Small-molecule Semiconductors Research Articles

Automated Scanning Dielectric Microscopy Toolbox for Operando Nanoscale Electrical Characterization of Electrolyte‐Gated Organic Transistors

AbstractElectrolyte‐gated organic transistors (EGOTs) leveraging organic semiconductors' electronic and ionic transport characteristics are the key enablers for many biosensing and bioelectronic applications that can selectively sense, record, and monitor different biological and biochemical processes at the nanoscale and translate them into macroscopic electrical signals. Understanding such transduction mechanisms requires multiscale characterization tools to comprehensively probe local electrical properties and link them with device behavior across various bias points. Here, an automated scanning dielectric microscopy toolbox is demonstrated that performs operando in‐liquid scanning dielectric microscopy measurements on functional EGOTs and carries out extensive data analysis to unravel the evolution of local electrical properties in minute detail. This paper emphasizes critical experimental considerations permitting standardized, accurate, and reproducible data acquisition. The developed approach is validated with EGOTs based on blends of organic small molecule semiconductor and insulating polymer that work as accumulation‐mode field‐effect transistors. Furthermore, the degradation of local electrical characteristics at high gate voltages is probed, which is apparently driven by the destruction of local crystalline order due to undesirable electrochemical swelling of the organic semiconducting material near the source electrode edge. The developed approach paves the way for systematic probing of EGOT‐based technologies for targeted optimization and fundamental understanding.

High-Performance Organic Field-Effect Transistors of Liquid Crystalline Organic Semiconductor by Laser Mapping Annealing.

Organic semiconductors (OSCs), especially small molecule semiconductors, have received increasing attention due to their good designability and variability. Phase transitions and interfacial properties have a decisive influence on device performance. Here, 2-Dodecyl-7-phenyl[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-12) devices are treated with low-power laser annealing, which is able to avoid the influence of the dewetting effect on the hole mobility of organic semiconductor materials. Ultraviolet ozone treatment and self-assembled monolayer treatment can improve the performance and stability of the device. Moreover, after low-temperature thermal annealing, the hole mobility of the device can even reach as high as 4.80 cm2 V-1 s-1, and we tested the optical response of the device to the ultraviolet wavelength and found that its maximum optical responsivity was 8.2 AW-1.

Impact of hydrophilic side chains on the thin film transistor performance of a benzothieno-benzothiophene derivative.

Side-chain engineering in molecular semiconductors provides a versatile toolbox for precisely manipulating the material's processability, crystallographic properties, as well as electronic and optoelectronic characteristics. This study explores the impact of integrating hydrophilic side chains, specifically oligoethylene glycol (OEG) units, into the molecular structure of the small molecule semiconductor, 2,7-bis(2(2-methoxy ethoxy)ethoxy) benzo[b]benzo[4,5] thieno[2,3-d] thiophene (OEG-BTBT). The investigation includes a comprehensive analysis of thin film morphology and crystallographic properties, along with the optimization of deposition parameters for improving the device performance. Despite the anticipated benefits, such as enhanced processability, our investigation into OEG-BTBT-based organic field-effect transistors (OFETs) reveals suboptimal performance marked by a low effective charge carrier mobility, a low on/off ratio, and a high threshold voltage. The study unveils bias stress effects and device degradation attributed to the high ionization energy of OEG-BTBT alongside the hydrophilic nature of the ethylene-glycol moieties, which lead to charge trapping at the dielectric interface. Our findings underscore the need for a meticulous balance between electronic properties and chemical functionalities in molecular semiconductors to achieve stable and efficient performance in organic electronic devices.

Unveiling the significance of adduct formation between thiocarbonyl Lewis donors and diiodine for the structural organization of rhodanine-based small molecule semiconductors

Rhodanine vinyl bithiophene was reacted with molecular iodine to give a 1 : 1 stoichiometric charge-transfer adduct whose crystals, structurally and spectroscopically characterized, exhibited remarkable stability and enhanced conductivity.

Ligand-Enhanced Neodymium Doping of Perovskite Quantum Dots for Superior Exciton Confinement.

