Organic Electronic Applications Research Articles

Spintronic Pathways in a Nonconjugated Radical Polymer Glass

AbstractRadical chemistries have attracted burgeoning attention due to their intriguing technological applications in organic electronics, optoelectronics, and magneto‐responsive systems. However, the potential of these magnetically active glassy polymers to transport spin‐selective currents has not been demonstrated. Here, the spin‐transport characteristics of the radical polymer poly(4‐glycidyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl) (PTEO) allow for sustained spin‐selective currents when incorporated into typical device geometries with magnetically polarized electrodes. Annealing thin films of PTEO above its glass transition temperature results in a giant magnetoresistance effect (i.e., an MR of ≈80%) at 4 K. Additionally, ferromagnetic resonance spin‐pumping results in a relatively large effective spin‐mixing conductance of 1.18 × 1019 m−2 at the NiFe/PTEO interface. Due to the large spin‐density and radical‐radical exchange interactions, there is effective propagation of pure spin currents through PTEO in the NiFe/PTEO/Pd multilayer devices. This results in the transport of spin current over long distances with a spin diffusion length of 90.4 nm. The spin diffusion length and spin mixing conductance values surpass those reported in inorganic and metallic systems and are comparable to conventional doped conjugated polymers. This is the first example of spin transport in a nonconjugated radical polymer, and these findings underscore the promising spin‐transporting potential of radical polymers.

In-Device Ballistic-Electron-Emission Spectroscopy for Accurately In Situ Mapping Energy Level Alignment at Metal-Organic Semiconductors Interface.

Energy level alignment at metal/organic semiconductors (OSCs) interface governs electronic processes in organic electronics devices, making its precise determination essential for understanding carrier transport behaviors and optimizing device performance. However, it is proven that accurately characterizing the energy barrier at metal/OSC interface under operational conditions remains challenging due to the technical limitations of traditional methods. Herein, through integrating highly-improved device constructions with an ingenious derivative-assisted data processing method, this study demonstrates an in-device ballistic-electron-emission spectroscopy using hot-electron transistors to accurately characterize the energy barrier at metal/OSC interface under in-operando conditions. This technique is found that a remarkable improvement in measurement accuracy, reaching up to ±0.03eV, can be achieved-surpassing previous techniques (±0.1-0.2eV). The high accuracy allows us to monitor subtle changes in energy barriers at metal/OSC interface caused by variations in the aggregation state of OSCs, a phenomenon that is theoretically possible but failed to be directly demonstrated through conventional methods. Moreover, this study makes demonstration that this technology is universally applicable to various metal/OSC interfaces consisting of electron-transporting, hole-transporting, and ambipolar OSCs. These findings manifest the great potential of this method to advance both theoretical exploration and technical applications in organic electronics.

Two-Level Electronic Switching in Individual Manganese-Phthalocyanine Molecules with Jahn-Teller Distortion.

Understanding single molecular switches is a crucial step in designing and optimizing molecular electronic devices with highly nonlinear functionalities, e.g., gate voltage-dependent current switching. An atomically thin insulating template, in combination with scanning probe techniques, is an ideal platform to study such switches on the single-molecule level. In this study, we investigate manganese-phthalocyanine (MnPc) molecules on monolayer-thin epitaxial hexagonal boron nitride (h-BN) on Rh(111) by scanning tunneling microscopy (STM), spectroscopy (STS), and theoretical calculations. Several interesting phenomena are found: (1) high-resolution STM imaging of the molecular orbitals reveals symmetry breaking from D4h to D2h, observed in one type of MnPc. By comparison with simulations, this phenomenon can be attributed to the Jahn-Teller effect due to the negative charging of the molecule. (2) Ambipolar transitions at the molecule occur at fixed sample biases of about ±0.4 V, which manifest as negative differential conductance signatures in dI/dV spectroscopy. (3) The stochastic two-level switching, resulting in telegraphic noise in the tunneling current, manifests as a one-electron activated process. We present a two-level switching model to accurately describe a bias-dependent current-driven transition between the levels and reveal a first-order transition. The understanding and tailoring of molecular switches on the ultrathin insulating layer will be very helpful for future organic electronics design and application.

Organic BODIPY based gels: Optical, electrochemical and self-assembly properties.

