact of interfacial properties on the spin injection efficiency systematically. We show that both the spin injection efficiency at the interface and the spin diffusion length can be tuned sensitively by the interfacial molecular structure and side chain substitution of the molecule.

Molecular Semiconductors for Logic Operations: Dead-End or Bright Future?

The field of organic electronics has been prolific in the last couple of years, leading to the design and synthesis of several molecular semiconductors presenting a mobility in excess of 10 cm2 V-1 s-1 . However, it is also started to recently falter, as a result of doubtful mobility extractions and reduced industrial interest. This critical review addresses the community of chemists and materials scientists to share with it a critical analysis of the best performing molecular semiconductors and of the inherent charge transport physics that takes place in them. The goal is to inspire chemists and materials scientists and to give them hope that the field of molecular semiconductors for logic operations is not engaged into a dead end. To the contrary, it offers plenty of research opportunities in materials chemistry.

Chasing the "Killer" Phonon Mode for the Rational Design of Low-Disorder, High-Mobility Molecular Semiconductors.

Molecular vibrations play a critical role in the charge transport properties of weakly van der Waals bonded organic semiconductors. To understand which specific phonon modes contribute most strongly to the electron-phonon coupling and ensuing thermal energetic disorder in some of the most widely studied high-mobility molecular semiconductors, state-of-the-art quantum mechanical simulations of the vibrational modes and the ensuing electron-phonon coupling constants are combined with experimental measurements of the low-frequency vibrations using inelastic neutron scattering and terahertz time-domain spectroscopy. In this way, the long-axis sliding motion is identified as a "killer" phonon mode, which in some molecules contributes more than 80% to the total thermal disorder. Based on this insight, a way to rationalize mobility trends between different materials and derive important molecular design guidelines for new high-mobility molecular semiconductors is suggested.

N-Doped TiO2 Photocatalyst Coatings Synthesized by a Cold Atmospheric Plasma.

This work presents a simple, fast (20 min treatment), inexpensive, and highly efficient method for synthesizing nitrogen-doped titanium dioxide (N-TiO2) as an enhanced visible light photocatalyst. In this study, N-TiO2 coatings were fabricated by atmospheric pressure dielectric barrier discharge (DBD) at room temperature. The composition and the chemical bonds of the TiO2 and N-TiO2 coatings were characterized by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (ToF-SIMS). The results indicate that the nitrogen element has doped the TiO2 lattice, which was further confirmed by Raman spectroscopy and grazing incidence X-ray diffraction (GIXRD). The doping mechanism was investigated using OES to study the plasma properties under different conditions. It suggests that the NH radicals play a key role in doping TiO2. The concentration of nitrogen in the N-TiO2 coatings can be controlled by changing the concentration of NH3 in the plasma or the applied power to adjust the concentration of NH radicals in the plasma. The band gap of N-TiO2 was reduced after NH3/Ar plasma treatment from 3.25 to 3.18 eV. Consequently, the N-TiO2 coating showed enhanced photocatalytic activity under white-light-emitting-diode (LED) irradiation. The photocatalytic degradation rate for the N-TiO2 coating was about 1.4 times higher than that of the undoped TiO2 coating.

Insight from electron density and energy framework analysis on the structural features of Fx-TCNQ (x = 0, 2, 4) family of molecules.

In this study, the nature and characteristics of the intramolecular and intermolecular interactions in crystal structures of the fluoro-substituted 7,7,8,8-tetracyanoquinodimethane (TCNQ) family of molecules, i.e. Fx-TCNQ (x = 0, 2, 4), are explored. The molecular geometry of the reported crystal structures is directly dependent on the degree of fluorination in the molecule, which consequently also results in the presence of an intramolecular N[triple-bond]C...F-C π-hole tetrel bond. Apart from this, the energy framework analysis performed along the respective transport planes provides new insights into the energetic distribution in this class of molecules.

Terthiophene Functionalized Conjugated Triarm Polymers Containing Poly(fluorene-2,7-vinylene) Arms Having Different Cores-Synthesis and Their Unique Optical Properties.

Optical properties of three types of terthiophene (3T) functionalized conjugated triarm (star-shaped) polymers consisting of poly(9,9-di-n-octyl-fluorene-2,7-vinylene) (PFV) arms and different [2,4,6-tri(biphenyl)benzene (TBP), 1,3,5-tri(benzyl)benzene (TBB), and triphenylamine (TPA)] cores, prepared by combined olefin metathesis with Wittig coupling, have been studied. Relative intensities [increases in the higher vibronic bands, (0, 1) fluorescence (FL)] of the fully conjugated TPA-core polymers, TPA(PFV-3T)3, in the fluorescence (FL) spectra in tetrahydrofuran (toluene) solution were higher than those in the other triarm polymers, TBP(PFV-3T)3, TBB(PFV-3T)3, whereas no significant differences were observed in their UV-vis spectra; notable temperature dependences were not observed in the UV-vis and FL spectra (at -5, 25, and 55 °C). Remarkable differences were not observed in the spectra in these polymer thin films, whereas λmax values red-shifted due to the formation of J-type aggregates. The observation for the time-resolved study well corresponds to results for the steady-state fluorescence measurements. The observed unique emission by the star-shaped (triarm) polymer containing the TPA core would be assumed to be due to a difference in nature of the core (higher coplanarity) compared to that of the others.