In this study, all-inorganic perovskite quantum dots (QDs) for pure blue emission are explored for full-color displays. We prepared CsPbBr3 and Cs3NdCl6 QDs via hot injection methods and mixed in various ratios at room temperature for color blending. Nd-doped CsPb(Cl/Br)3 QDs showed a blueshift in emission, and the photoluminescence quantum yields (PLQY, ΦPL) were lower in the 460-470 nm range due to surface halogen and Cs vacancies. To address this, we introduced a silane molecule, APTMS, via a ligand exchange process, effectively repairing these vacancies and enhancing Nd doping into the lattice. This modification promotes the PLQY to 94% at 466 nm. Furthermore, combining these QDs with [1]Benzothieno[3,2-b][1]benzothiophene (BTBT), a conjugated small-molecule semiconductor, in a composite film reduced PLQY loss caused by FRET in solid-state QD films. This approach achieved a wide color gamut of 124% National Television System Committee (NTSC), using a UV LED backlight and RGB perovskite QDs in a BTBT-based organic matrix as the color conversion layer. Significantly, the photostability of this composite was enhanced when used as a color conversion layer (CCL) under blue-LED excitation.

Intrinsically Stretchable Fiber‐Shaped Solar Cells with Polymer‐Based Active Layer

Fiber‐shaped organic solar cells (FOSCs) with intrinsic stretchability show great potential in stretchable and wearable electronics applications. However, limited by the poor stretchability of small molecule semiconductors, the stretchability of FOSCs is still not satisfied. Polymerized nonfullerene acceptors with excellent photovoltaic performance are a promising strategy for preparing stretchable semiconductors and photovoltaics. Herein, an efficient polymer‐based bulk‐heterojunction blend is adopted as the photoactive material of the stretchable all‐polymer FOSCs. The fabricated all‐polymer FOSCs show superior intrinsic stretchability that remains more than 90% of the initial efficiency under the stretch strain of 50% and maintains stable performance even when undergoing hundreds of stretching–releasing cycles. By adding the third component of polystyrene‐block‐poly(ethylene‐ran‐butylene)‐block‐polystyrene (SEBS) elastomer, the stretchable all‐polymer FOSCs can endure the ultrahigh stretch strains over 80%. This study demonstrates the superior mechanical properties of the all‐polymer FOSCs and the simple yet effective strategy of SEBS additive to enhance stretchability.

Influence of Excess Conjugated Wrapping Polymer in Semiconducting Single-Walled Carbon Nanotube Dispersions

Single-walled carbon nanotubes (SWNTs) are promising nanomaterials for incorporation into organic electronic devices (OEDs), with the potential to fabricate flexible devices while exploiting inexpensive solution-processing techniques. As-synthesized SWNTs are insoluble and comprised of a mixture of metallic and semiconducting SWNTs (sc-SWNTs), necessitating dispersal and purification before integration into OEDs. Refinement of conjugated polymer extraction techniques has allowed for the isolation of sc-SWNTs from metallic in a reproducible and scalable manner. The availability of highly-pure sc-SWNT materials has facilitated the production of thin-film transistors (TFTs) with very high charge carrier mobilities, outperforming organic small molecule and polymer semiconductors. However, the realization of commercial OED applications of polymer-sorted sc-SWNTs have not yet been achieved, partially due to the prohibitive time and materials costs associated with purifying sc-SWNTs.Current protocols for dispersing sc-SWNTs with conjugated polymers involve three broad steps: (1) dispersion of bulk SWNT material, (2) removal of non-dispersed carbonaceous materials, and (3) removal of excess polymer through filtration or centrifugation. The final step of removal of excess polymer is time-consuming and wasteful, but viewed as necessary for preparing high-performing TFTs, as the conjugated polymer has much lower performance compared to SWNTs.In this study we performed the first systematic investigation of the effect of excess polymer on SWNT TFT performance. Three SWNT concentrations were investigated, with varying ratios of excess polymer added to each. TFT device performance was monitored using several metrics, including: mobility, threshold voltage, on/off ratios and hysteresis. Characterization of large numbers of replicate TFT devices determined that below a threshold amount of excess polymer the presence of excess polymer did not have a negative impact on device performance. Detailed analysis of the sc-SWNT films through Raman spectroscopy and atomic force microscopy (AFM) confirmed that a simple rinsing step was sufficient to remove all the unbound conjugated polymer from the substrate surface without affecting the sc-SWNT network. The volume of solvent required for the rinsing step was substantially lower than that required for filtration or centrifugation steps. Furthermore, at higher SWNT concentrations the excess polymer prevented nanotube bundling, resulting in moderate improvements in both mobility and on/off ratios. Our results were reproducible for two different conjugated polymer sc-SWNT systems, demonstrating the versatility of this procedure.

