Organic Electronic Applications Research Articles

Understanding the effects of sulfur di-oxidation and side chain engineering on absorption and fluorescence of oligothiophene: A theoretical study

Oligothiophene and its derivatives have broad applications in organic electronics because of its stability, easy functionalization, and broad color adjustability, and excellent charge carrier mobility. However, the effects of sulfur di-oxidation and side alkyl chains on the absorption and fluorescence of oligothiophene are still not well understood. In this article, we have applied density functional theory (DFT) and time-dependent DFT (TDDFT) to study a series of quinquethiophene compounds functionalized with S,S-dioxide and side alkyl chains, which were experimentally synthesized. Through benchmark calculations, we have found a reliable computational method, and successfully reproduced experimental UV–Vis absorption and fluorescence emission spectra well. Furthermore, the calculated reorganization energy of these molecules could explain the energy differences between absorption and emission spectra. Last but not lease, we also have calculated the fluorescence quantum yield efficiency (Фfl) of two compounds with good planarity in this series, and the trend of calculated values is consistent with experiment. Our work gives an insight to the effects of sulfur di-oxidation and side chain engineering on absorption and fluorescence of oligothiophene.

Increasing Chemical Diversity of B2 N2 Anthracene Derivatives by Introducing Continuous Multiple Boron-Nitrogen Units.

Increasing the chemical diversity of organic semiconductors is essential to develop efficient electronic devices. In particular, the replacement of carbon-carbon (C-C) bonds with isoelectronic boron-nitrogen (B-N) bonds allows precise modulation of the electronic properties of semiconductors without significant structural changes. Although some researchers have reported the preparation of B2 N2 anthracene derivatives with two B-N bonds, no compounds with continuous multiple BN units have been prepared yet. Herein, we report the synthesis and characterization of a B2 N2 anthracene derivative with a BNBN unit formed by converting the BOBN unit at the zigzag edge. Compared to the all-carbon analogue 2-phenylanthracene, BNBN anthracene exhibits significant variations in the C-C bond length and a larger highest occupied molecular orbital-lowest unoccupied molecular orbital energy gap. The experimentally determined bond lengths and electronic properties of BNBN anthracene are confirmed through theoretical calculations. The BOBN anthracene organic light-emitting diode, used as a blue host, exhibits a low driving voltage. The findings of this study may facilitate the development of larger acenes with multiple BN units and potential applications in organic electronics.

Increasing Chemical Diversity of B2N2 Anthracene Derivatives by Introducing Continuous Multiple Boron‐Nitrogen Units

AbstractIncreasing the chemical diversity of organic semiconductors is essential to develop efficient electronic devices. In particular, the replacement of carbon‐carbon (C−C) bonds with isoelectronic boron‐nitrogen (B−N) bonds allows precise modulation of the electronic properties of semiconductors without significant structural changes. Although some researchers have reported the preparation of B2N2 anthracene derivatives with two B−N bonds, no compounds with continuous multiple BN units have been prepared yet. Herein, we report the synthesis and characterization of a B2N2 anthracene derivative with a BNBN unit formed by converting the BOBN unit at the zigzag edge. Compared to the all‐carbon analogue 2‐phenylanthracene, BNBN anthracene exhibits significant variations in the C−C bond length and a larger highest occupied molecular orbital–lowest unoccupied molecular orbital energy gap. The experimentally determined bond lengths and electronic properties of BNBN anthracene are confirmed through theoretical calculations. The BOBN anthracene organic light‐emitting diode, used as a blue host, exhibits a low driving voltage. The findings of this study may facilitate the development of larger acenes with multiple BN units and potential applications in organic electronics.

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

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

Rational Design of a Multifunctional Benzothiadiazole Derivative in Organic Photonics and Electronics.

In order to achieve a multifunctional compound with potential application in organic photonics and electronics, a multidonor benzothiadiazole derivative was rationally designed and synthesized employing microwave irradiation as energy source, increasing the process efficiency about yields and reaction times in comparison with conventional conditions. This powerful compound displayed solvatochromism and showed efficient behavior as red optical waveguide with low OLC around 10-2 dB μm-1 and with the capacity of light transmission in two directions. In addition, the proposed derivative acted as efficient p-type semiconductor in organic field-effect transistors (OFETs) with hole mobilities up 10-1 cm2 V-1 s-1 . This corroborates its multifunctional character, thus making it a potential candidate to be applied in hybrid organic field-effect optical waveguides (OFEWs).

