High-performance Organic Electronics Research Articles

N-Type Doping Effect of Anthracene-Based Cationic Dyes in Organic Electronics.

n-Type doping for improving the electrical characteristics and air stability of n-type organic semiconductors (OSCs) is important for realizing advanced future electronics. Herein, we report a selection method for an effective n-type dopant with an optimized structure and thickness based on anthracene cationic dyes with high miscibility induced by a molecular structure similar to that of OSCs. Among the doped OSCs evaluated, rhodamine B (RhoB)-doped OSC exhibits the highest density, a smallest roughness of 2.69 nm, a phase deviation of 0.85° according to atomic force microscopy measurements, and the highest electron mobility (μ), showing its high miscibility. Surface doping of RhoB affords the lowest contact resistance of 2.01 × 105 Ω cm compared to bulk and contact doping, resulting in an effective doping structure. The RhoB-doped OSC retains 81.63% of the original μ value of 6.13 × 10-2 cm2 V-1 s-1 after 15 days, whereas pristine OSC shows a lower μ of 2.33 × 10-2 cm2 V-1 s-1 and maintains only 4.41% of the original value after 15 days. Our findings demonstrate that this methodology is effective for the selection of a high-performance n-type dopant for OSCs toward the development of high-performance and air-stable n-type organic electronics.

Self-Assembly Behavior, Aggregation Structure, and the Charge Carrier Transport Properties of S-Heterocyclic Annulated Perylene Diimide Derivatives.

The construction of high-performance n-type semiconductors is crucial for the advancement of organic electronics. As an attractive n-type semiconductor, molecular systems based on perylene diimide derivatives (PDIs) have been extensively investigated over recent years. Owing to the fascinating aggregated structure and high performance, S-heterocyclic annulated PDIs (SPDIs) are receiving increasing attention. However, the relationship between the structure and the electrical properties of SPDIs has not been deeply revealed, restricting the progress of PDI-based organic electronics. Here, we developed two novel SPDIs with linear and dendronized substituents in the imide position, named linear SPDI and dendronized SPDI, respectively. A series of structural and property characterizations indicated that linear SPDI formed a long-range-ordered crystalline structure based on helical supramolecular columns, while dendronized SPDI, with longer alkyl side chains, formed a 3D-ordered crystalline structure at a low temperature, which transformed into a hexagonal columnar liquid crystal structure at a high temperature. Moreover, no significant charge carrier transport signal was examined for linear SPDI, while dendronized SPDI had a charge carrier mobility of 3.5 × 10-3 cm2 V-1 s-1 and 2.1 × 10-3 cm2 V-1 s-1 in the crystalline and liquid crystalline state, respectively. These findings highlight the importance of the structure-function relationship in PDIs, and also offer useful roadmaps for the design of high-performance organic electronics for down-to-earth applications.

Breaking Fundamental Limitation of Flow-Induced Anisotropic Growth for Large-Scale and Fast Printing of Organic Single-Crystal Films.

Advanced organic electronic technologies have put forward a pressing demand for cost-effective and high-throughput fabrication of organic single-crystal films (OSCFs). However, solution-printed OSCFs are typically plagued by the existence of abundant structural defects, which pose a formidable challenge to achieving large-scale and high-performance organic electronics. Here, it is elucidated that these structural defects are mainly originated from printing flow-induced anisotropic growth, an important factor that is overlooked for too long. In light of this, a surfactant-additive printing method is proposed to effectively overcome the anisotropic growth, enabling the deposition of uniform OSCFs over the wafer scale at a high speed of 1.2 mm s-1 at room temperature. The resulting OSCF exhibits appealing performance with a high average mobility up to 10.7 cm2 V-1 s-1, which is one of the highest values for flexible organic field-effect transistor arrays. Moreover, large-scale OSCF-based flexible logic circuits, which can be bent without degradation to a radius as small as 4.0 mm and over 1000 cycles are realized. The work provides profound insights into breaking the limitation of flow-induced anisotropic growth and opens new avenues for printing large-scale organic single-crystal electronics.

Wafer-Scale Epitaxial Growth of Two-dimensional Organic Semiconductor Single Crystals toward High-Performance Transistors.

