Thiophene/phenylene Co-oligomer Research Articles

Dual Optoelectronic Organic Field-Effect Device: Combination of Electroluminescence and Photosensitivity.

Merging the functionality of an organic field-effect transistor (OFET) with either a light emission or a photoelectric effect can increase the efficiency of displays or photosensing devices. In this work, we show that an organic semiconductor enables a multifunctional OFET combining electroluminescence (EL) and a photoelectric effect. Specifically, our computational and experimental investigations of a six-ring thiophene-phenylene co-oligomer (TPCO) revealed that this material is promising for OFETs, light-emitting, and photoelectric devices because of the large oscillator strength of the lowest-energy singlet transition, efficient luminescence, pronounced delocalization of the excited state, and balanced charge transport. The fabricated OFETs showed a photoelectric response for wavelengths shorter than 530 nm and simultaneously EL in the transistor channel, with a maximum at ~570 nm. The devices demonstrated an EL external quantum efficiency (EQE) of ~1.4% and a photoelectric responsivity of ~0.7 A W-1, which are among the best values reported for state-of-the-art organic light-emitting transistors and phototransistors, respectively. We anticipate that our results will stimulate the design of efficient materials for multifunctional organic optoelectronic devices and expand the potential applications of organic (opto)electronics.

Tuning Molecular Packing, Charge Transport, and Luminescence in Thiophene–Phenylene Co-Oligomer Crystals via Terminal Substituents

Tuning Molecular Packing, Charge Transport, and Luminescence in Thiophene–Phenylene Co-Oligomer Crystals via Terminal Substituents

Conduction band electronic states of ultrathin thiophene-phenylene co-oligomer and substituted biphenyl films on the surface of layer-by-layer grown ZnO

The results of studying the electronic states of the conduction band and interface potential barrier during the formation of ultrathin films of thiophene-phenylene co-oligomer CH3-phenylene-thiophene-thiophene-phenylene -CH3(CH3-PTTP-CH3) on the surface of ZnO and films of biphenyl tetracarboxylic dianhydride (BPDA) on the ZnO surface are presented. A 100 nm thick ZnO layer was prepared by atomic layer deposition (ALD). Organic CH3-PTTP-CH3 films and BPDA films up to 8 nm thick were formed by thermal vacuum deposition. During film deposition, the electronic characteristics of the surface were studied using total current spectroscopy (TCS) in the energy range from 5 eV to 20 eV above EF. In this energy range, the structure of the maxima of the unoccupied electronic states of CH3-PTTP-CH3 and BPDA films was determined. As a result of the CH3-PTTP-CH3 film deposition, a decrease in the work function to 4.0 eV was found, compared with the value of the work function of 4.2 eV measured from the ALD ZnO-substrate. This corresponds to the transfer of a negative charge from the CH3-PTTP-CH3 film to the substrate. The charge transfer at the interface between the BPDA film and the ALD ZnO-substrate occurs in the opposite direction, since a 4.7 eV increase of the work function was registered during the formation of this interface. The CH3-PTTP-CH3 and BPDA films studied and the layer-by-layer grown ZnO film represent a continuous coating on sufficiently large surface areas of the order of 10 μmx10 μm. The roughness of the ZnO surface does not exceed 4 nm, and the surface roughness of CH3-PTTP-CH3 and BPDA films was 10-15 nm. Keywords: thiophene-phenylene co-oligomers, biphenyl tetracarboxylic dianhydride, ultrathin films, ZnO, atomic layer deposition method, electronic properties, low-energy electron spectroscopy, interface potential barrier.

Электронные состояния зоны проводимости ультратонких пленок тиофен-фенилен со-олигомера и замещенного бифенила на поверхности послойно выращенного ZnO

The results of studying the electronic states of the conduction band and interface potential barrier during the formation of ultrathin films of thiophene-phenylene co-oligomer CH3-phenylene-thiophene-thiophene-phenylene-CH3 (CH3-PTTP-CH3) on the surface of ZnO and films of biphenyl tetracarboxylic dianhydride (BPDA) on the ZnO surface are presented. A 100 nm thick ZnO layer was prepared by atomic layer deposition (ALD). Organic CH3-PTTP-CH3 films and BPDA films up to 8 nm thick were formed by thermal vacuum deposition. During film deposition, the electronic characteristics of the surface were studied using total current spectroscopy (TCS) in the energy range from 5 eV to 20 eV above EF. In this energy range, the structure of the maxima of the unoccupied electronic states of CH3-PTTP-CH3 and BPDA films was determined. As a result of the CH3-PTTP-CH3 film deposition, a decrease in the work function to 4.0 eV was found, compared with the value of the work function of 4.2 eV measured from the ALD ZnO substrate. This corresponds to the transfer of a negative charge from the СH3-PTTP-CH3 film to the substrate. The charge transfer at the interface between the BPDA film and the ALD ZnO substrate occurs in the opposite direction, since a 4.7 eV increase of the work function was registered during the formation of this interface. The СH3-PTTP-СH3 and BPDA films studied and the layer-by-layer grown ZnO film represent a continuous coating on sufficiently large surface areas of the order of 10 micrometers x 10 micrometers. The roughness of the ZnO surface does not exceed 4 nm, and the surface roughness of CH3-PTTP-CH3 and BPDA films was 10–15 nm.

