Organic Semiconductors Research Articles

Effective redox reaction in a three-body smart photocatalyst through multi-interface modulation of organic semiconductor junctioned with metal and inorganic semiconductor

Forming metal/semiconductor heterojunctions is a well-known strategy to enhance photo-reaction through interface band bending. However, challenges remain in simultaneously minimizing fast charge carrier recombination and avoiding potential photo-corrosion in photocatalysts for high efficiency and long lifetime application in energy, environment, and green chemistry. We here design and propose a new strategy by which multi-interface band structure modulation occurs in a three-body photocatalyst, exemplified by Ag/PDA@Ag2S (PDA: polydopamine). Experimental analyses including in-situ x-ray photoelectron spectroscopy (XPS) and time-resolved photoluminescence (TRPL) spectroscopy together with projected density of states studies suggest an S-scheme heterojunction formation in the PDA@Ag2S, which greatly enhances the separation of photogenerated carriers. Consequently, we demonstrate that this multibody photocatalyst exhibits superior stability and selective oxidation of a series of ionic dyes under solar-simulated irradiation. The hydrogen generation efficiency (reduction) is also remarkably enhanced compared to virgin Ag/Ag2S photocatalysts. We believe this work brings a new insight into catalyst design.

Is the field of organic thermoelectrics stuck?

With the rising popularity of organic thermoelectrics, the interest in doping strategies for organic semiconductors has increased strongly over the last decade. Here, we use aggregate data to discuss how far the approaches pursued till date have brought the community in terms of typical performance indicators for doped semiconductors in the context of thermoelectric applications. Surprisingly, despite the superlinear increase in the number of publications on the subject matter, the performance indicators show no clear upward trend in the same time range. In the second part, we discuss possible approaches to break this deadlock. A specifically promising approach, controlling the distribution of dopant atoms in the host material, is discussed in some quantitative detail by experiments and numerical simulations. We show that spontaneous modulation doping, that is, the spatial separation between static dopant ions and mobile charge carriers, leads to a dramatic conductivity increase at low dopant loading.Graphical abstract

Electrical Doping of Metal Halide Perovskites by Co-evaporation and Application in PN Junctions.

Electrical doping of semiconductors is a revolutionary development that enabled many electronic and optoelectronic technologies. While doping of many inorganic and organic semiconductors has been well-established, controlled electrical doping of metal halide perovskites is yet to be demonstrated. In this work, we achieve efficient n- and p-type electrical doping of metal halide perovskites by co-evaporating the perovskite precursors alongside organic dopant molecules. We demonstrate that the Fermi level can be shifted by up to 500 meV towards the conduction band and by up to 400 meV towards the valence band by n- and p-doping, respectively, which increases the conductivity of the films. The doped layers were employed in PN and NP diodes, showing opposing trends in rectification. Demonstrating controlled electrical doping by a scalable, industrially relevant deposition method opens the route to developing perovskite devices beyond solar cells, such as thermoelectrics or complementary logic. This article is protected by copyright. All rights reserved.

Carrier Transport Switching of Ferroelectric BTBT Derivative.

Alkylamide-substituted [1]benzothieno[3,2-b][1]benzothiophene (BTBT) derivative of BTBT-NHCOC14H29 (1), which has ferroelectric N-H···O= hydrogen-bonding network of alkylamide group and two-dimensional (2D) electric structure of BTBT π-cores, was prepared to design the external electric field-responsive organic semiconductors. The short-chain derivative of BTBT-NHCOC3H7 (1') revealed the coexistence of a 2D electronic band structure based on the herringbone BTBT arrangement and the one-dimensional (1D) hydrogen-bonding chain. 1 formed a smectic E (SmE) liquid crystal phase above 412 K and showed ferroelectric hysteresis in the electric field-polarization (P-E) curves at 403-433 K. The remanent polarization (Pr) and coercive electric field (Ec) of 1 at 408 K, 0.1 Hz were 24.0 μC cm-2 and 5.54 V μm-1, respectively. By thermal annealing of thin-film 1 at 443 K, the molecular assembly structure of 1 changed from a monolayer to a bilayer structure with high crystallinity, resulting in conducting layers of BTBT parallel to the substrate surface. The organic field-effect transistor (OFET) device with thermally annealed thin-film 1 showed p-type semiconducting behavior with the hole mobility of 1.0 × 10-3 cm2 V-1 s-1. Furthermore, device 1 showed switching behavior of semiconducting properties by electric field poling and thermal annealing cycle. The electric field response of ferroelectrics modulated the molecular orientation and conduction properties of organic semiconductors, resulting in external electric field control of carrier transport properties.

