Organic Electronic Devices Research Articles

Molecular Engineering of Rylene Diimides via Sila-Annulation Toward High-Mobility Organic Semiconductors.

The continuous innovation of captivating new organic semiconducting materials remains pivotal in the development of high-performance organic electronic devices. Herein, a molecular engineering by combining sila-annulation with the vertical extension of rylene diimides (RDIs) toward high-mobility organic semiconductors is presented. The unilateral and bilateral sila-annulated quaterrylene diimides (Si-QDI and 2Si-QDI) are designed and synthesized. In particular, the symmetrical bilateral 2Si-QDI exhibits a compact, 1D slipped π-π stacking arrangement through the synergistic combination of a sizable π-conjugated core and intercalating alkyl chains. Combining the appreciable elevated HOMO levels and reduced energy gaps, the single-crystalline organic field-effect transistors (SC-OFETs) based on 2Si-QDI demonstrate exceptional ambipolar transport characteristics with an impressive hole mobility of 3.0 cm2 V-1 s-1 and an electron mobility of 0.03 cm2 V-1 s-1, representing the best ampibolar SC-OFETs based on RDIs. Detailed theoretical calculations rationalize that the larger transfer integral along the π-π stacking direction is responsible for the achievement of the superior charge transport. This study showcases the remarkable potential of sila-annulation in optimizing carrier transport performances of polycyclic aromatic hydrocarbons (PAHs).

Dual Clay Nanobrick Wall Thin Films with High Oxygen Barrier at High Humidity

AbstractThin polymer‐based coatings with high oxygen barrier at elevated humidity are needed for the protection of food and organic electronic devices. Polyelectrolyte‐based thin films (deposited via layer‐by‐layer assembly) perform well at ambient humidity, but their performance typically dwindles as humidity increases due to their hydrophilic nature. Retention of their high barrier can be achieved through the addition of chemical crosslinkers or the introduction of inorganic platelets that create a nanobrick wall structure. In this study, a nanobrick wall barrier prepared with two types of clay, with a thickness less than 200 nm, is shown to reduce the oxygen transmission rate (OTR) of 179 µm polyethylene terephthalate to less than 0.016 cm3 m−2 day−1 atm−1. At 90% relative humidity (RH), a quadlayer barrier consisting of polyethylenimine, boehmite clay, poly(acrylic acid), and vermiculite clay maintains nearly 90% of its barrier performance at 0% RH (OTR = 0.019 cm3 m−2 day−1 atm−1). This study demonstrates the potential of dual clay thin film nanocomposites to protect various consumer goods at high humidity.

Hydrophilic Conjugated Polymers for Sustainable Fabrication of Deep‐Red Light‐Emitting Electrochemical Cells

AbstractIt is crucial to develop functional electronic materials that can be processed from green solvents to achieve environmentally sustainable and cost‐efficient printing fabrication of organic electronic devices. Here, the design and cost‐efficient synthesis of two hydrophilic and emissive conjugated polymers, TQ‐OEG and TQ2F‐OEG, are presented, which are rendered hydrophilic through the grafting of oligo(ethylene glycol) (OEG) solubilizing groups onto the thiophene‐quinoxaline conjugated backbone and thereby can be processed from a water:ethanol solvent mixture. The results show that the introduction of the OEG groups enables for a direct dissolution of salts by the neat polymer for the attainment of solid‐state ion mobility. These properties are utilized for the design and development of light‐emitting electrochemical cells (LECs), the active materials of which can be solution cast from a water:ethanol‐based ink. It is specifically shown that such an LEC device, comprising an optimized blend of the TQ2F‐OEG emitter and a Li salt as the active material positioned between two air‐stabile electrodes, delivers deep‐red emission (peak wavelength = 670 nm) with a radiance of 185 µW m−2 at a low drive voltage of 2.3 V. This study contributes relevant information as to how polymers and LEC devices can be designed and fabricated to combine functionality with sustainability.

