Harnessing Molecular Vibrations to Probe Triplet Dynamics During Singlet Fission.

Ultrafast vibrational spectroscopy in the mid-infrared spectral range provides the opportunity to probe the dynamics of electronic states involved in all stages of the singlet fission reaction through their unique vibrational frequencies. This capability is demonstrated using a model singlet fission chromophore, 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pn). The alkyne groups of the TIPS side chains are coupled to the conjugated framework of the pentacene cores, enabling direct examination of the dynamics of triplet excitons that have successfully separated from correlated triplet pair states in crystalline films of TIPS-Pn. Relaxation processes during the separation of triplet excitons and triplet-triplet annihilation after their separation result in the formation of hot ground state molecules that also exhibit unique vibrational frequencies. Because all organic molecules possess native vibrational modes, ultrafast vibrational spectroscopy offers a new approach to examine the dynamics of electronic intermediates that may inform ongoing efforts to utilize singlet fission to overcome thermalization losses in photovoltaic applications.

Solution-Processed Organic and Halide Perovskite Transistors on Hydrophobic Surfaces.

Solution-processable electronic devices are highly desirable due to their low cost and compatibility with flexible substrates. However, they are often challenging to fabricate due to the hydrophobic nature of the surfaces of the constituent layers. Here, we use a protein solution to modify the surface properties and to improve the wettability of the fluoropolymer dielectric Cytop. The engineered hydrophilic surface is successfully incorporated in bottom-gate solution-deposited organic field-effect transistors (OFETs) and hybrid organic-inorganic trihalide perovskite field-effect transistors (HTP-FETs) fabricated on flexible substrates. Our analysis of the density of trapping states at the semiconductor-dielectric interface suggests that the increase in the trap density as a result of the chemical treatment is minimal. As a result, the devices exhibit good charge carrier mobilities, near-zero threshold voltages, and low electrical hysteresis.

Dynamic Exchange During Triplet Transport in Nanocrystalline TIPS-Pentacene Films.

The multiplication of excitons in organic semiconductors via singlet fission offers the potential for photovoltaic cells that exceed the Shockley-Quiesser limit for single-junction devices. To fully utilize the potential of singlet fission sensitizers in devices, it is necessary to understand and control the diffusion of the resultant triplet excitons. In this work, a new processing method is reported to systematically tune the intermolecular order and crystalline structure in films of a model singlet fission chromophore, 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pn), without the need for chemical modifications. A combination of transient absorption spectroscopy and quantitative materials characterization enabled a detailed examination of the distance- and time-dependence of triplet exciton diffusion following singlet fission in these nanocrystalline TIPS-Pn films. Triplet-triplet annihilation rate constants were found to be representative of the weighted average of crystalline and amorphous phases in TIPS-Pn films comprising a mixture of phases. Adopting a diffusion model used to describe triplet-triplet annihilation, the triplet diffusion lengths for nanocrystalline and amorphous films of TIPS-Pn were estimated to be ∼75 and ∼14 nm, respectively. Importantly, the presence of even a small fraction (<10%) of the amorphous phase in the TIPS-Pn films greatly decreased the ultimate triplet diffusion length, suggesting that pure crystalline materials may be essential to efficiently harvest multiplied triplets even when singlet fission occurs on ultrafast time scales.

Spray printing of organic semiconducting single crystals.

Single-crystal semiconductors have been at the forefront of scientific interest for more than 70 years, serving as the backbone of electronic devices. Inorganic single crystals are typically grown from a melt using time-consuming and energy-intensive processes. Organic semiconductor single crystals, however, can be grown using solution-based methods at room temperature in air, opening up the possibility of large-scale production of inexpensive electronics targeting applications ranging from field-effect transistors and light-emitting diodes to medical X-ray detectors. Here we demonstrate a low-cost, scalable spray-printing process to fabricate high-quality organic single crystals, based on various semiconducting small molecules on virtually any substrate by combining the advantages of antisolvent crystallization and solution shearing. The crystals' size, shape and orientation are controlled by the sheer force generated by the spray droplets' impact onto the antisolvent's surface. This method demonstrates the feasibility of a spray-on single-crystal organic electronics.

Grain Boundary Induced Bias Instability in Soluble Acene-Based Thin-Film Transistors.

Since the grain boundaries (GBs) within the semiconductor layer of organic field-effect transistors (OFETs) have a strong influence on device performance, a substantial number of studies have been devoted to controlling the crystallization characteristics of organic semiconductors. We studied the intrinsic effects of GBs within 5,11-bis(triethylsilylethynyl) anthradithiophene (TES-ADT) thin films on the electrical properties of OFETs. The GB density was easily changed by controlling nulceation event in TES-ADT thin films. When the mixing time was increased, the number of aggregates in as-spun TES-ADT thin films were increased and subsequent exposure of the films to 1,2-dichloroethane vapor led to a significant increase in the number of nuleation sites, thereby increasing the GB density of TES-ADT spherulites. The density of GBs strongly influences the angular spread and crystallographic orientation of TES-ADT spherulites. Accordingly, the FETs with higher GB densities showed much poorer electrical characteristics than devices with lower GB density. Especially, GBs provide charge trapping sites which are responsible for bias-stress driven electrical instability. Dielectric surface treatment with a polystyrene brush layer clarified the GB-induced charge trapping by reducing charge trapping at the semiconductor-dielectric interface. Our study provides an understanding on GB induced bias instability for the development of high performance OFETs.