Color tunable benzothiadiazole-based small molecules for lightening applications

Abstract 2,1,3-Benzothiadiazole (BTD) is a key motif for the chemistry of photoluminescence molecules and its application in lightening technology as well as cell imagining. Evaluating the characteristics and reaction mechanisms of the BTD derivatives in molecular is critical for molecular designing. Research has been turned to BTD-extended derivatives owing to their possible usage in organic photovoltaics, organic light-emitting diodes, liquid crystal devices, dye-sensitized solar cells, and many other applications. Herein, three small molecules with a BTD core, 4,7-di-m-tolylbenzo[c][1,2,5]thiadiazole (NK1), 4,7-bis(3,4,5-trifluorophenyl)benzo[c][1,2,5]thiadiazole (NK2), and 4,7-bis(5-(m-tolyl)thiophen-2-yl)benzo[c][1,2,5]thiadiazole (NK3), were designed and synthesized and their molecular structures were elucidated. Additionally, their photophysical and electrochemical behaviors as well as the aggregation-induced enhanced emission properties were examined to investigate their possible usage in cell imaging and organic electronic applications. The HOMO energy level of molecules has been found as −5.96, −5.58, and −5.60 eV, respectively. In the emission spectra, it was seen that molecules showed green, blue, and red emission, respectively.

Discovery of structure–property relations for molecules via hypothesis-driven active learning over the chemical space

The discovery of the molecular candidates for application in drug targets, biomolecular systems, catalysts, photovoltaics, organic electronics, and batteries necessitates the development of machine learning algorithms capable of rapid exploration of chemical spaces targeting the desired functionalities. Here, we introduce a novel approach for active learning over the chemical spaces based on hypothesis learning. We construct the hypotheses on the possible relationships between structures and functionalities of interest based on a small subset of data followed by introducing them as (probabilistic) mean functions for the Gaussian process. This approach combines the elements from the symbolic regression methods, such as SISSO and active learning, into a single framework. The primary focus of constructing this framework is to approximate physical laws in an active learning regime toward a more robust predictive performance, as traditional evaluation on hold-out sets in machine learning does not account for out-of-distribution effects which may lead to a complete failure on unseen chemical space. Here, we demonstrate it for the QM9 dataset, but it can be applied more broadly to datasets from both domains of molecular and solid-state materials sciences.

Photolithographic Rugged Electrode for High-Density Low-Contact-Resistance Coplanar Organic Transistors.

The realization of high-performance photolithographic coplanar organic thin film transistors (OTFTs) is fundamental to boost cosmicallycommercial applications of organic electronics. However, photolithographic coplanar OTFTs generally suffer from poor charge injection and therefore poor filed-effect performance. Here, a simple and effective strategy is developed to fabricate photolithographic rugged electrodes, and successfully achieve high-density low-contact-resistance photolithographic coplanar OTFTs. Based on this versatile electrode, the wafer-scale photolithographic rugged electrode can be easily achieved, and the device density of the coplanar OTFTs is as high as 28000cm-2 . The device shows excellent electrical properties with mobility up to 2.01cm2 V-1 s-1 and Rc as low as 7.8kΩcm, which is superior to all the reported Ag-electrode coplanar OTFTs. This work shows a reliable strategy to reduce the contact resistance of photolithographic coplanar OTFTs and elucidates the effect of injection resistance (Rinj ) and access resistance (Racc ) on coplanar OTFTs.

Guided diffusion for inverse molecular design.

The holy grail of materials science is de novo molecular design, meaning engineering molecules with desired characteristics. The introduction of generative deep learning has greatly advanced efforts in this direction, yet molecular discovery remains challenging and often inefficient. Herein we introduce GaUDI, a guided diffusion model for inverse molecular design that combines an equivariant graph neural net for property prediction and a generative diffusion model. We demonstrate GaUDI's effectiveness in designing molecules for organic electronic applications by using single- and multiple-objective tasks applied to a generated dataset of 475,000 polycyclic aromatic systems. GaUDI shows improved conditional design, generating molecules with optimal properties and even going beyond the original distribution to suggest better molecules than those in the dataset. In addition to point-wise targets, GaUDI can also be guided toward open-ended targets (for example, a minimum or maximum) and in all cases achieves close to 100% validity of generated molecules.

Multi-responsive Electropolymer Surface Coatings Based on Azo Molecular Switches and Carbazoles: Light, pH, and Electrochemical Control of Z→E Isomerization in Thin Films.