Synthesis and characterization of methoxy- or cyano-substituted thiophene/phenylene co-oligomers for lasing application.

As new candidates of thiophene/phenylene co-oligomer (TPCO) species, 5,5′′-bis(4′-methoxy-[1,1′-biphenyl]-4-yl)-2,2′:5′,2′′-terthiophene (BP3T-OMe) and 4′,4′′′-([2,2′:5′,2′′-terthiophene]-5,5′′-diyl)bis(([1,1′-biphenyl]-4-carbonitrile)) (BP3T-CN) were synthesized for lasing applications. Although most unsubstituted TPCO species crystallize in monoclinic form, BP3T-OMe and BP3T-CN crystallized in orthorhombic and triclinic forms, respectively. Since the unsubstituted species, 5,5′′-bis(4-biphenylyl)-2,2′:5′,2′′-terthiophene (BP3T), shows unique and superior lasing performance in single crystals, the newly synthesized BP3T-OMe and BP3T-CN have possibilities to show different or improved optoelectronic characteristics. Amplified spontaneous emission (ASE) and optically pumped lasing were observed from both of the single crystals based on their well-shaped crystalline cavity and high group refractive index values of 3.7–5.3 for excellent light confinement. The lasing threshold for the BP3T-OMe crystal was lower than that for the BP3T-CN crystal, which was attributed to their different molecular orientation, standing in the former and inclining in the latter.

Impact of N-substitution on structural, electronic, optical, and vibrational properties of a thiophene-phenylene co-oligomer.

Properties of the organic semiconductors can be finely tuned via changes in their molecular structure. However, the relationship between the molecular structure, molecular packing, and (opto)electronic properties of the organic semiconductors to guide their smart design remains elusive. In this study, we address computationally and experimentally the impact of subtle modification of a thiophene–phenylene co-oligomer CF3-PTTP-CF3 on the molecular properties, crystal structure, charge transport, and optoelectronic properties. This modification consists in the substitution of two C–H atom pairs by N atoms in the thiophene units and hence converting them to thiazole units. A dramatic effect of the N-substitution on the crystal structure—the crossover from the herringbone packing motif to π-stacking—is attributed to significant changes in the molecular electrostatic potential. The changes in the molecular and crystal structure resulting from the N-substitution clearly reveal themselves in the Raman spectra. The increase of the calculated electron mobility in the corresponding crystals as a result of the N-substitution is rationalized in terms of the changes in the molecular and crystal structure. The charge transport, electroluminescence, and photoelectric properties are compared in thin-film organic field-effect transistors based on CF3-PTTP-CF3 and its N-substituted counterpart. An intriguing similarity between the effects of N-substitution in the thiophene rings and fluorination of the thiophene–phenylene oligomer is revealed, which is probably associated with a more general effect of electronegative substitution. The obtained results are anticipated to facilitate the rational design of organic semiconductors.

Electroluminescence from double heterostructures of perovskite semiconductors and thiophene/phenylene co-oligomers

We report LED properties in perovskite semiconductor and thiophene/phenylene co-oligomer (TPCO) double heterostructures. Perovskite semiconductors were formed by using a simple solution process, the “cast-capping method”, on substrates with TPCOs. The electroluminescence was quenched rapidly, but it recovered to nearly its initial states. Under pulsed operation within 3 V, the device had rather long durability. We compared the LED properties with those of TPCO LEDs. Ion migrations and/or light-emitting electrochemical cell operations were strongly suggested in the perovskite/TPCO LEDs.

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.

The Electron-Vibrational Interaction in a Thiophene—Phenylene Cooligomer and Its Relationship to the Raman Spectrum

Electron-vibrational interactions play a key role in limiting charge mobility in organic semi-conductors. This paper reports a theoretical study of the electron—phonon interaction in the 5,5′-diphenyl-2,2′-bitiophene (PTTP) molecule, which belongs to the class of thiophene-phenylene cooligomers, which are of great interest for organic optoelectronics due to their electron-transport and luminescent properties; these results are compared with anthracene, which is a model organic semiconductor. The contributions of various vibrational modes to the reorganization energy of PTTP and the anthracene molecules are revealed and it is shown that these contributions correlate with the intensities of the corresponding bands in the Raman spectrum. In particular, it is found that for the PTTP molecule the so-called I-mode with a frequency of ∼1460 cm−1, which corresponds to collective vibration of atoms of all oligomer units, has the highest intensity in both spectra. These results indicate the promise of Raman spectroscopy for studying electron-vibrational interactions in organic semiconductors. Finally, the mobility of holes in PTTP and anthracene is estimated in the framework of the jump model and the reasons for their difference are analyzed. Based on these results, we propose some ways to reduce the electron-vibrational interaction in thiophene—phenylene cooligomers, which is important for the directional molecular design of organic semiconductors.

