Organic Semiconductor Thin Films Research Articles

Device-Based Probe of Triplet Exciton Diffusion in Singlet Fission Materials.

Probing triplet transport in singlet fission materials can be challenging due to the presence of multiple diffusing species. We present a device-based method to measure the intrinsic triplet diffusion length (LD) in organic semiconductor thin films exhibiting singlet fission. Triplet states are optically injected into the singlet fission material of interest via energy transfer from an adjacent thin film characterized by strong spin-orbit coupling. Injected triplets migrate through the full thickness of the material before undergoing dissociation at a donor-acceptor interface. By modeling the ratio of injector and acceptor photocurrent as a function of layer thickness, the triplet LD is extracted separate from processes of unknown efficiency including singlet fission and diffusion. In considering three archetypical fission systems, a wide range is found for the triplet LD, ranging from 3.3 ± 0.4 nm for 5,12-bis((triisopropylsilyl)ethynyl)tetracene to 17.1 ± 1.3 nm for pentacene and 32.1 ± 2.6 nm for tetracene.

Direct observation and evolution of electronic coupling between organic semiconductors

The electronic wave functions of an atom or molecule are affected by its interactions with its environment. These interactions dictate electronic and optical processes at interfaces, and is especially relevant in the case of thin film optoelectronic devices such as organic solar cells. In these devices, charge transport and interfaces between multiple layers occur along the thickness or vertical direction, and thus such electronic interactions between different molecules---same or different---are crucial in determining the device properties. Here, we introduce an in situ spectroscopic ellipsometry data analysis method called differential analysis in real time (DART) with the ability to directly probe electronic coupling due to intermolecular interactions along the thickness direction using vacuum-deposited organic semiconductor thin films as a model system. The analysis, which does not require any model fitting, reveals direct observations of electronic coupling between frontier orbitals under optical excitations leading to delocalization of the corresponding electronic wave functions with thickness or, equivalently, number of molecules away from the interface in C60 and MeO-TPD deposited on an insulating substrate $(\mathrm{Si}{\mathrm{O}}_{2})$. Applying the same methodology for C60 deposited on phthalocyanine thin films, the analyses shows strong, anomalous features---in comparison to C60 deposited on $\mathrm{Si}{\mathrm{O}}_{2}$---of the electronic wave functions corresponding to specific excitation energies in C60 and phthalocyanines. Translation of such interactions in terms of dielectric constants reveals plasmonic type resonance absorptions resulting from oscillations of the excited state wave functions between the two materials across the interface. Finally, reproducibility, angstrom-level sensitivity, and simplicity of the method are highlighted showcasing its applicability for studying electronic coupling between any vapor-deposited material systems where real-time measurements during thin film growth are possible.

Atomically Smooth Graphene‐Based Hybrid Template for the Epitaxial Growth of Organic Semiconductor Crystals

AbstractAtomically thin 2D materials are good templates to grow organic semiconductor thin films with desirable features. However, the 2D materials typically exhibit surface roughness and spatial charge inhomogeneity due to nonuniform doping, which can affect the uniform assembly of organic thin films on the 2D materials. A hybrid template is presented for preparation of highly crystalline small‐molecule organic semiconductor thin film that is fabricated by transferring graphene onto a highly ordered self‐assembled monolayer. This hybrid graphene template has low surface roughness and spatially uniform doping, and it yields highly crystalline fullerene thin films with grain sizes >300 nm, which is the largest reported grain size for C60 thin films on 2D materials. A graphene/fullerene/pentacene phototransistor fabricated directly on the hybrid template has five times higher photoresponsivity than a phototransistor fabricated on a conventional graphene template supported by a SiO2 wafer.

Transient grating spectroscopy of photocarrier dynamics in semiconducting polymer thin films

While charge carrier dynamics and thermal management are both keys to the operational efficiency and stability for energy-related devices, experimental techniques that can simultaneously characterize both properties are still lacking. In this paper, we use laser-induced transient grating (TG) spectroscopy to characterize thin films of the archetypal organic semiconductor regioregular poly(3-hexylthiophene) and its blends with the electron acceptor [6,6]-phenyl-C61-butyric acid methyl ester on glass substrates. While the thermal responses from the thin film and the substrate cannot be distinguished due to their similar thermal diffusivities, we show that the recombination dynamics of photocarriers in the organic semiconductor thin films occur on a similar timescale and can be separated from the thermal response. Our measurements indicate that the photocarrier dynamics are determined by multiple recombination processes and our extracted recombination rates are in good agreement with previous reports using other techniques. We further apply TG spectroscopy to characterize another conjugated polymer and a molecular fluorescent material to demonstrate its general applicability. Our study indicates the potential of transient grating spectroscopy to simultaneously characterize thermal transport and photocarrier dynamics in organic optoelectronic devices.