Recent Progress of Amorphous Porous Organic Polymers as Heterogeneous Photocatalysts for Organic Synthesis

AbstractThe establishment of green and environmental friendly sunlight‐driven organic reactions has received increasing attention since the 21st century. By virtue of their functional designability, micromesoporous structure, and thermal/chemical stability, porous organic polymers (POPs) have exhibited enormous promise in photocatalytic organic reactions as ideal potential alternatives to conventional small molecule and inorganic semiconductor catalysts. In particular, amorphous POPs are simplified in terms of preparation conditions and process flow. Herein, various amorphous POP materials based on polymers of intrinsic microporosity, hypercrosslinked polymers, conjugated microporous polymers, and porous aromatic frameworks are reviewed, while typical synthetic strategies are briefly introduced. It also highlights an overview of the research progress in photocatalytic oxidation, coupling, reduction, cycloaddition, and polymerization reactions at home and abroad in recent years. Finally, the challenges and prospects for future research on amorphous POPs are presented.

Integrated System Built for Small-Molecule Semiconductors via High-Throughput Approaches.

High-throughput synthesis of solution-processable structurally variable small-molecule semiconductors is both an opportunity and a challenge. A large number of diverse molecules provide a possibility for quick material discovery and machine learning based on experimental data. However, the diversity of the molecular structure leads to the complexity of molecular properties, such as solubility, polarity, and crystallinity, which poses great challenges to solution processing and purification. Here, we first report an integrated system for the high-throughput synthesis, purification, and characterization of molecules with a large variety. Based on the principle "Like dissolves like," we combine theoretical calculations and a robotic platform to accelerate the purification of those molecules. With this platform, a material library containing 125 molecules and their optical-electronic properties was built within a timeframe of weeks. More importantly, the high repeatability of recrystallization we design is a reliable approach to further upgrading and industrial production.

Nanocrystal Array Engineering and Optoelectronic Applications of Organic Small-Molecule Semiconductors.

Organic small-molecule semiconductor materials have attracted extensive attention because of their excellent properties. Due to the randomness of crystal orientation and growth location, however, the preparation of continuous and highly ordered organic small-molecule semiconductor nanocrystal arrays still face more challenges. Compared to organic macromolecules, organic small molecules exhibit better crystallinity, and therefore, they exhibit better semiconductor performance. The formation of organic small-molecule crystals relies heavily on weak interactions such as hydrogen bonds, van der Waals forces, and π-π interactions, which are very sensitive to external stimuli such as mechanical forces, high temperatures, and organic solvents. Therefore, nanocrystal array engineering is more flexible than that of the inorganic materials. In addition, nanocrystal array engineering is a key step towards practical application. To resolve this problem, many conventional nanocrystal array preparation methods have been developed, such as spin coating, etc. In this review, the typical and recent progress of nanocrystal array engineering are summarized. It is the typical and recent innovations that the array of nanocrystal array engineering can be patterned on the substrate through top-down, bottom-up, self-assembly, and crystallization methods, and it can also be patterned by constructing a series of microscopic structures. Finally, various multifunctional and emerging applications based on organic small-molecule semiconductor nanocrystal arrays are introduced.

Suppressing Excess Lead Iodide Aggregation and Reducing N-Type Doping at Perovskite/HTL Interface for Efficient Perovskite Solar Cells.

