Sterically Crowded Donor-Rich Imidazole Systems as Hole Transport Materials for Solution-Processed OLEDs.

Imidazole, being an interesting dinitrogenic five-membered heterocyclic core, has been widely explored during the last several decades for developing various fascinating materials. Among the different domains where imidazole-based materials find wide applications, the area of optoelectronics has seen an overwhelming growth of functional imidazole derivatives developed through remarkable design and synthesis strategies. The present work reports a design approach for integrating bulky donor units at the four terminals of an imidazole core, leading to the development of sterically populated imidazole-based molecular platforms with interesting structural features. Rationally chosen starting substrates led to the incorporation of a bulky donor at the four terminals of the imidazole core. In addition, homo- and cofunctional molecular systems were synthesized through a suitable combination of initial ingredients. Our approach was extended to develop a series of four molecular systems, i.e., Cz3PhI, Cz4I, Cz3PzI, and TPA3CzI, containing carbazole, phenothiazine, and triphenylamine as known efficient donors at the periphery. Given their interesting structural features, three sterically crowded molecules (Cz4I, Cz3PzI, and TPA3CzI) were screened by using DFT and TD-DFT calculations to investigate their potential as hole transport materials (HTMs) for optoelectronic devices. The theoretical studies on several aspects including hole reorganization and exciton binding energies, ionization potential, etc., revealed their potential as possible candidates for the hole transport layer of OLEDs. Single-crystal analysis of Cz3PhI and Cz3PzI established interesting structural features including twisted geometries, which may help attain high triplet energy. Finally, the importance of theoretical predictions was established by fabricating two solution-process green phosphorescent OLED devices using TPA3CzI and Cz3PzI as HTMs. The fabricated devices exhibited good EQE/PE and CE of ∼15%/56 lm/W/58 cd/A and ∼13%/47 lm/W/50 cd/A, respectively, at 100 cd/m2.

Overview of imidazole-based fluorescent materials with hybridized local and charge transfer and hot-exciton pathway characteristics in excited states.

Herein, we discuss an imidazole-based molecular framework, which can successfully transform triplet excitons present in high triplet levels into singlet states. We explain the working mechanisms of different methods for collecting triplet excitons, including hot excitons or HLCT states. After the development of an hot exciton material by Ma and Yang, many studies have demonstrated that the organic conjugated molecules having imidazole core have possibilities to show high efficiencies via hot exciton pathways. Finally, we provide a detailed investigation of recently published hot exciton luminogens based on imidazole molecular frameworks. This review provides an overview of the molecular structures, frontier molecular orbital information, and glass transition temperature of developed luminogens as well as the efficiency of organic light-emitting diodes (OLED) devices.

Indolo[3,2-a]carbazoles as Engineered Materials for Optoelectronic Applications: Synthesis, Structural Insights, and Computational Screening.

The biological and medicinal importance of indolocarbazoles has been known for the past several decades. However, in recent times, these compounds have been emerging as potential candidates for optoelectronic applications, although several challenges are associated with their synthesis. We report here a Pd(II)-catalyzed process for the synthesis of indolo[3,2-a]carbazoles. The reaction proceeded under neat conditions and in the presence of aqueous nonmetallic oxidant TBHP, and the products were purified directly after the completion of the reaction. Also, the possibility of employing the present method for reaction with gram-scale feed was investigated. A detailed single-crystal analysis of several indolo[3,2-a]carbazoles revealed how the molecular arrangement can be tuned by altering the functionalization. Finally, the developed molecules were screened computationally to assess their potential for possible use as hole transport materials (HTMs) for organic light-emitting diodes (OLEDs).

Self-assembled molecular network with waterwheel-like architecture: experimental and theoretical evaluation toward electron transport capabilities for optoelectronic devices.

In recent times, self-assembled electron transport materials for optoelectronic devices, both solar cells and organic light-emitting diodes (OLEDs), have been gaining much interest as they help in fabricating high-efficiency devices. However, designing organic small molecular materials with star-shaped self-assembled networks is a challenge. To achieve this sort of target, we chose triazine and benzene-1,3,5-tricarbonyl cores for developing such architecture, and we developed four molecular systems, vizTCpCN, TCmCN, TmCN, and TpCN. Successful isolation of single crystals followed by structural analysis of TmCN revealed interesting molecular arrangements in the solid state resulting in the formation of a waterwheel type architecture with an extended network bearing characteristic voids. Theoretical calculations was carried out to check their electron transportability. The natural transition orbital calculation helped in understanding the locally excited and charge transfer excited states. The low electron reorganization energies of these molecules indicated that these materials may have potential to be used in electron transport layers of optoelectronic devices, particularly in OLEDs. Moreover, the assembled networks have a relatively wide surface area and linked structures, which are advantageous for the conduction of carriers with poor electron recombination inside the ETL, and these may offer a straightforward channel for electron conduction to the emissive layer. Finally, the fabricated electron-only device indicated that the synthesized materials may be used as ETMs in the electron transport layer of optoelectronic devices.

