Quantitative evaluation of light-matter interaction parameters in organic single-crystal microcavities.

Investigation of physics on light-matter interaction and strong coupling formation in organic microcavities is important to characterize the device structure enabling efficient room-temperature polariton condensation. In this study, we evaluate quantitatively the light-matter interaction parameters for three types of organic single-crystal microcavities and discuss the effects of microcavity structures on the strong coupling formation. We found that improvement in cavity quality factor causes a reduction in the photon damping constant, which results in an increase in the Rabi splitting energy. Moreover, when we used a metal thin film as the cavity mirror, it was revealed that the exciton damping became 30 times stronger than that in a dielectric mirror cavity. These experimental findings are very intriguing to achieve low-threshold or electrically pumped organic polariton devices.

Organic Light-Emitting Diodes with Heterojunction of Thiophene/Phenylene Co-Oligomer Derivatives.

Organic light-emitting diodes are fabricated by heterojunction of thiophene/phenylene co-oligomer films using biphenyl-capped bithiophene (BP2T) and its cyano-substituted derivative (BP2T-CN). Strong electron-withdrawing cyano-groups in BP2T-CN transform the p-type BP2T into n-type. Photoluminescence and electroluminescence from their bilayered films dominantly result from the BP2T-CN layer since the lying molecular orientation of BP2T-CN facilitates surface emission while the standing orientation of BP2T is not suitable for the device configuration. The current density and electroluminescence intensity are considerably increased by carrier doping with MoO3 and Cs2CO3 into the BP2T and BP2T-CN films, respectively.

Amplified Emission and Field-Effect Transistor Characteristics of One-Dimensionally Structured 2,5-Bis(4-biphenylyl)thiophene Crystals.

One-dimensional (1D) structures of 2,5-bis(4-biphenylyl)thiophene (BP1T) crystals are fabricated for light amplification and field-effect transistor (FET) measurements. A strip-shaped 1D structure (10 µm width) made by photolitography of a vapor-deposited polycrystalline film shows amplified spontaneous emission and lasing oscillations under optical pumping. An FET fabricated with this 1D structure exhibits hole-conduction with a mobility of µh = 8.0 x 10(-3) cm2/Vs. Another 1 D-structured FET is fabricated with epitaxially grown needle-like crystals of BP1T. This needle-crystal FET exhibits higher mobility of µh = 0.34 cm2/Vs. This improved hole mobility is attributed to the single-crystal channel of epitaxial needles while the grain boudaries in the polycrystalline 1 D-structure decrease the carrier transport.

Exotic optoelectronic properties of organic semiconductors with super-controlled nanoscale sizes and molecular shapes.

We present several aspects of thiophene/phenylene co-oligomers (TPCOs). TPCOs are regarded as a newly occurring class of organic semiconductors. These materials are synthesized by hybridizing thiophene and phenylene rings at the molecular level with their various mutual arrangements. These materials are characterized by the super-controlled nanoscale sizes and molecular shapes. These produce peculiar crystallographic structures and high-performance optical and electronic properties. The crystals of TPCOs were obtained through both vapor phase and liquid phase. In the TPCO crystals, the molecules take upright configuration. These cause large carrier mobilities of field-effect transistors and laser oscillations under optical excitations. Spectrally-narrowed emissions (SNEs) were also achieved under weak optical excitation using a mercury lamp. The light-emitting field-effect transistors using these crystals for an active layer have shown the current-injected SNEs when the device was combined with an optical cavity and operated by an alternating-current gate-voltage method. Thus the TPCO materials will play an important role in the future in the fields of nanoscale technology and organic semiconductor materials as well as their optoelectronic device applications.

Photogeneration of charge carrier correlated with amplified spontaneous emission in single crystals of a thiophene/phenylene co-oligomer.