Excess lead iodide (PbI2 ) aggregation at the charge carrier transport interface leads to energy loss and acts as unstable origins in perovskite solar cells (PSCs). Here, a strategy is reported to modulate the interfacial excess PbI2 by introducing π-conjugated small-molecule semiconductors 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline] (TAPC) into perovskite films through an antisolvent addition method. The coordination of TAPC to PbI units through the electron-donating triphenylamine groups and π-Pb2+ interactions allows for a compact perovskite film with reduced excess PbI2 aggregates. Besides, preferred energy level alignment is achieved due to the suppressed n-type doping effect at the hole transport layer (HTL) interfaces. As a result, the TAPC-modified PSC based on Cs0.05 (FA0.85 MA0.15 )0.95 Pb(I0.85 Br0.15 )3 triple-cation perovskite achieved an improved PCE from 18.37% to 20.68% and retained ≈90% of the initial efficiency after 30 days of aging under ambient conditions. Moreover, the TAPC-modified device based on FA0.95 MA0.05 PbI2.85 Br0.15 perovskite produced an improved efficiency of 23.15% compared to the control (21.19%). These results provide an effective strategy for improving the performance of PbI2 -rich PSCs.

Sensitive photodetection below silicon bandgap using quinoid-capped organic semiconductors.

High-sensitivity organic photodetectors (OPDs) with strong near-infrared (NIR) photoresponse have attracted enormous attention due to potential applications in emerging technologies. However, few organic semiconductors have been reported with photoelectric response beyond ~1.1 μm, the detection limit of silicon detectors. Here, we extend the absorption of organic small-molecule semiconductors to below silicon bandgap, and even to 0.77 eV, through introducing the newly designed quinoid-terminals with high Mulliken-electronegativity (5.62 eV). The fabricated photodiode-type NIR OPDs exhibit detectivity (D*) over 1012 Jones in 0.41 to 1.2 μm under zero bias with a maximum of 2.9×1012 Jones at 1.02 μm, which is the highest D* for reported OPDs in photovoltaic-mode with response spectra beyond 1.1 μm. The high D* in 0.9 to 1.2 μm is comparable to those of commercial InGaAs photodetectors, despite the detection limit of our OPDs is shorter than InGaAs (~1.7 μm). A spectrometer prototype with a wide measurable region (0.4 to 1.25 μm) and NIR imaging under 1.2-μm illumination are demonstrated successfully in OPDs.

Self-Assembly and Electrical Conductivity of a New [1]benzothieno[3,2-b][1]-benzothiophene (BTBT)-Peptide Hydrogel

The conjugation of small-molecule semiconductors with self-assembling peptides is a powerful tool for the fabrication of supramolecular soft materials for organic electronics and bioelectronics. Herein, we introduced the benchmark organic semiconductor [1]benzothieno[3,2-b][1]-benzothiophene (BTBT) within the structure of a self-assembling amphipathic peptide. The molecular structure of the conjugate was rationally designed to favour π-π stacking between BTBT cores and π-delocalization within the self-assembled architectures. Hydrogels with fibrillar structure were obtained upon self-assembly. Spectroscopic studies confirmed that both hydrogen bonding between peptide segments and π-π stacking between BTBT chromophores are responsible for the formation of the 3D fibrillar network observed by transmission electron microscopy. The hydrogel was successfully deposited on gold interdigitated electrodes and a conductivity up to 1.6 (±0.1) × 10-5 S cm-1 was measured.