Molecular Electronics: From Nanostructure Assembly to Device Integration.

Integrated electronics and optoelectronics based on organic semiconductors have attracted considerable interest in displays, photovoltaics, and biosensing owing to their designable electronic properties, solution processability, and flexibility. Miniaturization and integration of devices are growing trends in molecular electronics and optoelectronics for practical applications, which requires large-scale and versatile assembly strategies for patterning organic micro/nano-structures with simultaneously long-range order, pure orientation, and high resolution. Although various integration methods have been developed in past decades, molecular electronics still needs a versatile platform to avoid defects and disorders due to weak intermolecular interactions in organic materials. In this perspective, a roadmap of organic integration technologies in recent three decades is provided to review the history of molecular electronics. First, we highlight the importance of long-range-ordered molecular packing for achieving exotic electronic and photophysical properties. Second, we classify the strategies for large-scale integration of molecular electronics through the control of nucleation and crystallographic orientation, and evaluate them based on factors of resolution, crystallinity, orientation, scalability, and versatility. Third, we discuss the multifunctional devices and integrated circuits based on organic field-effect transistors (OFETs) and photodetectors. Finally, we explore future research directions and outlines the need for further development of molecular electronics, including assembly of doped organic semiconductors and heterostructures, biological interfaces in molecular electronics and integrated organic logics based on complementary FETs.

Carbon Quantum Dots Confined into Covalent Triazine Frameworks for Efficient Overall Photocatalytic H2O2 Production

AbstractPorous organic polymers have an outstanding performance in the field of photocatalysis with the advantage of diverse structure composition and purposeful molecular design. However, the inherent high impedance and poor electrical conductivity of organic semiconductors still restrict the charge transfer efficiency and thus discount the photocatalytic performance. Herein, the study reports a highly conductive covalent triazine framework (CTF) loading carbon quantum dots (CQDs) into porous as electron transport medium. The addition of CQDs (0.5 wt%) can enhance the electronic conductivity of CTF by tenfold. In addition, the as‐prepared CQD‐CTFs express much‐promoted charge separation and transfer efficiency. Furthermore, the embedded CQDs can improve the oxidization capacity and increase the affinity of H+ due to the more negative zeta potential. The enhanced oxidizing ability and increased H+ affinity are positive for water oxidation reaction (WOR) and oxygen reduction reaction (ORR) process in hydrogen peroxide (H2O2) generation, respectively. The optimized CQD‐CTF exhibits a high H2O2 generation rate of up to 1036 µmol g−1 h−1 in pure water without any sacrificial agent under visible light, which is 4.6 times than pristine CTF. This work provides a new idea for efficient H2O2 production of organic semiconductors.

High-Performance Room Temperature Ammonia Sensors Based on Pure Organic Molecules Featuring B-N Covalent Bond.