Floating Film Transfer: A Facile and Cost-Effective Approach Towards Uniform Large Area Oriented Thin Films for Organic Electronic Devices

Floating Film Transfer: A Facile and Cost-Effective Approach Towards Uniform Large Area Oriented Thin Films for Organic Electronic Devices

High-Performance n-Type Polymeric Mixed Ionic-Electronic Conductors: The Impacts of Halogen Functionalization.

Developing high-performance n-type polymer mixed ionic-electronic conductors (PMIECs) is a grand challenge, which largely determines their applications in vaious organic electronic devices, such as organic electrochemical transistors (OECTs) and organic thermoelectrics (OTEs). Herein, two halogen-functionalized PMIECs f-BTI2g-TVTF and f-BTI2g-TVTCl built from fused bithiophene imide dimer (f-BTI2) as the acceptor unit and halogenated thienylene-vinylene-thienylene (TVT) as the donor co-unit are reported. Compared to the control polymer f-BTI2g-TVT, the fluorinated f-BTI2g-TVTF shows lower-positioned lowest unoccupied molecular orbital (LUMO), improved charge transport property, and greater ion uptake capacity. Consequently, f-BTI2g-TVTF delivers a state-of-the-artµC* of 90.2 F cm-1 V-1 s-1 with a remarkable electron mobility of 0.41 cm2 V-1 s-1 in OECTs and an excellent power factor of 64.2 µW m-1 K-2 in OTEs. An OECT-based inverter amplifier is further demonstrated with voltage gain up to 148V V-1 , which is among the highest values for OECT inverters. Such results shed light on the impacts of halogen atoms on developing high-performing n-type PMIECs.

Pyrazino[2,3-g]quinoxaline core-based organic liquid crystalline semiconductor: Proficient hole transporting material for optoelectronic devices

Hole transport materials (HTMs) have a significant impact on the effectiveness of organic electronic devices; therefore, we present a molecular architecture of pyrazino[2,3-g]quinoxaline (PQ10)-based room-temperature organic liquid crystalline semiconductor (OLCS) as an alternative HTM. The PQ10 compound exhibits three different rectangular columnar (Colr) phases offering an impressive hole mobility of 8.8 × 10−3 cm2V−1s−1 which is found to be dexterous than most of existing polymeric hole transport materials. The charge transport mechanism is governed by the hole polarons hopping through H-aggregates of the PQ10 molecules and the hole mobility remains nearly constant throughout the mesophase range, but it decreases with increasing applied electric field. The current-voltage characteristics of the PQ10 have also been investigated in all three Colr phases and explained via the Poole-Frenkel conduction mechanism. The dielectric spectroscopy has been eventually carried out to understand the nature of dielectric permittivity and conductivity as a function of temperature and a correlation is established between the molecular architecture of the Colr phases and aforementioned physical properties. Solar cell simulation has been additionally performed to demonstrate that the PQ10 material can be a better choice as HTM for organic electronics and photovoltaic applications.

Solvent Impact on Langmuir and Langmuir–Schaefer Films of Soluble Main‐Chain Poly(fullerene)s Based on C60

Understanding the morphology and electronic properties of poly(fullerene)s is crucial for the development of new organic devices. This work addresses the fabrication and characterization of Langmuir–Schaefer (LS) films of poly(fullerene)s based on C60 with short (HSS8) and long (HSS16) sidechains, solubilized in chloroform or xylene. In addition, density functional theory (DFT) calculations are used to optimize the molecular geometries, determine energies, and investigate the influence of solvent applied. Depending on the organic solvent, floating material isotherms indicate the formation of disordered aggregates in the aqueous subphase. The influence of solvent in LS films is also evidenced by way of atomic force microscopy (AFM), UV‐vis, and cyclic voltammetry (CV) measurements. From DFT calculations, the arms of the poly(fullerene)s start to extend from an initial position of surrounding the fullerene sphere. In AFM measurements, depending on the organic solvent, the roughness significantly reduces, while the homogeneity is much higher. In UV‐vis and CV measurements, the propensity to form aggregates depends mainly on the polarization of the solvent and is directly related to the maximum absorption, oxidation, and reduction peaks. From the optical bandgap energy values, the poly(fullerene)s studied here present high potential for application in organic electronic devices.

