Enhancing the Electrical Conductivity and Long-Term Stability of PEDOT:PSS Electrodes through Sequential Treatment with Nitric Acid and Cesium Chloride.

Solution-processable poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is an important polymeric conductor used extensively in organic flexible, wearable, and stretchable optoelectronics. However, further enhancing its conductivity and long-term stability while maintaining its superb mechanical properties remains challenging. Here, a novel post-treatment approach to enhance the electrical properties and stability of sub-20-nm-thin PEDOT:PSS films processed from solution is introduced. The approach involves a sequential post-treatment with HNO3 and CsCl, resulting in a remarkable enhancement of the electrical conductivity of PEDOT:PSS films to over 5500 S cm-1, along with improved carrier mobility. The post-treated films exhibit remarkable air stability, retaining over 85% of their initial conductivity even after 270 days of storage. Various characterization techniques, including X-ray photoelectron spectroscopy, atomic force microscopy, Raman spectroscopy, Hall effect measurements, and grazing incidence wide angle X-ray scattering, coupled with density functional theory calculations, provide insights into the structural changes and interactions responsible for these improvements. To demonstrate the potential for practical applications, the ultrathin PEDOT:PSS films are connected to an inorganic light-emitting diode with a battery, showcasing their suitability as transparent electrodes. This work presents a promising approach for enhancing the electrical conductivity of PEDOT:PSS while offering a comprehensive understanding of the underlying mechanisms that can guide further advances.

Intrinsic (Trap-Free) Transistors Based on Epitaxial Single-Crystal Perovskites.

The first experimental realization of the intrinsic (not dominated by defects) charge conduction regime in lead-halide perovskite field-effect transistors (FETs) is reported. The advance is enabled by: i) a new vapor-phase epitaxy technique that results in large-area single-crystalline cesium lead bromide (CsPbBr3 ) films with excellent structural and surface properties, including atomically flat surface morphology, essentially free from defects and traps at the level relevant to device operation; ii) an extensive materials analysis of these films using a variety of thin-film and surface probes certifying the chemical and structural quality of the material; and iii) the fabrication of nearly ideal (trap-free) FETs with characteristics superior to any reported to date. These devices allow the investigation of the intrinsic FET and (gated) Hall-effect carrier mobilities as functions of temperature. The intrinsic mobility is found to increase on cooling from ≈30 cm2 V-1 s-1 at room temperature to ≈250 cm2 V-1 s-1 at 50 K, revealing a band transport limited by phonon scattering. Establishing the intrinsic (phonon-limited) mobility provides a solid test for theoretical descriptions of carrier transport in perovskites, reveals basic limits to the technology, and points to a path for future high-performance perovskite electronic devices.

High-Quality Graphene Using Boudouard Reaction.

Following the game-changing high-pressure CO (HiPco) process that established the first facile route toward large-scale production of single-walled carbon nanotubes, CO synthesis of cm-sized graphene crystals of ultra-high purity grown during tens of minutes is proposed. The Boudouard reaction serves for the first time to produce individual monolayer structures on the surface of a metal catalyst, thereby providing a chemical vapor deposition technique free from molecular and atomic hydrogen as well as vacuum conditions. This approach facilitates inhibition of the graphene nucleation from the CO/CO2 mixture and maintains a high growth rate of graphene seeds reaching large-scale monocrystals. Unique features of the Boudouard reaction coupled with CO-driven catalyst engineering ensure not only suppression of the second layer growth but also provide a simple and reliable technique for surface cleaning. Aside from being a novel carbon source, carbon monoxide ensures peculiar modification of catalyst and in general opens avenues for breakthrough graphene-catalyst composite production.

n-type charge transport in heavily p-doped polymers.

It is commonly assumed that charge-carrier transport in doped π-conjugated polymers is dominated by one type of charge carrier, either holes or electrons, as determined by the chemistry of the dopant. Here, through Seebeck coefficient and Hall effect measurements, we show that mobile electrons contribute substantially to charge-carrier transport in π-conjugated polymers that are heavily p-doped with strong electron acceptors. Specifically, the Seebeck coefficient of several p-doped polymers changes sign from positive to negative as the concentration of the oxidizing agents FeCl3 or NOBF4 increase, and Hall effect measurements for the same p-doped polymers reveal that electrons become the dominant delocalized charge carriers. Ultraviolet and inverse photoelectron spectroscopy measurements show that doping with oxidizing agents results in elimination of the transport gap at high doping concentrations. This approach of heavy p-type doping is demonstrated to provide a promising route to high-performance n-type organic thermoelectric materials.