Solution-printed organic semiconductor blends exhibiting transport properties on par with single crystals.

Solution-printed organic semiconductors have emerged in recent years as promising contenders for roll-to-roll manufacturing of electronic and optoelectronic circuits. The stringent performance requirements for organic thin-film transistors (OTFTs) in terms of carrier mobility, switching speed, turn-on voltage and uniformity over large areas require performance currently achieved by organic single-crystal devices, but these suffer from scale-up challenges. Here we present a new method based on blade coating of a blend of conjugated small molecules and amorphous insulating polymers to produce OTFTs with consistently excellent performance characteristics (carrier mobility as high as 6.7 cm(2) V(-1) s(-1), low threshold voltages of<1 V and low subthreshold swings <0.5 V dec(-1)). Our findings demonstrate that careful control over phase separation and crystallization can yield solution-printed polycrystalline organic semiconductor films with transport properties and other figures of merit on par with their single-crystal counterparts.

Exciton delocalization drives rapid singlet fission in nanoparticles of acene derivatives.

We compare the singlet fission dynamics of five pentacene derivatives precipitated to form nanoparticles. Two nanoparticle types were distinguished by differences in their solid-state order and kinetics of triplet formation. Nanoparticles that comprise primarily weakly coupled chromophores lack the bulk structural order of the single crystal and exhibit nonexponential triplet formation kinetics (Type I), while nanoparticles that comprise primarily more strongly coupled chromophores exhibit order resembling that of the bulk crystal and triplet formation kinetics associated with the intrinsic singlet fission rates (Type II). In the highly ordered nanoparticles, singlet fission occurs most rapidly. We relate the molecular packing arrangement derived from the crystal structure of the pentacene derivatives to their singlet fission dynamics and find that slip stacking leads to rapid, subpicosecond singlet fission. We present evidence that exciton delocalization, coincident with an increased relative admixture of charge-transfer configurations in the description of the exciton wave function, facilitates rapid triplet pair formation in the case of single-step singlet fission. We extend the study to include two hexacene derivatives and find that these conclusions are generally applicable. This work highlights acene derivatives as versatile singlet fission chromophores and shows how chemical functionalization affects both solid-state order and exciton interactions and how these attributes in turn affect the rate of singlet fission.

Electrospray-processed soluble acenes toward the realization of high-performance field-effect transistors.

Functionalized acenes have proven to be promising compounds in the field of molecular electronics because of their unique features in terms of the stability, performance, and ease of processing. The emerging concept of large-area-compatible techniques for flexible electronics has brought about a wide variety of well-established techniques for the deposition of soluble acenes, with spray-coating representing an especially fruitful approach. In the present study, electrostatic spray deposition is proposed as an alternative to the conventional spray-coating processes, toward the realization of high-performance organic field-effect transistors (OFETs), on both rigid and flexible substrates. Particularly, a thorough study on the effect of the solvent and spraying regime on the resulting crystalline film's morphology is performed. By optimization of the process conditions in terms of control over the size as well as the crystallization scheme of the droplets, desirable morphological features along with high-quality crystal domains are obtained. The fabricated OFETs exhibit excellent electrical characteristics, with high field-effect mobility up to 0.78 cm(2)/(V s), I(on)/I(off) >10(4), and near-zero threshold voltages. Additionally, the good performance of the OFETs realized on plastic substrates gives great potentiality to the proposed method for applications in the challenging field of large-area electronics.

Difluorinated 6,13-Bis(triisopropylsilylethynyl)pentacene: Synthesis, Crystallinity, and Charge-Transport Properties.

Fluorination has been demonstrated to improve stability and processing in thiophene-containing small-molecule semiconductors. Here, the impact of partial fluorination on these parameters in a pentacene derivative is examined. Although the improvement in photostability is not as dramatic, there is a clear improvement in the stability of the chromophore upon fluorination. The improvement in processability is more dramatic; devices formed by spin-coating with the fluorinated derivative perform substantially better than those formed from the nonfluorinated compound.

Strongly correlated alignment of fluorinated 5,11-bis(triethylgermylethynyl)anthradithiophene crystallites in solution-processed field-effect transistors.

The crystallinity of an organic semiconductor film determines the efficiency of charge transport in electronic devices. This report presents a micro-to-nanoscale investigation on the crystal growth of fluorinated 5,11-bis(triethylgermylethynyl)anthradithiophene (diF-TEG-ADT) and its implication for the electrical behavior of organic field-effect transistors (OFETs). diF-TEG-ADT exhibits remarkable self-assembly through spin-cast preparation, with highly aligned edge-on stacking creating a fast hole-conducting channel for OFETs.