Extremely Stable Perylene Bisimide-Bridged Regioisomeric Diradicals and Their Redox Properties.

Excellent stability is an essential premise for organic diradicals to be used in organic electronic and spintronic devices. We have attached two tris(2,4,6-trichlorophenyl)methyl (TTM) radical building blocks to the two sides of perylene bisimide (PBI) bridges and obtained two regioisomeric diradicals (1,6-TTM-PBI and 1,7-TTM-PBI). Both of the isomers show super stability rather than the monomeric TTM under ambient conditions, due to the increased conjugation and the electron-withdrawing effects of the PBI bridges. The diradicals show distinct and reversible multistep redox processes, and a spectro-electrochemistry investigation revealed the generation of organic mixed-valence (MV) species during reduction processes. The two diradicals have singlet ground states, very small singlet-triplet energy gaps (ΔES-T ) and a pure open-shell character (with diradical character y0 =0.966 for 1,6-TTM-PBI and 0.967 for 1,7-TTM-PBI). This work opens a window to developing very stable diradicals and offers the opportunity of their further application in optical, electronic and magnetic devices.

Zinc phthalocyanine compound-based photo-electric organic shock-proof disposable flexible sensors

This research study introduces a multifunctional photo-electric sensor that utilises a semiconductor composite material and is implemented on a cellulose substrate. The flex electronic devices were manufactured using a rubbing-in technique that does not require energy. The investigation focused on using a compound consisting of zinc phthalocyanine and multi-walled carbon nanotubes (MWCNTs) as an active layer. However, aluminium top electrodes were utilized for photo-electric characterization, respectively. The surface type symmetry was designed to achieve disposable organic, shock-proof, and vibration-free electronic devices. They are then analyzed and characterized for their morphological and electrical parameters. The material structural analysis was performed with x-ray diffraction of materials, UV–Vis, photo luminance, Fourier-transform infrared spectroscopy, and for electrical characterization, the capacitance and impedance at varying ultra-violet (0–1300 W/cm), infrared (0–1580 W/m2), and frequency (0.1–200 kHz) were performed. Each parameter's influence is broken out in detail to illuminate the underlying physics of the results further. The results show that when Infrared intensity rises, impedance falls, whereas UV intensity increases. In the context of capacitance, it is observed that exposure to ultraviolet radiation leads to a decrease or increase in capacitance, while intensification of infrared light also results in a corresponding change in capacitance.Moreover, it can be observed that the sensitivity of electronic equipment exhibits a reduction when the frequency is increased. These devices have a wide range of applications, such as their use in food supply chains to safeguard food from the detrimental impact of high ultraviolet and infrared radiation on public health. They can also be employed in the medical industry for optical physiotherapy treatments and in universities for research purposes in countries that fall below the international poverty line, owing to their cost-effective fabrication technique.

Potential Application of Organic Electronics in Electrical Sensing of Insects and Integrated Pest Management towards Developing Ecofriendly Replacements for Chemical Insecticides.

Synthetic insecticides are widely used against plant pest insects to protect the crops. However, many insecticides have poor selectivity and are toxic also to beneficial insects, animals, and humans. In addition, insecticide residues can remain on fruits for many days, jeopardizing food safety. For these reasons, a reusable, low-cost electronic trap that can attract, detect, and identify, but attack only the pest while leaving beneficial insects unharmed could provide a sustainable, nature-friendly replacement. Here, for the first time, research results are presented suggesting the great potential and compatibility of organic electronic devices and technologies with pest management. Electrical characterizations confirm that an insect's body has relatively high dielectric permittivity. Adaptive memcapacitor circuits can track the impedance change for insect detection. Other experiments show that printed polymer piezoelectric transducers on a plastic substrate can collect information about the weight and activity of insects for identification. The breakdown voltage of most insects´ integument is measured to be <200V. Long channel organic transistors easily work at such high voltages while being safe to touch for humans thanks to their inherent low current. This feasibility study paves the way for the future development of organic electronics for physical pest control and biodiversity protection.

