Rubrene Crystals Research Articles

Spectroscopy of Resonant Intermediate States for Triplet-Triplet Annihilation Upconversion in Crystalline Rubrene: Radical Ions as Sensitizers.

Photoluminescence upconversion in crystalline rubrene can proceed without an added sensitizer, but the mechanism for this process has not been well-understood. In particular, the species responsible for photon absorption has not been identified to date. To gain insight into the identity of the intermediate state, we measured the near-infrared (NIR) upconversion photoluminescence (UCPL) excitation spectrum of rubrene crystals and found three distinct spectral features. The UCPL yield has a quartic dependence on the laser intensity, implying a four-photon process. On the basis of electronic spectra of radical cations and anions of rubrene, we propose a mechanism in which photoexcited radical anions and cations undergo recombination, forming an excited neutral triplet while conserving spin. The triplets formed this way ultimately undergo triplet-triplet annihilation, resulting in the observed photoluminescence. This mechanism explains the origin of the NIR absorption as well as the four-photon nature of the UCPL process.

Morphology and transport characterization of solution-processed rubrene thin films on polymer-modified substrates

In this report, the morpho-structural peculiarities and the crystallization mechanisms in solution-processed, solvent vapor annealed (SVA) thin films of rubrene (5,6,11,12-tetraphenylnaphthacene) on different substrates were investigated. The high-quality rubrene crystal films with a triclinic crystal structure were successfully prepared on the FTO substrates (glass slide coated with fluorine-tin-oxide) modified by PLA (polylactic acid) for the first time. The area coverage of rubrene crystal and the sizes of rubrene dendritic crystals increased with increasing thickness of PLA film and concentration of rubrene solution. For rubrene molecules, FTO wafers with rough surface provided the possibility of heterogeneous nucleation. During the SVA process, there were two kinds of forces acting on the diffusion of rubrene molecules: one force was provided by the residual chloroform solvent, which was perpendicular to the substrate, and the other force was provided by gaseous dichloromethane, which was parallel to the substrate. The synergy of these two forces was proposed to explain the nucleation and the crystallization processes of rubrene films. The higher nucleus of PLA/rubrene dendrites and the layer-by-layer stacking of needle-shaped nanocrystalline PLA/rubrene were important for exploring their kinetic formation process.

Suppression of Persistent Photoconductivity of Rubrene Crystals using Gate-Tunable Rubrene/Bi2 Se3 Diodes with Photoinduced Negative Differential Resistance.

Organic single-crystalline semiconductors show great potential in high-performance photodetectors. However, they suffer from persistent photoconductivity (PPC) due to the charge trapping, which has severely hindered high-speed imaging applications. Here, a universal strategy of solving the PPC by integrating with topological insulator Bi2 Se3 is provided. The rubrene/Bi2 Se3 heterojunctions are selected as an example for general demonstration due to the reproducibly high mobility and broad optoelectronic applications of rubrene crystals. By virtue of high carrier concentration on Bi2 Se3 surface and the strong built-in electrical field, the photoresponse of the heterotransistor is significantly reduced for more than two orders (from over 10 s to 54ms), meanwhile the photoresponsivity can reach 124 A W-1 . To the best of knowledge, this operating speed is among the fastest responses in organic-inorganic heterojunctions. The heterotransistor also shows unique negative differential resistance under positive gate bias, which can be explained by photoinduced de-trapping of electron trap states in the bulk rubrene crystals. Besides, the rubrene/Bi2 Se3 heterojunction behaves as a gate-tunable backward-like diode due to the inhomogenous carrier distribution in the thick rubrene crystal and inversion of relative Fermi level positions. The findings demonstrate versatile functionalities of the rubrene/Bi2 Se3 heterojunctions for various emerging optoelectronic applications.

Electronic and Crystallographic Examinations of the Homoepitaxially Grown Rubrene Single Crystals.

Homoepitaxial growth of organic semiconductor single crystals is a promising methodology toward the establishment of doping technology for organic opto-electronic applications. In this study, both electronic and crystallographic properties of homoepitaxially grown single crystals of rubrene were accurately examined. Undistorted lattice structures of homoepitaxial rubrene were confirmed by high-resolution analyses of grazing-incidence X-ray diffraction (GIXD) using synchrotron radiation. Upon bulk doping of acceptor molecules into the homoepitaxial single crystals of rubrene, highly sensitive photoelectron yield spectroscopy (PYS) measurements unveiled a transition of the electronic states, from induction of hole states at the valence band maximum at an adequate doping ratio (10 ppm), to disturbance of the valence band itself for excessive ratios (≥ 1000 ppm), probably due to the lattice distortion.

