Organic Optoelectronic Devices Research Articles

High responsivity photodetector based on MEH-PPV/CsPbBr3 heterojunction

Perovskite quantum dots (QDs) and organic materials have great research potential in the field of optoelectronic devices. In this paper, MEH-PPV/CsPbBr3 heterojunction photodetectors (PDs) are prepared by spin coating method based on the good photoelectric properties of CsPbBr3 perovskite QDs and MEH-PPV. The MEH-PPV/CsPbBr3 heterojunction improves the energy level arrangement, and CsPbBr3 QDs can passivate the surface defects of MEH-PPV films to achieve effective charge separation and transfer, thus inhibiting the dark current and improving the photoelectric performance of the device. Under 532 nm laser irradiation, the responsivity (R) of MEH-PPV/CsPbBr3 heterojunction PD is 11.98 A W−1, the specific detectivity (D*) is 6.98 × 1011 Jones, and the response time is 15/16 ms. This work provides experience for the study of perovskite QDs and organic materials heterojunction optoelectronic devices.

Structure-property relationships in dicyanopyrazinoquinoxalines and their hydrogen-bonding-capable dihydropyrazinoquinoxalinedione derivatives.

Presented here is the design, synthesis, and study of a variety of novel hydrogen-bonding-capable π-conjugated N-heteroacenes, 1,4-dihydropyrazino[2,3-b]quinoxaline-2,3-diones (DPQDs). The DPQDs were accessed from the corresponding weakly hydrogen-bonding dicyanopyrazinoquinoxaline (DCPQ) suspensions with excess potassium hydroxide, resulting in moderate to good yields. Both families of compounds were analyzed by UV-vis and NMR spectroscopy, where the consequences of hydrogen bonding capability could be assessed through the structure-property studies. Conversion of the DCPQs into hydrogen-bonding capable DPQDs results in modulation of frontier MO energies, higher molar extinction coefficients, enhanced crystallinity, and on-average higher thermal stability (where in some cases the 5% weight loss temperature is increased by up to 100 °C). Single crystal X-ray diffraction data could be obtained for three DPQDs. One reveals pairwise hydrogen bonding in the solid state as well as a herringbone packing arrangement rendering it a promising candidate for additional studies in the context of organic optoelectronic devices.

Fluorescent Schiff Bases with Phenothiazine and Coumarin Moieties: Synthesis, Characterization, Photophysical, Electrochemical, Computational and Biological Studies.

We present the design and synthesis of four new schiff bases viz., two each of phenothiazine and coumarin derivatives. The structures were proposed based on FT-IR, 1H NMR, 13C NMR and mass spectral data. The photophysical, solvatochromic and electrochemical studies of all the compounds were carried out. Furthermore, theoretical studies such as density functional theory (DFT) were carried out to gain a better understanding of the compounds' intramolecular charge transfer properties and electronic structures. Good agreement was noticed between the HOMO-LUMO energy gap obtained from DFT studies and that calculated from absorption threshold wavelengths. All the compounds showed Stokes shifts in the range of 6345-11,405cm-1. These findings showed that the new schiff bases could be considered as attractive candidates for use in the development of OLEDs, organic electrical devices and optoelectronic devices. Newly synthesized compounds were tested for biological activities. When compared to conventional standards, gallic acid and indomethacin, the schiff bases showed better antioxidant and antiinflammatory activities, respectively.

Thermally Induced Phase Separation of the PEDOT:PSS Layer for Highly Efficient Laminated Polymer Light-Emitting Diodes.

Among various conductive polymers, the poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) film has been studied as a promising material for use as a transparent electrode and a hole-injecting layer in organic optoelectronic devices. Due to the increasing demand for the low-cost fabrication of organic light-emitting diodes (OLEDs), PEDOT:PSS has been employed as the top electrode by using the coating or lamination method. Herein, a facile method is reported for the fabrication of highly efficient polymer light-emitting diodes (PLEDs) based on a laminated transparent electrode (LTE) consisting of successive PEDOT:PSS and silver-nanowire (AgNW) layers. In particular, thermally induced phase separation (TIPS) of the PEDOT:PSS film is found to depend on the annealing temperature (Tanneal) during preparation of the LTE. At Tanneal close to the glass transition temperature of the PSS chains, a PSS-rich phase with a large number of PSS- molecules enhances the work function of the PEDOT:PSS on the glass-side surface relative to the air side. By using the optimized LTEs, bidirectional laminated PLEDs are obtained with a total external quantum efficiency of 2.9% and a turn-on voltage of 2.6 V, giving a comparable performance to that of the reference bottom-emitting PLED based on a costly evaporated metal electrode. In addition, an analysis of the angular characteristics, including the variation in the electroluminescence spectra and the change in luminance according to the emission angle, indicates that the laminated PLED with the LTE provides a more uniform angular distribution regardless of the direction of emission. Detailed optical and electrical analyses are also performed to evaluate the suitability of LTEs for the low-cost fabrication of efficient PLEDs.