A Large Anisotropic Enhancement of the Charge Carrier Mobility of Flexible Organic Transistors with Strain: A Hall Effect and Raman Study.

Utilizing the intrinsic mobility-strain relationship in semiconductors is critical for enabling strain engineering applications in high-performance flexible electronics. Here, measurements of Hall effect and Raman spectra of an organic semiconductor as a function of uniaxial mechanical strain are reported. This study reveals a very strong, anisotropic, and reversible modulation of the intrinsic (trap-free) charge carrier mobility of single-crystal rubrene transistors with strain, showing that the effective mobility of organic circuits can be enhanced by up to 100% with only 1% of compressive strain. Consistently, Raman spectroscopy reveals a systematic shift of the low-frequency Raman modes of rubrene to higher (lower) frequencies with compressive (tensile) strain, which is indicative of a reduction (enhancement) of thermal molecular disorder in the crystal with strain. This study lays the foundation of the strain engineering in organic electronics and advances the knowledge of the relationship between the carrier mobility, low-frequency vibrational modes, strain, and molecular disorder in organic semiconductors.

Polarization-Dependent Photoinduced Bias-Stress Effect in Single-Crystal Organic Field-Effect Transistors.

Photoinduced charge transfer between semiconductors and gate dielectrics can occur in organic field-effect transistors (OFETs) operating under illumination, leading to a pronounced bias-stress effect in devices that are normally stable while operating in the dark. Here, we report an observation of a polarization-dependent photoinduced bias-stress effect in two prototypical single-crystal OFETs, based on rubrene and tetraphenylbis(indolo{1,2-a})quinolin. We find that the decay rate of the source-drain current in these OFETs under illumination is a periodic function of the polarization angle of incident photoexcitation with respect to the crystal axes, with a periodicity of π. The angular positions of maxima and minima of the bias-stress rate match those of the optical absorption coefficient of the corresponding crystals. The analysis of the effect shows that it stems from a charge transfer of "hot" holes, photogenerated in the crystal within a very short thermalization length (≪µm) from the semiconductor-dielectric interface. The observed phenomenon is a type of intrinsic structure-property relationship, revealing how molecular packing affects parameter drift in organic transistors under illumination. We also demonstrate that a photoinduced charge transfer in OFETs can be used for recording rewritable accumulation channels with an optically defined geometry and resolution, which can be used in a number of potential applications.

Intrinsic Charge Transport across Phase Transitions in Hybrid Organo-Inorganic Perovskites.

Hall effect measurements in CH3 NH3 PbBr3 single crystals reveal that the charge-carrier mobility follows an inverse-temperature power-law dependence, µ ∝ T(-) (γ) , with the power exponent γ = 1.4 ± 0.1 in the cubic phase, indicating an acoustic-phonon-dominated carrier scattering, and γ = 0.5 ± 0.1 in the tetragonal phase, suggesting another dominant mechanism, such as a piezoelectric or space-charge scattering.

Tuning the metal-insulator crossover and magnetism in SrRuO3 by ionic gating.

Reversible control of charge transport and magnetic properties without degradation is a key for device applications of transition metal oxides. Chemical doping during the growth of transition metal oxides can result in large changes in physical properties, but in most of the cases irreversibility is an inevitable constraint. Here we report a reversible control of charge transport, metal-insulator crossover and magnetism in field-effect devices based on ionically gated archetypal oxide system - SrRuO3. In these thin-film devices, the metal-insulator crossover temperature and the onset of magnetoresistance can be continuously and reversibly tuned in the range 90-250 K and 70-100 K, respectively, by application of a small gate voltage. We infer that a reversible diffusion of oxygen ions in the oxide lattice dominates the response of these materials to the gate electric field. These findings provide critical insights into both the understanding of ionically gated oxides and the development of novel applications.

Oxygen incorporation in rubrene single crystals.

