Thermoelectric Properties of Benzothieno-Benzothiophene Self-Assembled Monolayers in Molecular Junctions.

We report a combined experimental (C-AFM and SThM) and theoretical (DFT) study of the thermoelectric properties of molecular junctions made of self-assembled monolayers on Au of thiolated benzothieno-benzothiophene (BTBT) and alkylated BTBT derivatives (C8-BTBT-C8). We measure the thermal conductance per molecule at 15 and 8.8 pW/K, respectively, among the lowest values for molecular junctions so far reported (10-50 pW/K).

Polystyrene Chain Geometry Probed by Ion Mobility Mass Spectrometry and Molecular Dynamics Simulations.

Polystyrene (PS) is a thermoplastic polymer commonly used in various applications due to its bulk properties. Designing functional polystyrenes with well-defined structures for targeted applications is of significant interest due to the rigid and apolar nature of the polymer chain. Progress is hindered to date by the limitations of current analytical methods in defining the atomistic-level folding of the polymer chain.

Impact of hydrophilic side chains on the thin film transistor performance of a benzothieno-benzothiophene derivative.

Side-chain engineering in molecular semiconductors provides a versatile toolbox for precisely manipulating the material's processability, crystallographic properties, as well as electronic and optoelectronic characteristics. This study explores the impact of integrating hydrophilic side chains, specifically oligoethylene glycol (OEG) units, into the molecular structure of the small molecule semiconductor, 2,7-bis(2(2-methoxy ethoxy)ethoxy) benzo[]benzo[4,5] thieno[2,3-] thiophene (OEG-BTBT). The investigation includes a comprehensive analysis of thin film morphology and crystallographic properties, along with the optimization of deposition parameters for improving the device performance.

Operando Investigation of WS Gas Sensors: Simultaneous Ambient Pressure X-ray Photoelectron Spectroscopy and Electrical Characterization in Unveiling Sensing Mechanisms during Toxic Gas Exposure.

Ambient pressure X-ray photoelectron spectroscopy (APXPS) is combined with simultaneous electrical measurements and supported by density functional theory calculations to investigate the sensing mechanism of tungsten disulfide (WS)-based gas sensors in an dynamic experiment. This approach allows for the direct correlation between changes in the surface potential and the resistivity of the WS sensing active layer under realistic operating conditions. Focusing on the toxic gases NO and NH, we concurrently demonstrate the distinct chemical interactions between oxidizing or reducing agents and the WS active layer and their effect on the sensor response.

Molecular Junctions for Terahertz Switches and Detectors.

Molecular electronics targets tiny devices exploiting the electronic properties of the molecular orbitals, which can be tailored and controlled by the chemical structure and configuration of the molecules. Many functional devices have been experimentally demonstrated; however, these devices were operated in the low-frequency domain (mainly dc to MHz). This represents a serious limitation for electronic applications, although molecular devices working in the THz regime have been theoretically predicted.

Grafting Electron-Accepting Fragments on [4]cyclo-2,7-carbazole Scaffold: Tuning the Structural and Electronic Properties of Nanohoops.

Since the first applications of nanohoops in organic electronics appear promising, the time has come to go deeper into their rational design in order to reach high-efficiency materials. To do so, systematic studies dealing with the incorporation of electron-rich and/or electron-poor functional units on nanohoops have to be performed. Herein, the synthesis, the electrochemical, photophysical, thermal, and structural properties of two [4]cyclo-2,7-carbazoles, [4]C-Py-Cbz, and [4]C-Pm-Cbz, possessing electron-withdrawing units on their nitrogen atoms (pyridine or pyrimidine) are reported.

One-step synthesis of photoluminescent nanofluids by direct loading of reactively sputtered cubic ZrN nanoparticles into organic liquids.

ZrN nanofluids may exhibit unique optoelectronic properties because of the matching of the solar spectrum with interband transitions and localized surface plasmon resonance (LSPR). Nevertheless, these nanofluids have scarcely been investigated, mainly because of the complexity of the current synthetic routes that involve aggressive chemicals and high temperatures. This work aims to validate reactive dc magnetron sputtering of zirconium in Ar/N as an environmentally benign, annealing-free method to produce 22 nm-sized, highly crystalline, stoichiometric, electrically conductive, and plasmonic ZrN nanoparticles (NPs) of cubic shape and to load them into vacuum-compatible liquids of different chemical compositions (polyethylene glycol (PEG), paraffin, and pentaphenyl trimethyl trisiloxane (PTT)) in one step.

Polar Polymorphism: A New Intermediate Structure toward the Thin-Film Phase in Asymmetric Benzothieno[3,2-][1]-benzothiophene Derivatives.