Doubly Spiro-Conjugated Chiral Carbocycles Exhibiting SOMO-HOMO Inversion in Persistent Radical Cations.

Persistent chiral organic open-shell systems have captured growing interest due to their potential applications in organic spintronic and optoelectronic devices. Nevertheless, the integration of configurationally stable chirality into an organic open-shell system continues to pose challenges in molecular design. The π-extended skeleton incorporated in spiro-conjugated carbocycles can provide robust chiroptical properties and a significant stabilization of the excited and ionic radical states. However, this approach has been relatively less explored in the design of persistent organic open-shell systems. We report here the (S,S)-, (R,R)-, and meso-isomers of doubly spiro-conjugated carbocycles featuring flat and rigid carbon-bridged para-phenylenevinylene (CPV) of different conjugation lengths connected by two spiro-carbon centers, which we denote D-spiro-CPV for its quasi-dimeric structure. Our synthetic method based on a double lithiation cyclization approach enables facile production of D-spiro-CPV. D-spiro-CPVs exhibit circularly polarized luminescence (CPL) with high fluorescence quantum yields (ΦFL) resulting in a high CPL brightness of 21 M-1 cm-1 and also exhibit high thermal and photostability. The monoradical cation of D-spiro-CPV absorbing near-infrared light is notably persistent, exhibiting a half-life of 570 h under ambient conditions due to doubly spiro-conjugative stabilization. Theoretical and electrochemical studies indicate the radical cation of D-spiro-CPVs presents a non-Aufbau electron filling, exhibiting inversion of the energy level of the singly occupied molecular orbital (SOMO) and the highest (doubly) occupied molecular orbitals with the SOMO level even below the HOMO-1 level (double SHI effect). Our discoveries provide valuable insights into non-Aufbau molecules and the development of configurationally stable, optically active persistent radicals.

Abnormal temperature-dependent transient electroluminescence spikes induced by the leakage of hole carriers in organic light-emitting diodes

The amplitude of the emission spike at the transient electroluminescence (TEL) falling edge is an important benchmark for evaluating the quantities of trapped charges existed in organic light-emitting diodes and often shows a normal temperature dependence which increases with the decreasing temperature. Surprisingly, an unreported abnormal temperature-dependent TEL spike was observed in this work. A series of experimental results relevant to the electroluminescence spectrum and TEL measurements demonstrate that this abnormal temperature-dependent behavior is induced by the leakage of hole carriers from the emission layer (EML) to an electron transport layer (ETL). After the voltage pulse is turned off, these holes already leaked into the ETL drift back toward the EML, subsequently engaging in radiative recombination with trapped electrons on guest molecules to generate a spike at the TEL falling edge. However, the drift process is hindered by the reduced carrier mobility of the ETL material with the decrease in temperature. As a result, the spike intensity weakens as the temperature decreases, which contradicts the conclusions reported in previous literatures. Therefore, this study not only leads to the reconsideration for the judgment criteria of the number of trapped charges but also provides valuable insight into the TEL research field of organic optoelectronic devices.

All-solution-processed ultraflexible wearable sensor enabled with universal trilayer structure for organic optoelectronic devices.

All-solution-processed organic optoelectronic devices can enable the large-scale manufacture of ultrathin wearable electronics with integrated diverse functions. However, the complex multilayer-stacking device structure of organic optoelectronics poses challenges for scalable production. Here, we establish all-solution processes to fabricate a wearable, self-powered photoplethysmogram (PPG) sensor. We achieve comparable performance and improved stability compared to complex reference devices with evaporated electrodes by using a trilayer device structure applicable to organic photovoltaics, photodetectors, and light-emitting diodes. The PPG sensor array based on all-solution-processed organic light-emitting diodes and photodetectors can be fabricated on a large-area ultrathin substrate to achieve long storage stability. We integrate it with a large-area, all-solution-processed organic solar module to realize a self-powered health monitoring system. We fabricate high-throughput wearable electronic devices with complex functions on large-area ultrathin substrates based on organic optoelectronics. Our findings can advance the high-throughput manufacture of ultrathin electronic devices integrating complex functions.

Universal Design and Efficient Synthesis for High Ambipolar Mobility Emissive Conjugated Polymers.