Exploring organic semiconductor gas sensors with high sensitivity and selectivity is crucial for the development of sensor technology. Herein, for the first time, a promising chemiresistive organic polymer P-BNT based on a novel π-conjugated triarylboron building block is reported, showcasing an excellent responsivity over 30000 (Ra/Rg) against 40ppm of NH3 , which is ≈3300 times higher than that of its B-N organic small molecule BN-H. More importantly, a molecular induction strategy to weaken the bond dissociation energy between polymer and NH3 caused by strong acid-base interaction is further executed to optimize the response and recovery time. As a result, the BN-H/P-BNT system with rapid response and recovery times can still exhibit a high responsivity of 718, which is among the highest reported NH3 chemiresistive sensors. Supported by in situ FTIR spectroscopy and theoretical calculations, it is revealed that the N-H fractions in BN-H small molecule promoted the charge distribution on phenyl groups, which increases charge delocalization and is more conducive to gas adsorption in such molecular systems. Notably, these distinctive small molecules also promoted charge transfer and enhanced electron concentration of the P-BNT sensing polymer, thus achieving superior B-N-containing organic molecules with excellent sensing performance.

Self-Assembly of Organic Semiconductors on Strained Graphene under Strain-Induced Pseudo-Electric Fields.

Graphene is used as a growth template for van der Waals epitaxy of organic semiconductor (OSC) thin films. During the synthesis and transfer of chemical-vapor-deposited graphene on a target substrate, local inhomogeneities in the graphene-in particular, a nonuniform strain field in the graphene template-can easily form, causing poor morphology and crystallinity of the OSC thin films. Moreover, a strain field in graphene introduces a pseudo-electric field in the graphene. Here, the study investigates how the strain and strain-induced pseudo-electric field of a graphene template affect the self-assembly of π-conjugated organic molecules on it. Periodically strained graphene templates are fabricated by transferring graphene onto an array of nanospheres and then analyzed the growth and nucleation behavior of C60 thin films on the strained graphene templates. Both experiments and a numerical simulation demonstrated that strained graphene reduced the desorption energy between the graphene and the C60 molecules and thereby suppressed both nucleation and growth of the C60 . A mechanism is proposed in which the strain-induced pseudo-electric field in graphene modulates the binding energy of organic molecules on the graphene.

Removing trace oxygen to obtain truly intrinsic transport in organic semiconductors

Removing trace oxygen to obtain truly intrinsic transport in organic semiconductors

Fluorenone‐Based Covalent Triazine Frameworks/Twinned Zn0.5Cd0.5S S‐scheme Heterojunction for Efficient Photocatalytic H2 Evolution

AbstractPhotocatalytic hydrogen evolution reaction (HER) is a very promising and sustainable technology, yet precisely exploring effective HER photocatalysts remains a critical challenge due to the rapid charge recombination. In this work, a brand‐new S‐scheme heterojunction is successfully designed and constructed by in situ growth of twinned Zn0.5Cd0.5S Solid Solution (CZS) on a novel fluorenone‐based covalent triazine framework (FOCTF). The S‐scheme heterojunctions is identified via in situ irradiation XPS, and electron spin resonance, which can greatly improve the photocatalytic HER rate and stability. Under illumination, the highest photocatalytic HER rate of well‐designed CZS‐FOCTF is 247.62 mmolg−1h−1, 3.83 times as high as that of pure CZS. Experimental and theoretical investigations corroborate that the new FOCTF has a well‐matched staggered band alignment and work function difference with CZS. The as‐fabricated CZS‐FOCTF S‐scheme heterojunction can establish a favorable internal electric field, which accelerates the directional S‐scheme charge migration, thereby enhancing the separation and utilization efficiency of carriers. This finding precisely achieves the spatially oriented powerful electron transport and separation at the interfaces of inorganic–organic hybrid heterojunctions. It is thus desirable that this work can furnish an alternative strategy to rationally design new CZS‐based S‐scheme heterojunction photocatalysts based on novel organic oxidation semiconductors for diversified photocatalytic reactions.

Organic nanowire sensor with seeing, smelling and heat sensation capabilities

Ultra-long high aspect ratio one dimensional (1D) organic semiconductor nanowire is extremely valuable but very challenging to prepare. Based on diacetylene-bridged perylene mono-imide small molecule, scalable 1D nanowire is prepared by simple method, lengths of wires are more than 3 mm and aspect ratios are higher up to ∼9000. Organic flexible conductive wires made devices exhibit good multi-functional sensibilities to light, organic gases and heat. Single wire photodetector shows 80 mA/W responsivity and 3.05×1012 Jones detectivity at 532 nm. Mass-wire sensors demonstrate excellent sensibility, (tetrahydrofuran 0.0166 Ω/ppm; acetone 0.0139 Ω/ppm; ethanol 0.0164 Ω/ppm), low detection limitation and good repeatability to various volatile compounds and sensitive temperature variation response (0.394 mA K−1). The nanowires provide flexible media of sensors for the next generation miniature devices.

