Organic Devices Research Articles

A Rigid Multiple Resonance Thermally Activated Delayed Fluorescence Core Toward Stable Electroluminescence and Lasing

AbstractThe investigation of organic light‐emitting diodes (OLEDs) and organic laser devices with thermally activated delayed fluorescence (TADF) molecules is emerging due to the potential of harnessing triplets. In this work, a boron/nitrogen multiple‐resonance TADF polycyclic framework fusing carbazole units (CzBNPh) was proposed. CzBNPh exhibited a narrowband emission (<30 nm), a unity photoluminescence quantum yield, and a fast radiative rate. Consequently, CzBNPh demonstrated a low distributed feedback (DFB) lasing threshold of 0.68 μJ cm−2. Furthermore, the stimulated emission zone of CzBNPh was effectively separated from its singlet and triplet absorption, thereby minimizing the singlet‐triplet annihilation under long‐pulsed excitation ranging from 20 μs to 2.5 ms. Significantly, the enhanced rigid molecular conformation, thermal stability, and photo‐stability resulted in improved lasing and electroluminescence stability compared to that of 5,9‐diphenyl‐5,9‐diaza‐13b‐boranaphtho[3,2,1‐de]anthracene (DABNA)‐core. These findings indicate the potential of CzBN‐core as a promising framework for achieving long‐pulsed wave and electrically‐pumped lasing in the future.

Boosting the generality of catalytic systems by the synergetic ligand effect in Pd-catalyzed C-N cross-coupling

In the areas of catalysis and organic chemistry, the development of versatile and efficient catalytic systems has long been a challenge, primarily due to the intricate relationship between ligands and transition metal centers. This study addresses this challenge by exploring the concept of ligand synergy to enhance the generality of catalytic systems, a crucial metric for their practical utility. By combining N-heterocyclic carbene (NHC) and phosphine ligands, we unveil a novel catalytic system that exhibits high level of generality in the Buchwald-Hartwig cross-coupling reaction. Our findings not only demonstrate the enhanced efficiency of this system, leading to the synthesis of valuable compounds with applications in organic electroluminescent devices and the pharmaceutical industry, but also shed light on the broader potential of ligand synergy in catalysis. Through machine learning analysis, we uncover the critical role of specific ligand properties, further paving the way for rational catalyst design.

Selective Detection of Functionalized Carbon Particles based on Polymer Semiconducting and Conducting Devices as Potential Particulate Matter Sensors.

This paper reports a new mechanism for particulate matter detection and identification. Three types of carbon particles are synthesized with different functional groups to mimic the real particulates in atmospheric aerosol. After exposing polymer-based organic devices in organic field effect transistor (OFET) architectures to the particle mist, the sensitivity and selectivity of the detection of different types of particles are shown by the current changes extracted from the transfer curves. The results indicate that the sensitivity of the devices is related to the structure and functional groups of the organic semiconducting layers, as well as the morphology. The predominant response is simulated by a model that yielded values of charge carrier density increase and charge carriers delivered per unit mass of particles. The research points out that polymer semiconductor devices have the ability to selectively detect particles with multiple functional groups, which reveals a future direction for selective detection of particulate matter.

Impact of Intermittent Deposition on Spontaneous Orientation Polarization of Organic Amorphous Films Revealed by Rotary Kelvin Probe.

The control of the molecular orientation and resultant polarization is essential for improving the performance of organic optoelectronic devices. Conventionally, the substrate temperature and deposition rate are tuned to control the molecular orientation of vapor-deposited films. In this study, we proposed a novel method, referred to as "intermittent deposition", in which the polarization direction and magnitude are controlled by introducing intervals during physical vapor deposition. The rotary Kelvin probe measurement of the Alq3 and TPBi films clearly showed a time-dependent decrease in the surface potential owing to the surface relaxation of the molecular orientation immediately after deposition. Through a series of intermittent depositions, in which the deposition shutter is repeatedly opened and closed at certain intervals, a relaxed surface layer was built up, and we could control the polarization magnitude. For the Alq3 film, even the polarization direction was switched. The proposed new deposition method is applicable to general organic molecules, not limited to polar molecules, thereby potentially tuning the conduction properties of organic devices and fabricating novel devices.

