Organic Electronic Applications Research Articles

Bay-substituted Perylene diimides (PDIs) as redox mediators in dye-sensitized solar cells and active electrode material in supercapacitors

In recent years, innovations in materials design have improved the optoelectronic properties of advanced materials and facilitated their efficient utilization. A significant amount of research has been conducted on developing perylene diimide (PDI) dyes for their use in various energy-related applications. In the present work, we have synthesized bay-substituted PDI derivatives and explored their dual applications in energy harvesting and storage devices. The nucleophilic substitution reaction of 1,7/1,6-brominated Val-PDI was performed by using 2-naphthol (N) and its Nitrogen analogue 8-hydroxy quinoline (Q) for analysing the effect of N-heterocycle at the bay position. The prepared 1,7 (N1/Q1) and 1,6 (N2/Q2) PDIs underwent thorough photophysical and electrochemical analyses and their structures were optimized through density functional theory (DFT) using B3LYP approach with a 6-31+G (d,p) basis set. Although all the prepared bay-substituted PDIs showed reasonable redox activity, N1 was chosen as an electrolyte dopant in dye-sensitized solar cells (DSSC) owing to its band alignment. This aided in enhanced electron lifetime and charge transfer properties, which led to an enhanced efficiency of 2.04 % while the conventional DSSC delivered only 1.84 % at 200 W m−2 illumination. Additionally, the symmetrical supercapacitor fabricated by using Q1 as electrode material generated a high specific capacitance of 146.54 F g−1. Thus, the proposed work opens avenues for the utility of bay-substituted PDI derivatives for organic electronic applications.

A Strongly Reducing sp2 Carbon-Conjugated Covalent Organic Framework Formed by N-Heterocyclic Carbene Dimerization.

Covalent organic frameworks linked by carbon-carbon double bonds (C=C COFs) are an emerging class of crystalline, porous, and conjugated polymeric materials with potential applications in organic electronics, photocatalysis, and energy storage. Despite the rapidly growing interest in sp2 carbon-conjugated COFs, only a small number of closely related condensation reactions have been successfully employed for their synthesis to date. Herein, we report the first example of a C=C COF, CORN-COF-1 (CORN = Cornell University), prepared by N-heterocyclic carbene (NHC) dimerization. In-depth characterization reveals that CORN-COF-1 possesses a two-dimensional layered structure and hexagonal guest-accessible pores decorated with a high density of strongly reducing tetraazafulvalene linkages. Exposure of CORN-COF-1 to tetracyanoethylene (TCNE, E1/2 = 0.13 V and -0.87 V vs. SCE) oxidizes the COF and encapsulates the radical anion TCNE•- and the dianion TCNE2- as guest molecules, as confirmed by spectroscopic and magnetic analysis. Notably, the reactive TCNE•- radical anion, which generally dimerizes in the solid state, is uniquely stabilized within the pores of CORN-COF-1. Overall, our findings broaden the toolbox of reactions available for the synthesis of redox-active C=C COFs, paving the way for the design of novel materials.

Linking Electronic and Structural Disorder Parameters to Carrier Transport in a Modern Conjugated Polymer.

Understanding charge transport in conjugated polymers is crucial for the development of next-generation organic electronic applications. It is presumed that structural disorder in conjugated polymers originating from their semicrystallinity, processing, or polymorphism leads to a complex energetic landscape that influences charge carrier transport properties. However, the link between polymer order parameters and energetic landscape is not well established experimentally. In this work, we successfully link statistical surveys of the local polymer electronic structure with paracrystalline structural disorder, a measure of statistical fluctuations away from the ideal polymer packing structure. We use scanning tunneling microscopy/spectroscopy to measure spatial variability in electronic band edges in PM6 films, a high-performance conjugated polymer, and find that films with higher paracrystallinity exhibit greater electronic disorder, as expected. In addition, we show that macroscopic charge carrier mobility in field effect transistors and and trap influence in hole-only diode devices is positively correlated with these microscopic structural and electronic parameters.