Two novel BODIPY dyes, BOC3 and BC12, were synthesized with variable alkyl chains at terminal amide functional units. BC12, featuring a longer alkyl chain (-C12H25), formed a gel compared to BOC3, which has a shorter alkyl chain (-CH2OCH3), due to supra molecular self-assembly in film. Both dyes exhibited absorption peaks around 530 nm in the visible region, with a red shift of about 30 nm in the film state, essential for organic electronic applications. Concentration variation studies revealed π-π stacking/aggregates in the solid state causing red shifts in absorption and emission. BC12 exhibited more significant red shifts in film compared to its solution state due to supra molecular self-assembly. Electronic structure analysis using density functional theories (BMK and O3LYP) showed better correlation with absorption using the O3LYP method. Both dyes displayed quasi-irreversible oxidation and reduction couples with suitable HOMO (5.46 eV) and LUMO (3.32 eV) energy levels for organic electronic applications. Transient photoluminescence studies indicated a longer lifetime for BC12 (5.28 ns) than BOC3 (4.50 ns), suggesting π-π aggregation and supra molecular self-assembly. BC12's gelation, attributed to its long alkyl chain and two-dimensional motifs of the BODIPY core, forms spherical-shaped nano networks.

One-Pot Divergent Synthesis of a 13-Ring Triquinone and its Facile Conversion to a [4.4.4]Tridecastarphene.

Acenes are notable for their optoelectronic properties and applications in organic electronics. Starphenes are structurally related molecules possessing three acene arms that radiate linearly from a central benzene ring (i. e., linearly annellated triphenylenes). Large starphenes have been prepared using convergent syntheses involving transition metal catalyzed cyclotrimerizations of either preformed acenes or arynes. Here, we report a one-pot divergent synthesis of a 13-ring triquinone that is readily converted to a [4.4.4]tridecastarphene derivative. The one-pot procedure involves the sequential reactions of three 1,4-anthraquinones with o-quinodimethane derivatives that are generated sequentially from a stable, trisulfone precursor. The resulting [4.4.4]tridecastarphene derivative bearing p-(t-butyl)phenyl substituents was characterized by 1H NMR, 13C NMR and UV-vis spectroscopies, as well as mass spectrometry, cyclic voltammetry and differential pulse voltammetry. Theoretical and experimental studies reveal a relatively high-lying HOMO orbital (about -4.70 to -4.86 eV) and a relatively small HOMO-LUMO gap (2.1 eV), suggesting utility as a p-type organic semiconductor. Our [4.4.4]tridecastarphene derivative photooxidizes in a CH2Cl2 solution exposed to ambient light and air with a half-life of 150 minutes at room temperature, but shows no sign of degradation after 12 months in the solid-state. Our [4.4.4]tridecastarphene derivative also shows excellent solubility in a number of organic solvents including dichloromethane, chloroform and toluene, potentially enabling printed electronic applications.

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

AbstractCovalent 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.

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.

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.

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.

Synthesis of Substituted 4-Styrylcoumarins via Wittig Reaction: An Approach to Photophysical and DFT Studies

A novel coumarin derivative of4-(4-aminostyryl)-7-methyl-2H-chromen-2-one (5)was synthesized by the reaction of 4-(bromomethyl)-7-methyl-2H-chromen-2-one and p-nitro benzaldehyde using toluene at 120Co via standard Wittig reaction condition. The molecules were characterized by spectral analysis and the photophysicalproperties for organic electronic applications were examined, such as thermal stability, strong and broad optical absorption and emission studies. Optical properties are explicated by UV-Vis absorption and fluorescence spectroscopy andoptical band gaps of the molecules 4 and 5 are found to be 3.35eV-3.65eV as estimated from their onset absorption edge. The 4-(4-aminostyryl)-2H-chrome-2-one a coumarin showed high thermal stability up to 239-367 °C. Density functional theory computations were performed to understandintermolecular charge transfer property.

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.

Electroactive and Self‐healing Polyurethane Doped Tin Oxide Interlayers for Efficient Organic Solar Cells†

Comprehensive SummaryTin oxide (SnO2) has been widely used as an electron transport layer (ETL) in optoelectronic devices. However, there are numerous surface or bulk defects in SnO2, working as charge recombination centers to degrade device. Here, an electroactive and self‐healing polyurethane (PHNN) was designed by integrating conjugated unit – naphthalene diimide (NDI) into a typical polyurethane backbone. Numerous hydrogen bonds and π interactions in PHNN work as non‐covalent interactions to endow this polymer with superior self‐healing properties. PHNN contains lots of aliphatic amine and carbonyl groups, which effectively passivate the defects in SnO2. The π stacking of NDI units will facilitate electron delocalization, endowing PHNN with electrical activity compared with traditional polyurethane. Doping SnO2 with PHNN can improve the conductivity and reduce the work function of SnO2 layer, which is conducive to efficient charge extraction and transport. Using PHNN doped SnO2 as ETL for PM6: Y6 and PM6: BTP‐eC9 based inverted organic solar cells can achieve a high efficiency of 17.16% and 17.51%, respectively. Devices containing doped SnO2 ETL show significantly improved efficiency and stability. Thus, the electroactive polyurethane doped SnO2 interlayers show high performance interfacial modification to align energy‐levels in solar cell devices, which have promising applications in organic electronics.

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.