Designing Organic and Hybrid Surfaces and Devices with Initiated Chemical Vapor Deposition (iCVD).

The initiated chemical vapor deposition (iCVD) technique is an all-dry method for designing organic and hybrid polymers. Unlike methods utilizing liquids or line-of-sight arrival, iCVD provides conformal surface modification over intricate geometries. Uniform, high-purity, and pinhole-free iCVD films can be grown with thicknesses ranging from >15µm to <5nm. The mild conditions permit damage-free growth directly onto flexible substrates, 2D materials, and liquids. Novel iCVD polymer morphologies include nanostructured surfaces, nanoporosity, and shaped particles. The well-established fundamentals of iCVD facilitate the systematic design and optimization of polymers and copolymers. The functional groups provide fine-tuning of surface energy, surface charge, and responsive behavior. Further reactions of the functional groups in the polymers can yield either surface modification, compositional gradients through the layer thickness, or complete chemical conversion of the bulk film. The iCVD polymers are integrated into multilayer device structures as desired for applications in sensing, electronics, optics, electrochemical energy storage, and biotechnology. For these devices, hybrids offer higher values of refractive index and dielectric constant. Multivinyl monomers typically produce ultrasmooth and pinhole-free and mechanically deformable layers and robust interfaces which are especially promising for electronic skins and wearable optoelectronics.

Enhancing Piezoelectricity of Silk Fibroin Through In Situ Growth of Metal‐Free Perovskite for Organic and Eco‐friendly Wearable Bioelectronics

AbstractThe biosafety and sustainability of inorganic perovskites or organic piezopolymers is a major concern in the field of wearable piezoelectric sensors. Naturally occurring, silk fibroin (SF), is a promising alternative for the realization of organic piezoelectric devices due to its excellent biocompatibility and tunable material properties. Nevertheless, its scope for practical sensing applications is limited by the weak innate piezoelectricity of 1 pC N−1. This research aims to improve the piezoelectricity of pristine SF by intrinsically growing non‐toxic metal‐free perovskite (MFP) to achieve organic and bendable silk fibroin‐metal free perovskite (SF‐MFP) composite films. The increase in MFP loading has an influence on the resulting morphology and crystallinity of SF‐MFP films. In comparison to pristine SF, the films with the highest perovskite loading exhibit an enhanced normal piezoelectric response of 4.6 pm V−1. The poled SF‐MFP sensors display an appreciable sensitivity of 0.61 ± 0.05 V N−1 with a fast response time and outstanding stability arising from a synergistic combination of mechanically robust SF and piezoelectric MFP. Furthermore, these sensors can detect various joint bending and muscle movements in human subjects, proving their suitability for wearable bioelectronics. This research demonstrates the potential of biomaterials and organic perovskites for the development of biocompatible and sustainable wearable piezoelectric solutions.

Advances in flexible inorganic thermoelectrics

AbstractSolid‐state bismuth telluride‐based thermoelectric devices enable the generation of electricity from temperature differences and have been commercially applied in various fields. However, in many scenarios, the surface of the heat source is not flat. Therefore, it is crucial to develop flexible thermoelectric materials and devices to efficiently utilize heat sources and expand their applications. Compared with organic thermoelectric materials and devices, inorganic flexible thermoelectric materials and devices have much higher thermoelectric performance and stability. Considering the rapid development in this research field, we carefully summarize the design principles, structures, and thermoelectric properties of inorganic flexible materials and their devices reported in the recent 3 years, including sulfides, selenides, tellurides, and composite materials designed based on these inorganics. The structural designs of flexible thermoelectric devices based on micro‐sized bulk materials are also carefully summarized. Additionally, we overview the mechanical stability and methods for reducing internal resistance for designs of inorganic flexible thermoelectric devices. In the end, we provide outlooks on future research directions for inorganic flexible thermoelectric materials and devices. This review will help guide thermoelectric researchers, beginners, and students.