Hybrid System of Polystyrene and Semiconductor for Organic Electronic Applications

While organic semiconductors hold significant promise for the development of flexible, lightweight electronic devices such as organic thin-film transistors (OTFTs), photodetectors, and gas sensors, their widespread application is often limited by intrinsic challenges. In this article, we first review these challenges in organic electronics, including low charge carrier mobility, susceptibility to environmental degradation, difficulties in achieving uniform film morphology and crystallinity, as well as issues related to poor interface quality, scalability, and reproducibility that further hinder their commercial viability. Next, we focus on reviewing the hybrid system comprising an organic semiconductor and polystyrene (PS) to address these challenges. By examining the interactions of PS as a polymer additive with several benchmark semiconductors such as pentacene, rubrene, 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS pentacene), 2,8-difluoro-5,11-bis(triethylsilylethynyl) anthradithiophene (diF-TES-ADT), and 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT), we showcase the versatility of PS in enhancing the crystallization, thin film morphology, phase segregation, and electrical performance of organic semiconductor devices. This review aims to highlight the potential of an organic semiconductor/PS hybrid system to overcome key challenges in organic electronics, thereby paving the way for the broader adoption of organic semiconductors in next-generation electronic devices.

Controlled two-step synthesis of n-type conjugated ladder polymers using a flow reactor

The coplanar backbone of conjugated ladder polymers (cLPs) enhances electron transfer and π-π interactions, making cLPs promising materials for various applications in organic electronics and optoelectronics. Nevertheless, the limited solubility and intricate synthetic processes for cLPs make it challenging to control their molecular weight and corresponding properties, and pose as significant obstacles to their widespread application. Here, an n-type cLP, PNDI-2BocL, was synthesized using a flow reactor for the first time, with controlled molecular weights. The polymerization reaction conditions to synthesize a precursor polymer, PNDI-2Boc, were first optimized in flow, followed by sequential ladderization in batch through the injection of an acid solution. The reaction time of polymerization was varied from 7.5 to 15 min, yielding soluble PNDI-2BocL with a number-averaged molecular weight (Mn) ranging from 9.8 to 54.0 kg/mol with a deviation of 11 %. Additionally, 15 min of polymerization and ladderization were successfully conducted in a single flow system sequentially for the first time. In the molecular weight-dependent studies, higher optical absorption at longer wavelengths, increased degrees of crystallinity, and higher electron mobilities in organic field-effect transistors (OFETs) were observed for higher molecular weight PNDI-2BocL. Our results highlight the importance of controlling the molecular weights of cLPs and demonstrate that the flow synthesis technique provides a viable solution for synthesizing soluble cLPs in a controlled, reproducible, and rapid manner.

Exploring Thiophene Compounds: Pioneering Applications in Organic Electronics

Exploring Thiophene Compounds: Pioneering Applications in Organic Electronics

Advances in the Fabrication, Properties, and Applications of Electrospun PEDOT-Based Conductive Nanofibers.

The production of nanofibers has become a significant area of research due to their unique properties and diverse applications in various fields, such as biomedicine, textiles, energy, and environmental science. Electrospinning, a versatile and scalable technique, has gained considerable attention for its ability to fabricate nanofibers with tailored properties. Among the wide array of conductive polymers, poly(3,4-ethylenedioxythiophene) (PEDOT) has emerged as a promising material due to its exceptional conductivity, environmental stability, and ease of synthesis. The electrospinning of PEDOT-based nanofibers offers tunable electrical and optical properties, making them suitable for applications in organic electronics, energy storage, biomedicine, and wearable technology. This review, with its comprehensive exploration of the fabrication, properties, and applications of PEDOT nanofibers produced via electrospinning, provides a wealth of knowledge and insights into leveraging the full potential of PEDOT nanofibers in next-generation electronic and functional devices by examining recent advancements in the synthesis, functionalization, and post-treatment methods of PEDOT nanofibers. Furthermore, the review identifies current challenges, future directions, and potential strategies to address scalability, reproducibility, stability, and integration into practical devices, offering a comprehensive resource on conductive nanofibers.

