Organic Semiconductor Thin Films Research Articles

Synergistic Effect of Solvent Vapor Annealing and Chemical Doping for Achieving High-Performance Organic Field-Effect Transistors with Ideal Electrical Characteristics.

Contact resistance and charge trapping are two key obstacles, often intertwined, that negatively impact on the performance of organic field-effect transistors (OFETs) by reducing the overall device mobility and provoking a nonideal behavior. Here, we expose organic semiconductor (OSC) thin films based on blends of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT-C8) with polystyrene (PS) to (i) a CH3CN vapor annealing process, (ii) a doping I2/water procedure, and (iii) vapors of I2/CH3CN to simultaneously dope and anneal the films. After careful analysis of the OFET electrical characteristics and by performing local Kelvin probe force microscopy studies, we found that the vapor annealing process predominantly reduces interfacial shallow traps, while the chemical doping of the OSC film is responsible for the diminishment of deeper traps and promoting a significant reduction of the contact resistance. Remarkably, the devices treated with I2/CH3CN reveal ideal electrical characteristics with a low level of shallow/deep traps and a very high and almost gate-independent mobility. Hence, this work demonstrates the promising synergistic effects of performing simultaneously a solvent vapor annealing and doping procedure, which can lead to trap-free OSC films with negligible contact resistance problems.

The impact of film deposition and annealing on the nanostructure and dielectric constant of organic semiconductor thin films.

The strategy of using a bulk-heterojunction light-absorbing layer has led to the most efficient organic solar cells. However, optimising the blend morphology to maximise light absorption, charge generation and extraction can be challenging. Homojunction devices containing a single component have the potential to overcome the challenges associated with bulk heterojunction films. A strategy towards this goal is to increase the dielectric constant of the organic semiconductor to ≈10, which in principle would lead to free charge carrier generation upon photoexcitation. However, the factors that affect the thin film dielectric constants are still not well understood. In this work we report an organic semiconductor material that can be solution processed or vacuum evaporated to form good quality thin films to explore the effect of chromophore structure and film morphology on the dielectric constant and other optoelectronic properties. 2,2'-[(4,4,4',4'-Tetrakis{2-[2-methoxyethoxy]ethyl}-4H,4'H-{2,2'-bi[cyclo-penta[2,1-b:3,4-b']dithiophene]}-6,6'-diyl)bis(methaneylylidene)]dimalononitrile [D(CPDT-DCV)] was designed to have high electron-affinity end groups and low ionisation-potential central moieties. It can be processed from solution or be thermally evaporated, with the film morphology changing from face-on to a herringbone arrangement upon solvent or thermal annealing. The glycol solubilising groups led to the static dielectric constant (taken from capacitance measurements) of the films to be between 6 and 7 (independent of processing conditions), while the optical frequency dielectric constant depended on the processing conditions. The less ordered solution processed film was found to have the lowest optical frequency dielectric constant of 3.6 at 2.0 × 1014 Hz, which did not change upon annealing. In contrast, the more ordered evaporated film had an optical frequency dielectric constant 20% higher at 4.2 and thermal annealing further increased it to 4.5, which is amongst the highest reported for an organic semiconductor at that frequency. Finally, the more ordered evaporated films had more balanced charge transport, which did not change upon annealing.

Reducing Trap Density in Organic Solar Cells via Extending the Fused Ring Donor Unit of an A-D-A-Type Nonfullerene Acceptor for Over 17% Efficiency.

The high trap density (generally 1016 to 1018 cm-3 ) in thin films of organic semiconductors is the primary reason for the inferior charge-carrier mobility and large nonradiative recombination energy loss (ΔEnr ) in organic solar cells (OSCs), limiting improvement in power conversion efficiencies (PCEs). In this study, the trap density in OSCs is efficiently reduced via extending the donor core of nonfullerene acceptors (NFAs) from a heptacyclic unit to a nonacyclic unit. TTPIC-4F with a nonacyclic unit has stronger intramolecular and intermolecular interactions, affording higher crystallinity in thin films relative to its counterpart BTPIC-4F. Thus, the D18:TTPIC-4F-based device achieves a lower trap density of 4.02×1015 cm-3 , comparable to some typical high-performance inorganic/hybrid semiconductors, with higher mobility and inhibited charge-carrier recombination in devices. Therefore, the D18:TTPIC-4F-based OSC exhibits an impressive PCE of 17.1% with a low ΔEnr of 0.208eV, which is the best known value for A-D-A-type NFAs. Therefore, extending the donor core of NFAs is an efficient method for suppressing trap states in OSCs for high PCEs.