Recent Insights about the Role of Gels in Organic Photonics and Electronics.

This review article provides an in-depth exploration of the role of gels in the fields of organic electronics and photonics, focusing on their unique properties and applications. Despite their remarkable potential, gel-based innovations remain relatively uncharted in these domains. This brief review aims to bridge the knowledge gap by shedding light on the diverse roles that gels can fulfil in the enhancement of organic electronic and photonic devices. From flexible electronics to light-emitting materials, we delve into specific examples of gel applications, highlighting their versatility and promising outcomes. This work serves as an indispensable resource for researchers interested in harnessing the transformative power of gels within these cutting-edge fields. The objective of this review is to raise awareness about the overlooked research potential of gels in optoelectronic materials, which have somewhat diminished in recent years.

Progress of Polycyclic Boron-Doped Molecular Carbons

Molecular carbons, namely molecular cutout of carbon materials, are of importance for understanding accurate structures of carbon allotropes and developing functional π-electron materials. Doping the boron atoms into π-conjugated skeletons of molecular carbons enables the construction of boron-doped molecular carbons (BMCs), further leading to new chemistry and attractive material systems, which are distinct from carbon-based and other heteroatom-doped molecular carbons. Herein, the bottom-up organic synthesis methodologies have been employed to synthesize BMCs that feature the boron atoms at the edge or in the center of π-skeletons. They have not only amazing topological structures and good stability but also intriguing photophysical and electronic properties. Moreover, they have sufficient Lewis acidity and can coordinate with Lewis bases to form Lewis acid–base complexes, which exhibit stimuli-responsive functions. Notably, some of these BMCs can be utilized in the fields of organic reactions, optical and electronic devices, as well as supramolecular chemistry and photothermal materials. In this short review, we aim to highlight the design and synthetic strategies of polycyclic BMCs, and their unique physical properties and practical applications.

New Insight into Nanoscale Identification of the Polar Axis Direction in Organic Ferroelectric Films.

Ferroelectric poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-co-TrFE)] thin films have been deposited by spin-coating onto the Bi0.5Na0.5TiO3(BNT)/LNO/SiO2/Si heterostructure. The copolymer microstructure investigated by using grazing-incidence wide-angle X-ray diffraction (GIWAXD) and deduced from the (200)/(110) reflections demonstrates that the b-axis in the P(VDF-co-TrFE) orthorhombic unit cell is either in the plane or out of the plane, depending on the face-on or on the two types of edge-on (called I and II) lamellar structures locally identified by atomic force microscopy (AFM). For edge-on I lamellae regions, the electroactivity (dzzeff ∼ -50.3 pm/V) is found to be twice as high as that measured for both edge-on II or face-on crystalline domains, as probed by piezoresponse force microscopy (PFM). This result is directly correlated to the direction of the ferroelectric polarization vector in the P(VDF-co-TrFE) orthorhombic cell: larger nanoscale piezoactivity is related to the b-axis which lies along the normal to the substrate plane in the case of the edge-on I domains. Here, the ability to thoroughly gain access to the as-grown polar axis direction within the edge-on crystal lamellae of the ferroelectric organic layers is evidenced by combining the nanometric resolution of the PFM technique with a statistical approach based on its spectroscopic tool. By the gathering of information at the nanoscale, two orientations for the polar b-axis are identified in edge-on lamellar structures. These findings contribute to a better understanding of the structure-property relationships in P(VDF-co-TrFE) films, which is a key issue for the design of future advanced organic electronic devices.

Overcoming Downscaling Limitations in Organic Semiconductors: Strategies and Progress.