Structural, optical spectroscopic, and density functional theory calculations of squaraine dye for organic electronic applications

The structural, optical spectroscopic, and density functional theory calculations of 2,4-Bis[4-(N,N-diisobutylamino)−2,6-dihydroxyphenyl] squaraine dye (SQ) are promising investigations that can be useful in photochemical mechanisms explanation and in designing promising chemosensors. The nature of the bonds, the chemical composition of SQ, crystallographic structure, morphology, and quality characteristics were explored by FTIR, XRD, and SEM investigations. The crystallite size, the dislocation density, and the lattice strain were found to be 57.3 nm, 3.045 × 10−4 nm−2, and 3.065 × 10−3, respectively. The spectrum behavior of the absorbance and molar absorption coefficient spectra of SQ in DCM with three concentrations were analyzed to get some important optical properties of SQ dye. The determined optical gap transition equals Egapopt=1.81eV. Quantum chemical computations and optimized molecular geometries identified where electrophilic attacks are likely and analyzed the molecule’s electrostatic potential. Using DFT calculations at the B3LYP/6-31+G(d,p) level, the electronic structure of the squaraine molecule was confirmed, showing a HOMO–LUMO gap of 1.73 eV. MEP analysis indicated that the oxygen atoms are electron-rich, suggesting potential for hydrogen bonding and electrophilic interactions.

Organic Heterostructures with Dendrimer Based Mixed Layer for Electronic Applications.

Recently, much research has focused on the search for new mixed donor-acceptor layers for applications in organic electronics. Organic heterostructures with layers based on the generation 1 poly(propylene thiophenoimine) (G1PPT) dendrimer, N,N'-diisopropylnaphthalene diimide (MNDI), and a combination of the two were prepared and their electrical properties were investigated. Single layers of G1PPT and MNDI and a mixed layer (G1PPT:MNDI) were obtained via spin coating on quartz glass, silicon, and glass/ITO substrates, using chloroform as a solvent. The absorption mechanism was investigated, the degree of disorder was estimated, and the emission properties of the layers were highlighted using spectroscopic methods (UV-Vis transmission and photoluminescence). The effects of the concentration and surface topographical particularities on the properties of the layers were analyzed via atomic force microscopy. All of the heterostructures realized with ITO and Au electrodes showed good conduction, with currents of the order of mA. Additionally, the heterostructure with a mixed layer exhibited asymmetry in the current-voltage curve between forward and reverse polarization in the lower range of the applied voltages, which was more significant at increased concentrations and could be correlated with rectifier diode behavior. Consequently, the mixed-layer generation 1 poly(propylene thiophenoimine) dendrimer with N,N'-diisopropylnaphthalene diimide can be considered promising for electronic applications.

Closed-loop transfer enables artificial intelligence to yield chemical knowledge.

Artificial intelligence-guided closed-loop experimentation has emerged as a promising method for optimization of objective functions1,2, but the substantial potential of this traditionally black-box approach to uncovering new chemical knowledge has remained largely untapped. Here we report the integration of closed-loop experiments with physics-based feature selection and supervised learning, denoted as closed-loop transfer (CLT), to yield chemical insights in parallel with optimization of objective functions. CLT was used to examine the factors dictating the photostability in solution of light-harvesting donor-acceptor molecules used in a variety of organic electronics applications, and showed fundamental insights including the importance of high-energy regions of the triplet state manifold. This was possible following automated modular synthesis and experimental characterization of only around 1.5% of the theoretical chemical space. This physics-informed model for photostability was strengthened using multiple experimental test sets and validated by tuning the triplet excited-state energy of the solvent to break out of the observed plateau in the closed-loop photostability optimization process. Further applications of CLT to additional materials systems support the generalizability of this strategy for augmenting closed-loop strategies. Broadly, these findings show that combining interpretable supervised learning models and physics-based features with closed-loop discovery processes can rapidly provide fundamental chemical insights.

