Excited state dynamics and exciton diffusion in triphenylamine/dicyanovinyl push-pull small molecule for organic optoelectronics.

Triphenylamine-based small push-pull molecules have recently attracted substantial research attention due to their unique optoelectronic properties. Here, we investigate the excited state de-excitation dynamics and exciton diffusion in TPA-T-DCV-Ph-F small molecule, having simple chemical structure with asymmetrical architecture and end-capped with electron-withdrawing p-fluorodicyanovinyl group. The excited state lifetime in diluted solutions (0.04 ns in toluene and 0.4 ns in chloroform) are found to be surprisingly shorter compared to the solid state (3 ns in PMMA matrix). Time-dependent density functional theory indicates that this behavior originates from non-radiative relaxation of the excited state through a conical intersection between the ground and singlet excited state potential energy surfaces. Exciton diffusion length of ~ 16 nm in solution processed films was retrieved by employing time-resolved photoluminescence volume quenching measurements with Monte Carlo simulations. As means of investigating the device performance of TPA-T-DCV-Ph-F, we manufactured solution and vacuum processed bulk heterojunction solar cells that yielded efficiencies of ~ 1.5% and ~ 3.7%, respectively. Our findings demonstrate that the short lifetime in solutions does not hinder per se long exciton diffusion length in films thereby granting applications of TPA-T-DCV-Ph-F and similar push-pull molecules in vacuum and solution processable devices.

Phase Transitions and Formation of a Monolayer-Type Structure in Thin Oligothiophene Films: Exploration with a Combined In Situ X-ray Diffraction and Electrical Measurements.

A combination of in situ electrical and grazing-incidence X-ray diffraction (GIXD) is a powerful tool for studies of correlations between the microstructure and charge transport in thin organic films. The information provided by such experimental approach can help optimizing the performance of the films as active layers of organic electronic devices. In this work, such combination of techniques was used to investigate the phase transitions in vacuum-deposited thin films of a common organic semiconductor dihexyl-quarterthiophene (DH4T). A transition from the initial highly crystalline phase to a mesophase was detected upon heating, while only a partial backward transition was observed upon cooling to room temperature. In situ electrical conductivity measurements revealed the impact of both transitions on charge transport. This is partly accounted for by the fact that the initial crystalline phase is characterized by inclination of molecules in the plane perpendicular to the π-π stacking direction, whereas the mesophase is built of molecules tilted in the direction of π-π stacking. Importantly, in addition to the two phases of DH4T characteristic of the bulk, a third interfacial substrate-stabilized monolayer-type phase was observed. The existence of such interfacial structure can have important implications for the charge mobility, being especially favorable for lateral two-dimensional charge transport in the organic field-effect transistors geometry.

Impact of terminal substituents on the electronic, vibrational and optical properties of thiophene-phenylene co-oligomers.

Owing to the combination of efficient charge transport and bright luminescence, thiophene-phenylene co-oligomers (TPCOs) are promising materials for organic light-emitting devices such as diodes, transistors and lasers. The synthetic flexibility of TPCOs enables facile tuning of their properties. In this study, we address the effect of various electron-donating and electron-withdrawing symmetric terminal substituents (fluorine, methyl, trifluoromethyl, methoxy, tert-butyl, and trimethylsilyl) on frontier orbitals, charge distribution, static polarizabilities, molecular vibrations, bandgaps and photoluminescence quantum yields of 5,5'-diphenyl-2,2'-bithiophene (PTTP). By combining DFT calculations with cyclic voltammetry and absorption, photoluminescence, and Raman spectroscopies, we show that symmetric terminal substitution tunes the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energies of TPCOs within a range of ∼0.7 eV, shifts the frequencies of the vibrational modes associated with the phenyl rings, changes the photoluminescence quantum yield by about two-fold and slightly changes the bandgap by ∼0.1 eV. We demonstrate that these effects are governed by two factors: the Hammet constant of the substituents and their involvement in the π-conjugation/hyperconjugation described by the effective conjugation length of the substituted oligomer. A detailed picture underlying the effect of the terminal substituents on the electronic, vibrational and optical properties of TPCOs is presented. Overall, the unraveled relationships between the structure and the properties of the substituted PTTPs should facilitate a rational design of π-conjugated (co-)oligomers for efficient organic optoelectronic devices.