Light-responsive surfaces are attracting increasing interest, not least because their physicochemical properties can be selectively and temporally controlled by a non-invasive stimulus. Most existing immobilization strategies involve the chemical attachment of light-responsive moieties to the surface, although this approach often suffers from a low surface concentration of active species or a high inhomogeneity of applied coatings. Herein, electropolymerization of carbazoles as a facile and rapid approach for preparing light-responsive azo-based surface coatings is presented. The electrochemical oxidative polymerization of bis-carbazole containing azo-monomers yields stable films, in which the photochemical properties and specific pH sensitivity of azo molecular switches are retained. Moreover, the molecular design enables electrocatalytic control over Z→E azo double bond isomerization facilitated by the conductive polycarbazole backbone. Ultimately, the high degree of control over macromolecular properties yields conductive surface coatings responsive to a range of stimuli, showing great promise as a strategy for versatile application in organic electronics.

Non-Covalent Interactions between Polyvinyl Chloride and Conjugated Polymers Enable Excellent Mechanical Properties and High Stability in Organic Solar Cells.

The incorporation of insulating polymers into conjugated polymers has been widely explored as a strategy to improve mechanical properties of flexible organic electronics. However, phase separation due to the immiscibility of these polymers has limited their effectiveness. In this study, we report the discovery of multiple non-covalent interactions that enhances the miscibility between insulating and conjugated polymers, resulting in improved mechanical properties. Specifically, we have added polyvinyl chloride (PVC) into the conjugated polymer PM6 and observed a significant increase in solution viscosity, indicative of favorable miscibility between these two polymers. This phenomenon has been rarely observed in other insulating/conjugated polymer composites. Thin films of PM6/PVC exhibit a much-improved crack-onset strain of 19.35 %, compared to 10.12 % for pristine PM6 films. Analysis reveal that a "cyclohexyl-like" structure formed through dipole-dipole interactions and hydrogen bonding between PVC and PM6 acted as a cross-linking site in the thin films, leading to improved mechanical properties. Moreover, PM6/PVC blend films have demonstrated excellent thermal and bending stability when applied as an electron donor in organic solar cells. These findings provide new insights into non-covalent interactions that can be utilized to enhance the properties of conjugated polymers and may have potential applications in flexible organic electronics.

Non‐Covalent Interactions between Polyvinyl Chloride and Conjugated Polymers Enable Excellent Mechanical Properties and High Stability in Organic Solar Cells

AbstractThe incorporation of insulating polymers into conjugated polymers has been widely explored as a strategy to improve mechanical properties of flexible organic electronics. However, phase separation due to the immiscibility of these polymers has limited their effectiveness. In this study, we report the discovery of multiple non‐covalent interactions that enhances the miscibility between insulating and conjugated polymers, resulting in improved mechanical properties. Specifically, we have added polyvinyl chloride (PVC) into the conjugated polymer PM6 and observed a significant increase in solution viscosity, indicative of favorable miscibility between these two polymers. This phenomenon has been rarely observed in other insulating/conjugated polymer composites. Thin films of PM6/PVC exhibit a much‐improved crack‐onset strain of 19.35 %, compared to 10.12 % for pristine PM6 films. Analysis reveal that a “cyclohexyl‐like” structure formed through dipole‐dipole interactions and hydrogen bonding between PVC and PM6 acted as a cross‐linking site in the thin films, leading to improved mechanical properties. Moreover, PM6/PVC blend films have demonstrated excellent thermal and bending stability when applied as an electron donor in organic solar cells. These findings provide new insights into non‐covalent interactions that can be utilized to enhance the properties of conjugated polymers and may have potential applications in flexible organic electronics.

Superatom Molecular Orbitals of Endohedral C82.

Understanding superatom molecular orbital (SAMO) states in fullerene derivatives has been in the limelight ever since the first discovery of SAMOs owing to the fundamental interest in this topic as well as to the possible applications in molecular switches and other organic electronics. Nevertheless, very few reports have been published on SAMO states of larger fullerenes so far. Using density functional theory, we attempt to partially remedy this situation by presenting a study on SAMO states in C82 and its Ca and Sc endohedrally doped derivatives, comparing results with previous relevant findings for C60. We find that C82 possesses higher SAMO energies compared to C60, as associated with the symmetry of the molecule, and that endohedral doping leads to energetically favorable side positions of Ca and Sc inside the C82 cage. Among the two, Sc@C82 has more stable SAMO states compared to Ca@C82 as reflected by the shift in the density of states, while the charge states are found to be similar. In the case of the monolayer form, the pz- and 2s-SAMO orbitals overlap with the nearest neighbors, causing parabolic band dispersion with the formation of near free electron states and that the SAMO state energies move closer to the Fermi energy compared to the related molecules. These findings provide promising information about the distribution of SAMO states in C82 fullerene, which can be further relevant in studies of SAMO states of higher fullerenes and for coming applications of these systems.