Advances in Charge Carrier Mobility of Diketopyrrolopyrrole-Based Organic Semiconductors

In recent years, the charge carrier mobility study of organic semiconductors has seen significant progress and surpassed that of amorphous silicon thanks to the development of various molecular engineering, solution processing, and external alignment methods. These advances have allowed the implementation of organic semiconductors for fabricating high-performance organic electronic devices. In particular, diketopyrrolopyrrole-based small-molecular and polymeric organic semiconductors have garnered considerable research interest due to their ambipolar charge-carrier properties. In this article, we focus on conducting a comprehensive review of previous studies that are dedicated to the external alignment, thermal annealing, and molecular engineering of diketopyrrolopyrrole molecular structures and side-chain structures in order to achieve oriented crystal orientation, optimized thin-film morphology, and enhanced charge carrier transport. By discussing these benchmark studies, this work aims to provide general insights into optimizing other high-mobility, solution-processed organic semiconductors and sheds lights on realizing the acceleration of organic electronic device applications.

Ultrafast Intersystem Crossing in Benzanthrone: Effect of Hydrogen Bonding and Viscosity.

Understanding the intricate factors governing intersystem crossing (ISC) in aromatic carbonyl compounds remains a long-standing interest among researchers. This study unveils the crucial roles of vibration in influencing the ISC of a typical aromatic carbonyl chromophore, benzanthrone, and how hydrogen bonding and solvent viscosity affect these vibrations and, thus, the associated ISC kinetics. We demonstrate that for benzanthrone, the ISC is exceedingly facile in an aprotic solvent, while in protic solvents, the ISC is significantly suppressed through the formation of the hydrogen-bonded state. Moreover, in a high-viscosity medium, ISC is further retarded due to restrictions of volume-changing motions, which may assist ISC. Theoretical calculations revealed that the C═O bond vibration and specific out-of-plane vibrations accompanying a volume change could be the probable coordinates for ISC. These findings provide valuable insights for tailoring the excited-state behavior of carbonyl-functionalized materials for diverse applications in photocatalysis, organic electronics, and biomedicine.

Exploring New Carbon Allotropes and Nanographenes on Surfaces

The quest for planar sp2-hybridized carbon allotropes other than graphene has stimulated substantial research efforts because of their predicted unique mechanical, electronic, and transport properties. However, the syntheses of these nonbenzenoid networks remain challenging due to the lack of reliable protocols for generating nonhexagonal rings. We have developed various on-surface synthesis strategies by which straight polymer chains are linked to form the nonbenzenoid carbon networks. In this way, we synthesized biphenylene network, a new carbon allotrope with 4-6-8-membered rings, which is metallic already at very small dimensions. Similarly, we generated phagraphene nanoribbons, which are based on 5-6-7-membered rings.Acenes are another interesting class of carbon materials that have fascinated chemists and physicists due to their potential for use in organic electronic applications. We show the synthesis of tridecacene (13ac) and pentadecacene (15ac), the longest acenes known to date, via multistep single-molecule manipulation of suitable precursor molecules on Au(111). We find antiferromagnetic open-shell ground state electron configurations for both acenes. 15ac shows a low-bias spin-excitation feature, indicating a singlet-triplet gap of around 124 meV. Investigation of 15ac complexes with up to 6 gold atoms suggest considerable multiradical contributions to the electronic ground state of 15ac.Altering the electronic and magnetic properties of carbon-based nanomaterials can also be achieved by doping with heteroatoms. We present an access to a variety of nitrogen-containing 0D and 1D carbon nanostructures including planar and curved cycloarenes with different cavities as well as N-doped graphene nanoribbons.

Probing the Electron Accepting Ability of Phosphaphenalenes.