Effects of solution-shearing process parameters on charge carrier mobility in green solvent-processed organic field-effect transistors

In this work, we explored the effect of solution-shearing processing parameters, coating speed and substrate temperature, on the electrical properties of solution-processed organic field-effect transistors (OFETs) based on 2-decyl-7-phenyl[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-C10) when green solvents are used. Organic semiconductor thin films were solution-sheared with various coating speeds and substrate temperatures and film morphologies/microstructures were investigated by atomic force microscopy (AFM) and X-ray diffraction (XRD) analysis. Our data demonstrate that crystal growth of Ph-BTBT-C10 molecule is highly affected by the two solution shearing processing parameters and, especially, the OFET devices fabricated with cyclohexanone as green solvent exhibited the charge carrier mobility as high as 5.1 cm2/Vs with optimized processing condition. This work could further provide a guideline for process optimization for fabricating high-performance green solvent-processed OFETs.

Trap States Ruling Photoconductive Gain in Tissue‐Equivalent, Printed Organic X‐Ray Detectors

AbstractOrganic semiconductors are excellent candidates for X‐ray detectors that can adapt to new applications, with unique properties including mechanical flexibility and the ability to cover large surfaces. Their chemical composition, primarily carbon and hydrogen, makes them human tissue equivalent in terms of radiation absorption. This is a highly desirable property for a radiation dosimeter to be employed in medical diagnostics and therapy, however a low‐Z composition limits the absorption of ionizing radiation. The detection efficiency can be enhanced by considering the photoconductive gain (PG) effect, a significant contributor to the ionizing radiation detection mechanism in this class of materials. In this work, a process of controlled solution deposition by nozzle printing and crystallization of an organic semiconductor thin film is demonstrated whereby a flexible, arrayed thin‐film X‐ray detector with record X‐ray sensitivities among flexible radiation detectors (S = (9.0 ± 0.4) × 107 µC Gy−1 cm−3) is developed. The excitonic peaks responsible for the activation of the PG effect are investigated and identified using a novel technique called photocurrent spectroscopy optical quenching, and the analysis of the changes in trap states is further demonstrated.

Structural reconstruction of organic semiconductor thin films via grazing-incidence diffraction tomography

Structural reconstruction of organic semiconductor thin films via grazing-incidence diffraction tomography

Template and Temperature-Controlled Polymorph Formation in Squaraine Thin Films.

Controlling the polymorph formation in organic semiconductor thin films by the choice of processing parameters is a key factor for targeted device performance. Small molecular semiconductors such as the prototypical anilino squaraine compound with branched butyl chains as terminal functionalization (SQIB) allow both solution and vapor phase deposition methods. SQIB has been considered for various photovoltaic applications mainly as amorphous isotropic thin films due to its broad absorption within the visible to deep-red spectral range. The two known crystalline polymorphs adopting a monoclinic and orthorhombic crystal phase show characteristic Frenkel excitonic spectral signatures of overall H-type and J-type aggregates, respectively, with additional pronounced Davydov splitting. This gives a recognizable polarized optical response of crystalline thin films suitable for identification of the polymorphs. Both phases emerge with a strongly preferred out-of-plane and rather random in-plane orientation in spin-casted thin films depending on subsequent thermal annealing. By contrast, upon vapor deposition on dielectric and conductive substrates, such as silicon dioxide, potassium chloride, graphene, and gold, the polymorph expression depends basically on the choice of growth substrate. The same pronounced out-of-plane orientation is adopted in all crystalline cases, but with a surface templated in-plane alignment in case of crystalline substrates. Strikingly, the amorphous isotropic thin films obtained by vapor deposition cannot be crystallized by thermal postannealing, which is a key feature for the spin-casted thin films, here monitored by polarized in situ microscopy. Combining X-ray diffraction, atomic force microscopy, ellipsometry, and polarized spectro-microscopy, we identify the processing-dependent evolution of the crystal phases, correlating morphology and molecular orientations within the textured SQIB films.