Band Transport and Trapping in Didodecyl[1]benzothieno[3,2-b][1]benzothiophene Probed by Terahertz Spectroscopy.

Terahertz electromodulation spectroscopy provides insight into the material-inherent transport properties of charge carriers in organic semiconductors. Experiments on didodecyl[1]benzothieno[3,2-b][1]benzothiophene (C12-BTBT-C12) devices yield for holes an intraband mobility of 9 cm2 V-1 s-1. The short duration of the THz pulses advances the understanding of the hole transport on the molecular scale. The efficient screening of Coulomb potentials leads to a collective response of the hole gas to external fields, which can be well described by the Drude model. Bias stress of the devices generates deep traps that capture mobile holes. Although the resulting polarization across the device hinders the injection of mobile holes, the hole mobilities are not affected.

DFT-Assisted Polymorph Identification from Lattice Raman Fingerprinting.

A combined experimental and theoretical approach, consisting of lattice phonon Raman spectroscopy and density functional theory (DFT) calculations, is proposed as a tool for lattice dynamics characterization and polymorph phase identification. To illustrate the reliability of the method, the lattice phonon Raman spectra of two polymorphs of the molecule 2,7-dioctyloxy[1]benzothieno[3,2-b]benzothiophene are investigated. We show that DFT calculations of the lattice vibrations based on the known crystal structures, including many-body dispersion van der Waals (MBD-vdW) corrections, predict experimental data within an accuracy of ≪5 cm-1 (≪0.6 meV). Due to the high accuracy of the simulations, they can be used to unambiguously identify different polymorphs and to characterize the nature of the lattice vibrations and their relationship to the structural properties. More generally, this work implies that DFT-MBD-vdW is a promising method to describe also other physical properties that depend on lattice dynamics like charge transport.

Unraveling Unprecedented Charge Carrier Mobility through Structure Property Relationship of Four Isomers of Didodecyl[1]benzothieno[3,2-b][1]benzothiophene.

The structural and electronic properties of four isomers of didodecyl[1]-benzothieno[3,2-b][1]benzothiophene (C12-BTBT) have been investigated. Results show the strong impact of the molecular packing on charge carrier transport and electronic polarization properties. Field-induced time-resolved microwave conductivity measurements unravel an unprecedented high average interfacial mobility of 170 cm(2) V(-1) s(-1) for the 2,7-isomer, holding great promise for the field of organic electronics.

Organic ferroelectric/semiconducting nanowire hybrid layer for memory storage.

Ferroelectric materials are important components of sensors, actuators and non-volatile memories. However, possible device configurations are limited due to the need to provide screening charges to ferroelectric interfaces to avoid depolarization. Here we show that, by alternating ferroelectric and semiconducting nanowires over an insulating substrate, the ferroelectric dipole moment can be stabilized by injected free charge carriers accumulating laterally in the neighboring semiconducting nanowires. This lateral electrostatic coupling between ferroelectric and semiconducting nanowires offers new opportunities to design new device architectures. As an example, we demonstrate the fabrication of an elementary non-volatile memory device in a transistor-like configuration, of which the source-drain current exhibits a typical hysteretic behavior with respect to the poling voltage. The potential for size reduction intrinsic to the nanostructured hybrid layer offers opportunities for the development of strongly miniaturized ferroelectric and piezoelectric devices.

Structural Evolution of an Organic Semiconducting Molecule onto a Soft Substrate.

The structural organization and evolution of the organic semiconducting molecule 2,7-dioctyloxy[1]benzothieno[3,2-b]-benzothiophene on a soft matrix is studied. Thin films of a blend formed from polystyrene and the molecule were prepared by spin-coating onto silicon substrates, which were subsequently studied by using a combination of microscopy and scattering techniques. The organic semiconducting molecule segregated to the surface and developed a phase with a different structure to the bulk, as in the case of a substrate induced phase observed previously. Under a solvent vapor annealing procedure, the growth of micrometer-sized tetragonal crystals onto the polymer surface was observed, which was not evidenced for the silicon substrates.

Bulky end-capped [1]benzothieno[3,2-b]benzothiophenes: reaching high-mobility organic semiconductors by fine tuning of the crystalline solid-state order.

A series of bulky end-capped [1]benzothieno[3,2-b]benzothiophenes (BTBTs) are developed in order to tune the packing structure via terminal substitution. A coupled theoretical and experimental study allows us to identify 2,7-di-tert-butylBTBT as a new high-performance organic semiconductor with large and well-balanced transfer integrals, as evidenced by quantum-chemical calculations. Single-crystal field-effect transistors show a remarkable average saturation mobility of 7.1 cm(2) V(-1) s(-1) .