The success of state-of-the-art electronics and optoelectronics relies heavily on the capability to fabricate semiconductor single-crystal wafers. However, the conventional epitaxial growth strategy for inorganic wafers is invalid for growing organic semiconductor single crystals due to the lack of lattice-matched epitaxial substrates and intricate nucleation behaviors, severely impeding the advancement of organic single-crystal electronics. Here, an anchored crystal-seed epitaxial growth method for wafer-scale growth of 2D organic semiconductor single crystals is developed for the first time. The crystal seed is firmly anchored on the viscous liquid surface, ensuring the steady epitaxial growth of organic single crystals from the crystal seed. The atomically flat liquid surface effectively eliminates the disturbance from substrate defects and greatly enhances the 2D growth of organic crystals. Using this approach, a wafer-scale few-layer bis(triethylsilythynyl)-anthradithphene (Dif-TES-ADT) single crystal is formed, yielding a breakthrough for organic field-effect transistors with a high reliable mobility up to 8.6 cm2 V-1 s-1 and an ultralow mobility variable coefficient of 8.9%. This work opens a new avenue to fabricate organic single-crystal wafers for high-performance organic electronics.

Large-Area Monolayer n-Type Molecular Semiconductors with Improved Thermal Stability and Charge Injection

We fabricated monolayer n-type two-dimensional crystalline semiconducting films with millimeter-sized areas and remarkable morphological uniformity using an antisolvent-confined spin-coating method. The antisolvent can cause a downstream Marangoni flow, which improves the film morphologies. The deposited crystalline monolayer films exhibit excellent thermal stabilities after annealing, which reveals the annealing-induced enhancement of crystallinity. The transistors based on the n-type monolayer crystalline films show linear output characteristics and superior electron mobilities. The improved charge injection between monolayer films and Au electrodes results from the energy level shift as the films decrease to the monolayer, which leads to a lower injection barrier. This work demonstrates a promising method for fabricating air-stable, low-cost, high-performance, and large-area organic electronics.

Direct Writing of Aligned Conjugated Polymer Micro-Ribbons for High-Performance Organic Electronics

Organic semiconductors (OSCs) and relevant devices have presented their great potential in flexible and wearable electronics. Controlled solution deposition of organic semiconductors at a limited local region is highly expected because it can realize feasible and low-cost fabrication of highly integrated devices with low current leakage and free crosstalk between adjacent devices. Here, we reported a feasible microscale meniscus-guided direct writing method to purposely deposit conjugated polymer poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno[3,2-b]thiophene)] micro-ribbons at preset local regions. The direct writing of OSCs was carried out on a microscale with the width of written micro-ribbons down to 5 μm, which was seldomly reported before. Direct writing operation induced anisotropic crystallization of organic semiconducting micro-ribbons, which further enhanced the electrical performance of organic transistors with a device on/off ratio of 5.1 × 104 and carrier mobility of 1.05 cm2 V–1 s–1. Small-angle X-ray diffraction analysis further proved the existence of anisotropic crystallization behavior. This technique shed light on the feasible and convenient fabrication of future high-performance organic electronics.

Organic bipolar transistors

Devices made using thin-film semiconductors have attracted much interest recently owing to new application possibilities. Among materials systems suitable for thin-film electronics, organic semiconductors are of particular interest; their low cost, biocompatible carbon-based materials and deposition by simple techniques such as evaporation or printing enable organic semiconductor devices to be used for ubiquitous electronics, such as those used on or in the human body or on clothing and packages1–3. The potential of organic electronics can be leveraged only if the performance of organic transistors is improved markedly. Here we present organic bipolar transistors with outstanding device performance: a previously undescribed vertical architecture and highly crystalline organic rubrene thin films yield devices with high differential amplification (more than 100) and superior high-frequency performance over conventional devices. These bipolar transistors also give insight into the minority carrier diffusion length—a key parameter in organic semiconductors. Our results open the door to new device concepts of high-performance organic electronics with ever faster switching speeds.

Influence of the molecular weight and size distribution of PSS on mixed ionic-electronic transport in PEDOT:PSS.