Going beyond polaronic theories in describing charge transport in rubrene single crystals

We show that the charge transport properties of single crystals of rubrene can be well described without using polaron theories along the two high-mobility axes. The charge carriers can be considered as holes with coupling to the lattice but not to the degree, which requires the use of polaron theories. It is possible to use the Boltzmann Transport Equation (BTE) in the relaxation time approximation (RTA) to evaluate mobilities due to various scattering mechanisms after introducing a transport reduction factor (PTRF). PTRF takes into account the fraction of charge carriers, which have path lengths that are larger than the lattice constant, and permits the use of the BTE in the RTA even when the magnitude of the overall mobility is lower than the value typically required for the use of the BTE. We are then able to calculate mobilities due to various scattering mechanisms. We calculate the effective electron–phonon coupling constant from the published values for various phonon modes. The values of the effective mass from calculations and measurements reported in the literature vary slightly; we assume an intermediate value for the effective mass. With no fitting parameters needed for calculating temperature-dependent mobilities for trap-free crystals, we are able to get excellent agreement with the measured values along the two high-mobility crystallographic directions. In samples, with some trapping, a small density of exponentially distributed trap states is assumed and gives a very good fit to the measured data. Our work provides strong evidence that it is not necessary to invoke polaronic effects to understand charge transport in rubrene crystals.

Long-Range Exciton Diffusion via Singlet Revival Mechanism.

We clarify the mechanism that leads to extended exciton diffusion length in organic materials which exhibit a strong anisotropy of electronic coupling. We analyze the cooperative effects of singlet fission and triplet-triplet annihilation in the exciton diffusion by means of the dynamic Monte Carlo simulations. As a model system, we consider the rubrene crystal which exhibits a long-range exciton diffusion. The deexcitation of the singlet exciton is suppressed by singlet → triplet conversion via singlet fission. Even though the triplet exciton would hardly diffuse along the c-axis in the rubrene crystal (perpendicular to the high mobility plane) because of the small electronic coupling, the regeneration of the singlet exciton via triplet-triplet annihilation enables long-range exciton diffusion along the c-axis. This singlet revival mechanism can extend the overall lifetime and the diffusion length of the exciton, through back-and-forth transitions between an isotropically diffusing singlet exciton and a long-lived triplet exciton.

Routes to singlet exciton fission in rubrene crystals and amorphous films

By using wavelength-tunable, low fluence picosecond pulses at a 1 kHz repetition rate in a transient grating pump and probe configuration, we show that photoexcitation to higher vibrational levels leads to slower singlet exciton fission rates in rubrene. After the 1 ps photoexcitation, the initial growth of the triplet exciton population is exponential, with its time-constant systematically varying from 2.5 ± 0.7 ps to 40 ± 15 ps as the excitation photon energy is increased from the lowest to the third main vibrational band in the vibrational progression of rubrene’s absorption spectrum. We also determine that short-pulse-induced fluorescence in amorphous rubrene films deposited by molecular beam epitaxy in high vacuum decays as a single exponential with a lifetime of 15.2 ns, close to rubrene’s radiative lifetime for molecules in solution. This shows that singlet fission is non-existent in fully amorphous rubrene films, despite the close molecular packing, which indicates that in these films there is no short range molecular order matching the molecular arrangement in orthorhombic rubrene crystals.

Ultrasensitive Charged Object Detection Based on Rubrene Crystal Sensor

An ultrasensitive flexible organic sensor that uses the microsized rubrene crystal as the sensing element is demonstrated. The organic sensor with facile two-terminal device configuration can accurately perceive external charged objects, such as human hair, fiber cloth, plastic sheet, and paper scrap. The touch of these charged objects causes the effect of “gate” voltage of the traditional field-effect transistor, which modulates the carrier transport characteristics in the rubrene crystal. Benefiting from the unique sensing mechanism, the organic sensor is capable to resist the effect of gravity with high orientation stability. Our sensor shows a feasible route to realize the charged objects perception, making it a promising candidate for possible applications in artificial intelligence and human-machine interactive.

Photocarrier injection by two-photon excitation in rubrene single crystal

We performed photocarrier injection by two-photon excitation in rubrene crystal using laser pulses of nanosecond-duration at various wavelengths under an external electric field. Based on the excitation spectra, it is revealed that photocarriers are injected at excitation energies corresponding to the intrinsic absorption by two-photon process, in contrast to the midgap-states-mediated injection by one-photon process. This result means that the two-photon excitation method is useful to inject photocarriers free from the surface traps.

Exciton-Phonon Interaction Model for Singlet Fission in Prototypical Molecular Crystals.