When dendrimers are not better - rational design of nanolayers for high-performance organic electronic devices.

Several generations of carbosilane dendrimers with quaterthiophene end groups were studied by X-ray scattering in small and wide angles, differential scanning calorimetry, polarizing optical and atomic force microscopy and molecular modelling. It was established that the semiconducting properties of such materials are determined by the formation of smectic structures in which aliphatic regions, possessing a low degree of the ordering, alternate with highly ordered herring-bone type crystallites formed by aromatic fragments. The presence of long aliphatic spacers in the dendrimers' structure allows easy formation of such crystallites. Such dendrimers assume flattened conformations, as a smectic mesophase is thermodynamically preferable in a wide temperature range. Only in the dendrimers of the fifth generation, as the density of periphery regions increases substantially, π-π stacking of oligothiophene groups is not enough to hold together, and the molecules take on a spherical shape. As a result, extended conducting conjugated regions do not form, and dendrimers of high generations possess comparatively low semiconducting properties. From the technological point of view, quaterthiophene based carbosilane dendrimers are able to form highly uniform functional films. However, the use of lower generation dendrimers is much more preferable, as additional synthetic steps for the production of higher generation compounds do not lead to the improvement of functional properties.

Large-Size Single-Crystal Oligothiophene-Based Monolayers for Field-Effect Transistors.

High structural quality of crystalline organic semiconductors is the basis of their superior electrical performance. Recent progress in quasi two-dimensional (2D) organic semiconductor films challenges bulk single crystals because both demonstrate competing charge-carrier mobilities. As the thinnest molecular semiconductors, monolayers offer numerous advantages such as unmatched flexibility and light transparency as well  they are an excellent platform for sensing. Oligothiophene-based materials are among the most promising ones for light-emitting applications because of the combination of efficient luminescence and decent charge-carrier mobility. Here, we demonstrate single-crystal monolayers of unprecedented structural order grown from four alkyl-substituted thiophene and thiophene-phenylene oligomers. The monolayer crystals with lateral dimensions up to 3 mm were grown from the solution on substrates with various surface energies and roughness by drop or spin-casting with subsequent slow solvent evaporation. Our data indicate that 2D crystallization resulting in single-crystal monolayers occurs at the receding gas-solution-substrate contact line. The structural properties of the monolayers were studied by grazing-incidence X-ray diffraction/reflectivity, atomic force and differential interference contrast microscopies, and imaging spectroscopic ellipsometry. These highly ordered monolayers demonstrated an excellent performance in organic field-effect transistors approaching the best values reported for the thiophene or thiophene-phenylene oligomers. Our findings pave the way for efficient monolayer organic electronics highlighting the high potential of simple solution-processing techniques for the growth of large-size single-crystal monolayers with excellent structural order and electrical performance competing against bulk single crystals.

Highly luminescent crystals of a novel linear π-conjugated thiophene-phenylene co-oligomer with a benzothiadiazole fragment.

The synthesis, growth from solutions and structure of crystals of a new linear thiophene-phenylene co-oligomer with a central benzothiadiazole fragment with a conjugated core, (TMS-2T-Ph)2-BTD, are presented. Single-crystal samples in the form of needles with a length of up to 7 mm were grown and their crystal structure was determined at 85 K and 293 K using single-crystal X-ray diffraction. The conformational differences between the crystal structures are insignificant. The parameters of melting and liquid crystalline phase transitions of (TMS-2T-Ph)2-BTD were established using differential scanning calorimetry and the thermal stability of the crystals was investigated using thermogravimetric analysis. The optical absorption and photoluminescence spectra of the solutions and crystals of (TMS-2T-Ph)2-BTD were obtained, and the kinetics of their photodegradation under the action of UV radiation were studied.

Highly Sensitive Air-Stable Easily Processable Gas Sensors Based on Langmuir-Schaefer Monolayer Organic Field-Effect Transistors for Multiparametric H2S and NH3 Real-Time Detection.