The commercially available polyelectrolyte complex poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is ubiquitous in organic and hybrid electronics. As such, it has often been used as a benchmark material for fundamental studies and the development of new electronic devices. Yet, most studies on PEDOT:PSS have focused on its electronic conductivity in dry environments, with less consideration given to its ion transport, coupled ionic-electronic transport, and charge storage properties in aqueous environments. These properties are essential for applications in bioelectronics (sensors, actuators), charge storage devices, and electrochromic displays. Importantly, past studies on mixed ionic-electronic transport in PEDOT:PSS neglected to consider how the molecular structure of PSS affects mixed ionic-electronic transport. Herein, we therefore investigated the effect of the molecular weight and size distribution of PSS on the electronic properties and morphology of PEDOT:PSS both in dry and aqueous environments, and overall performance in organic electrochemical transistors (OECTs). Using reversible addition-fragmentation chain transfer (RAFT) polymerization with two different chain transfer agents, six PSS samples with monomodal, narrow (Đ = 1.1) and broad (Đ = 1.7) size distributions and varying molecular weights were synthesized and used as matrices for PEDOT. We found that using higher molecular weight of PSS (M n = 145 kg mol-1) and broad dispersity led to OECTs with the highest transconductance (up to 16 mS) and [μC * ] values (~140 F·cm-1V-1s-1) in PEDOT:PSS, despite having a lower volumetric capacitance (C * = 35 ± 4 F cm-3). The differences were best explained by studying the microstructure of the films by atomic force microscopy (AFM). We found that heterogeneities in the PEDOT:PSS films (interconnected and large PEDOT- and PSS-rich domains) obtained from high molecular weight and high dispersity PSS led to higher charge mobility (μ OECT ~ 4 cm2V-1s-1) and hence transconductance. These studies highlight the importance of considering molecular weight and size distribution in organic mixed ionic-electronic conductor, and could pave the way to designing high performance organic electronics for biological interfaces.

Tailoring the charge transport characteristics in ordered small-molecule organic semiconductors by side-chain engineering and fluorine substitution.

Crystalline and liquid-crystalline conjugated small molecules represent a promising family of semiconductor materials for organic electronics applications. The control of the morphology and optoelectronic properties of small molecules allows tuning their charge transport characteristics and hence, improving the performance of electronic devices. Here, we designed four pentamers based on alternating thiophene and benzothiadiazole moieties and investigated the effect of their structure on the optoelectronic properties, ordering and charge transport characteristics. It is shown that thermal annealing of conjugated pentamers leads to remarkable changes in the microstructure and domain texture of thin films. As a result, an increase in hole mobility for compound M4 by one order of magnitude was achieved. These findings provide a valuable insight into the structure-property relationships for designed small molecules featuring them as promising semiconductor materials for further developing high-performance organic electronics.

Phase Change-Driven Radical Population and Electrical Conductivity Increases of Organic Radical Crystals by Mild Heating

Carrier doping in conductive radical crystal systems is one of the most important and challenging issues in employing radicals as charge carriers, i.e., electronic radicals for high-performance organic electronics. Here, we report an experimental demonstration of the increase in the radical population and the corresponding increase in electrical conductivity by water desorption-involved crystal structure change upon mild heating. The electrical conductivity of the dihydrophenazinium radical cation (H₂PNZ·⁺) crystal is enhanced by 4 orders of magnitude with an increase in radical population by 1.5 times according to the electron paramagnetic resonance signal after heating at 333 K. Single-crystal X-ray analyses show that the increase in radical population originates from the phase transformation from dimer-like radical units to monomer-like radical units upon mild heating in a narrow temperature range. The increase in intermolecular distance results in producing more independent radicals and reducing the band gap. Therefore, the electrical conductivity is increased by the synergistic effects of the radical population increase and band gap reduction.

Vacuum processed large area doped thin-film crystals: A new approach for high-performance organic electronics

Rubrene single crystal domains with hundreds of micrometers size fully covering different substrates are achieved by thermal annealing of evaporated amorphous thin films with the help of a thin glassy underlayer. The sufficiently large energy level offset of the underlayer material and rubrene enables high performance staggered bottom gate rubrene crystalline transistors with maximum field-effect linear mobility over 5 cm2V−1s−1 (μAvg = 4.35 ± 0.76 cm2V−1s−1) for short channel devices of 20 μm, comparable to high quality rubrene bulk single crystals. Moreover, since molecular dopants up to several mole percent can be incorporated into the single crystals with a minimal disturbance of the lattice, the contact resistance of the transistors is significantly reduced to around 1 kOhm.cm by contact doping via adlayer epitaxy of p-type doped rubrene. Our results pave the way for novel high-performance organic electronics using crystalline active materials with mass-production compatible deposition techniques.