(Invited) Structural Analysis of Organic Semiconducting Materials By Solid State NMR

Recently, our group have successfully developed several blue and green thermally activated delayed fluorescence (TADF) emitters showing high external quantum efficiencies in OLEDs through high-throughput screening based on quantum chemical calculations. Although a number of highly efficient TADF emitters have been reported, the study about their conformation and aggregated structure in an amorphous states, which is expected to be the origin of high device performance, is still limited. Thus we have carried out multiscale simulations and solid-state NMR (ssNMR) analysis of organic amorphous thin films. The ssNMR is one of the powerful technique to acquire the structural information of amorphous aggregated materials, which has been difficult by diffraction techniques due to the lack of long range order for amorphous state. In this presentation, we demonstrate ssNMR analysis of amorphous organic semiconducting materials.Reference(1) “Analysis of Molecular Orientation in Organic Semiconducting Thin Films Using Static Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy”, Suzuki, K.; Kubo, S.; Aussenac, F.; Engelke, F.; Fukushima, T.; Kaji, H. Angew. Chem. Int. Ed. 2017, 56, 14842.(2) “Efficient blue thermally activated delayed fluorescence emitters showing very fast reverse intersystem crossing”, Ren, Y., Wada, Y., Suzuki, K., Kusakabe, Y., Geldsetzer, J. and Kaji, H. Appl. Phys. Express, 2021, 14, 071003.(3) “Solution-processable thermally activated delayed fluorescence emitters for application in organic light emitting diodes”, Suzuki, K.; Adachi, C.; Kaji, H. J. Soc. Inf. Disp. 2017, 25, 480.(4) “Combined Inter- and Intramolecular Charge-Transfer Processes for Highly Efficient Fluorescent Organic Light-Emitting Diodes with Reduced Triplet Exciton Quenching”, Moon, C.-K.; Suzuki, K.; Shizu, K.; Adachi, C.; Kaji, H.; Kim, J.-J. Adv. Mater. 2017, 131, 6614.(5) “Triarylboron-based Fluorescent Organic Light-emitting Diodes with External Quantum Efficiencies Exceeding 20%”, Suzuki, K.; Kubo, S.; Shizu, K.; Fukushima, T.; Wakamiya, A.; Murata, Y.; Adachi, C.; Kaji, H.; Angew. Chem. Int. Ed. 2015, 54, 15231.(5) “Purely organic electroluminescent material realizing 100% conversion from electricity to light”, Kaji, H.; Suzuki, H.; Fukushima, T.; Shizu, K.; Suzuki, K.; Kubo, S.; Komino, T.; Oiwa, H.; Suzuki, F.; Wakamiya, A.; Murata, Y.; Adachi, C. Nat. Commun. 2015, 6, 8476.

Flexible Perovskite and Organic Semiconductor Heterojunction Devices for Tunable Band-Selective Photodetection

Filter-free band-selective photodetectors with tunable band edges possess extensive applications in smart sensors, artificial intelligence, the internet of everything, and so forth. However, such photodetectors operated with the charge collection narrowing effect require a thick active layer over millimeters, leading to rather a large device size, high material cost, and limited mechanical flexibility. In this work, we report a flexible thin-film perovskite and organic semiconductor (OSC) heterojunction device, which can achieve adjustable band-selective photodetection by utilizing the easy tunability of the perovskite band gap. First, heterojunction photodiodes with only two active layers of perovskites and OSCs are fabricated, in which the perovskite contributes to light absorption and rectification characteristics simultaneously. The fundamental device operation mechanism is investigated by combining the band alignments of the heterojunctions and their potential distributions observed with Kelvin probe force microscopy. It uncovers that the presence of built-in electric fields in the heterojunctions caused by moderate band alignments and appropriate difference in hole and electron concentrations between the perovskites and the OSCs is significant for the properties of the photodiodes. The resultant photodiodes exhibit a high rectification ratio of up to 103, decent photodetection performance, and mechanical flexibility. Furthermore, photodetectors based on perovskite/OSC/perovskite stack heterojunctions can realize the functions of filterless band-selective photodetection in a single device, and the band edges in the photodetection can be modulated by tuning the perovskite band gap. Therefore, this work provides flexible thin-film photodiodes with the potential of miniaturization and low-cost fabrication and demonstrates tunable band-selective photodetection for advanced applications.