Microcrystalline array structures induced by heat treatment of friction-transferred organic semiconductor films

The correlation between molecular orientation and optoelectrical properties is most critical to the future design of molecular materials. We made highly-anisotropic microcrystalline array structures with an organic semiconductor, a methoxy-substituted thiophene/phenylene co-oligomer (TPCO), by depositing it on friction-transferred poly(tetrafluoroethylene) (PTFE) layers fabricated on substrates with several heat treatments. Polarising microscope observation, polarised emission and absorption spectra measurements indicated that the TPCO molecules aligned along the drawing direction of PTFE. Using these films, we fabricated two types of field-effect transistors (FETs) and compared them with those using non-heated TPCO films which provide aligned pleats structures. Ones had the channel length direction parallel to the drawing direction of PTFE and the others had the channel length direction perpendicular to that drawing direction. As for the microcrystalline array films, the mobility ratio of the former FET to that of the latter device was about 27 in the saturation region, while the emission polarisation ratio was 4.5. The heat treatment promoted the crystal growth to enhance the mobility while retaining the high anisotropy. The results demonstrate that the heat treatments of the TPCO films on the friction-transferred layers were useful for controlling crystallinity and orientation of the molecules.

Optically pumped lasing of cyano-substituted thiophene/phenylene co-oligomer microcrystals fabricated by the slide boat method

Optically pumped lasing is observed in cyano-substituted thiophene/phenylene co-oligomer (TPCO) microcrystals fabricated by the slide boat method. Dot-shaped crystals approximately 10 μm in size are obtained. Needle- and platelet-like crystals are also obtained in other TPCO derivatives. The needle and platelet crystals show a lower lasing threshold than that of the dot-shaped crystals with clear multimode lasing spectra. A brief discussion follows on how to improve film fabrication from microdot and platelet crystals to film-like morphology.

Microneedle crystals of cyano-substituted thiophene/phenylene co-oligomer epitaxially grown on KCl surface

A cyno-substituted thiophene/phenylene co-oligomer (TPCO), 5,5′-bis(4′-cyanobiphenyl-4-yl)−2,2′-bithiophene (BP2T-CN), is vapor-deposited on KCl (001) surface kept at 220°C by the mask-shadowing method. Transmission electron microscopy and fluorescence microscopy reveal that the deposited BP2T-CN crystallizes in two types of morphologies: microneedles and thin film crystallites. In particular, the predominant microneedles epitaxially grow in four directions in the manner that the BP2T-CN molecules align along the [110]KCl or [−110]KCl. X-ray diffraction patterns indicate that the BP2T-CN molecules in the microneedle lie parallel while those in the thin film crystallite obliquely stand on the KCl surface.

Strong exciton-photon coupling in organic single crystal microcavity with high molecular orientation

Strong exciton-photon coupling has been observed in a highly oriented organic single crystal microcavity. This microcavity consists of a thiophene/phenylene co-oligomer (TPCO) single crystal laminated on a high-reflection distributed Bragg reflector. In the TPCO crystal, molecular transition dipole was strongly polarized along a certain horizontal directions with respect to the main crystal plane. This dipole polarization causes significantly large anisotropies in the exciton transition and optical constants. Especially the anisotropic exciton transition was found to provide the strong enhancement in the coupling with the cavity mode, which was demonstrated by a Rabi splitting energy as large as ∼100 meV even in the “half-vertical cavity surface emitting lasing” microcavity structure.

Improved electroluminescence with reversed bilayers of thiophene/phenylene co-oligomer derivatives

Organic electroluminescence (EL) devices were fabricated with bilayered thiophene/phenylene co-oligomer (TPCO) derivatives: p-type 5,5′-bis(4-biphenylyl)-2,2′-bithiophene (BP2T) and n-type 5,5′-bis(4′-cyanobiphenyl-4-yl)-2,2′-bithiophene (BP2T-CN). Two types of EL device, Al:Li/BP2T-CN/BP2T/ITO (device A) and Au/BP2T/BP2T-CN/ITO (device B), were investigated using vapor-deposited films of BP2T and BP2T-CN by changing the order of deposition onto the indium–tin-oxide (ITO)/glass substrate. The EL performance was significantly improved for device B in which the two molecules had a lying orientation suitable for efficient carrier injection and transport as well as surface emission. In device A, on the other hand, the standing BP2T orientation resulted in much lower current density and EL intensity.