Thiophene/phenylene co-oligomers have substantial promise for the use of not only organic electronics but also organic optical devices. However, considerably less is known about the correlation between their optical and optoelectronic properties. We have investigated the charge carrier generation in 1,4-bis(5-phenylthiophen-2-yl)benzene (AC5) single crystals by flash-photolysis time-resolved microwave conductivity (TRMC) and transient absorption spectroscopy (TAS). It was found that the dependence of photocarrier generation efficiency on excitation photon density differed from that of emission efficiency once amplified spontaneous emission (ASE) and resultant spectrally narrowed emission occur upon exposure to 355 nm. In contrast, the dependences of emission and photocarrier generation efficiencies were identical when ASE was not involved at a different excitation wavelength (193 nm). An approximated analytical solution of rate equation considering ASE or singlet-singlet annihilation was applied to the experiments, exhibiting good agreement. On the basis of TRMC, TAS, and extinction coefficient of radical cation assessed by pulse radiolysis, the minimum charge carrier mobility was estimated, without electrodes, to be 0.12 cm(2) V(-1) s(-1). The dynamics of charge carrier and triplet excited state is discussed, accompanying with examination by time-dependent density functional theory. The present work would open the way to a deeper understanding of the fate of excited state in optically robust organic semiconducting crystals.

Organic-crystal light-emitting field-effect transistors driven by square-wave gate voltages.

We have improved the operation method of organic light-emitting field-effect transistors by applying a square wave to the gate electrode. A thiophene/phenylene co-oligomer crystal was used as the organic layer. Compared with the sinusoidal wave gate bias application, the square-wave bias produces the emission intensity ten times as large as that of the former. The effective emissions take place through electrons injection from the source contact when the gate bias traverses 0 V so as to be positive. When asymmetric electrodes were used for the source and drain contacts, the resulting emission exhibited the narrowed spectral line at 491.5 nm with its FWHM approximately 1.1 nm. The line narrowing is expected to be a consequence of the emission intensity increment caused by the enhanced electrons injection from the Ag source contact. The location of the emission line is closely related to those of the multimodes due to the laser oscillation by cavity resonance.

Grating-assisted spectrally-narrowed emissions from an organic slab crystal excited with a mercury lamp.

We report spectrally-narrowed emissions that take place from an organic semiconductor slab crystal of 2,5-bis(4-biphenylyl)thiophene (BP1T) under a low excitation-intensity regime. These emissions are caused with a mercury lamp that operates on a household power supply with an electric current approximately 1 A. The BP1T slab crystal is equipped with a distributed Bragg reflector. To complete this structure the slab crystal is attached to a diffraction grating that is engraved on a surface of a quartz glass substrate. The diffraction gratings have precisely been formed using a focused ion beam with a nanometer-defined precision. The spectral narrowing accompanied by the emission intensity increment is related to the strong mode-coupling between the forward electromagnetic wave and the backward (i.e., reflected) wave within the grating zone. Using a laser we also carried out the emission measurements on the BP1T crystals under a high excitation-intensity regime. The emissions are characterized as the longitudinal multimode laser oscillation, enabling us to determine the group refractive index of 4.56 for the BP1T slab crystal. Under both the low and high excitation-intensity regimes excitons are dominant species of the emission. Their participation in the spectrally-narrowed emissions is briefly discussed.

A high optical-gain organic crystal comprising thiophene/phenylene co-oligomer nanomolecules.

We have estimated the optical gain for a crystal of a thiophene/phenylene co-oligomer, 1,4-bis(5-phenylthiophen-2-yl)benzene. We prepared the crystal by a vapor phase growth method and measured emission spectra by exciting it with a pulse laser and changing the pumped stripe lengths. With increasing the stripe lengths, the emission intensity was increased and the emission spectra were gain narrowed around 516 nm with its full width at half maximum down to approximately 6 nm. The optical gain spectrum was determined from the emission spectra that varied as a function of the pumped stripe lengths. The gain spectrum was peaked at 516 nm with the maximum net optical gain coefficient being 75 cm(-1). This peak location is in excellent agreement with the peak position of the gain narrowed emission spectra. The results indicate that the determination of the gain spectrum is important for laser applications of the material. The oligomer crystal in the present studies is a good candidate for them.

An field-effect transistor based upon thiophene/phenylene co-oligomer nanomolecules combined with a composite polymer gate insulator.

We have studied the FET device characteristics of the thiophene/phenylene co-oligomers chosen as organic semiconductors. The FET devices were made of two kinds of co-oligomer materials with different morphologies (i.e., the thin film and crystal). We show different device fabrication procedures depending upon the difference in the morphologies. The device characteristics were also investigated on various polymer gate insulators. The composite polymer gate insulators play an important role in achieving a good device performance. More specifically, the combination of poly(vinylphenol) and poly(methyl methacrylate) turned out very effective in attaining the pinch-off at larger drain voltages. This composite gate insulator is responsible for the steady device performance as well. A normal electrical feature is maintained under a reduced (or dry) pressure where conventional polymer gate FET devices did not function normally. The relevant results are evaluated and compared. The importance of the thiophene/phenylene co-oligomers as the nanomaterials (or nanomolecules) is briefly mentioned as well.