A Doped Hole Transport Layer Qualified for 100 °C‐Tolerant Perovskite Solar Cells

AbstractDue to the extremely low intrinsic carrier density and disordered nature of organic semiconductor thin films, unintentional or intentional chemical doping is inevitable for sufficiently high carrier density and charge mobility unless charges are either injected from appropriate electrodes or by photoexcitation. However, doping often results in a reduction in thermal tolerance. The charge transport layers for thermostable perovskite solar cells (PSCs) need to possess a heat‐resistant morphology and to suppress the diffusion of volatile species. Here the authors report a molecular semiconductor with a molecular mass of >2000 Daltons but free of any flexible side chains. Its air‐doped composite with thermally stable acid salt exhibits an electrical conductivity of over 50 μS cm−1 and a glass transition temperature of 142 °C. Molecular dynamics simulations reveal that molecules and ions in this composite do not experience significant translational motion even at 150 °C. These unusual features allow for the fabrication of 21.5%‐efficiency PSCs that can withstand 200 h at 100 °C.

Accurate Polarization-Resolved Absorption Spectra of Organic Semiconductor Thin Films Using First-Principles Quantum-Chemical Methods: Pentacene as a Case Study.

Theoretical studies using clusters as model systems have been extremely successful in explaining various photophysical phenomena in organic semiconductor (OSC) thin films. But they have not been able to satisfactorily simulate total and polarization-resolved absorption spectra of OSCs so far. In this work, we demonstrate that accurate spectra are predicted by time-dependent density functional theory (TD-DFT) when the employed cluster reflects the symmetry of the crystal structure and all monomers feel the same environment. Additionally, long-range corrected optimal tuned functionals are mandatory. For pentacene thin films, the computed electronic spectra for thin films then reach an impressive accuracy compared with experimental data with a deviation of less than 0.1 eV. This allows for accurate peak assignments and mechanistic studies, which paves the way for a comprehensive understanding of OSCs using an affordable and easy-to-use cluster approach.

Robustness of organic physically unclonable function with buskeeper circuit for flexible security devices

Flexible devices have been studied to realize IoT or novel wearable devices. The data that flexible devices deal with can include personal information when application areas further expand. A security system for flexible devices becomes more important in this case. In this study, we investigate the thermal stability of an organic flexible security system. The security system utilizes fabrication variation of a chip, and it is called a physically unclonable function (PUF). As a result, the bit error rate of the organic PUF is 1.8% and the index of ID uniqueness (i.e., randomness) has an almost theoretical value of 0.48. The generated ID remains even after annealing at 100 °C for 97 h by using CYTOP encapsulation. X-ray diffraction measurement implies that degradation of PUF characteristics partially derives from structure changes of the organic n-type semiconductor thin film after annealing.

Ultrathin P(NDI2OD‐T2) Films with High Electron Mobility in Both Bottom‐Gate and Top‐Gate Transistors

AbstractUltrathin organic films (typically < 10 nm) attracted great attention due to their (semi)transparency and unique optoelectronic properties that benefit applications such as sensors and flexible electronics. At the core of that, achieving high mobility in an ultrathin film is essential for the efficient operation of relevant electronic devices. While the state‐of‐the‐art material systems, e.g., P(NDI2OD‐T2) also known as N2200 can achieve high mobility in a thin film (typically > 20 nm), multitudinous challenges remain in processing an ultrathin film exhibiting desired charge transport morphology within a preferred thickness limit. Here, high electron mobility (a tenfold increase compared to annealed spin‐coated films) is reported in both the top and bottom‐gate configuration organic field‐effect transistors comprising ultrathin N2200 films produced with a water‐floating film transfer method. A range of characterization techniques are used to investigate these ultrathin films and their microstructure, and conclude that favorable edge‐on polymer orientation at the top as well as throughout the ultrathin film thickness and the quality of π–π ordering as captured by the largest coherences length resulted in this high mobility in N2200 ultrathin films, in stark contrast to the commonly observed microstructural gradient in spin‐coated thin films. The results provide new insight into the electronic and microstructural properties of thin films of organic semiconductors.