Surface enthalpy recovery/relaxation of organic films determined by Mg deposition property

Estimating the surface glass transition temperature (T g) of materials is important for making organic devices by vacuum evaporation because the surface T g affects the interface of layered devices and their performance. The enthalpy state of organic films is related to T g. Bulk T g is ordinarily measured by differential scanning calorimetry (DSC), although there is no established method for measuring the surface T g. The Mg deposition property reflects the surface T g; no Mg deposition denotes a low surface T g. In this study, we investigated how annealing affects the bulk and surface T g of N,N′-Bis-(1-naphthalenyl)-N,N′-bis-phenyl-(1,1′-biphenyl)-4,4′-diamine (NPB) using DSC and the Mg deposition properties. For bulk NPB, enthalpy relaxation occurred after annealing at a temperature below T g. On the other hand, for vacuum-deposited NPB film, the enthalpy was in a relaxed state just after preparation, although the surface’s enthalpy recovered by annealing at same condition, as identified by the Mg deposition property.

Organic Optoelectronic Materials: A Rising Star of Bioimaging and Phototherapy.

Recently, many organic optoelectronic materials (OOMs), especially those used in organic light-emitting diodes (OLEDs), organic solar cells (OSCs), and organic field-effect transistors (OFETs), are explored for biomedical applications including imaging and photoexcited therapies. In this review,recently developed OOMs for fluorescence imaging, photoacoustic imaging, photothermal therapy, and photodynamic therapy, are summarized. Relationships between their molecular structures, nanoaggregation structures, photophysical mechanisms, and properties for various biomedical applications are discussed. Mainly four kinds of OOMs are covered: thermally activated delayed fluorescence materials in OLEDs, conjugated small molecules and polymers in OSCs, and charge-transfer complexes in OFETs. Based on the OOMs unique optical properties, including excitation light wavelength and exciton dynamics, they are respectively exploited for suitable biomedical applications. This review is intended to serve as a bridge between researchers in the area of organic optoelectronic devices and those in the area of biomedical applications. Moreover, it provides guidance for selecting or modifying OOMs for high-performance biomedical uses. Current challenges and future perspectives of OOMs are also discussed with the hope of inspiring further development of OOMs for efficient biomedical applications.

A drift‐diffusion based electrothermal model for organic thin‐film devices including electrical and thermal environment

AbstractWe derive and investigate a stationary model for the electrothermal behavior of organic thin‐film devices including their electrical and thermal environment. Whereas the electrodes are modeled by Ohm's law, the electronics of the organic device itself is described by a generalized van Roosbroeck system with temperature‐dependent mobilities and using Gauss–Fermi integrals for the statistical relation. The currents give rise to Joule heat which together with the heat generated by the generation/recombination of electrons and holes in the organic device occur as source terms in the heat flow equation that has to be considered on the whole domain. The crucial task is to establish that the quantities in the transfer conditions at the interfaces between electrodes and the organic semiconductor device have sufficient regularity. Therefore, we restrict the analytical treatment of the system to two spatial dimensions. We consider layered organic structures, where the physical parameters (total densities of transport states, reference energy levels , disorder parameter, basic mobilities, activation energies, relative dielectric permittivity, heat conductivity) are piecewise constant, and we work in a setting for some . We prove the existence of weak solutions using Schauder's fixed point theorem and a regularity result for strongly coupled systems with nonsmooth data and mixed boundary conditions that is verified by Caccioppoli estimates and a Gehring‐type lemma.

Asymmetric Schottky Barrier in Rubrene Transistor via Monolayer Graphene Insertion toward Self-Powered Imaging

Organic semiconductor materials featuring lightweight, and flexibility may play a significant role in various future applications, such as foldable displays, wearable devices, and artificial skin. For developing high-performance organic devices, organic crystals are highly desired, while a remaining fundamental issue is their contact problem. Here, we have grown a high-quality rubrene single crystal by utilizing a simple in-air sublimation technique. The contact characteristics (barrier height and contact resistance) are detail-studied by resist-free transfer electrodes (Au metal or graphene/Au). The Schottky barrier of the rubrene/graphene interface is lower and can be also modulated by gate bias, which is confirmed by spatial photocurrent mapping. Finally, we demonstrated the zero-bias photocurrent imaging application by constructing the asymmetrical device employing different electrode contacts. Our work would be of significance for studying the contact issue of organic crystals and wireless imaging.