In singlet fission (SF), a spin-conserving splitting of one singlet exciton into two triplet excitation states, the transition between localized electronic states can be controlled and modulated by delocalized lattice phonons. In this work, we built an exciton-phonon (ex-ph) interaction model accounting local electronic states coupled with both local molecular vibrations and low frequency intermolecular phonon modes for SF in crystalline tetracene and rubrene. On the basis of the calculated electronic couplings at the equilibrium structure of the molecular dimer, a superexchange path for SF was found for tetracene while couplings between the triplet pair (TT) state and other diabatic states are zero for rubrene due to the high symmetry. Our further ex-ph spectral density analysis and quantum dynamics simulation based on our ex-ph interaction model suggested a thermal-activated mechanism for SF in rubrene crystal via symmetry breaking by nuclear vibration, which is in agreement with recent experiments. It is also shown that thermal fluctuations of electronic couplings in both tetracene and rubrene are mostly in the same order of magnitude at room temperature, and this could be one of the reasons for both tetracene and rubrene to exhibit SF time scales within a close range (hundreds to thousands of femtoseconds) in experiments.

Evolution of crystallinity at a well-defined molecular interface of epitaxial C60 on the single crystal rubrene

Uniform and well-defined interfaces are required for clarification of fundamental processes at internal interfaces between donor and acceptor molecules constituting organic optoelectronic devices. In this study, evolution of a well-ordered molecular interface, epitaxially grown C60 on the single crystal rubrene (C42H28) surface, was accurately investigated by grazing incidence x-ray diffraction (GIXD) techniques. Contrasting to the case of C60 on the single crystal pentacene forming uniquely aligned epitaxial interfaces, coexistence of two inequivalent crystalline domains of C60 was identified on the single crystal rubrene. Nevertheless, crystallinity of C60/rubrene exhibited even more remarkable improvement to extend its in-plane average crystallite size up to 250 nm as the growth temperature was raised. Probable leading factors determining the structures and crystallinity of the well-defined molecular interfaces are discussed based on close comparison of the present results with the C60/pentacene interfaces. The techniques presented herein for enhancement of the crystallinity in epitaxial molecular interfaces are potentially applicable to development in the photoelectric power conversion efficiency of organic photovoltaics (OPVs) via improved charge carrier mobility in donor-acceptor interfaces.

Solution-processed organic phototransistors based on controllable crystal growth of rubrene thin films with polymer-assisted layer

Crystalline rubrene films were fabricated by polymer-assisted layer in a sequential solution deposition process. Controllable crystal growth was achieved through varying the solution concentration of the polystyrene layers of the bilayer thin films. And the transitions from dendrites to spherulites were observed. The formation mechanism of rubrene crystals was proposed. Phototransistors based on rubrene thin film modified by PS-assisted layer showed a mobility of 1.67 × 10−3 cm2/Vs, a photoresponsivity of 4.7 μA/W, and a photosensitivity of 6900 under 200 mW/cm2 light power conditions. This process provides a valuable platform for studying the organic crystal growth and its photoelectric properties.

Second-Order Cumulant Approach for the Evaluation of Anisotropic Hole Mobility in Organic Semiconductors

The anisotropic field effect mobilities of four prototypical semiconducting materials, that is, single crystals of pentacene, tetracene, picene, and rubrene, are evaluated by using the hopping model with time averaged rates obtained at the second-order cumulant (SOC) expansion of the time-dependent reduced density matrix. It is shown that the SOC approach allows for correcting the two known failures of the hopping mechanism: the highly overestimated mobilities provided by the Fermi golden rule and the incorrect temperature dependence predicted by the semiclassical Marcus’ approach.

Evidence of exciton dissociation into carriers induced by electric field in rubrene crystals

We investigated an optical carrier injection mechanism in an organic semiconductor rubrene crystal. We simultaneously measured exciton photoluminescence (PL) and photocurrent under an electric field higher than 1 kV/cm at room temperature. An anti-correlation between the exciton PL intensity and photocurrent was observed. This directly indicates that carriers are generated through an exciton dissociation induced by the electric field. The estimated exciton dissociation efficiency is on the order of 10−2 for an excitation wavelength of 442 nm under an electric field of 12 kV/cm at room temperature. In addition, we revealed that both carriers and excitons are trapped at oxidation sites at the surface area of the crystal and more efficiently emit a modified luminescence.

Correlating Crystal Thickness, Surface Morphology, and Charge Transport in Pristine and Doped Rubrene Single Crystals.