Organic semiconductors have great potential to revolutionize electronics by enabling flexible and eco-friendly manufacturing of electronic devices on plastic film substrates. Recent research and development led to the creation of printed displays, radio-frequency identification tags, smart labels, and sensors based on organic electronics. Over the last 3 decades, significant progress has been made in realizing electronic devices with unprecedented features, such as wearable sensors, disposable electronics, and foldable displays, through the exploitation of desirable characteristics in organic electronics. Neverthless, the down-scalability of organic electronic devices remains a crucial consideration. To address this, efforts are extensively explored. It is of utmost importance to further develop these alternative patterning methods to overcome the downscaling challenge. This review comprehensively discusses the efforts and strategies aimed at overcoming the limitations of downscaling in organic semiconductors, with a particular focus on four main areas: 1) lithography-compatible organic semiconductors, 2) fine patterning of printing methods, 3) organic material deposition on pre-fabricated devices, and 4) vertical-channeled organic electronics. By discussing these areas, the full potential of organic semiconductors can be unlocked, and the field of flexible and sustainable electronics can be advanced.

Organic Electronics-Microfluidics/Lab on a Chip Integration in Analytical Applications.

Organic electronics (OE) technology has matured in displays and is advancing in solid-state lighting applications. Other promising and growing uses of this technology are in (bio)chemical sensing, imaging, in vitro cell monitoring, and other biomedical diagnostics that can benefit from low-cost, efficient small devices, including wearable designs that can be fabricated on glass or flexible plastic. OE devices such as organic LEDs, organic and hybrid perovskite-based photodetectors, and organic thin-film transistors, notably organic electrochemical transistors, are utilized in such sensing and (bio)medical applications. The integration of compact and sensitive OE devices with microfluidic channels and lab-on-a-chip (LOC) structures is very promising. This survey focuses on studies that utilize this integration for a variety of OE tools. It is not intended to encompass all studies in the area, but to present examples of the advances and the potential of such OE technology, with a focus on microfluidics/LOC integration for efficient wide-ranging sensing and biomedical applications.

Gamma irradiation-induced changes in structural, linear/nonlinear optical, and optoelectrical properties of PVB/BiVO4 nanocomposite for organic electronic devices

Herein, nanocomposite films based on polyvinyl butyral (PVB) and BiVO4 plates were synthesized through solution casting. The present study aims to investigate the impact of varying doses of gamma irradiation (0, 15, 30, 60, and 90 kGy) on the structural, dispersion, linear/nonlinear optical, and optoelectrical properties of PVB/BiVO4 nanocomposite films. The effects of gamma irradiation on various optical characteristics, such as refractive index (n), extinction coefficient (k), and other related parameters, have been observed. The study of dielectric behavior and the derivation of optoelectrical parameters, including high-frequency dielectric constant (ε∞), plasma frequency (ωP), relaxation time (τ), and optical mobility (µopt.), were conducted using the real and imaginary parts of the dielectric constants εr and εi. In addition, the linear optical susceptibility (χ(1)), the third-order nonlinear optical susceptibility (χ(3)), and the nonlinear refractive index (n2) were studied as a function of gamma irradiation doses. Furthermore, the results demonstrate that the average oscillator wavelength (λ0) values, oscillator strength (S0), and optical conductivity (σopt) vary significantly after gamma radiation treatment. Overall, the strong correlations between the linear/nonlinear optical and optoelectrical parameters of the irradiated PVB/BiVO4 nanocomposite films make them suitable for application in flexible organic electronic devices.

Fused-Ring Electron-Acceptor Single Crystals with Chiral 2D Supramolecular Organization for Anisotropic Chiral Optoelectronic Devices.