A combination of low limit of detection, low power consumption, and portability makes organic field-effect transistor (OFET) chemical sensors promising for various applications in the areas of industrial safety control, food spoilage detection, and medical diagnostics. However, the OFET sensors typically lack air stability and restoration capability at room temperature. Here, we report on a new design of highly sensitive gas sensors based on Langmuir-Schaefer monolayer organic field-effect transistors (LS OFETs) prepared from organosilicon derivative of [1]benzothieno[3,2- b][1]-benzothiophene. The devices fabricated are able to operate in air and allow an ultrafast detection of different analytes at low concentrations down to tens of parts per billion. The sensors are reusable and can be utilized in real-time air-quality monitoring systems. We show that a direct current response of the LS OFET can be split into the alteration of various transistor parameters, responsible for the interactions with different toxic gases. The sensor response acquiring approach developed allows distinguishing two different gases, H2S and NH3, with a single sensing device. The results reported open new perspectives for the OFET-based gas-sensing technology and pave the way for easy detection of the other types of gases, enabling the development of complex air analysis systems based on a single sensor.

Luminescent Organic Semiconducting Langmuir Monolayers.

In recent years, monolayer organic field-effect devices such as transistors and sensors have demonstrated their high potential. In contrast, monolayer electroluminescent organic field-effect devices are still in their infancy. One of the key challenges here is to create an organic material that self-organizes in a monolayer and combines efficient charge transport with luminescence. Herein, we report a novel organosilicon derivative of oligothiophene-phenylene dimer D2-Und-PTTP-TMS (D2, tetramethyldisiloxane; Und, undecylenic spacer; P, 1,4-phenylene; T, 2,5-thiophene; TMS, trimethylsilyl) that meets these requirements. The self-assembled Langmuir monolayers of the dimer were investigated by steady-state and time-resolved photoluminescence spectroscopy, atomic force microscopy, X-ray reflectometry, and grazing-incidence X-ray diffraction, and their semiconducting properties were evaluated in organic field-effect transistors. We found that the best uniform, fully covered, highly ordered monolayers were semiconducting. Thus, the ordered two-dimensional (2D) packing of conjugated organic molecules in the semiconducting Langmuir monolayer is compatible with its high-yield luminescence, so that 2D molecular aggregation per se does not preclude highly luminescent properties. Our findings pave the way to the rational design of functional materials for monolayer organic light-emitting transistors and other optoelectronic devices.

Triphenylamine-Based Push-Pull Molecule for Photovoltaic Applications: From Synthesis to Ultrafast Device Photophysics.

Small push-pull molecules attract much attention as prospective donor materials for organic solar cells (OSCs). By chemical engineering, it is possible to combine a number of attractive properties such as broad absorption, efficient charge separation, and vacuum and solution processabilities in a single molecule. Here we report the synthesis and early time photophysics of such a molecule, TPA-2T-DCV-Me, based on the triphenylamine (TPA) donor core and dicyanovinyl (DCV) acceptor end group connected by a thiophene bridge. Using time-resolved photoinduced absorption and photoluminescence, we demonstrate that in blends with [70]PCBM the molecule works both as an electron donor and hole acceptor, thereby allowing for two independent channels of charge generation. The charge-generation process is followed by the recombination of interfacial charge transfer states that takes place on the subnanosecond time scale as revealed by time-resolved photoluminescence and nongeminate recombination as follows from the OSC performance. Our findings demonstrate the potential of TPA-DCV-based molecules as donor materials for both solution-processed and vacuum-deposited OSCs.

Highly Luminescent Solution-Grown Thiophene-Phenylene Co-Oligomer Single Crystals.

Thiophene-phenylene co-oligomers (TPCOs) are among the most promising materials for organic light emitting devices. Here we report on record high among TPCO single crystals photoluminescence quantum yield reaching 60%. The solution-grown crystals are stronger luminescent than the vapor-grown ones, in contrast to a common believe that the vapor-processed organic electronic materials show the highest performance. We also demonstrate that the solution-grown TPCO single crystals perform in organic field effect transistors as good as the vapor-grown ones. Altogether, the solution-grown TPCO crystals are demonstrated to hold great potential for organic electronics.

Polymer Surface Engineering for Efficient Printing of Highly Conductive Metal Nanoparticle Inks.