The relationship between charge transport and surface morphology is investigated by utilizing rubrene single crystals of varying thicknesses. In the case of pristine crystals, the surface conductivities decrease exponentially as the crystal thickness increases until ∼4 μm, beyond which the surface conductivity saturates. Investigation of the surface morphology using optical and atomic force microscopy reveals that thicker crystals have a higher number of molecular steps, increasing the overall surface roughness compared with thin crystals. The density of molecular steps as a surface trap is further quantified with the subthreshold slope of rubrene air-gap transistors. This thickness-dependent surface conductivity is rationalized by a shift from in-plane to out-of-plane transport governed by surface roughness. The surface transport is disrupted by roughening of the crystal surface and becomes limited by the slower vertical crystallographic axis on molecular step edges. Separately, we investigate surface-doping of rubrene crystals by using fluoroalkyltrichrolosilane and observe a different mechanism for charge transport which is independent of surface roughness. This work demonstrates that the correlation between crystal thickness, surface morphology, and charge transport must be taken into account when measuring organic single crystals. Considering the fact that these molecular steps are universally observed on organic/inorganic and single/polycrystals, we believe that our findings can be widely applied to improve charge transport understanding.

Epitaxially Grown Ferroelectric PVDF-TrFE Film on Shape-Tailored Semiconducting Rubrene Single Crystal.

Epitaxial crystallization of thin poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) films is important for the full utilization of their ferroelectric properties. Epitaxy can offer a route for maximizing the degree of crystallinity with the effective orientation of the crystals with respect to the electric field. Despite various approaches for the epitaxial control of the crystalline structure of PVDF-TrFE, its epitaxy on a semiconductor is yet to be accomplished. Herein, the epitaxial growth of PVDF-TrFE crystals on a single-crystalline organic semiconductor rubrene grown via physical vapor deposition is presented. The epitaxy results in polymer crystals globally ordered with specific crystal orientations dictated by the epitaxial relation between the polymer and rubrene crystal. The lattice matching between the c-axis of PVDF-TrFE crystals and the (210) plane of orthorhombic rubrene crystals develops two degenerate crystal orientations of the PVDF-TrFE crystalline lamellae aligned nearly perpendicular to each other. Thin PVDF-TrFE films with epitaxially grown crystals are incorporated into metal/ferroelectric polymer/metal and metal/ferroelectric polymer/semiconductor/metal capacitors, which exhibit excellent nonvolatile polarization and capacitance behavior, respectively. Furthermore, combined with a printing technique for micropatterning rubrene single crystals, the epitaxy of a PVDF-TrFE film is formed selectively on the patterned rubrene with characteristic epitaxial crystal orientation over a large area.

Effect of electrode design on crosstalk between neighboring organic field-effect transistors based on one single crystal

The design of high-integration organic circuits must be such that the interference between neighboring devices is eliminated. Here, rubrene crystals were used to study the effect of the electrode design on crosstalk between neighboring organic field-effect transistors (OFETs). Results show that a decreased source/drain interval and gate electrode width can decrease the diffraction distance of the current, and therefore can weaken the crosstalk. In addition, the inherent low carrier concentration in organic semiconductors can create a high-resistance barrier at the space between gate electrodes of neighboring devices, limiting or even eliminating the crosstalk as a result of the gate electrode width being smaller than the source/drain electrode width.

High-performance organic transistors based on solution-processed rubrene crystals directly grown on a polymeric dielectric

Abstract High-quality rubrene crystals were directly grown on a polymeric gate dielectric-coated ITO/glass substrate by a simple solution process. Organic field-effect transistors were fabricated based on these rubrene crystals, and their electrical performance was investigated. Atomic force micrographs of the rubrene crystal reveal that its surface has a conventional terrace structure, confirming the well-ordered rubrene molecules. The organic transistor with the rubrene crystal shows the highest charge carrier hole mobility of 3.74 cm2/V·s that can be attributed to the strong π-π overlap between the adjacent rubrene molecules. The device shows a stable static and dynamic electrical stress response under ambient conditions. For evaluating the applicability of the transistor in a logic circuit, a simple load-type inverter is fabricated by combining the rubrene transistor and a 10 MΩ load-resistor, to achieve a clear dynamic switching response up to 100 Hz.

Microspacing In-Air Sublimation Growth of Organic Crystals

Organic single crystals manifest the intrinsic physical properties of materials. However, traditional growth of organic single crystals is limited by low solubility from solutions or complexity from physical vapor deposition. Here we report a new method to grow organic single crystals by microspacing in-air sublimation, which avoids costly vacuum system and time-consuming procedures and is practical for a wide range of organic crystals. In situ crystal growth observation revealed an unprecedented vapor-to-melt-to-crystal mechanism, resulting from the micrometer scale spacing distance between the source and the growth position. FET devices based on the rubrene crystals directly grown on Si/SiO2 substrate exhibited higher mobility than the best record using SiO2 as the gate dielectric. This effective organic crystal growth technique can be affordable and handled for almost every lab, which may be beneficial for future research and application of organic crystals.

溶液法制备PVP为界面修饰层的红荧烯结晶性薄膜

溶液法制备PVP为界面修饰层的红荧烯结晶性薄膜