Size Isn't Everything: Geometric Tuning in Polycyclic Aromatic Hydrocarbons and Its Implications for Carbon Nanodots.

Recent developments in light-emitting carbon nanodots and molecular organic semiconductors have seen renewed interest in the properties of polycyclic aromatic hydrocarbons (PAHs) as a family. The networks of delocalized π electrons in sp2-hybridized carbon grant PAHs light-emissive properties right across the visible spectrum. However, the mechanistic understanding of their emission energy has been limited due to the ground state-focused methods of determination. This computational chemistry work, therefore, seeks to validate existing rules and elucidate new features and characteristics of PAHs that influence their emissions. Predictions based on (time-dependent) density functional theory account for the full 3-dimensional electronic structure of ground and excited states and reveal that twisting and near-degeneracies strongly influence emission spectra and may therefore be used to tune the color of PAHs and, hence, carbon nanodots. We particularly note that the influence of twisting goes beyond torsional destabilization of the ground-state and geometric relaxation of the excited state, with a third contribution associated with the electric transition dipole. Symmetries and peri-condensation may also have an effect, but this could not be statistically confirmed. In pursuing this goal, we demonstrate that with minimal changes to molecular size, the entire visible spectrum may be spanned by geometric modification alone; we have also provided a first estimate of emission energy for 35 molecules currently lacking published emission spectra as well as clear guidelines for when more sophisticated computational techniques are required to predict the properties of PAHs accurately.

Impact of Photoluminescence Imaging Methodology on Transport Parameters in Semiconductors.

Triplet-triplet annihilation-induced delayed emission provides a pathway for investigating triplets via emission spectroscopy. This bimolecular annihilation depends directly on the transport properties of triplet excitons in disordered organic semiconductors. Photoluminescence (PL) imaging is a direct method for studying exciton and charge-carrier diffusivity. However, most of these studies neglect dispersive transport. Early time scale measurements using this technique can lead to an overestimation of the diffusion coefficient (DT) or diffusion length (Ld). In this study, we investigated the time-dependent triplet DT using PL imaging. We observed an overestimation of Ld in classical delayed PL imaging, often 1 order of magnitude higher than the actual Ld value. We compared various thicknesses of polymeric thin films to study the dispersive nature of triplet excitons. Transient analysis of delayed PL imaging and steady state imaging reveals the importance of considering the time-dependent nature of DT for the triplet excitons in disordered electronic materials.

Assessing molecular doping efficiency in organic semiconductors with reactive Monte Carlo.

The addition of molecular dopants into organic semiconductors (OSCs) is a ubiquitous augmentation strategy to enhance the electrical conductivity of OSCs. Although the importance of optimizing OSC-dopant interactions is well-recognized, chemically generalizable structure-function relationships are difficult to extract due to the sensitivity and dependence of doping efficiency on chemistry, processing conditions, and morphology. Computational modeling for an integrated OSC-dopant design is an attractive approach to systematically isolate fundamental relationships, but requires the challenging simultaneous treatment of molecular reactivity and morphology evolution. We present the first computational study to couple molecular reactivity with morphology evolution in a molecularly doped OSC. Reactive Monte Carlo is employed to examine the evolution of OSC-dopant morphologies and doping efficiency with respect to dielectric, the thermodynamic driving for the doping reaction, and dopant aggregation. We observe that for well-mixed systems with experimentally relevant dielectric constants, doping efficiency is near unity with a very weak dependence on the ionization potential and electron affinity of OSC and dopant, respectively. At experimental dielectric constants, reaction-induced aggregation is observed, corresponding to the well-known insolubility of solution-doped materials. Simulations are qualitatively consistent with a number of experimental studies showing a decrease of doping efficiency with increasing dopant concentration. Finally, we observe that the aggregation of dopants lowers doping efficiency and thus presents a rational design strategy for maximizing doping efficiency in molecularly doped OSCs. This work represents an important first step toward the systematic integration of molecular reactivity and morphology evolution into the characterization of multi-scale structure-function relationships in molecularly doped OSCs.