Meniscus‐Guided Deposition of Organic Semiconductor Thin Films: Materials, Mechanism, and Application in Organic Field‐Effect Transistors

Solution-processable organic semiconductors are one of the promising materials for the next generation of organic electronic products, which call for high-performance materials and mature processing technologies. Among many solution processing methods, meniscus-guided coating (MGC) techniques have the advantages of large-area, low-cost, adjustable film aggregation, and good compatibility with theroll-to-roll process, showing good research results in the preparation of high-performance organic field-effect transistors. In this review, the types of MGC techniques are first listed and the relevant mechanisms (wetting mechanism, fluid mechanism, and deposition mechanism) are introduced. The MGC processes are focused and the effect of the key coating parameters on the thin film morphology and performance with examples is illustrated. Then, the performance of transistors based on small molecule semiconductors and polymer semiconductor thin films prepared by various MGC techniques is summarized. In the third section, various recent thin film morphology control strategies combined with the MGCs are introduced. Finally, the advanced progress of large-area transistor arrays and the challenges for roll-to-roll processes are presented using MGCs. Nowadays, the application of MGCs is still in the exploration stage, its mechanism is still unclear, and the precise control of film deposition still needs experience accumulation.

Recent Research Progress of Organic Small-Molecule Semiconductors with High Electron Mobilities.

Organic electronics has made great progress in the past decades, which is inseparable from the innovative development of organic electronic devices and the diversity of organic semiconductor materials. It is worth mentioning that both of these great advances are inextricably linked to the development of organic high-performance semiconductor materials, especially the representative n-type organic small-molecule semiconductor materials with high electron mobilities. The n-type organic small molecules have the advantages of simple synthesis process, strong intermolecular stacking, tunable molecular structure, and easy to functionalize structures. Furthermore, the n-type semiconductor is a remarkable and important component for constructing complementary logic circuits and p-n heterojunction structures. Therefore, n-type organic semiconductors play an extremely important role in the field of organic electronic materials and are the basis for the industrialization of organic electronic functional devices. This review focuses on the modification strategies of organic small molecules with high electron mobility at molecular level, and discusses in detail the applications of n-type small-molecule semiconductor materials with high mobility in organic field-effect transistors, organic light-emitting transistors, organic photodetectors, and gas sensors.

Fully Atomistic Molecular Dynamics Simulation of a TIPS-Pentacene:Polystyrene Mixed Film Obtained via the Solution Process

Organic thin-film transistors using small-molecule semiconductor materials such as 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-P) have been recently studied for the production of flexible and printed electronic devices. Blending a semiconductor with an insulating polymer, such as polystyrene, is known to improve the device performance; however, its molecular-level structure remains unknown. In this study, we performed molecular dynamics (MD) simulations on a mixed system of TIPS-P and atactic polystyrene (aPS) with fully atomistic models to understand the structure of the mixed thin film at the molecular level and the influence on the device properties. To reproduce the deposition from the solution, we gradually reduced the number of toluene molecules in the simulation. The dynamic characteristics of the system, mean squared displacement, diffusion coefficient, density profile, and P2 order parameter were analyzed. Some of the simulated systems reached the equilibrium state. In these systems, the simulated structures suggested the presence of more TIPS-P molecules on the surface than inside the bulk, even at the low molecular weight of aPS, where phase separation was not observed experimentally. The results of the fully atomistic MD simulations are also a basis for the coarse-grained model to increase the speed of the MD simulation.

Enhancing the Performance of N-Type Thermoelectric Devices via Tuning the Crystallinity of Small Molecule Semiconductors.

In the development of high-performance organic thermoelectric devices, n-type materials, especially with small molecule semiconductors, lags far behind p-type materials. In this paper, three small molecules are synthesized based on electron-deficient naphthalene bis-isatin building blocks bearing different alkyl chains with the terminal functionalized with 3-ethylrhodanine unit and studied their aggregation and doping mechanism in detail. It is found that crystallinity plays an essential role in tuning the doping behavior of small molecules. Molecules with too strong crystallinity tend to aggregate with each other to form large crystalline domains, which cause significant performance degradation. While molecules with weak crystallinity can tolerate more dopants, most of them exhibit low mobility. By tuning the crystallinity carefully, organic thermoelectric devices based on C12NR can maintain high mobility and realize effective doping simultaneously, and a high power factor of 1.07 µW m-1 K-2 at 100°C is realized. This delicate molecular design by modulating crystallinity provides a new avenue for realizing high-performance organic thermoelectric devices.