Water-Surface Drag Coating: A New Route Toward High-Quality Conjugated Small-Molecule Thin Films with Enhanced Charge Transport Properties.

Electronic properties of organic semiconductor (OSC) thin films are largely determined by their morphologies and crystallinities. However, solution-processed conjugated small-molecule OSC thin films usually exhibit abundant grain boundaries and impure grain orientations because of complex fluid dynamics during solution coating. Here, a novel methodology, water-surface drag coating, is demonstrated to fabricate high-quality OSC thin films with greatly enhanced charge transport properties. This method utilizes the water surface to alter the evaporation dynamics of solution to enlarge the grain size, and a unique drag-coating process to achieve the unidirectional growth of organic crystals. Using 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (Dif-TES-ADT) as an example, thin films with millimeter-sized single-crystal domains and pure crystallographic orientations are achieved, revealing a significant enhancement (4.7 times) of carrier mobility. More importantly, the resulting film can be directly transferred onto any desired flexible substrates, and flexible transistors based on the Dif-TES-ADT thin films show a mobility as high as 16.1 cm2 V-1 s-1 , which represents the highest mobility value for the flexible transistors reported thus far. The method is general for the growth of various high-quality OSC thin films, thus opening up opportunities for high-performance organic flexible electronics.

Unveiling photophysical and photonic phenomena by means of optical gain measurements in waveguides and solutions

The increasing number of solution-processed laser compounds that can be implemented as low-cost, flexible, and/or integrated devices, makes necessary the development of reliable methods to delineate all their amplifying signatures and thus to open the door to appropriate cross-sample comparisons. Seeking to solve this problem, a new formalism to retrieve the losses and the optical gains from Amplified Spontaneous Emission (ASE) spectra as a function of the excitation density has been recently reported. In this manuscript, we explore the potential of this methodology to unveil relevant information on the photonic properties of the waveguiding devices and on the photophysics of the active materials. We demonstrate that the Variable Pump Intensity method opens the door to understand the relationship between the ASE thresholds and the optical gains and losses, it enables the extraction of the scattering/modal losses of the passive devices, and it can unveil the presence of leaky-modes and excited state absorption. In contrast, it does not perform too well in samples with multiple active species in its current implementation. We have substantiated all these findings using organic semiconductor thin films, several dye-doped polymer thin films and solutions of boron hydride.

Optical-field driven charge-transfer modulations near composite nanostructures

Optical activation of material properties illustrates the potentials held by tuning light-matter interactions with impacts ranging from basic science to technological applications. Here, we demonstrate for the first time that composite nanostructures providing nonlocal environments can be engineered to optically trigger photoinduced charge-transfer-dynamic modulations in the solid state. The nanostructures explored herein lead to out-of-phase behavior between charge separation and recombination dynamics, along with linear charge-transfer-dynamic variations with the optical-field intensity. Using transient absorption spectroscopy, up to 270% increase in charge separation rate is obtained in organic semiconductor thin films. We provide evidence that composite nanostructures allow for surface photovoltages to be created, which kinetics vary with the composite architecture and last beyond optical pulse temporal characteristics. Furthermore, by generalizing Marcus theory framework, we explain why charge-transfer-dynamic modulations can only be unveiled when optic-field effects are enhanced by nonlocal image-dipole interactions. Our demonstration, that composite nanostructures can be designed to take advantage of optical fields for tuneable charge-transfer-dynamic remote actuators, opens the path for their use in practical applications ranging from photochemistry to optoelectronics.

Simulation of two-transistor parallel and series circuits for gas sensing validated by experimental data

Organic field effect transistors (OFETs) in parallel and series circuit configurations are simulated and tested for gas sensing activity. The devices are based on PQT12 and PQTS12 organic semiconductor thin films. A two-dimensional finite element simulation methodology is implemented. It is assumed that traps due to defects and grain boundaries are uniformly distributed throughout the semiconductor film. Gaussian trap distributions are used in the simulation. Gas sensing is accounted for by a doping-dependent hopping mobility model in the organic active material. Interface traps and charges at the interface between the polymer channel and gate insulator are incorporated. Transistors in both parallel and series configurations are studied. Compared to individual OFET-based sensors, the circuit configuration achieves significantly increased sensitivity to analyte, as indicated by the simulation and in agreement with experimental observations. This supports the concept of combining transistors to enhance analyte sensitivity and provides a method for advance screening of combinations of OFETs for high signal-to-drift ratios. The absolute value of drain currents for series circuits is lower than that of parallel circuits; however, the series circuits display higher analyte sensitivity.