Vertical cavity lasing from melt-grown crystals of cyano-substituted thiophene/phenylene co-oligomer

Vertical-cavity organic lasers are fabricated with melt-grown crystals of a cyano-substituted thiophene-phenylene co-oligomer. Due to lying molecular orientation, surface-emitting lasing is achieved even in the half-cavity crystal grown on a distributed Bragg reflector (DBR) under optical pumping at room temperature. Anticrossing splits in angle-resolved photoluminescence spectra suggest the formation of exciton-polaritons between the cavity photons and the confined Frenkel excitons. By constructing the full-cavity structure sandwiched between the top and bottom DBRs, the lasing threshold is reduced to one order, which is as low as that of the half cavity. Around the threshold, the time profile of the full-cavity emission is collapsed to a pulsed shape accompanied by a finite turn-on delay. We discuss these observed characteristics in terms of a polariton contribution to the conventional photon lasing.

Vertical cavity surface emitting lasing from cyano-substituted thiophene/phenylene co-oligomer single crystals

We have achieved to observe vertical cavity surface emitting lasing (VCSEL) from an optically pumped organic single crystal. A vapor-grown thiophene/phenylene co-oligomer (TPCO) single crystal with in-plane polarization component was used as the gain medium in an optical microcavity. Since the top and bottom surfaces of the TPCO crystal serve as high-quality resonators, well-defined Fabry-Pérot resonance is achieved. Furthermore, by using high reflectivity distributed Bragg reflector as the cavity resonator, we have observed lasing emissions with a line width of 0.9 nm and a threshold of ∼3 mJ/cm2. The VCSEL-type optical feedback configuration demonstrated in this study is expected to be one of the available means to realize the electrically pumped organic laser device.

Structure-Photoluminescence Correlation for Two Crystalline Polymorphs of a Thiophene-Phenylene Co-Oligomer with Bulky Terminal Substituents.

Two crystal polymorphs of a thiophene-phenylene hexamer with bulky terminal substituents are characterized by different molecular conformations and parallel versus herringbone packing. Irrespective of their similar emissive spectra and common H-aggregate features, evidenced by crystal structure analysis and confirmed by solid-phase and excited-state first-principles calculations, their luminescence is relatively high and, for one form, nearly double than that for the other. Interaromatic packing energy contributions are established by quantum chemical calculations and can be compared quantitatively as the same species in different crystal environments is examined. The different luminescence efficiency of the two phases highlights the crucial role of the interaromatic packing for the luminescence properties of polyaromatic oligomers.

Crystallization of thiophene/phenylene co-oligomers by dropping of their solutions into poor solvents

We prepared thiophene/phenylene co-oligomer (TPCO) crystals through an efficient method, the dropping of its solution onto a poor solvent droplet on a substrate. In the present study, 2,5-bis(4-biphenylyl)thiophene (BP1T) and chlorobenzene are used as one of the TPCOs and a solvent, respectively. We obtained sub-millimeter sized BP1T crystals using N,N-dimethylformamide as poor solvent. Furthermore, we employed four kinds of solvents, hexane, benzene, 1,4-dioxane, and toluene, as poor solvents. The size of the BP1T crystals obtained using 1,4-dioxane was 55 times larger than that using hexane.

Light-Emitting Field-Effect Transistors Having Metal Electrodes Modified with an Organic Thin Film

We have improved the emission properties and the carrier mobilities of organic light-emitting field-effect transistors (OLEFETs) by modifying the metal electrode(s) with a thin film of n-type thiophene/phenylene co-oligomer (TPCO). Their semiconductor layer was a p-type TPCO crystal. When we used the modified electrode for electron injection, the device exhibited eight times higher emission intensity than a device with unmodified electrodes. By contrast, employing the modified electrode as the hole injection contact, we achieved the maximum hole mobility of 0.11 cm2·V-1·s-1 under the hole-enhancement mode. The modified electrodes effectively functioned for injecting both electrons and holes into the p-type crystal. The origin of this is briefly discussed.

Light-Emitting Field-Effect Transistors Having Metal Electrodes Modified with an Organic Thin Film

We have improved the emission properties and the carrier mobilities of organic light-emitting field-effect transistors (OLEFETs) by modifying the metal electrode(s) with a thin film of n-type thiophene/phenylene co-oligomer (TPCO). Their semiconductor layer was a p-type TPCO crystal. When we used the modified electrode for electron injection, the device exhibited eight times higher emission intensity than a device with unmodified electrodes. By contrast, employing the modified electrode as the hole injection contact, we achieved the maximum hole mobility of 0.11 cm2·V-1·s-1 under the hole-enhancement mode. The modified electrodes effectively functioned for injecting both electrons and holes into the p-type crystal. The origin of this is briefly discussed.