Superior High‐Temperature Energy Density in Molecular Semiconductor/Polymer All‐Organic Composites

AbstractHigh‐temperature dielectric polymers are in constant demand for the multitude of high‐power electronic devices employed in hybrid vehicles, grid‐connected photovoltaic and wind power generation, to name a few. There is still a lack, however, of dielectric polymers that can work at high temperature (> 150 °C). Herein, a series of all‐organic dielectric polymer composites have been fabricated by blending the n‐type molecular semiconductor 1,4,5,8‐naphthalenetetracarboxylic dianhydride (NTCDA) with polyetherimide (PEI). Electron traps are created by the introduction of trace amounts of n‐type small molecule semiconductor NTCDA into PEI, which effectively reduces the leakage current and improves the breakdown strength and energy storage properties of the composite at high temperature. Especially, excellent energy storage performance is achieved in 0.5 vol.% NTCDA/PEI at the high temperatures of 150 and 200 °C, e.g., ultrahigh discharge energy density of 5.1 J cm−3 at 150 °C and 3.2 J cm−3 at 200 °C with high discharge efficiency of 85–90%, which is superior to its state‐of‐the‐art counterparts. This study provides a facile and effective strategy for the design of high‐temperature dielectric polymers for advanced electronic and electrical systems.

Role of oxygen within end group substituents on film morphology and charge carrier transport in thiophene/phenylene small-molecule semiconductors

In this study, the end group polarity of (5,5′)-biphenyl-(2,2’)-bithiophenes (PTTPs) was systematically varied from alkyl (1) to alkoxy (2) with one oxygen atom to glycol (3) with two oxygen atoms while the overall length of the end groups is kept constant. Thin films of the three compounds were sublimated at different substrate temperatures and their morphology, crystallinity and charge carrier transport in field-effect transistors was investigated to draw structure-property relationships for the PTTP derivatives. For all three compounds, the effective charge carrier mobility is improved with higher substrate temperatures at which films with higher crystallinity and larger grains are formed. The effective mobility decreases with higher polarity of the end groups from alkyl to alkoxy and glycol. The reliability factor of the alkyl (1) and alkoxy (2) substituted PTTPs decreases with higher substrate temperature, but at the same time this value is enhanced for the glycol substituted molecules (3). The transistors of 3 prepared at higher substrate temperatures also show a reduced threshold voltage and smaller hysteresis in the transfer characteristics. These insights are important for the understanding of the impact of oxygen incorporation into side chain/end group substituents of organic semiconductors and their implementation in organic electrochemical transistors, thermoelectrics and photovoltaics.

Pyrene-based chalcones as functional materials for organic electronics application

Though new generation organic electronic devices have evolved from mere scientific perceptions to real-life marketed applications, considerably less research attention has been focused on n-type or electron transporting small molecule semiconductors. The present study is focused on the exploration of structural, thermal, electrochemical, electrical, and optical properties of two pyrene-based chalcones: PC1 and PC2, synthesized through Claisen Schmidt condensation reaction. The chalcones displayed good thermal stability and wide bandgap n-type semiconducting behaviour with high charge carrier concentration and dielectric constant. The experimental evidences including fluorescence measurements, nanoaggregate size, and morphology analysis, supported by DFT calculations and molecular dynamic simulations advocated the intramolecular charge transfer and aggregation-induced enhanced emission features of the molecules. Successful fabrication of a diode in combination with the current-voltage characteristics established the candidature of PC1 and PC2 for electro-optical devices. The dielectric studies were performed to measure dielectric constant and AC conductivity at different frequency ranges. The cyclic voltammetry and AC impedance response of PC2 differed from PC1 due to the inclusion of a fluorine atom in the molecular scaffold. Further, the functional implication of PC2 as an electrode material was explored by constructing a supercapacitor, which offered a specific capacitance of 220 Fg-1 at a scan rate of 10 mV s−1. Moreover, these chalcone-based organic semiconductors displayed high thermal and charge carrier concentration as well as compatibility with other layers in an OLED device. Hence PC1/PC2 can be further investigated as dopants along with other emissive layers as host materials in OLEDs.