Improved device performance of organic crystal field-effect transistors fabricated on friction-transferred substrates.

We have improved performance of organic field-effect transistors (OFETs) composed of organic nanomolecular single crystals of a thiophene/phenylene co-oligomer. A poly(tetrafluoroethylene) thin layer was applied with friction-transfer technique to an insulator layer of silicon dioxide covering a silicon substrate. The crystals were grown in a liquid phase on the friction-transferred substrate such that the bottom-contact device was completed through depositing the crystals in firm contact with the premade metal electrodes. This technique ensures an excellent electrical contact between the crystal and the electrodes. The device shows the carrier mobility up to 0.26 cm2/Vs. The linear increase in the drain currents is clearly noted around the origin of the drain current-drain voltage action diagram. Thus we have achieved a high performance with the OFETs whose fabrication is based upon the friction-transfer technique.

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.

Clarification of the Molecular Doping Mechanism in Organic Single-Crystalline Semiconductors and their Application in Color-Tunable Light-Emitting Devices.

Organic single-crystalline semiconductors with long-range periodic order have attracted much attention for potential applications in electronic and optoelectronic devices due to their high carrier mobility, highly thermal stability, and low impurity content. Molecular doping has been proposed as a valuable strategy for improving the performance of organic semiconductors and semiconductor-based devices. However, a fundamental understanding of the inherent doping mechanism is still a key challenge impeding its practical application. In this study, solid evidence for the "perfect" substitutional doping mechanism of the stacking mode between the guest and host molecules in organic single-crystalline semiconductors using polarized photoluminescence spectrum measurements and first-principles calculations is provided. The molecular host-guest doping is further exploited for efficient color-tunable and even white organic single-crystal-based light-emitting devices by controlling the doping concentration. The clarification of the molecular doping mechanism in organic single-crystalline semiconductor host-guest system paves the way for their practical application in high-performance electronic and optoelectronic devices.

The entangled triplet pair state in acene and heteroacene materials.

Entanglement of states is one of the most surprising and counter-intuitive consequences of quantum mechanics, with potent applications in cryptography and computing. In organic materials, one particularly significant manifestation is the spin-entangled triplet-pair state, which mediates the spin-conserving fission of one spin-0 singlet exciton into two spin-1 triplet excitons. Despite long theoretical and experimental exploration, the nature of the triplet-pair state and inter-triplet interactions have proved elusive. Here we use a range of organic semiconductors that undergo singlet exciton fission to reveal the photophysical properties of entangled triplet-pair states. We find that the triplet pair is bound with respect to free triplets with an energy that is largely material independent (∼30 meV). During its lifetime, the component triplets behave cooperatively as a singlet and emit light through a Herzberg-Teller-type mechanism, resulting in vibronically structured photoluminescence. In photovoltaic blends, charge transfer can occur from the bound triplet pairs with >100% photon-to-charge conversion efficiency.

Conformational polymorphism and thermochemical analysis of 5,5' ''-bis[(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)ethyl]-2,2':5',2' ':5' ',2' ''-quaterthiophene.

The titled compound exists as two polymorphic solid phases (denoted form-I and form-II). Form-I obtained by as-synthesized material is a more stable phase. Form-II is a less stable phase. Spontaneous solid-solid transformation from form-II to form-I is observed in the temperature range between room temperature and the melting point of form-I (Tm = 156.5 degrees C), and its activation energy is estimated to be 96 kJ mol-1 by Arrhenius plot. The solid-solute-solid transformation (recrystallization from solution) from form-II to form-I is also observed. In contrast, form-II is obtained only by a solid-melt-solid transformation from form-I. Therefore, the system of two polymorphs is monotropic. The solid-state NMR measurement shows that form-I has the molecular conformation of complete S-syn-anti-syn in the oligothiophene backbone, whereas form-II has that of S-all-anti. With the solution NMR data, the polymorphism could not be observed. Therefore, the polymorphs originate from the different molecular packing involving the conformational change of the molecule. This unique property is attributed to the extra bulky terminal groups of the compounds. However, despite the extra bulky terminal groups, the mentioned polymorphism is not observed in the titled compound analogue which has S-all-anti conformation (like form-II).