Enhancing Long‐Term Device Stability Using Thin Film Blends of Small Molecule Semiconductors and Insulating Polymers to Trap Surface‐Induced Polymorphs

AbstractThe lack of long‐term stability in thin films of organic semiconductors can often be caused by the low structural stability of metastable phases that are frequently formed upon deposition on a substrate surface. Here, thin films of 2,7‐dioctyloxy[1]benzothieno[3,2‐b]benzothiophene (C8O‐BTBT‐OC8) and blends of this material with polystyrene by solution shearing are fabricated. Both types of films exhibit the metastable surface‐induced herringbone phase (SIP) in all the tested coating conditions. The blended films reveal a higher device performance with a field‐effect mobility close to 1 cm2 V−1 s−1, a threshold voltage close to 0 V, and an on/off current ratio above 107. In situ lattice phonon Raman microscopy is used to study the stability of the SIP polymorph. It is found that films based on only C8O‐BTBT‐OC8 slowly evolve to the Bulk cofacial phase, significantly impacting device electrical performance. In contrast, the blended films stabilize the SIP phase, leading to devices that maintain a high performance over 1.5 years. This work demonstrates that blending small‐molecule organic semiconductors with insulating binding polymers can trap metastable polymorphs, which can lead to devices with both improved performance and long‐term stability.

Insight into the structures and dynamics of organic semiconductors through solid-state NMR spectroscopy

Organic semiconductors (OSCs) are of fundamental and technological interest, owing to their properties and functions in a range of optoelectronic devices, including organic light-emitting diodes, organic photovoltaics and organic field-effect transistors, as well as emerging technologies, such as bioelectronic devices. The solid-state organization of the subunits in OSC materials, whether molecular or polymeric, determines the properties relevant to device performance. Nevertheless, the systematic relationships between composition, structure and processing conditions are rarely fully understood, owing to the complexity of the organic architectures and the resulting solid-state structures. Characterization over different length scales and timescales is essential, especially for semi-ordered or amorphous regions, for which solid-state NMR (ssNMR) spectroscopy yields nanoscale insight that can be correlated with scattering measurements and macroscopic property analyses. In this Review, we assess recent results, challenges and opportunities in the application of ssNMR to OSCs, highlighting its role in state-of-the-art materials design and characterization. We illustrate how insight is obtained on local order and composition, interfacial structures, dynamics, interactions and how this information can be used to establish structure–property relationships. Finally, we provide our perspective on applying ssNMR to the next generation of OSCs and the development of new ssNMR methods. The structure of organic semiconductor thin films influences their performance in optoelectronic devices. This Review highlights how solid-state NMR techniques can be used to investigate the structure, composition and dynamics of organic semiconductors and, thus, establish structure–property relationships.

Evolution and Morphology of Thin Films Formed by Solvent Evaporation: An Organic Semiconductor Case Study.

The crucial role played by the solution-vapor interface in determining the growth and morphology of an organic semiconductor thin film formed by solvent evaporation has been examined in atomic detail. Specifically, how the loss of individual solvent molecules from the surface of the solution induces solute assembly has been studied using molecular dynamics simulations. The system consisted of bis(2-phenylpyridine) (acetylacetonate)iridium(III) [Ir(ppy)2(acac)] and 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP) in chloroform at 310 K. The simulations clearly indicate that (a) the system does not undergo uniform phase separation (spinodal decomposition), (b) solute aggregation initiates at the solution-vapor interface, (c) the distribution of solvent in the film is nonhomogeneous, (d) this nonhomogeneous distribution can induce preferential alignment of host molecules, and (e) a portion of the solvent likely remains trapped within the film. The work not only demonstrates the ability to directly model evaporation in atomic detail on the relevant length scales but also shows that atomistic simulations have the potential to shed new light on morphological properties of a wide range of organic semiconductor devices manufactured using solution-processing methods.

Orientation-Dependent Host-Dopant Interactions for Manipulating Charge Transport in Conjugated Polymers.