In Search of Hosts for Blue OLEDs: Computational Design and Experimental Validation.

Considering the difficulties associated with the conventional 'trial and error' method for a complete analysis of a giant molecular space, we took the aid of computational pathway (DFT) in screening a large space search of 780 (12×13×5) molecules to search for a host for the blue emitter. The selection process was completed in three Tiers with the conditions of highest theoretical triplet energy (>2.81 eV), aligned HOMO/LUMO levels w.r.t blue dopant (FIrpic), and position of substituents to meet the optimal requirements as host materials. Tier 1 screened twelve different imidazole heterocycle derivatives as base space groups which resulted in the selection of 4,5-diphenyl-1H-imidazole. Tier 2 process converged the search to mCN-CZ having the highest triplet energy and appropriate HOMO/LUMO level relative to FIrpic and ETL. Further, the carbazole of mCN-CZ was replaced with different aromatic hydrocarbons to find the other best compound in terms of triplet energy and HOMO/LUMO. Tier 3 resulted in another promising candidate (mCN-FL) as possible host materials. The band alignment with guest predicted mCN-FL and mCN-CZ to have optimal device performances compared to CZ-CZ and the experimentally observed device performance was in accordance with virtual screening results when TAPC was utilized as the hole transporter. The device results of mCN-CZ and mCN-FL were better than the reference host TCTA. The obtained results thus proved that a virtual screening process will be a useful tool for synthetic chemists in designing task-specific materials.

Improvement of interfacial contact for efficient PCBM/MAPbI3planar heterojunction solar cells with a binary antisolvent mixture treatment.

Atomic-force microscopic images, x-ray diffraction patterns, Urbach energies and photoluminescence quenching experiments show that the interfacial contact quality between the hydrophobic [6,6]-phenyl-C61-buttric acid methyl ester (PCBM) thin film and hydrophilic CH3NH3PbI3(MAPbI3) thin film can be effectively improved by using a binary antisolvent mixture (toluene:dichloromethane or chlorobenzene:dichloromethane) in the anti-solvent mixture-mediated nucleation process, which increases the averaged power conversion efficiency of the resultant PEDOT:PSS (P3CT-Na) thin film based MAPbI3solar cells from 13.18% (18.52%) to 13.80% (19.55%). Beside, the use of 10% dichloromethane (DCM) in the binary antisolvent mixture results in a nano-textured MAPbI3thin film with multicrystalline micrometer-sized grains and thereby increasing the short-circuit current density and fill factor (FF) of the resultant solar cells. It is noted that a remarkable FF of 80.33% is achieved, which can be used to explain the stable photovoltaic performance without additional encapsulations.

Efficiency improvement of P3CT-Na based MAPbI3solar cells with a simple wetting process.

The averaged power conversion efficiency of polyelectrolytes (P3CT-Na) based MAPbI3solar cells can be increased from 14.94% to 17.46% with a wetting method before the spin-coating process of MAPbI3precursor solutions. The effects of the wetting process on the surface, structural, optical and excitonic properties of MAPbI3thin films are investigated by using the atomic-force microscopic images, x-ray diffraction patterns, transmittance spectra, photoluminescence spectra and Raman scattering spectra. The experimental results show that the wetting process of MAPbI3precursor solution on top of the P3CT-Na/ITO/glass substrate can be used to manipulate the molecular packing structure of the P3CT-Na thin film, which determines the formation of MAPbI3thin films.

Study of conduction mechanisms of InSeSb nano-chalcogenide alloys.

The electrical conduction mechanisms for bulk samples of In0.1Se0.9-xSbx(x= 0, 0.04, 0.08 and 0.12) nano-chalcogenide system, synthesized by the melt-quenching technique are investigated through current-voltage (I-V) characteristics. For the detailed study of conduction mechanism pellets of bulk samples are prepared. A thorough examination of electrical conductivity is done in the temperature range of 295-318 K and 0-50 V voltage range. FromI-Vmeasurements it is observed that samples are showing ohmic nature at lower field and non-ohmic nature at relatively higher field values. The temperature dependence of DC conductivity is analyzed using the Arrhenius relationship which is found to increase with Sb content. The value of activation energy and pre-exponential factor are calculated, which revealed that the conduction is due to the hopping of charge carriers among the localized states. Different parameters of Mott's variable range hopping such as degree of disorderT0, density of localized statesN(EF), hopping distance (Rhop), and hopping energy (W) are calculated. For the high field conduction process Poole-Frenkel, and Schottky processes are studied.

The Significance of Systemic Inflammatory Markers in Prognosis of Head and Neck Squamous Cell Cancers.