An ultrasmall organic synapse for neuromorphic computing

High‐performance organic neuromorphic devices with miniaturized device size and computing capability are essential elements for developing brain‐inspired humanoid intelligence technique. However, due to the structural inhomogeneity of most organic materials, downscaling of such devices to nanoscale and their high‐density integration into compact matrices with reliable device performance remain challenging at the moment. Herein, based on the design of a semicrystalline polymer PBFCL10 with ordered structure to regulate dense and uniform formation of conductive nanofilaments, we realize an organic synapse with the smallest device dimension of 50 nm and highest integration size of 1 Kb reported thus far. The as‐fabricated PBFCL10 synapses can switch between 32 conductance states linearly with a high cycle‐to‐cycle uniformity of 98.89% and device‐to‐device uniformity of 99.71%, which are the best results of organic devices. A mixed-signal neuromorphic hardware system based on the organic neuromatrix and FPGA controller is implemented to execute spiking‐plasticity‐related algorithm for decision-making tasks.

Organic Excitonic State Management by Surface Metallic Coupling of Inorganic Lanthanide Nanocrystals

AbstractThe ability to harness charges and spins for control of organic excitonic states is critical in developing high‐performance organic luminophores and optoelectronic devices. Here we report a facile strategy to efficiently manipulate the electronic energy states of various organic phosphors by coupling them with inorganic lanthanide nanocrystals. We show that the metallic atoms exposed on the nanocrystal surface can introduce strong coupling effects to 9‐(4‐ethoxy‐6‐phenyl‐1,3,5‐triazin‐2‐yl)‐9H‐carbazole (OCzT) and some organic chromophores with carbazole functional groups when the organics are approaching the nanocrystals. This unconventional organic–inorganic hybridization enables a nearly 100 % conversion of the singlet excitation to fast charge transfer luminescence that does not exist in pristine organics, which broadens the utility of organic phosphors in hybrid systems.

Organic Excitonic State Management by Surface Metallic Coupling of Inorganic Lanthanide Nanocrystals.

The ability to harness charges and spins for control of organic excitonic states is critical in developing high-performance organic luminophores and optoelectronic devices. Here we report a facile strategy to efficiently manipulate the electronic energy states of various organic phosphors by coupling them with inorganic lanthanide nanocrystals. We show that the metallic atoms exposed on the nanocrystal surface can introduce strong coupling effects to 9-(4-ethoxy-6-phenyl-1,3,5-triazin-2-yl)-9H-carbazole (OCzT) and some organic chromophores with carbazole functional groups when the organics are approaching the nanocrystals. This unconventional organic-inorganic hybridization enables a nearly 100 % conversion of the singlet excitation to fast charge transfer luminescence that does not exist in pristine organics, which broadens the utility of organic phosphors in hybrid systems.

Multifunctional Organic Polymer Synaptic Devices for Artificial Nociceptor and Health Monitoring System

Multifunctional Organic Polymer Synaptic Devices for Artificial Nociceptor and Health Monitoring System

Microregion Characterization of Grain Boundary Defects and Electron Capture of CsPbI2Br Perovskite

All‐inorganic CsPbI2Br perovskite solar cell shows superior thermal stability, but the power conversion efficiency falls behind organic devices, due to the existence of abundant defects. Halogen and metal ions at the grain boundaries induce the formation of defect states, which increases the probability of carrier recombination. Grain boundaries are also the channels of ion migration. Herein, as relatively simple interface engineering strategy is used at the molecular level, using a multifunctional 2,5‐thiophene dicarboxylic acid to passivate the interface between the perovskite surface and the carbon electrode. The 2,5‐thiophene dicarboxylic acid can effectively coordinate the undercoordinated Pb2+, reduce the defect concentration of perovskite, and suppress the nonradiative recombination. The device with carbon electrode exhibits a power conversion efficiency of 13.4%. The microscopic passivation mechanism is investigated by Kelvin probe force microscopy. It is observed that the surface treatment effectively passivates the defects at the grain boundary and reduces the capture rate of photogenerated carriers of the grain boundary.

Oxygen-Induced Lattice Strain for High-Performance Organic Transistors with Enhanced Stability.