Supramolecular chiral organization gives π-conjugated molecules access to fascinating specific interactions with circularly polarized light (CPL). Such a feature enables the fabrication of high-performance chiral organic electronic devices that detect or emit CPL directly. Herein, it is shown that chiral fused-ring electron-acceptor BTP-4F single-crystal-based phototransistors demonstrate distinguished CPL discrimination capability with current dissymmetry factor exceeding 1.4, one of the highest values among state-of-the-art direct CPL detectors. Theoretical calculations prove that the chirality at the supramolecular level in these enantiomeric single crystals originates from chiral exciton coupling of a unique quasi-2Dsupramolecular organization consisting of interlaced molecules with opposite helical conformation. Impressively, such supramolecular organization produces a higher dissymmetry factor along the preferred growth direction of the chiral single crystals in comparison to that of the short axis direction. Furthermore, the amplified, inverted, and also anisotropic current dissymmetry compared to optical dissymmetry is studied by finite element simulations. Therefore, a unique chiral supramolecular organization that is responsible for the excellent chiroptical response and anisotropic electronic properties is developed, which not only enables the construction of high-performance CPL detection devices but also allows a better understanding of the structure-property relationships in chiral organic optoelectronics.

Effects of source/drain electrode thickness on water-induced instability of laminated organic single-crystal field-effect transistors

Water is known to be the main cause of operational instability in organic electronic devices under ambient conditions. The water-induced hysteresis of lithography-friendly bottom-gate-bottom-contact-type organic field-effect transistors (FETs) with a laminated single-crystal channel was investigated using varying electrode thicknesses. As the amount of water in the air gap enveloped by the semiconductor layer and insulating substrate, adjacent to the electrode, increases, the mechanism dominating the hysteresis phenomenon shifted in the following order: (1) current increase owing to the decreasing charge-injection barrier because of a drain-induced change in the electrode work function, (2) current decrease because of the gate bias stress, and (3) current increase because of the gate enhancement effect owing to the dipole orientation of the water molecules penetrating the semiconductor-insulator interface. Changes in the electrode thickness had the same effect on the hysteretic behavior as the relative humidity of the experimental environment. Thus, this study provides a comprehensive understanding of the water-induced operational instability of laminated organic single-crystal FETs and should aid the realization of stable-operation organic devices, as well as foreign-molecule sensors, by controlling the electrode thickness.

Synaptic transistor based on PVK mixed with oxadiazole and its logic gate application

Because of the simplicity of device integration, high energy efficiency, and the ability to achieve robust neuromorphic calculation, the explore of artificial synaptic devices has attracted extensive attention. In this work, an electronic synaptic organic transistor based on a mixture of p-type polymer and n-type small molecule semiconductor colloids by spin coating was designed to achieve synaptic plasticity. Typical synaptic behavior, including excitatory postsynaptic current and paired-pulse facilitation, is simulated using electrical impulse stimulation. In addition, the transition from short-term plasticity to long-term plasticity were realized by adjusting input pulse operation. More importantly, the logic function of “AND” and “NAND” gate is designed and realized based on the operability of organic transistor pulse modulation. Our work offers a new approach for the exploitation of organic multifunctional neuromorphic electronic devices.

Surface Modification of ITO with N-Heterocyclic Carbene Precursors Results in Electron Selective Contacts in Organic Photovoltaic Devices.

Surface modification of indium tin oxide (ITO) electrodes with organic molecules is known to tune their work function which results in higher charge carrier selectivity in corresponding organic electronic devices and hence influences the performance of organic solar cells. In recent years, N-heterocyclic carbenes (NHCs) have also been proven to be capable to modify the work function of metals and semimetals compared to the unfunctionalized surface via the formation of strong covalent bonds. In this report, we have designed and performed the modification of the ITO surface with NHC by using the zwitterionic bench stable IPr-CO2 as the NHC precursor, applied via spin coating. Upon modification, the work function of ITO electrodes was reduced significantly which resulted in electron selective contacts in corresponding organic photovoltaic devices. In addition, various characterization techniques and analytical methods are used to elucidate the nature of the bound species and the corresponding binding mechanism of the material to the ITO surface.