Single crystal rubrene is a model organic electronic material showing high carrier mobility and long exciton lifetime. These properties are detrimentally affected when rubrene is exposed to intense light under ambient conditions for prolonged periods of time, possibly due to oxygen up-take. Using photoelectron, scanning probe and ion-based methods, combined with an isotopic oxygen exposure, we present direct evidence of the light-induced reaction of molecular oxygen with single crystal rubrene. Without a significant exposure to light, there is no reaction of oxygen with rubrene for periods of greater than a year; the crystal's surface (and bulk) morphology and chemical composition remain essentially oxygen-free. Grand canonical Monte Carlo computations show no sorbtion of gases into the bulk of rubrene crystal. A mechanism for photo-induced oxygen inclusion is proposed.

Ultra-flexible solution-processed organic field-effect transistors.

Organic semiconductors might enable new applications in low-cost, light-weight, flexible electronics. To build a solid foundation for these technologies, more fundamental studies of electro-mechanical properties of various types of organic semiconductors are necessary. Here we perform basic studies of charge transport in highly crystalline solution-processed organic semiconductors as a function of applied mechanical strain. As a test bed, we use small molecules crystallized on thin plastic sheets, resulting in high-performance flexible field-effect transistors. These devices can be bent multiple times without degradation to a radius as small as ~200 µm, demonstrating that crystalline solution-processed organic semiconductors are intrinsically highly flexible. This study of electro-mechanical properties suggests that solution-processable organic semiconductors are suitable for applications in flexible electronics, provided that integration with other important technological advances, such as device scalability and low-voltage operation, is achieved in the future.

The origin of a 650 nm photoluminescence band in rubrene.

Commonly observed variations in photoluminescence (PL) spectra of crystalline organic semiconductors, including the appearance or enhancement of certain PL bands, are shown to originate from a small amount of structural disorder (e.g., amorphous inclusions embedded in a crystal), rather than be necessarily related to chemical impurities or material oxidation. For instance, in rubrene, a minute amount of such disorder can lead to the appearance of a dominant PL band at 650 nm as a result of triplet excitons captured and fused at these sites, with a subsequent emission from the amorphous phase.

Chromophore fluorination enhances crystallization and stability of soluble anthradithiophene semiconductors.

We report dramatic improvements in the stability and crystallinity arising from partial fluorination of soluble anthradithiophene derivatives. These fluorinated materials still behave as p-type semiconductors but with dramatic increases in thermal and photostability compared to the non-fluorinated derivatives. The triethylsilyl-substituted material forms highly crystalline films even from spin-cast solutions, leading to devices with maximum hole mobility greater than 1.0 cm(2)/V s. In contrast, the triisopropylsilyl derivative forms large, high-quality crystals that could serve as the substrate for transistor fabrication. For this compound, mobility as high as 0.1 cm(2)/V s was measured on the free-standing crystal.

Primary photoexcitations and the origin of the photocurrent in rubrene single crystals.

By simultaneously measuring the excitation spectra of transient luminescence and transient photoconductivity after picosecond pulsed excitation in rubrene single crystals, we show that free excitons are photoexcited starting at photon energies above 2.0 eV. We observe a competition between photoexcitation of free excitons and photoexcitation into vibronic states that subsequently decays into free carriers, while molecular excitons are instead formed predominantly through the free exciton. At photon energies below 2.25 eV, free charge carriers are created only through a long-lived intermediate state with a lifetime of up to 0.1 ms and no free carriers appear during the exciton lifetime.

Elastomeric transistor stamps: reversible probing of charge transport in organic crystals.

We introduce a method to fabricate high-performance field-effect transistors on the surface of freestanding organic single crystals. The transistors are constructed by laminating a monolithic elastomeric transistor stamp against the surface of a crystal. This method, which eliminates exposure of the fragile organic surface to the hazards of conventional processing, enables fabrication of rubrene transistors with charge carrier mobilities as high as approximately 15 cm2/V.s and subthreshold slopes as low as 2nF.V/decade.cm2. Multiple relamination of the transistor stamp against the same crystal does not affect the transistor characteristics; we exploit this reversibility to reveal anisotropic charge transport at the basal plane of rubrene.