Integrating the merits of low cost, flexibility, and large-area processing, organic semiconductors (OSCs) are promising candidates for the next-generation electronic materials.The mobility and stability are the key figures of merit for its practical application. However, it is greatly challenging to improve the mobility and stability simultaneously owing to the weak interactions and poor electronic coupling between OSCs molecules. Here, an oxygen-induced lattice strain (OILS) strategy is developed to achieve OSCs with both high mobility and high stability. Utilizing the strategy, the maximum mobility of dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) organic field-effect transistor (OFET) rises to 15.3cm2 V-1 s-1 and the contact resistance lowers to 25.5Ωcm. Remarkably, the thermal stability of DNTT is much improved, and a record saturated power density of ≈3.4×104 Wcm-2 is obtained. Both the experiments and theoretical calculations demonstrate that the lattice compressive strain induced by oxygen is responsible for their high performance and stability. Furthermore, the universality of the strategy is manifested in both n-type and p-type small OSCs. This work provides a novel strategy to improve both the mobility and the stability of OSCs, paving the way for the practical applications of organic devices.

Evaluating energy generation of a building-integrated organic photovoltaic vertical façade: A case study of Latin America's pioneering installation

Building-integrated photovoltaics play a key role in the reduction of greenhouse gases emission towards sustainability in the building and construction sector. Organic solar technology holds several advantages such as lightweight, flexibility and semitransparency, suiting well for this type of application. When integrated into windows and facades, it provides a dual benefit: it acts as a solar radiation barrier, improving indoor thermal comfort, while also generating off-grid power. Besides that, organic devices are known to be more efficient than traditional photovoltaics based in silicon in diffuse and low light conditions. Nevertheless, only a few studies have been conducted in the area employing large-area commercial modules, in real operational conditions and for a long-term period. This work has the purpose of reducing this gap and shine a light on this debate bringing an analysis based on real data of a set of organic panels laminated in glass in a vertical pioneer installation in Latin America. For this, several linear regression models were tested to predict the energy generation from meteorological data and solar position throughout four years of operation, and the best models developed achieved 0.76 and 0.81 values for R2 with validation data, respectively for simple and multiple regressions. A visual analysis showed that the OPV system produced more energy in winter due to lower solar altitude, despite lower global radiation levels. The most significant variables in the models were the global solar radiation and the solar altitude. The use of glass lamination and vertical orientation likely preserved the performance of the panels, keeping energy generation consistent over four years, akin to the first year.

Uncovering the Electronic State Interplay at Metal Oxide Electron Transport Layer/Nonfullerene Acceptor Interfaces in Stable Organic Photovoltaic Devices.

The implementation of sputter-deposited TiOx as an electron transport layer in nonfullerene acceptor-based organic photovoltaics has been shown to significantly increase the long-term stability of devices compared to conventional solution-processed ZnO due to a decreased photocatalytic activity of the sputtered TiOx. In this work, we utilize synchrotron-based photoemission and absorption spectroscopies to investigate the interface between the electron transport layer, TiOx prepared by magnetron sputtering, and the nonfullerene acceptor, ITIC, prepared in situ by spray deposition to study the electronic state interplay and defect states at this interface. This is used to unveil the mechanisms behind the decreased photocatalytic activity of the sputter-deposited TiOx and thus also the increased stability of the organic solar cell devices. The results have been compared to similar measurements on anatase TiOx since anatase TiOx is known to have a strong photocatalytic activity. We show that the deposition of ITIC on top of the sputter-deposited TiOx results in an oxidation of Ti3+ species in the TiOx and leads to the emergence of a new O 1s peak that can be attributed to the oxygen in ITIC. In addition, increasing the thickness of ITIC on TiOx leads to a shift in the O 1s and C 1s core levels toward higher binding energies, which is consistent with electron transfer at the interface. Resonant photoemission at the Ti L-edge shows that oxygen vacancies in sputtered TiOx lie mostly in the surface region, which contrasts the anatase TiOx where an equal distribution between surface and subsurface oxygen vacancies is observed. Furthermore, it is shown that the subsurface oxygen vacancies in sputtered TiOx are strongly reduced after ITIC deposition, which can reduce the photocatalytic activity of the oxide, while the oxygen vacancies in model anatase TiOx are not affected upon ITIC deposition. This difference can explain the inferior photocatalytic activity of the sputter-deposited TiOx and thus also the increased stability of devices with sputter-deposited TiOx used as an electron transport layer.

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.