Emission Behavior of Crystalline 1,4-Bis(4-phenylthiophene-2-yl)benzene Film Under Optical Excitation with Ultra Short Pulses.

We evaluated emission behaviors of crystallized films of 1,4-bis(5-phenylthiophene-2-yl)benzene (AC5) in detail which was a representative thiophene/phenylene co-oligomer. The crystallized AC5 films were prepared by vapor deposition onto a substrate and thermal treatment. The AC5 films consisted of a crystalline domain with the size of several tens of micrometers. We used femtosecond laser pulses for the excitation of the AC5 films. As a result, the femtosecond laser pulses did not induce re-absorption above excitation energy densities of their laser threshold. The obtained gain value for AC5 crystallized film was large, over 150 cm-1. Furthermore, the emission cross section of the crystallized AC5 film was nearly 10(-16) cm2.

Spectrally-Narrowed Emissions from Organic Crystals Having a One-Dimensional Grating on Their Surface.

We have succeeded in directly engraving one-dimensional diffraction gratings on the surface of organic semiconducting oligomer crystals by using focused ion beam (FIB) lithography and laser ablation (LA) methods. The FIB method enabled us to shape the gratings with varying periods down to ~150 nm. With the LA method a large-area grating with a ~500-nm period was readily accessible. All the above crystals indicated spectrally-narrowed emission (SNE) lines even in the case of shallow groove depths ~2-4 nm. In particular, we definitively observed the SNE pertinent to the first-order diffraction with the crystal having the diffraction grating of a 148.3-nm average period. The present results indicate utility of the built-in gratings that can directly be fabricated on the surface of the crystals.

Ambipolar light-emitting organic single-crystal transistors with a grating resonator.

Electrically driven organic lasers are among the best lasing devices due to their rich variety of emission colors as well as other advantages, including printability, flexibility, and stretchability. However, electrically driven lasing in organic materials has not yet been demonstrated because of serious luminescent efficiency roll-off under high current density. Recently, we found that the organic ambipolar single-crystal transistor is an excellent candidate for lasing devices because it exhibits less efficient roll-off, high current density, and high luminescent efficiency. Although a single-mode resonator combined with light-emitting transistors (LETs) is necessary for electrically driven lasing devices, the fragility of organic crystals has strictly limited the fabrication of resonators, and LETs with optical cavities have never been fabricated until now. To achieve this goal, we improved the soft ultraviolet-nanoimprint lithography method and demonstrated electroluminescence from a single-crystal LET with a grating resonator, which is a crucial milestone for future organic lasers.

Intrinsic Polarization and Tunable Color of Electroluminescence from Organic Single Crystal-based Light-Emitting Devices.

A single crystal-based organic light-emitting device (OLED) with intrinsically polarized and color-tunable electroluminescence (EL) has been demonstrated without any subsequent treatment. The polarization ratio of 5:1 for the transversal-electric (TE) and transversal-magnetic (TM) polarization at the emission peak of 575 nm, and 4.7:1 for the TM to TE polarization at the emission peak of 635 nm, respectively, have been obtained. The emitting color is tunable between yellow, yellow-green and orange by changing the polarization angle. The polarized EL and the polarization-induced color tunability can be attributed to the anisotropic microcavity formed by the BP3T crystal with uniaxial alignment of the molecules.

Triplet dynamics in pentacene crystals: applications to fission-sensitized photovoltaics.

The decay and transport of triplet excitons photogenerated via singlet exciton fission in polycrystalline and single-crystalline pentacene is reported. Using transient absorption spectroscopy, we find evidence for diffusion-mediated triplet-triplet annihilation. We estimate monomolecular lifetimes, bimolecular annihilation rate constants, and triplet exciton diffusion lengths. We discuss these results in the context of current solar cell device architectures.

Light-emitting field-effect transistors having combined organic semiconductor and metal oxide layers.

A new organic light-emitting field-effect transistor characterized by a metal oxide layer inserted between the organic layer and the gate insulator is proposed. The metal oxide is indirectly connected with source and drain electrodes through the organic layer. Upon increasing the potential difference between the source and drain electrodes, the emission becomes exceedingly strong and the emission region encompasses the whole channel zone.