A Domino Protocol toward High‐performance Unsymmetrical Dibenzo[d,d′]thieno[2,3‐b;4,5‐b′]dithiophenes Semiconductors

AbstractUnsymmetric organic semiconductors have many advantages such as good solubility, rich intermolecular interactions for potential various optoelectronic applications. However, their synthesis is more challenging due to intricate structures thus normally suffering tedious synthesis. Herein, we report a trisulfur radical anion (S3⋅−) triggered domino thienannulation strategy for the synthesis of dibenzo[d,d′]thieno[2,3‐b;4,5‐b′]dithiophenes (DBTDTs) using readily available 1‐halo‐2‐ethynylbenzenes as starting materials. This domino protocol features no metal catalyst and the formation of six C−S and one C−C bonds in a one‐pot reaction. Mechanistic study revealed a unique domino radical anion pathway. Single crystal structure analysis of unsymmetric DBTDT shows that its unique unsymmetric structure endows rich and multiple weak S⋅⋅⋅S interactions between molecules, which enables the large intermolecular transfer integrals of 86 meV and efficient charge transport performance with a carrier mobility of 1.52 cm2 V−1 s−1. This study provides a facile and highly efficient synthetic strategy for more high‐performance unsymmetric organic semiconductors.

A Domino Protocol toward High-performance Unsymmetrical Dibenzo[d,d']thieno[2,3-b;4,5-b']dithiophenes Semiconductors.

Unsymmetric organic semiconductors have many advantages such as good solubility, rich intermolecular interactions for potential various optoelectronic applications. However, their synthesis is more challenging due to intricate structures thus normally suffering tedious synthesis. Herein, we report a trisulfur radical anion (S3⋅-) triggered domino thienannulation strategy for the synthesis of dibenzo[d,d']thieno[2,3-b;4,5-b']dithiophenes (DBTDTs) using readily available 1-halo-2-ethynylbenzenes as starting materials. This domino protocol features no metal catalyst and the formation of six C-S and one C-C bonds in a one-pot reaction. Mechanistic study revealed a unique domino radical anion pathway. Single crystal structure analysis of unsymmetric DBTDT shows that its unique unsymmetric structure endows rich and multiple weak S⋅⋅⋅S interactions between molecules, which enables the large intermolecular transfer integrals of 86 meV and efficient charge transport performance with a carrier mobility of 1.52 cm2 V-1 s-1. This study provides a facile and highly efficient synthetic strategy for more high-performance unsymmetric organic semiconductors.

Mixing Insulating Commodity Polymers with Semiconducting n-type Polymers Enables High-Performance Electrochemical Transistors.

Diluting organic semiconductors with a host insulating polymer is used to increase the electronic mobility in organic electronic devices, such as thin film transistors, while considerably reducing material costs. In contrast to organic electronics, bioelectronic devices such as the organic electrochemical transistor (OECT) rely on both electronic and ionic mobility for efficient operation, making it challenging to integrate hydrophobic polymers as the predominant blend component. This work shows that diluting the n-type conjugated polymer p(N-T) with high molecular weight polystyrene (10KDa) leads to OECTs with over three times better mobility-volumetric capacitance product (µC*) with respect to the pristine p(N-T) (from 4.3 to 13.4 F V-1 cm-1 s-1 ) while drastically decreasing the amount of conjugated polymer (six times less). This improvement in µC* is due to a dramatic increase in electronic mobility by two orders of magnitude, from 0.059 to 1.3 cm2 V-1 s-1 for p(N-T):Polystyrene 10 KDa 1:6. Moreover, devices made with this polymer blend show better stability, retaining 77% of the initial drain current after 60 minutes operation in contrast to 12% for pristine p(N-T). These results open a new generation of low-cost organic mixed ionic-electronic conductors where the bulk of the film is made by a commodity polymer.