This present study aimed to assess the predictive significance of two systemic inflammatory markers, the neutrophilic to lymphocytic ratio (NLR) and platelet to lymphocytic ratio (PLR), in evaluating the prognosis of individuals. The research involved 47 patients diagnosed with head and neck squamous cell carcinoma, all of whom were histo-pathologically confirmed and aged over 18 years. The patients were monitored every 6 months for a period of 18 months. The average age of the study participants was 57.66 ± 13.5 years, with 42 (89.36%) being male and 5 (10.64%) female. After 6 months, the mean PLR in patients with residual/recurrence was 161.5 ± 8.5, which was significantly, exceeded that of patients without residual/recurrence (109.07 ± 36.29; p value < 0.0001). However, no significant correlation was seen between the NLR (p value = 0.822) and residual/recurrence after 6 months. After 12 months, the mean NLR in patients with recurrence was 4.89 ± 0.69, which was significantly higher compared to patients without recurrence (3.48 ± 1.01; p value = 0.025). Conversely, no significant association was found between the PLR (p value = 0.751) and recurrence after 12 months. Notably, there were no significant associations observed in NLR and PLR at the 18-month mark. Elevated levels of the NLR and PLR can serve as indicators of poor prognosis and the presence of residual/recurrent disease in head and neck malignancies.

0.342 nW Class-AB enhanced flipped source follower low pass filter for biomedical applications.

Owing to the impact of process voltage and temperature variations, the design of low-power low-pass filters (LPFs) with improved linearity is still one of the most challenging tasks for effective biological signal processing. This paper presents the design of a fourth-order Class-AB enhanced flipped source follower (EFSF) LPF circuit aimed at the detection of electroencephalography signals. The simulated results attained using complementary metal-oxide-semiconductor 180 nm technology node in Cadence Analog Design Environment demonstrate that the EFSF LPF emulates a DC-gain of -88 mdB with a bandwidth of 100 Hz and consumes 0.342 nW power from a supply voltage of 0.5 V. The calculated figure of merit for the proposed filter is 5.983 × 10-15 J with a dynamic range (DR) of 43.54 dB and input-referred noise of 91 µVrms. It consumes an area of 0.0458 mm2. To check the robustness of the proposed filter circuit, we performed Monte Carlo simulations with 200 runs. The statistical results achieved for the DC-gain, DR, and total harmonic distortion of the proposed filter show mean values of -188.09 mdB, 43.10 dB, and -41.85 dB along with standard deviation values of 285.21 mdB, 718.72 mdB, and 4.52 dB, respectively. The proposed Class-AB EFSF LPF can be used to achieve high power efficiency in future low-voltage and low-power biological systems.

A Review on Spike and Recovery Method in Analytical Method Development and Validation.

In multidisciplinary science, Analytical approaches based on spike and recovery (SAR) play a substantial role in analytical testing. The spike and recovery method is an important technique for analyzing and accessing the accuracy of analytical methods. The goal of this review seeks to provide clarity on the role of SAR methods in the forensic science discipline. Recent literature has been searched from numerous databases like Google, Web of Sciences, Scopus, PubMed, Google Scholar, and SciFinder. Websites like Science Direct are critically explored to gather scientific reports related to SAR utility. This review discusses the applications and current role of the SAR methods in Forensic Toxicology. It is suggested as one of the major parameters in the validation of the analytical method. SAR methodology is extremely important for the identification and quantitation of analytes in the sample matrix. Moreover, the extension of SAR methods to any scientific discipline is equally important for quality assurance. All relevant processes like method development and its optimization, quality control, and assurance rely on SAR-based studies. However, the method requires better apprehension and needs to be utilized using standard guidelines.

Stable and efficient soft perovskite crystalline film based solar cells prepared with a facile encapsulation method.

The quasi Fermi level for electrons in a soft perovskite crystalline thin film and the contact qualities at the PCBM/perovskite and perovskite/P3CT-Na interfaces can be increased using a facile encapsulation method, which improves the device performance and stability of the resultant perovskite solar cells. In the encapsulated perovskite solar cells, the averaged open-circuit voltage (VOC) largely increases from 0.981 V to 1.090 V after 9 days mainly due to the increased quasi Fermi levels. Besides, the reflectance and photoluminescence (PL) spectra show improved contact qualities at the PCBM/perovskite and perovskite/P3CT-Na interfaces, which can be used to explain the increase in the short-circuit current density (JSC) from 21.68 mA cm-2 to 23.48 mA cm-2 after the encapsulation process. Besides, nanosecond time-resolved PL and temperature-dependent PL spectra can be used to explain the increased VOC, which is mainly due to the increased shallow defect density and thereby increasing the exciton binding energy of the encapsulated perovskite sample. It is noted that the averaged power conversion efficiency (PCE) slowly decreases from 18.24% to 16.52% within 45 days.