All-printed flexible organic transistors enabled by surface tension-guided blade coating.

A combination of surface energy-guided blade coating and inkjet printing is used to fabricate an all-printed high performance, high yield, and low variability organic thin film transistor (OTFT) array on a plastic substrate. Functional inks and printing processes were optimized to yield self-assembled homogenous thin films in every layer of the OTFT stack. Specifically, we investigated the effect of capillary number, semiconductor ink composition (small molecule-polymer ratio), and additive high boiling point solvent concentrations on film fidelity, pattern design, device performance and yields.

Systematic reliability study of top-gate p- and n-channel organic field-effect transistors.

We report on a systematic investigation on the performance and stability of p-channel and n-channel top-gate OFETs, with a CYTOP/Al2O3 bilayer gate dielectric, exposed to controlled dry oxygen and humid atmospheres. Despite the severe conditions of environmental exposure, p-channel and n-channel top-gate OFETs show only minor changes of their performance parameters without undergoing irreversible damage. When correlated with the conditions of environmental exposure, these changes provide new insight into the possible physical mechanisms in the presence of oxygen and water. Photoexcited charge collection spectroscopy experiments provided further evidence of oxygen and water effects on OFETs. Top-gate OFETs also display outstanding durability, even when exposed to oxygen plasma and subsequent immersion in water or operated under aqueous media. These remarkable properties arise as a consequence of the use of relatively air stable organic semiconductors and proper engineering of the OFET structure.

Vibration-assisted crystallization improves organic/dielectric interface in organic thin-film transistors.

Solution processability of organic semiconductors allows high-throughput fabrication on arbitrary substrates at low-cost, but the films often exhibit low performance. Here, we report on a new method for device fabrication, vibration assisted crystallization (VAC) that produces superior films, which approach the fundamental performance limits shown in corresponding single-crystal measurements.

Solvent vapor annealing in the molecular regime drastically improves carrier transport in small-molecule thin-film transistors.

We demonstrate a new way to investigate and control the solvent vapor annealing of solution-cast organic semiconductor thin films. Solvent vapor annealing of spin-cast films of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pn) is investigated in situ using quartz crystal microbalance with dissipation (QCM-D) capability, allowing us to monitor both solvent mass uptake and changes in the mechanical rigidity of the film. Using time-resolved grazing incidence wide angle X-ray scattering (GIWAXS) and complementary static atomic force microscopy (AFM), we demonstrate that solvent vapor annealing in the molecular regime can cause significant performance improvements in organic thin film transistors (OTFTs), whereas allowing the solvent to percolate and form a liquid phase results in catastrophic reorganization and dewetting of the film, making the process counterproductive. Using these lessons we devise processing conditions which prevent percolation of the adsorbed solvent vapor molecules for extended periods, thus extending the benefits of solvent vapor annealing and improving carrier mobility by nearly two orders of magnitude. Ultimately, it is demonstrated that QCM-D is a very powerful sensor of the state of the adsorbed solvent as well as the thin film, thus making it suitable for process development as well as in-line process monitoring both in laboratory and in future manufacturing settings.

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.

Isomerically pure syn-anthradithiophenes: synthesis, properties, and FET performance.

The synthesis of isomerically pure syn-anthradithiophene derivatives (syn-ADTs) is described. X-ray crystallography is used to compare the solid-state arrangement of syn-ADT derivatives 2a,b to the analogous mixture of syn- and anti-ADTs. Single-crystal OFETs based on isomerically pure syn-ADTs 2a,b display device performance comparable to those based on a mixture of ADT isomers syn/anti-2a,b with mobilities as high as 1 cm(2)/(V s).

Functionalized higher acenes: hexacene and heptacene.

We have extended our functionalization strategy for pentacene to the higher acenes hexacene and heptacene. Provided a large enough alkyne substituent is used, these large aromatic rods are both stable and soluble and can be characterized spectroscopically as well as by single-crystal X-ray diffraction.

Organic field-effect transistors from solution-deposited functionalized acenes with mobilities as high as 1 cm2/V x s.

We present the device parameters for organic field-effect transistors fabricated from solution-deposited films of functionalized pentacene and anthradithiophenes. These materials are easily prepared in one or two steps from commercially available starting materials and are purified by simple recrystallization. For a solution-deposited film of functionalized pentacene, hole mobility of 0.17 cm2/V.s was measured. The functionalized anthradithiophenes showed behavior strongly dependent on the substituents, with hole mobilities as high as 1.0 cm2/V.s.

Stable, crystalline acenedithiophenes with up to seven linearly fused rings.

[structure: see text] We report the synthesis of a series of crystalline acenedithiophenes with up to seven linearly fused rings and silylethynyl substituents. These functional groups are designed to both improve solubility and enhance cofacial interactions in the solid. We discuss the crystal packing of these materials, as well as their physical properties such as oxidation potential, UV-vis absorption, fluorescence emission, and decomposition pathways.