Tuning charge transport in organic semiconductors with nanoparticles and hexamethyldisilazane

In this study, we showcase the use of silicon dioxide (SiO2) nanoparticles and hexamethyldisilazane (HMDS) treatment to regulate the thin film morphology and manipulate charge transport of solution-processed, small-molecular, organic semiconductors. 6,13-Bis(triisopropylsilylethynyl) pentacene (TIPS pentacene) was blended with SiO2 nanoparticles as an exemplary organic semiconductor. A higher concentration of SiO2 nanoparticles were observed near the edge of TIPS pentacene crystals and enlarged the width of crystal edges. This greatly reduced the dendritic crystal growth pattern of TIPS pentacene and contributed to its enhanced orientation uniformity. In addition, the HMDS treatment effectively passivated the silanol groups on the hydrophilic gate dielectrics. As a result, bottom-gate, top-contact TIPS pentacene/SiO2 nanoparticle-based organic thin-film transistors boosted a performance consistency enhancement (defined by the ratio of average mobility to the standard deviation of mobility). The combinational approach to employ SiO2 nanoparticles and HMDS treatment as demonstrated in this work sheds light on important applications in high-performance organic electronics devices on flexible substrate.

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.

Lithographical Fabrication of Organic Single-Crystal Arrays by Area-Selective Growth and Solvent Vapor Annealing.

Miniaturized organic single-crystal arrays that are addressed by reading-out circuits are crucial for high performance and high-level integration organic electronics. Here, we report a lithography compatible strategy to fabricate organic single-crystal arrays via area-selective growth and solvent vapor annealing (SVA). The organic semiconducting molecules can first selectively grow on photographically patterned drain-source electrodes, forming ordered amorphous aggregates that can further be converted to discrete single-crystal arrays by SVA. This strategy can be applied to self-align the microsized organic single crystals on predesigned locations. With this method, suppression of cross-talk among devices, organic field-effect transistors, and basic logic gate arrays with reading-out electrodes are further demonstrated.

Electrochemical investigation on adsorption kinetics of long chain alkylsilanes and influence of solvents on their self-assembly and electron transfer behavior on indium tin oxide

In situ adsorption kinetics of hexadecyltrimethoxy silane (HDTMS) and octadecyltrimethoxy silane (ODTMS) on indium tin oxide (ITO) surface at short time intervals were measured by electrochemical impedance (EIS) spectroscopy technique at constant frequency. The studies suggest that, self-assembly of silanes on ITO proceeds through two distinct adsorption steps, a fast first step followed by a slower second step. The inhibition of electron transfer by self-assembled silanes prepared in ethanol, toluene and hexane solvents were evaluated by cyclic voltammetry (CV) and EIS using [Fe(CN)6]3−/4− and [Ru(NH3)6]3+/2+ redox species. It is shown that, the quality of silane films are influenced by the polarity of solvent, chain length of silane and ITO substrate–solvent interactions. The effect of annealing on electron transfer barrier property of silane monolayers after their formation were studied. The pinhole characteristics of silane films on ITO prepared from various solvents under study were measured using EIS. This study demonstrates a strategy of producing an ultra-smooth and close-packed silane films on ITO surfaces which can have potential applications towards high performance organic electronics.

Noncovalent π-stacked robust topological organic framework

Organic frameworks (OFs) offer a novel strategy for assembling organic semiconductors into robust networks that facilitate transport, especially the covalent organic frameworks (COFs). However, poor electrical conductivity through covalent bonds and insolubility of COFs limit their practical applications in organic electronics. It is known that the two-dimensional intralayer π∙∙∙π transfer dominates transport in organic semiconductors. However, because of extremely labile inherent features of noncovalent π∙∙∙π interaction, direct construction of robust frameworks via noncovalent π∙∙∙π interaction is a difficult task. Toward this goal, we report a robust noncovalent π∙∙∙π interaction-stacked organic framework, namely πOF, consisting of a permanent three-dimensional porous structure that is held together by pure intralayer noncovalent π∙∙∙π interactions. The elaborate porous structure, with a 1.69-nm supramaximal micropore, is composed of fully conjugated rigid aromatic tetragonal-disphenoid-shaped molecules with four identical platforms. πOF shows excellent thermostability and high recyclability and exhibits self-healing properties by which the parent porosity is recovered upon solvent annealing at room temperature. Taking advantage of the long-range π∙∙∙π interaction, we demonstrate remarkable transport properties of πOF in an organic-field-effect transistor, and the mobility displays relative superiority over the traditional COFs. These promising results position πOF in a direction toward porous and yet conductive materials for high-performance organic electronics.