An approach to polymer surface modification using self-assembled layers (SALs) of functional alkoxysilanes has been developed in order to improve the printability of silver nanoparticle inks and enhance adhesion between the metal conducting layer and the flexible polymer substrate. The SALs have been fully characterized by AFM, XPS, and WCA, and the resulting printability, adhesion, and electrical conductivity of the screen-printed metal contacts have been estimated by cross-cut tape test and 4-point probe measurements. It was shown that (3-mercaptopropyl)trimethoxysilane SALs enable significant adhesion improvements for both aqueous- and organic-based silver inks, approaching nearly 100% for PEN and PDMS substrates while exhibiting relatively low sheet resistance up to 0.1 Ω/sq. It was demonstrated that SALs containing functional -SH or -NH2 end groups offer the opportunity to increase the affinity of the polymer substrates to silver inks and thus to achieve efficient patterning of highly conductive structures on flexible and stretchable substrates.

Easily processable highly ordered Langmuir-Blodgett films of quaterthiophene disiloxane dimer for monolayer organic field-effect transistors.

Self-assembly of highly soluble water-stable tetramethyldisiloxane-based dimer of α,α'-dialkylquaterthiophene on the water-air interface was investigated by Langmuir, grazing incidence X-ray diffraction, and X-ray reflectivity techniques. The conditions for formation of very homogeneous crystalline monolayer Langmuir-Blodgett (LB) films of the oligomer were found. Monolayer organic field-effect transistors (OFETs) based on these LB films as a semiconducting layer showed hole mobilities up to 3 × 10(-3) cm(2)/(V s), on-off ratio of 10(5), small hysteresis, and high long-term stability. The electrical performance of the LB films studied is close to that for the same material in the bulk or in the monolayer OFETs prepared from water vapor sensitive chlorosilyl derivatives of quaterthiophene by self-assembling from solution. These findings show high potential of disiloxane-based LB films in monolayer OFETs for large-area organic electronics.

Nanostructured organosilicon luminophores and their application in highly efficient plastic scintillators.

Organic luminophores are widely used in various optoelectronic devices, which serve for photonics, nuclear and particle physics, quantum electronics, medical diagnostics and many other fields of science and technology. Improving their spectral-luminescent characteristics for particular technical requirements of the devices is a challenging task. Here we show a new concept to universal solution of this problem by creation of nanostructured organosilicon luminophores (NOLs), which are a particular type of dendritic molecular antennas. They combine the best properties of organic luminophores and inorganic quantum dots: high absorption cross-section, excellent photoluminescence quantum yield, fast luminescence decay time and good processability. A NOL consists of two types of covalently bonded via silicon atoms organic luminophores with efficient Förster energy transfer between them. Using NOLs in plastic scintillators, widely utilized for radiation detection and in elementary particles discoveries, led to a breakthrough in their efficiency, which combines both high light output and fast decay time. Moreover, for the first time plastic scintillators, which emit light in the desired wavelength region ranging from 370 to 700 nm, have been created. We anticipate further applications of NOLs as working elements of pulsed dye lasers in photonics, optoelectronics and as fluorescent labels in biology and medical diagnostics.

Monolayer properties of asymmetrically substituted sexithiophene.

We present a structural comparison of monolayers on a SiO2 substrate of two asymmetrically substituted sexithiophenes (6T). Molecule 1 consists of 6T with a branched alkyl chain at one end only and shows a crystalline structure. In molecule 2, the bifunctional 6T has in addition at the other end a linear alkyl chain. It displays thermotropic liquid crystalline (LC) behavior. Both compounds form readily single molecular layers from solution. Remarkably, full monolayer coverage can be achieved before multilayer growth starts. LC properties promote preordering near the interface as well as exchange of molecules between the growing domains, thus regulating the domain sizes. As a result, the LC compound 2 forms single-molecule islands with larger domain sizes compared to compound 1. Surface X-ray investigations indicate that the 6T cores are tilted relative to the layer normal. The tilt angle is as large as 54° for compound 2 compared to 28° for compound 1. For molecule 2, interfacial constraints and packing requirements because of the asymmetric substitution cause a rather loosely organized core structure.

Formation of self-assembled organosilicon-functionalized quinquethiophene monolayers by fast processing techniques.