Phosphaphenalenes, extended π conjugates with the incorporation of phosphorus, are attractive avenues towards molecular materials for the applications in organic electronics, but their electron accepting ability have not been investigated. Herein we present systematic studies on the reductive behavior of a representative phosphaphenalene and its oxide by chemical and electrochemical methods. The chemical reduction of the phosphaphenalene by alkali metals reveals the facile P-C bond cleavage to form phosphaphenalenide anion, which functions as a transfer block for structure modification on the phosphorus atom. In contrast, the pentavalent P-oxide reacts with one or two equivalents of elemental sodium to form stable radical anion and dianion salts, respectively.

Aggregation of N-Heteropolycyclic Aromatic Molecules: The Acridine Dimer and Trimer.

Polycyclic aromatic hydrocarbons and their nitrogen-substituted analogues are of great interest for various applications in organic electronics. The performance of such devices is determined not only by the properties of the single molecules, but also by the structure of their aggregates, which often form via self-aggregation. Gaining insight into such aggregation processes is a challenging task, but crucial for a fine-tuning of the materials properties. In this work, an efficient approach for the generation and characterisation of aggregates is described, based on matrix-isolation experiments and quantum-chemical calculations. This approach is exemplified for aggregation of acridine. The acridine dimer and trimer are thoroughly analysed on the basis of experimental and calculated UV and IR absorption spectra, which agree well with each other. Thereby a novel structure of the acridine dimer is found, which disagrees with a previously reported one. The calculations also show the changes from excitonic coupling towards orbital interactions between two molecules with decreasing distance to each other. In addition, a structure of the trimer is determined. Finally, an outlook is given on how even higher aggregates can be made accessible through experiment.

Optimizing the preparation of bromo phthalonitriles and piloting them to peripherally brominated boron subphthalocyanines

Boron subphthalocyanines (BsubPcs) are versatile molecules with advantageous properties for applications. The BsubPcs are synthesized by the cyclotrimerization of a phthalonitrile and are composed of three isoindole subunits bound by three aza-/imine-bridging nitrogens. There are a variety of BsubPc derivatives shown within the literature due to the differentiation of a phthalonitrile precursor. The differentiation of a phthalonitrile enables the peripheral functional groups. The BsubPcs can be derivatized in two steps: First step is the cyclotrimerization of a phthalonitrile in the presence of a strong Lewis Acid, typically a boron trihalide (BX3) and enables a remaining axial substituent that is a B-X[Formula: see text] bond; second step is optional, the B-X[Formula: see text] bond can react with a nucleophile and results in B-X[Formula: see text]. If the starting phthalonitrile is asymmetric, it will result in a combination of isomers. For this study, our approach is to have bromine substituents and to study their physical properties to see if applicable to organic electronic applications; chlorine and fluorine have been in past studies as halogens are unique and variations may present useful tools as they are known for electronegativities. The general phthalonitrile with no substitutions is produced in industry from [Formula: see text]-xylene. There are a variety of ways to synthesize other phthalonitriles with halogens. However, phthalonitriles can also be made by a method that has the most versatility with its substituents and can start with phthalic acid and go to phthalic anhydride to phthalimide to phthalamide and final to phthalonitrile; it is also possible to synthesize a phthalimide directly from phthalic acid, and this is part of this study as we were focusing on bromination, we also wanted to optimize the synthetic pathways to brominated phthalonitriles, and we took an engineering perspective and for this study, we wish to show you.