Structural Motifs in Covalent Organic Frameworks for Photocatalysis

AbstractCovalent organic frameworks (COFs) attract significant attention due to their ordered, crystalline, porous, metal‐free, and predictable structures. These unique characteristics offer great opportunities for the diffusion and transmission of photogenerated charges during photocatalysis. Currently, a considerable number of COFs are used as metal‐free organic semiconductor photocatalysts. This review aims to understand the relationships between the structure and photocatalysis performance of COFs and provides in‐depth insight into the synthetic strategy to improve photocatalysis performance. Subsequently, the review focuses on the structural motif of COFs in sustainable photocatalytic hydrogen evolution, carbon dioxide reduction, hydrogen peroxide generation, and organic compound transformations. Last, in conjunction with the significant progress achieved and the challenges yet to be overcome, a candid discussion is undertaken regarding the challenges and opportunities in the field of COF photocatalysis, accompanied by the presentation of potential research avenues and future directions. This review seeks to provide readers with a comprehensive understanding of the pivotal role of COFs in the field of photocatalysis, to offer robust guidance for the innovative utilization of COFs in future sustainable photocatalysis.

In-plane oxygen diffusion measurements in polymer films using time-resolved imaging of programmable luminescent tags

Oxygen diffusion properties in thin polymer films are key parameters in industrial applications from food packaging, over medical encapsulation to organic semiconductor devices and have been continuously investigated in recent decades. The established methods have in common that they require complex pressure-sensitive setups or vacuum technology and usually do not come without surface effects. In contrast, this work provides a low-cost, precise and reliable method to determine the oxygen diffusion coefficient D in bulk polymer films based on tracking the phosphorescent pattern of a programmable luminescent tag over time. Our method exploits two-dimensional image analysis of oxygen-quenched organic room-temperature phosphors in a host polymer with high spatial accuracy. It avoids interface effects and accounts for the photoconsumption of oxygen. As a role model, the diffusion coefficients of polystyrene glasses with molecular weights between 13k and 350k g/mol are determined to be in the range of (0.8–1.5) × 10–7 cm2/s, which is in good agreement with previously reported values. We finally demonstrate the reduction of the oxygen diffusion coefficient in polystyrene by one quarter upon annealing above its glass transition temperature.

Ligand-Directed Self-Assembly of Organic-Semiconductor/Quantum-Dot Blend Films Enables Efficient Triplet Exciton-Photon Conversion.

Blends comprising organic semiconductors and inorganic quantum dots (QDs) are relevant for many optoelectronic applications and devices. However, the individual components in organic-QD blends have a strong tendency to aggregate and phase-separate during film processing, compromising both their structural and electronic properties. Here, we demonstrate a QD surface engineering approach using electronically active, highly soluble semiconductor ligands that are matched to the organic semiconductor host material to achieve well-dispersed inorganic-organic blend films, as characterized by X-ray and neutron scattering, and electron microscopies. This approach preserves the electronic properties of the organic and QD phases and also creates an optimized interface between them. We exemplify this in two emerging applications, singlet-fission-based photon multiplication (SF-PM) and triplet-triplet annihilation-based photon upconversion (TTA-UC). Steady-state and time-resolved optical spectroscopy shows that triplet excitons can be transferred with near unity efficiently across the organic-inorganic interface, while the organic films maintain efficient SF (190% yield) in the organic phase. By changing the relative energy between organic and inorganic components, yellow upconverted emission is observed upon 790 nm NIR excitation. Overall, we provide a highly versatile approach to overcome longstanding challenges in the blending of organic semiconductors with QDs that have relevance for many optical and optoelectronic applications.