Chemical Doping of the Organic Semiconductor C8‐BTBT‐C8 Using an Aqueous Iodine Solution for Device Mobility Enhancement

AbstractThe performance of organic field‐effect transistors is still severely limited by factors such as contact resistance and charge trapping. Chemical doping is considered to be a promising key enabler for improving device performance, although there is a limited number of established doping protocols as well as a lack of understanding of the doping mechanisms. Here, a very simple doping methodology based on exposing an organic semiconductor thin film to an aqueous iodine solution is reported. The doped devices exhibit enhanced device mobility, which becomes channel‐length independent, a decreased threshold voltage and a reduction in the density of interfacial traps. The device OFF current is not altered, which is in agreement with the spectroscopic data that points out that no charge transfer processes are occurring. Kelvin probe force microscopy characterization of the devices under operando conditions unambiguously proves that an important reduction of the contact resistance takes place after their exposition to the iodine solution, reaching almost ohmic contact.

The Solution is the Solution: Data-Driven Elucidation of Solution-to-Device Feature Transfer for π-Conjugated Polymer Semiconductors.

The advent of data analytics techniques and materials informatics provides opportunities to accelerate the discovery and development of organic semiconductors for electronic devices. However, the development of engineering solutions is limited by the ability to control thin-film morphology in an immense parameter space. The combination of high-throughput experimentation (HTE) laboratory techniques and data analytics offers tremendous avenues to traverse the expansive domains of tunable variables offered by organic semiconductor thin films. This Perspective outlines the steps required to incorporate a comprehensive informatics methodology into the experimental development of polymer-based organic semiconductor technologies. The translation of solution processing and property metrics to thin-film behavior is crucial to inform efficient HTE for data collection and application of data-centric tools to construct new process-structure-property relationships. We argue that detailed investigation of the solution state prior to deposition in conjunction with thin-film characterization will yield a deeper understanding of the physicochemical mechanisms influencing performance in π-conjugated polymer electronics, with data-driven approaches offering predictive capabilities previously unattainable via traditional experimental means.

Organic Field‐Effect Transistors Based on Ternary Blends Including a Fluorinated Polymer for Achieving Enhanced Device Stability

AbstractThe stability of organic semiconductors (OSCs) is strongly hampered by the presence of water molecules. One approach that has been proved to lead to organic field‐effect transistors with an enhanced performance is the use of blends of OSCs with insulating binding polymers. In this work, the fabrication of OSC thin films based on polymeric ternary blends including a hydrophobic fluorinated polymer is reported as a novel route to engineer long‐term reliable organic field‐effect transistors (OFET) devices. In particular, OFETs based on blends of bis(triisopropylsilylethynyl)pentacene (TIPS) with polystyrene (PS) and poly(pentafluorostyrene) (PFS) are explored. The PS:PFS ratio is tuned in order to find the optimum formulation. It is shown that films including 20% of PFS in the polymeric blend exhibit an improved device performance, which is reflected by a low bias stress and an exceptional environmental stability, without significantly hampering the OFET mobility. This work advocates that adding a small percentage of fluorinated polymers in OSC blends is a promising route to realize more reliable and stable devices without importantly compromising the device mobility.

Structural insights into Lewis acid- and F4TCNQ-doped conjugated polymers by solid-state magnetic resonance spectroscopy.