Molecular orientation plays a critical role in controlling carrier transport in organic semiconductors (OSCs). However, this aspect has not been explored for surface doping of OSC thin films. The challenge lies in lack of methods to precisely modulate relative molecular orientation between the dopant and the OSC host. Here, the impact of molecular orientation on dopant-host electronic interactions by large modulation of conjugated polymer orientation via solution coating is reported. Combining synchrotron-radiation X-ray measurements with spectroscopic and electrical characterizations, a quantitative correlation between doping-enhanced charge carrier mobility and the Herman's orientation parameter is presented. This direct correlation can be attributed to enhanced charge-transfer interactions at host/dopant interface with increasing face-on orientation of the polymer. These results demonstrate that the surface doping effect can be fundamentally manipulated by controlling the molecular orientation of the OSC layer, enabling optimization of carrier transport.

Nanostructure of organic semiconductor thin films: Molecular dynamics modeling with solvent evaporation

We present a procedure for simulating solution deposition of organic thin-films on explicitly modeled substrates via solvent evaporation simulations in a molecular dynamics framework. Additionally, we have developed force fields for the family of IDTBR nonfullerene acceptors, which have been widely employed in the literature as $n$-type materials in several types of organic semiconductor devices, and we analyzed their structure-property relationships using a combination of grazing incidence x-ray scattering measurements, atomistic molecular dynamics simulations, and quantum chemical calculations. We find that thermal fluctuations can have a significant impact on calculated electron transfer integrals, and that the $\ensuremath{\pi}$-stacking interactions of the electron withdrawing benzothiadiazole building blocks are key to high electron coupling in amorphous thin films of $n$-type materials.

Developing molecular-level models for organic field-effect transistors.

Organic field-effect transistors (OFETs) are not only functional devices but also represent an important tool for measuring the charge-transport properties of organic semiconductors (OSs). Thus, efforts to understand the performance and characteristics of OFET devices are not only useful in helping achieve higher device efficiencies but also critical to ensuring accuracy in the evaluations of OS charge mobilities. These studies rely on OFET device models, which connect the measured current characteristics to the properties of the OSs. Developing such OFET models requires good knowledge of the charge-transport processes in OSs. In device active layers, the OS thin films are either amorphous (e.g. in organic light-emitting diodes and organic solar cells) or crystalline (e.g. those optimized for charge transport in OFETs). When the electronic couplings between adjacent OS molecules or polymer chain segments are weak, the charge-transport mechanism is dominated by hopping processes, which is the context in which we frame the discussion in this Review. Factors such as disorder, mobility anisotropy, traps, grain boundaries or film morphology all impact charge transport. To take these features fully into account in an OFET device model requires considering a nano-scale, molecular-level resolution. Here, we discuss the recent development of such molecular-resolution OFET models based on a kinetic Monte Carlo approach relevant to the hopping regime. We also briefly describe the applicability of these models to high-mobility OFETs, where we underline the need to extend them to incorporate aspects related to charge delocalization.

Lyotropic Liquid Crystalline Mesophase Governs Interfacial Molecular Orientation of Conjugated Polymer Thin Films

Interfacial out-of-plane molecular orientation critically influences the electronic performance of organic semiconductor thin films. The appearance of a lyotropic liquid crystalline (LC) mesophase ...

Scalable Ultrahigh-Speed Fabrication of Uniform Polycrystalline Thin Films for Organic Transistors.

The fabrication of organic semiconductor thin films by printing technologies is expected to enable the low-cost production of devices such as flexible display drivers, RF-ID tags, and various chemical/biological sensors. However, large-scale high-speed fabrication of uniform semiconductor thin films with adequate electrical properties for these devices remains a big challenge. Herein, we demonstrate an ultrafast and scalable fabrication of uniform polycrystalline thin films with 100% surface coverage using liquid crystalline semiconductors such as 2-phenyl-7-decyl[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-10) and 2.7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT-C8), at a rate of 3 orders of magnitude higher than before, i.e., 40 mm/s (2.4 m/min) or more by dip-coating in the drainage regime. Organic transistors fabricated with polycrystalline thin films of Ph-BTBT-10 show average mobilities of 4.13 ± 0.75 cm2/(V s) in the bottom-gate-bottom-contact configuration and 10.90 ± 2.40 cm2/(V s) in the bottom-gate-top-contact configuration comparable to those of the devices prepared with single-crystalline thin films. More importantly, these films almost maintain the FET performance when the substrate size is extended up to 4 square inch. The present findings are available for other liquid crystalline semiconductors and bring us one step closer to the realization of printed electronics.