Thermal, kinetic of decomposition, theoretical and experimental photoluminescent studies of two Eu3+-betadiketonate containing the 5,5′-dimethyl-2,2′-bipyridine ancillary ligand: Preparation of two efficient OLEDs devices

The Eu3+-betadiketonate coordination compounds are intensively studied due to their intense photoluminescence, which places them as promising materials with different applications, such as ammunition markers, biological sensors, and mainly as electroluminescent materials in Organic Light Emitting Diodes (OLEDs). This work reports the synthesis, thermal and kinetic study, crystal structures, experimental and theoretical photoluminescence analysis of two new Eu3+-betadiketonates of general formula [Eu(tta)3(5,5′-dmbpy)] 1 and [Eu(btfa)3(5,5′-dmbpy)] 2, where Htta = 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione, Hbtfa = 4,4,4-trifluoro-1-phenyl-1,3-butanedione and 5,5′-dmbpy = 5,5′-dimethyl-2,2′-bipyridine. Photoluminescence spectroscopy data revealed that the compounds can be sensitized directly by the metal ion or through of the excitation of the excited states of the ligand system. Due to the high quantum efficiencies found for both complexes, they were used in the preparation of two OLED devices, with these devices exhibiting excellent efficiency and color purity, making them well-suited for organic electronic applications.

How to Stabilize Large Soluble (Hetero-)Acenes.

The higher acenes and azaacenes (>(aza)heptacenes) are fascinating, yet elusive materials. Their reactivity and sensitivity increases concomitantly with their size. In recent years, confinement techniques, that is isolation of acenes in matrices and on surfaces, has surpassed solution-based chemistry with respect to accessing the larger (hetero)acenes at the price of the accessibility of no more than a couple thousands of molecules. Isolating acenes in bulk quantities and in processable form is vital for applications in organic electronics as well as from a viewpoint from basic research. In this Perspective, we will discuss after a short historical outline their degradation pathways, and then will selectively highlight recent efforts in stabilizing soluble (aza)acenes.

Optoelectronic properties of β-Cyclodextrin compound and doped with Na: Comparative study by experimental and DFT approaches

The chemical and physical properties of β-Cyclodextrin (β-CD) and doped with Na can be useful in drug delivery, organic solar cells and photoprotective applications. Physicochemical properties of pure β-CD and doped with Na were investigated by both density functional theory (DFT) and experimental methods. Theoretical calculations and the experimental measurements revealed that β-CD has a direct band gap of 3.44 and 4.14 eV, respectively. The optical absorption measurements indicate that band gap value decreases by Na doping to 3.09 eV. DOS spectra confirmed the stabilization of β-CD by the strong covalent bonds between C and O atoms. Obtained small effective mass of charge carriers with the high carrier mobility in β-CD show that it is a good candidate for using in the organic electronic applications. The significant isotropic behavior was observed in all optical spectra. The positive values of the real part of dielectric function confirm the dielectric nature of β-CD. Maximum dielectric polarization is observed at the ultraviolet region with the static dielectric constant of 2.03. High reflectivity at the ultraviolet region and beyond that confirm the photoprotective properties of β-CD compound against harmful solar radiations. There is a good agreement between the obtained experimental and DFT spectra. Our findings may be useful in design of new organic optoelectronic devices.

Dual Optoelectronic Organic Field-Effect Device: Combination of Electroluminescence and Photosensitivity.

Merging the functionality of an organic field-effect transistor (OFET) with either a light emission or a photoelectric effect can increase the efficiency of displays or photosensing devices. In this work, we show that an organic semiconductor enables a multifunctional OFET combining electroluminescence (EL) and a photoelectric effect. Specifically, our computational and experimental investigations of a six-ring thiophene-phenylene co-oligomer (TPCO) revealed that this material is promising for OFETs, light-emitting, and photoelectric devices because of the large oscillator strength of the lowest-energy singlet transition, efficient luminescence, pronounced delocalization of the excited state, and balanced charge transport. The fabricated OFETs showed a photoelectric response for wavelengths shorter than 530 nm and simultaneously EL in the transistor channel, with a maximum at ~570 nm. The devices demonstrated an EL external quantum efficiency (EQE) of ~1.4% and a photoelectric responsivity of ~0.7 A W-1, which are among the best values reported for state-of-the-art organic light-emitting transistors and phototransistors, respectively. We anticipate that our results will stimulate the design of efficient materials for multifunctional organic optoelectronic devices and expand the potential applications of organic (opto)electronics.