Controlled 2D growth of organic semiconductor crystals by suppressing “coffee-ring” effect

Owing to enhanced charge transport efficiency arising from the ultrathin nature, two-dimensional (2D) organic semiconductor single crystals (OSSCs) are emerging as a fascinating platform for high-performance organic field-effect transistors (OFETs). However, “coffee-ring” effect induced by an evaporation-induced convective flow near the contact line hinders the large-area growth of 2D OSSCs through a solution process. Here, we develop a new strategy of suppressing the “coffee-ring” effect by using an organic semiconductor: polymer blend solution. With the high-viscosity polymer in the organic solution, the evaporation-induced flow is remarkably weakened, ensuring the uniform molecule spreading for the 2D growth of the OSSCs. As an example, wafer-scale growth of crystalline film consisting of few-layered 2,7-didecylbenzothienobenzothiophene (C10-BTBT) crystals was successfully accomplished via blade coating. OFETs based on the crystalline film exhibited a maximum hole mobility up to 12.6 cm2·V−1·s−1, along with an average hole mobility as high as 8.2 cm2·V−1·s−1. Our work provides a promising strategy for the large-area growth of 2D OSSCs toward high-performance organic electronics.

Solvent Vapor-Assisted Magnetic Manipulation of Molecular Orientation and Carrier Transport of Semiconducting Polymers.

Effective control of the molecular orientation and the degree of ordering in organic semiconductors is important to achieve high-performance organic electronics. Herein, we have successfully achieved highly oriented films in centimeter scale for a naphthalenedicarboximide-based semiconducting polymer (P(NDI2OD-T2)) by solvent vapor annealing (SVA) of precast films under a high magnetic field (HMF). As revealed by the microstructural studies, the SVA-HMF films exhibit a remarkably higher degree of chain alignment and high morphological uniformity compared to the HMF-guided drop-cast films. Based on the structural evolution of the films with the SVA time, a mechanism is proposed to elucidate the alignment process, which emphasizes that the chain aggregates re-formed in the swollen films trigger magnetic alignment and determine the film order. Compared with the unaligned films, field-effect transistors of the magnetic aligned P(NDI2OD-T2) films have exhibited a 19-fold enhancement of electron mobility and an extraordinarily large mobility anisotropy of 125. Furthermore, a significantly reduced energetic barrier for activated transport is observed on the aligned devices from temperature-variable measurements. The improved performance achieved by the HMF-SVA process has indicated its potential for high-performance organic electronic applications.

Phase segregation controlled semiconductor crystallization for organic thin film transistors

Abstract In this article, we provide an in-depth review of important works on phase segregation which occurs as a result of mixing organic semiconductors with polymeric additives. Throughout the discussion, the indispensable correlations among phase segregation, crystal growth, layer structure and film morphology are showcased using specific examples that mainly entail small-molecule organic semiconductors such as 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS pentacene) and 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (diF-TES-ADT). The various factors that impact the phase segregation are analyzed, which include surface energy, solvent choice, additive nature, and substrate interaction. The beneficial effects of phase segregation on charge transport and operational stabilities of organic semiconductor based organic thin film transistors (OTFTs) are also assessed. We believe that the phase segregation examples discussed in this work shed light on optimizing the electrical performance of organic semiconductors and unlock favorable features useful for their application in high-performance organic electronics on flexible substrates.

Super- and Ferroelastic Organic Semiconductors for Ultraflexible Single-Crystal Electronics.

Like silicon, single crystals of organic semiconductors are pursued to attain intrinsic charge transport properties. However, they are intolerant to mechanical deformation, impeding their application in flexible electronic devices. Such contradictory properties, namely exceptional molecular ordering and mechanical flexibility, are unified in this work. We found that bis(triisopropylsilylethynyl)pentacene (TIPS-P) crystals can undergo mechanically induced structural transitions to exhibit superelasticity and ferroelasticity. These properties arise from cooperative and correlated molecular displacements and rotations in response to mechanical stress. By utilizing a bending-induced ferroelastic transition of TIPS-P, flexible single-crystal electronic devices were obtained that can tolerate strains (ϵ) of more than 13 % while maintaining the charge carrier mobility of unstrained crystals (μ>0.7 μ0 ). Our work will pave the way for high-performance ultraflexible single-crystal organic electronics for sensors, memories, and robotic applications.