Merging of Azulene and Perylene Diimide for Optical pH Sensors.

Polycyclic aromatic hydrocarbons (PAHs) have emerged as promising materials for organic electronics, including organic photovoltaics (OPVs), organic field-effect transistors (OFETs), and organic light-emitting diodes (OLEDs). Particularly, non-hexagonal ring-fused PAHs are highly desirable due to their unique optoelectronic properties. Herein, a new redox-active azulene-perylene diimide triad 1 and its ring-fused counterpart, diazulenocoronene diimide 2, were synthesized and fully characterized by a combination of NMR, cyclic voltammetry, and UV-visible absorption spectroscopy. Direct comparison of their electronic properties leads us to the conclusion that a significant change in the localization of HOMO and LUMO occurs upon the fusion of azulene and perylene diimide in 2, leading to the lack of intramolecular charge-transfer character for transitions in the visible spectral region. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were performed to gain further insight into various electronic transitions. Moreover, we found that the adaptive response to acids and bases manifests itself in a reversible two-color change that can be attributed to changes in the chemical structures. Our findings pave the way for manipulating the relative HOMO and LUMO energy levels of organic chromophores by fusing non-alternant azulenes to an otherwise flat PAH, which could possibly lead to applications in organic electronics and optical sensors.

Morphological, optical and electrochemical properties of tin(II) 2,3-naphthalocyanine for organic electronic applications

Herein, tin(II) 2,3-naphthalocyanine (SnNC) organic dye was successfully thermally deposited onto different optical transparent substrates such as glass, quartz, ITO, and FTO. FE-SEM technique reveals that SnNC film shows a uniform and symmetrical spherical-shaped with an average diameter of ∼50 nm. Annealing up to 473 K for 4 h increases the crystallite size of SnNC thin film. SnNC thin film shows absorption bands centered at 858 nm, 313 nm, and 249 nm with two shoulders at 775 nm and 350 nm. We present the absorbance, specular transmittance, specular reflectance and fluorescence properties of SnNc deposited on the different transparent substrates. The oscillator strengths (f) and the electric dipole strength (q2) of SnNC thin film were estimated from the molar absorptivity () spectra. According to the Tauc model, two optical gap transitions were estimated as 1.03 eV and 3.48 eV. Annealing up to 473 K for 4 h slightly increases them to 1.15 eV and 3.59 eV, respectively. At excitation wavelength = 360 nm, two emission bands were observed at around 403 nm and 674 nm. Upon annealing at 373 K and 473 K, the real part of the refractive index of SnNC thin film decreases, which is correlated with a decrease in mass density. Electrochemical HOMO—LUMO band gaps of SnNC estimated from the cyclic voltammetry (CV) measurements () agree well with the observed optical energy gap estimated from the optical measurements. The wide range absorption, emission, good thermal stability, suitable optical band gap, and electrochemical properties, prove an effective example of organic dye suitable for organic electronic applications.

Conjugated Nanohoop Polymers based on Antiaromatic Dibenzopentalenes for Charge Storage in Organic Batteries

AbstractWith their bent π‐systems, cyclic conjugation and inherent cavities, conjugated nanohoops are attractive for organic electronics applications. For ease of processing and morphological stability, an incorporation into polymers is desirable, but to date was hampered with few exceptions by synthetic difficulties. We herein present a unique strategy for the synthesis of conjugated nanohoop polymers using a dibenzo[a,e]pentalene (DBP) as central connector. We demonstrate this versatility by synthesizing three electronically diverse copolymers with dithienyldiketo(pyrrolopyrrol), fluorene and carbazole comonomers, and report the first donor‐acceptor nanohoop polymer. Optoelectronic investigations reveal the prevalence of cyclic or linear conjugation, depending on the comonomer unit, and ambipolar electrochemical properties through the antiaromatic character of the DBP units. As the first report on using conjugated nanohoops for charge storage as positive electrode materials, we show a significant improvement in battery performance in a nanohoop‐containing polymer compared to an equivalent nanohoop‐free reference polymer. We believe this study will pave the way for the synthesis of a diverse range of nanohoop polymers and further stimulate their exploration for charge storage in batteries.