Molecular doping strategies facilitate orders of magnitude enhancement in the charge carrier mobility of organic semiconductors (OSCs). Understanding the different doping mechanisms and molecular-level constraints on doping efficiency related to the material energy levels is crucial to develop versatile dopants for OSCs. Given the compositional and structural heterogeneities associated with OSC thin films, insight into dopant-polymer interactions by long-range techniques such as X-ray scattering and electron microscopy is exceedingly challenging to obtain. This study employs short-range probes, solid-state (ss)NMR and EPR spectroscopy, to resolve local structures and intermolecular interactions between dopants such as F4TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), Lewis acid BCF (tris[pentafluorophenyl] borane) and Lewis base conjugated polymer, PCPDTBT (P4) (poly[2,6-(4,4-bis(2-hexadecyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)]). Analysis of 1H and 13C ssNMR spectra of P4, P4 : F4TCNQ and P4 : BCF blends indicates that the addition of dopants induces local structural changes in the P4 polymer, and causes paramagnetism-induced signal broadening and intensity losses. The hyperfine interactions in P4 : BCF and P4 : F4TCNQ are characterized by two-dimensional pulsed EPR spectroscopy. For P4 : F4TCNQ, 19F ssNMR analysis indicates that the F4TCNQ molecules are distributed and aggregated into different local chemical environments. By comparison, BCF molecules are intermixed with the P4 polymer and interact with traces of water molecules to form BCF-water complexes that serve as Brønsted acid sites, as revealed by 11B ssNMR spectroscopy. These results indicate that the P4-dopant blends exhibit complex morphology with different distributions of dopants, whereby the combined use of ssNMR and EPR provides essential insights into how higher doping efficiency is observed with BCF and a mediocre efficiency is associated with F4TCNQ molecules.

Dynamic processes in transient phases during self-assembly of organic semiconductor thin films

Crystallization of organic semiconductor small molecules from solution proceeds in multiple steps. This study describes how asymmetric molecules lead to long-lived transient phases and their impact on carrier mobility for electronic devices.

De Novo Calculation of the Charge Carrier Mobility in Amorphous Small Molecule Organic Semiconductors.

Organic semiconductors (OSC) are key components in applications such as organic photovoltaics, organic sensors, transistors and organic light emitting diodes (OLED). OSC devices, especially OLEDs, often consist of multiple layers comprising one or more species of organic molecules. The unique properties of each molecular species and their interaction determine charge transport in OSCs—a key factor for device performance. The small charge carrier mobility of OSCs compared to inorganic semiconductors remains a major limitation of OSC device performance. Virtual design can support experimental R&D towards accelerated R&D of OSC compounds with improved charge transport. Here we benchmark a de novo multiscale workflow to compute the charge carrier mobility solely on the basis of the molecular structure: We generate virtual models of OSC thin films with atomistic resolution, compute the electronic structure of molecules in the thin films using a quantum embedding procedure and simulate charge transport with kinetic Monte-Carlo protocol. We show that for 15 common amorphous OSC the computed zero-field and field-dependent mobility are in good agreement with experimental data, proving this approach to be an effective virtual design tool for OSC materials and devices.

Atomistic insights into dynamic growth of pentacene thin films on metal surfaces functionalized with self-assembled monolayers

The fabrication of high-quality organic semiconductor thin films has crucial impact on the electrical properties of organic electronic devices. Here, we provide atomistic insights into dynamic growth of pentacene thin films on different Au surfaces functionalized with self-assembled monolayers (SAMs). First, disordered crystal structures are formed on both bare Au and smooth SAM functionalized Au surfaces, while the upright crystalline islands emerge on rough SAM surfaces. During the growth process on rough SAM surfaces, organic semiconductor molecules undergo the nucleation and reorientation, and eventually form thin films with terrace morphologies. In addition, the interaction energies among pentacene molecules and between pentacene and SAM molecules will affect the formation and reorientation of the seed nucleus. Furthermore, the effect of substrate temperature on the pentacene growth is also evaluated. The high substrate temperature delays the onset of nucleus reorientation but accelerate the reorientation process. Finally, free energy calculations demonstrate that the surface roughness plays an important role in the formation and orientation of the seed nucleus. Meanwhile, the energy barrier at the step edge of the terrace morphology can prevent molecules from crossing the step edge.