Anodization for Simplified Processing and Efficient Charge Transport in Vertical Organic Field‐Effect Transistors

AbstractVertical organic transistors are an attractive alternative to realize short channel transistors, which are required for powerful electronic devices and flexible electronic circuits operating at high frequencies. Unfortunately, the vertical device architecture comes along with an increased device fabrication complexity, limiting the potential of this technology for application. A new design of vertical organic field‐effect transistors (VOFETs) with superior electrical performance and simplified processing is reported. By using electrochemical oxidized aluminum oxide (AlOx) as a pseudo self‐aligned charge‐blocking structure in vertical organic transistors, direct leakage current between the source and drain can be effectively suppressed, enabling VOFETs with very low off‐current levels despite the short channel length. The anodization technique is easy to apply and can be surprisingly used on both n‐type and p‐type organic semiconductor thin films with significant signs of degradation. Hence, the anodization technique enables a simplified process of high‐performance p‐type and n‐type VOFETs, paving the road toward complementary circuits made of vertical transistors.

Ferrocene on Insulator: Silane Coupling to a SiO2 Surface and Influence on Electrical Transport at a Buried Interface with an Organic Semiconductor Layer.

A silane coupling-based procedure for decoration of an insulator surface containing abundant hydroxy groups by constructing redox-active self-assembled monolayers (SAMs) is described. A newly synthesized ferrocene (Fc) derivative containing a triethoxysilyl group designated FcSi was immobilized on SiO2/Si by a simple operation that involved immersing the substrate in a toluene solution of the Fc silane coupling reagent and then rinsing the resulting substrate. X-ray photoelectron spectroscopy (XPS) measurements confirmed that the Fc group was immobilized on SiO2/Si in the Fe(II) state. Cyclic voltammetry measurements showed that the Fc groups were electrically insulated from the Si electrode by the SiO2 layer. The FcSi on SiO2/Si structures were found to serve as a good scaffold for formation of organic semiconductor thin films by vacuum thermal evaporation of C8-BTBT (2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene), which is well-known as an organic field-effect transistor (OFET) material. The X-ray diffraction profile indicated that the conventional standing-up conformation of the C8-BTBT molecules perpendicular to the substrates was maintained in the thin films formed on FcSi@SiO2/Si. Further vacuum thermal evaporation of Au provided an FcSi-based OFET structure with good transfer characteristics. The FcSi-based OFET showed pronounced source-drain current hysteresis between the forward and backward scans. The degree of this hysteresis was varied reversibly via gate bias manipulation, which was presumably accompanied by trapping and detrapping of hole carriers at the Fc-decorated SiO2 surface. These findings provide new insights into application of redox-active SAMs to nonvolatile OFET memories while also creating new interfaces through junctions with functional thin films, in which the underlying redox-active SAMs play supporting roles.

Ordered Donor–Acceptor Complex Formation and Electron Transfer in Co-deposited Films of Structurally Dissimilar Molecules

The electrical and optoelectronic properties of organic semiconductor thin films can be tailored by mixing two molecular materials, e.g., by co-deposition. Possible resulting morphologies include p...

Continuous and highly ordered organic semiconductor thin films via dip-coating: the critical role of meniscus angle

Dip-coating is a low-cost, high-throughput technique for the deposition of organic semiconductors over large area on various substrates. Tremendous studies have been done and many parameters such as withdrawal speed, solvent type and solution concentration have been investigated. However, most of the depositions were ribbons or dendritic crystals with low coverage of the substrate due to the ignorance of the critical role of dynamic solution-substrate interactions during dip-coating. In this study, meniscus angle (MA) was proposed to quantify the real-time in-situ solution-substrate interactions during dip-coating. By proper surface treatment of the substrate, the value of MA can be tuned and centimeter-sized, continuous and highly ordered organic semiconductor thin films were achieved. The charge transport properties of the continuous thin films were investigated by the construction of organic field-effect transistors. Maximum (average) hole mobility up to 11.9(5.1) cm2 V−1s−1 was obtained. The average mobility was 82% higher than that of ribbon crystals, indicating the high crystallinity of the thin films. Our work reveals the critical role of dynamic solution-substrate interactions during dip-coating. The ability to produce large-area, continuous and highly ordered organic semiconductor thin films by dip-coating could revival the old technique for the application in various optoelectronics.