Understanding structure and polymorphism is relevant for any organic device optimization, and it is of particular relevance in 7-decyl-2-phenyl[1]benzothieno[3,2-][1]benzothiophene (Ph-BTBT-10) since high carrier mobility in Ph-BTBT-10 thin films has been linked to the structural transformation from the metastable thin-film phase to the thermodynamically stable bilayer structure via thermal annealing. We combine here a systematic nanoscale morphological analysis with local Kelvin probe force microcopy (KPFM) that demonstrates the formation of a polar polymorph in thin films as an intermediate structure for thicknesses lower than 20 nm. The polar structure develops with thickness a variable amount of structural defects in the form of individual flipped molecules (point defects) or sizable polar domains, and evolves toward the reported nonpolar thin-film phase.

Memory Effect by Melt Crystallization Observed in Polymorphs of a Benzothieno-Benzothiophene Derivative.

This work provides a comprehensive illustration of a crystalline melt memory effect recorded for three solvates of the 2,7-bis(2-(2-methoxyethoxy)ethoxy)benzo[]benzo[4,5] thieno[2,3-]thiophene (OEG-BTBT) molecule with dichloromethane (DCM) molecules. Combined optical microscopy and X-ray diffraction measurements at different temperatures are used to get an overview of the structural and morphological properties like melting points, isotropic transition temperatures, induction times, and crystallization kinetics of the three forms. An outstanding observation is made upon annealing the three polymorphs at temperatures well above their respective melting points as well as above the optical clearance temperature.

Site Selectivity of Peptoids as Azobenzene Scaffold for Molecular Solar Thermal Energy Storage.

Storing solar energy is a key challenge in modern science. MOlecular Solar Thermal (MOST) systems, in particular those based on azobenzene switches, have received great interest in the last decades. The energy storage properties of azobenzene (t <4 days; ΔH~270 kJ/kg) must be improved for future applications.

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.

Synthesis and Characterization of Tetraphenylethene AIEgen-Based Push-Pull Chromophores for Photothermal Applications: Could the Cycloaddition-Retroelectrocyclization Click Reaction Make Any Molecule Photothermally Active?

Three new tetraphenylethene (TPE) push-pull chromophores exhibiting strong intramolecular charge transfer (ICT) are described. They were obtained via [2 + 2] cycloaddition-retroelectrocyclization (CA-RE) click reactions on an electron-rich alkyne-tetrafunctionalized TPE (TPE-alkyne) using both 1,1,2,2-tetracyanoethene (TCNE), 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F-TCNQ) as electron-deficient alkenes. Only the starting TPE-alkyne displayed significant AIE behavior, whereas for TPE-TCNE, a faint effect was observed, and for TPE-TCNQ and TPE-F-TCNQ, no fluorescence was observed in any conditions.

Electronic and Charge Transport Properties in Bridged versus Unbridged Nanohoops: Role of the Nanohoop Size.

In the field of π-conjugated nanohoops, the size of the macrocycle has a strong impact on its structural characteristics, which in turn affect its electronic properties. In this work, we report the first experimental investigations linking the size of a nanohoop to its charge transport properties, a key property in organic electronics. We describe the synthesis and study of the first example of a cyclocarbazole possessing five constituting building units, namely [5]-cyclo-N-butyl-2,7-carbazole, [5]C-Bu-Cbz.

Plasmonic Ag/Cu/PEG nanofluids prepared when solids meet liquids in the gas phase.

Since the time of Faraday's experiments, the optical response of plasmonic nanofluids has been tailored by the shape, size, concentration, and material of nanoparticles (NPs), or by mixing different types of NPs. To date, water-based liquids have been the most extensively investigated host media, while polymers, such as poly(ethylene glycol) (PEG), have frequently been added to introduce repulsive steric interactions and protect NPs from agglomeration. Here, we introduce an inverse system of non-aqueous nanofluids, in which Ag and Cu NPs are dispersed in PEG (400 g mol), with no solvents or chemicals involved.

F-Center-Mediated Growth of Patterned Organic Semiconductor Films on Alkali Halides.

Organic semiconductors combine flexible tailoring of their optoelectronic properties by synthetic means with strong light-matter coupling, which is advantageous for organic electronic device applications. Although spatially selective deposition has been demonstrated, lateral patterning of organic films with simultaneous control of molecular and crystalline orientation is lacking as traditional lithography is not applicable. Here, a new patterning approach based on surface-localized F-centers (halide vacancies) generated by electron irradiation of alkali halides is presented, which allows structural control of molecular adlayers.

Electronic transport through single-molecule oligophenyl-diethynyl junctions with direct gold-carbon bonds formed at low temperature.