Conjugated Nanohoop Polymers based on Antiaromatic Dibenzopentalenes for Charge Storage in Organic Batteries.

With their bent π-systems, cyclic conjugation and inherent cavities, conjugated nanohoops are attractive for organic electronics applications. For ease of processing and morphological stability, an incorporation into polymers is desirable, but to date was hampered with few exceptions by synthetic difficulties. We herein present a unique strategy for the synthesis of conjugated nanohoop polymers using a dibenzo[a,e]pentalene (DBP) as central connector. We demonstrate this versatility by synthesizing three electronically diverse copolymers with dithienyldiketo(pyrrolopyrrol), fluorene and carbazole comonomers, and report the first donor-acceptor nanohoop polymer. Optoelectronic investigations reveal the prevalence of cyclic or linear conjugation, depending on the comonomer unit, and ambipolar electrochemical properties through the antiaromatic character of the DBP units. As the first report on using conjugated nanohoops for charge storage as positive electrode materials, we show a significant improvement in battery performance in a nanohoop-containing polymer compared to an equivalent nanohoop-free reference polymer. We believe this study will pave the way for the synthesis of a diverse range of nanohoop polymers and further stimulate their exploration for charge storage in batteries.

Donor-Acceptor-Based Organic Polymer Semiconductor Materials to Achieve High Hole Mobility in Organic Field-Effect Transistors.

Organic polymer semiconductor materials are conveniently tuned to energy levels because of their good chemically modifiable properties, thus enhancing their carrier transport capabilities. Here, we have designed and prepared a polymer with a donor-acceptor structure and tested its potential as a p-type material for organic field-effect transistor (OFET) applications using a solution-processing method. The conjugated polymers, obtained via the polymerization of the two monomers relying on the Stille coupling reaction, possess extremely high molecular weights and thermodynamic stability. Theoretical-based calculations show that PDPP-2S-Se has superior planarity, which is favorable for carrier transport within the main chain. Photophysical and electrochemical measurements systematically investigated the properties of the material and the energy levels with respect to the theoretical values. The maximum hole mobility of the PDPP-2S-Se-based OFET device is 0.59 cm2 V-1 s-1, which makes it a useful material for potential organic electronics applications.

Exploring the Charge Transport of a Natural Eumelanin for Sustainable Technologies.

Eumelanin, the main quinone-based biomaterial of the melanin family of compounds, is emerging as a model for medical and sustainable electronic interfaces due to its biocompatibility, biodegradability, and transducing abilities. The study utilizes current-voltage measurements and impedance/dielectric spectroscopy under a controlled hydration atmosphere to investigate the charge transport of eumelanin produced from the S. parvus BSB49 strain. We show no differences in the electrical response in highly hydrated conditions compared to the standard synthetic eumelanin. Hence, our findings provide the groundwork to assess the potential use of this natural eumelanin in sustainable organic (bio)electronic applications.

Supramolecular Polymerization of all-cis-Fluorinated Cyclohexanes: Influence of Side Chains

Custom-designed materials based on supramolecular polymers are of interest for applications in organic electronics and biomedicine. Recently, we have shown that derivatives of the highly polar compound all-cis hexafluorocyclohexane undergo seeded polymerization and can therefore be used to prepare soluble nanofibers with controlled length. In this work, we aimed to explore the scope of this process. We studied the supramolecular polymerization of six all-cis-fluorinated cyclohexane monomers, with five differing in the solubilizing side chains and one in the secondary supramolecular binding site. In studies on controlled supramolecular polymerization, we found that three of the monomers could be induced to polymerize by ultrasound irradiation and four by addition of seeds. For these latter examples, we were able to identify a solvent mixture that led to spontaneous polymerization and hysteresis in heating and cooling curves. These results show that the living supramolecular polymerization of fluorinated cyclohexanes is not limited to one particular monomer, but that side chains exhibiting a strong solvophobic effect that cannot be compensated within the binary solvent “window” represent a limitation to the approach. We also demonstrate that nanofibers based on stacks of fluorinated cyclohexanes can be dissociated by addition of chloride ions.