Different techniques for a relatively fast self-assembled monolayer film formation such as Langmuir-Blodgett (LB), spin-coating, and dip-coating methods have been compared using chloro[11-(5''''-ethyl-2,2':5',2″:5''',2''':5''',2''''-quinquethiophene-5-yl)undecyl]dimethylsilane as a reactive precursor. It was shown that both spin-coating and LB techniques are very promising methods for preparation of highly ordered monolayer films of organosilicon-functionalized quinquethiophene with vertical orientation of oligothiophene fragments, while dip-coating gives only partial coverage. Optimal conditions for complete filling out the substrate surface by the quinquethiophene-containing monolayer by spin-coating and LB methods have been found. Grazing incidence X-ray diffraction measurements confirmed formation of in-plane crystalline order within the monolayer film. Changes in the layer structure were established by X-ray reflectivity and grazing incidence X-ray diffraction methods.

Ordered semiconducting self-assembled monolayers on polymeric surfaces utilized in organic integrated circuits.

We report on a two-dimensional highly ordered self-assembled monolayer (SAM) directly grown on a bare polymer surface. Semiconducting SAMs are utilized in field-effect transistors and combined into integrated circuits as 4-bit code generators. The driving force to form highly ordered SAMs is packing of the liquid crystalline molecules caused by the interactions between the linear alkane moieties and the pi-pi stacking of the conjugated thiophene units. The fully functional circuits demonstrate long-range order over large areas, which can be regarded as the start of flexible monolayer electronics.

Monolayer coverage and channel length set the mobility in self-assembled monolayer field-effect transistors.

The mobility of self-assembled monolayer field-effect transistors (SAMFETs) traditionally decreases dramatically with increasing channel length. Recently, however, SAMFETs using liquid-crystalline molecules have been shown to have bulk-like mobilities that are virtually independent of channel length. Here, we reconcile these scaling relations by showing that the mobility in liquid crystalline SAMFETs depends exponentially on the channel length only when the monolayer is incomplete. We explain this dependence both numerically and analytically, and show that charge transport is not affected by carrier injection, grain boundaries or conducting island size. At partial coverage, that is when the monolayer is incomplete, liquid-crystalline SAMFETs thus form a unique model system to study size-dependent conductance originating from charge percolation in two dimensions.

Structure and properties of functionalized bithiophenesilane monodendrons.

This study reports a focal group modification of bithiophenesilane monodendrons and its effect on their molecular ordering in solution, bulk, and surface. We investigated hydrophobic MDn monodendrons and COOH-functionalized MDn-COOH monodendrons with generations, n=0, 1, 2, and 3. We observed that increasing the number of branches led to the progressive blue shift, indicating distorted packing of branched thiophene fragments of MDn. In contrast, MDn-COOH monodendrons showed a progressive red shift with the increasing generation number, indicating gradual domination of sigma-pi interactions. Moreover, the introduction of a focal carboxylic group resulted in the formation of a highly crystalline state for the linear MD0-COOH compound with separated alkyl tail-thiophene packing, which limits pi-pi interactions. Increasing branching in the COOH-containing monodendrons resulted in a hydrophobic-hybrophilic balance sufficient to form stable and uniform Langmuir monolayers at the air-water at a modest surface pressure (<10 mN/m), easily transferrable to a solid substrate. However, a further increase in the thickness of the surface layers from tens to hundreds of nanometers via Langmuir-Blodgett (LB) deposition or spin casting is limited by the formation of globular surface aggregates because of strong intermolecular interactions. A modest red shift observed for condensed Langmuir monolayers indicates densification of thiophene branches and limited intramonolayer crystallization, which preserves photoluminescence. In contrast, thicker surface films showed a significant red shift, confirming a dense molecular packing with strong pi-pi interactions, which results in photoluminescence quenching.

Facile synthesis and optical properties of bithiophenesilane monodendrons and dendrimers.

Three generations of bithiophenesilane monodendrons and dendrimers consisting of 3-45 2,2'-bithiene-5,5'-diyl units were synthesized by means of effective coupling reactions between the corresponding bithienyllithium derivatives and chlorosilanes. These compounds show efficient photoluminescence in the violet-blue region, the quantum yield of which is 5-15 times higher than that for the parent bithiophene or bithiophenesilanes.