We report on the first systematic transport study of alkynyl-ended oligophenyl-diethynyl (OPA) single-molecule junctions with direct Au-C anchoring scheme at low temperature using the mechanically controlled break junction technique. Through quantitative statistical analysis of opening traces, conductance histograms and density functional theory studies, we identified different types of junctions, classified by their conductance and stretching behavior, for OPA molecules between Au electrodes with two to four phenyl rings. We performed inelastic electron tunneling spectroscopy and observed the excitation of Au-C vibrational modes confirming the existence of Au-C bonds at low temperature and compared the stability of molecule junctions upon mechanical stretching.

Pure Hydrocarbon Materials as Highly Efficient Host for White Phosphorescent Organic Light-Emitting Diodes: A New Molecular Design Approach.

To date, all efficient host materials reported for phosphorescent OLEDs (PhOLEDs) are constructed with heteroatoms, which have a crucial role in the device performance. However, it has been shown in recent years that the heteroatoms not only increase the design complexity but can also be involved in the instability of the PhOLED, which is nowadays the most important obstacle to overcome. Herein, we design pure aromatic hydrocarbon materials (PHC) as very efficient hosts in high-performance white and blue PhOLEDs.

Terphenylthiazole-based self-assembled monolayers on cobalt with high conductance photo-switching ratio for spintronics.

Two new photo-switchable terphenylthiazole molecules are synthesized and self-assembled as monolayers on Au and on ferromagnetic Co electrodes. The electron transport properties probed by conductive atomic force microscopy in ultra-high vacuum reveal a larger conductance of the light-induced closed (c) form than for the open (o) form. We report an unprecedented conductance ratio of up to 380 between the closed and open forms on Co for the molecule with the anchoring group (thiol) on the side of the two N atoms of the thiazole unit.

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.

On the Conformation of Anionic Peptoids in the Gas Phase.

Although -()-phenylethyl peptoids are known to adopt helical structures in solutions, the corresponding positively charged ions lose their helical structure during the transfer from the solution to the gas phase due to the so-called charge solvation effect. We, here, considered negatively charged peptoids to investigate by ion mobility spectrometry-mass spectrometry whether the structural changes described in the positive ionization mode can be circumvented in the negative mode by a fine-tuning of the peptoid sequence, that is, by positioning the negative charge at the positive side of the helical peptoid macrodipole. -()-(1-carboxy-2-phenylethyl) (scp) and -()-phenylethyl (spe) were selected as the negative charge carrier and as the helix inductor, respectively.

Quantifying Image Charge Effects in Molecular Tunnel Junctions Based on Self-Assembled Monolayers of Substituted Oligophenylene Ethynylene Dithiols.

A number of factors contribute to orbital energy alignment with respect to the Fermi level in molecular tunnel junctions. Here, we report a combined experimental and theoretical effort to quantify the effect of metal image potentials on the highest occupied molecular orbital to Fermi level offset, ε, for molecular junctions based on self-assembled monolayers (SAMs) of oligophenylene ethynylene dithiols (OPX) on Au. Our experimental approach involves the use of both transport and photoelectron spectroscopy to extract the offsets, ε and ε, respectively.

Solvent-Free Design of Biobased Non-isocyanate Polyurethanes with Ferroelectric Properties.

Increasing energy autonomy and lowering dependence on lithium-based batteries are more and more appealing to meet our current and future needs of energy-demanding applications such as data acquisition, storage, and communication. In this respect, energy harvesting solutions from ambient sources represent a relevant solution by unravelling these challenges and giving access to an unlimited source of portable/renewable energy. Despite more than five decades of intensive study, most of these energy harvesting solutions are exclusively designed from ferroelectric ceramics such as Pb(Zr,Ti)O and/or ferroelectric polymers such as polyvinylidene fluoride and its related copolymers, but the large implementation of these piezoelectric materials into these technologies is environmentally problematic, related with elevated toxicity and poor recyclability.

Gas-phase structure of polymer ions: Tying together theoretical approaches and ion mobility spectrometry.

An increasing number of studies take advantage of ion mobility spectrometry (IMS) coupled to mass spectrometry (IMS-MS) to investigate the spatial structure of gaseous ions. Synthetic polymers occupy a unique place in the field of IMS-MS. Indeed, due to their intrinsic dispersity, they offer a broad range of homologous ions with different lengths.

Strong Suppression of Thermal Conductivity in the Presence of Long Terminal Alkyl Chains in Low-Disorder Molecular Semiconductors.

While the charge transport properties of organic semiconductors have been extensively studied over the recent years, the field of organics-based thermoelectrics is still limited by a lack of experimental data on thermal transport and of understanding of the associated structure-property relationships. To fill this gap, a comprehensive experimental and theoretical investigation of the lattice thermal conductivity in polycrystalline thin films of dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (Cn-DNTT-Cn with n = 0, 8) semiconductors is reported. Strikingly, thermal conductivity appears to be much more isotropic than charge transport, which is confined to the 2D molecular layers.