Functional Pyrene-Pyridine-Integrated Hole-Transporting Materials for Solution-Processed OLEDs with Reduced Efficiency Roll-Off.

A series of new functional pyridine-appended pyrene derivatives, viz., 2,6-diphenyl-4-(pyren-1-yl)pyridine (Py-03), 2,6-bis(4-methoxyphenyl)-4-(pyren-1-yl)pyridine (Py-MeO), 4-(pyren-1-yl)-2,6-di-p-tolylpyridine (Py-Me), and 2,6-bis(4-bromophenyl)-4-(pyren-1-yl)pyridine (Py-Br) were designed, developed, and studied as the hole-transporting materials (HTMs) for organic light-emitting diode (OLED) application. The crystal structures of two molecules revealed to have a large dihedral angle between the pyrene and pyridine units, indicating poor π-electronic communication between them due to ineffective orbital overlap across the pyrene-pyridine systems as the two p-orbitals of pivotal atoms are twisted at 66.80° and 68.75° angles to each other in Py-03 and Py-Me, respectively. The influence of variedly functionalized pyridine units on the electro-optical properties and device performance of the present integrated system for OLED application was investigated. All of the materials have suitable HOMO values (5.6 eV) for hole injection by closely matching the HOMOs of indium tin oxide (ITO) and the light-emitting layer. All of the synthesized molecules have suitable triplet energies, glass transition temperatures, and melting temperatures, which are highly desirable for good HTMs. The pyrene-pyridine-based devices demonstrated stable performance with low-efficiency roll-off. The device with Py-Br as HTM showed a maximum luminance of 17300 cd/m2 with a maximum current efficiency of 22.4 cd/A and an EQE of 9% at 3500 cd/m2 with 7% roll-off from 1000 to 10 000 cd/m2. Also, the devices with Py-Me and Py-03 showed performance roll-up while moving from 1000 to 10 000 cd/m2.

High-Throughput Virtual Screening of Host Materials and Rational Device Engineering for Highly Efficient Solution-Processed Organic Light-Emitting Diodes.

The appropriate choice of host and electron-transporting material (ETM) plays a very crucial role in the generation and collection of radiative excitons in the desired recombination zone of organic light-emitting diodes (OLEDs). Due to the sustainable development of material organic chemistry, there is a big library of functional materials that leads to uncountable combinations of device structures, which might achieve a desirable high device performance. However, there is no appropriate methodology available for the fast virtual screening of organic materials and designing a suitable device structure. Here, we have used the electrical software package SETFOS 4.5 for high-throughput virtual screening of host materials and developed a highly efficient multistack OLED device structure. To further enhance the device performance, a co-host approach has been used, and the final device structure has also been optimized with two different ETMs. The best-optimized Ir(ppy)3-based solution-processed green OLED device exhibited a maximum power efficiency (PE) of 83.20 lm/W and brightness of 61,362 cd/m2 with a driving voltage of 2.1 V without using any light extraction outcoupling techniques, which is the best among the OLEDs in its own category. The developed device structure has also been utilized to fabricate highly efficient blue hazard-free low-color temperature OLEDs for a physiologically friendly light at night. The resultant 2083 K OLED device displayed a maximum PE of 51.4 lm/W and luminance of 44,548 cd/m2 with a turn-on voltage of 2.1 V that is also 42 and 104 times safer in terms of retinal protection and ∼4 and ∼11 times safer in terms of melatonin generation when compared with those of a real candle and incandescent bulb, respectively. The observed excellent device performance may be attributed to the balanced charge carrier in the recombination zone, broader emissive layer due to a mixed-host system, less accumulation of charges at the injecting surfaces, well-aligned triplet energy and molecular orbital energy level of the host and guest, and high electron mobility and enhanced hole blocking ability of the employed ETM in the designed OLED device structure.

The Way to Pursue Truly High-Performance Perovskite Solar Cells.

The power conversion efficiency (PCE) of single-junction solar cells was theoretically predicted to be limited by the Shockley-Queisser limit due to the intrinsic potential loss of the photo-excited electrons in the light absorbing materials. Up to now, the optimized GaAs solar cell has the highest PCE of 29.1%, which is close to the theoretical limit of ~33%. To pursue the perfect photovoltaic performance, it is necessary to extend the lifetimes of the photo-excited carriers (hot electrons and hot holes) and to collect the hot carriers without potential loss. Thanks to the long-lived hot carriers in perovskite crystal materials, it is possible to completely convert the photon energy to electrical power when the hot electrons and hot holes can freely transport in the quantized energy levels of the electron transport layer and hole transport layer, respectively. In order to achieve the ideal PCE, the interactions between photo-excited carriers and phonons in perovskite solar cells has to be completely understood.