High ambipolar mobility emissive conjugated polymers (HAME-CPs) are perfect candidates for organic optoelectronic devices, such as polymer light emitting transistors. However, due to intrinsic trade-off relationship between high ambipolar mobility and strong solid-state luminescence, the development of HAME-CPs suffers from high structural and synthetic complexity. Herein, a universal design principle and simple synthetic approach for HAME-CPs are developed. A series of simple non-fused polymers composed of charge transfer units, π bridges and emissive units are synthesized via a two-step microwave assisted C-H arylation and direct arylation polymerization protocol with high total yields up to 61 %. The synthetic protocol is verified valid among 7 monomers and 8 polymers. Most importantly, all 8 conjugated polymers have strong solid-state emission with high photoluminescence quantum yields up to 24 %. Furthermore, 4 polymers exhibit high ambipolar field effect mobility up to 10-2 cm2 V-1 s-1, and can be used in multifunctional optoelectronic devices. This work opens a new avenue for developing HAME-CPs by efficient synthesis and rational design.

Universal Design and Efficient Synthesis for High Ambipolar Mobility Emissive Conjugated Polymers

AbstractHigh ambipolar mobility emissive conjugated polymers (HAME‐CPs) are perfect candidates for organic optoelectronic devices, such as polymer light emitting transistors. However, due to intrinsic trade‐off relationship between high ambipolar mobility and strong solid‐state luminescence, the development of HAME‐CPs suffers from high structural and synthetic complexity. Herein, a universal design principle and simple synthetic approach for HAME‐CPs are developed. A series of simple non‐fused polymers composed of charge transfer units, π bridges and emissive units are synthesized via a two‐step microwave assisted C−H arylation and direct arylation polymerization protocol with high total yields up to 61 %. The synthetic protocol is verified valid among 7 monomers and 8 polymers. Most importantly, all 8 conjugated polymers have strong solid‐state emission with high photoluminescence quantum yields up to 24 %. Furthermore, 4 polymers exhibit high ambipolar field effect mobility up to 10−2 cm2 V−1 s−1, and can be used in multifunctional optoelectronic devices. This work opens a new avenue for developing HAME‐CPs by efficient synthesis and rational design.

From monomer to polymer: Controlled synthesis and comprehensive analysis of poly(p-phenylene vinylene) via ROMP

This study focuses on synthesis and evaluation of [2.2] paracyclophane-1,9-diene to produce a soluble poly(p-phenylenevinylene) (PPV) derivative homopolymer using ring-opening metathesis polymerization (ROMP). The resulting homopolymer displayed a narrow polydispersity index (PDI) of 1.22, indicating precise control over polymerization. The PPV derivative exhibited excellent solubility in various organic solvents. Photophysical properties, including optical absorption and fluorescence emission spectra, were investigated to evaluate utilization in optoelectronic devices. Optical band gaps ranged from 2.21 to 2.25 eV for thin films and 2.07 to 2.19 eV for solutions, while the electrochemical band gap, determined by cyclic voltammetry, was 2.37 eV. These materials demonstrated promising fluorescence activity in various solvents and thin films, suggesting potential applications in organic light-emitting diodes (OLEDs) and related optoelectronic devices.

Investigation on structural, optical, thermal, and dielectric properties of cellulose propionate/styrene-maleic anhydride copolymer/molybdenum nanocomposite prepared by pulsed laser ablation

Polymer nanocomposite films of cellulose propionate/styrene-maleic anhydride copolymer/molybdenum (CP/SMAC/Mo) were fabricated by pulsed laser ablation of Mo in the polymer solution for 10, 20, and 30 min. The films were then characterized by various analytical methods. X-ray diffraction (XRD) revealed that the addition of Mo to CP/SMAC removed the crystalline peaks of Mo without changing the amorphous nature of the copolymer. According to the scanning electron microscopy (SEM) and atomic force microscopy (AFM) patterns, Mo atoms were trapped in the amorphous polymer stacks. The energy-dispersive X-ray (EDX) spectrum features C, O, and Mo. FTIR confirmed the embedding of Mo in the polymers. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were carried out on the samples. The pristine polymer film exhibited a band gap energy of 2.9 eV, which decreased to 2.05 eV because of the loading of the Mo nanoparticles. The intensity of the photoluminescence (PL) peak of the films increases with ablation time such that the absorption intensity of the film at a λmax of 426 nm increases by trifold during the 30 min of irradiation, which is consequently due to the increased amount of Mo in the nanostructure. The incorporation of Mo in the polymer matrix enhances the dielectric constant (ε') (6.28–18.13) and ac conductivity (σac) (3.19 × 10−5–1.12 × 10−4 S/cm) of the polymer with negligible dielectric loss. The results suggest possible technological utilization of these materials in such applications as supercapacitors, light-emitting diodes, and organic optoelectronic devices, among others.

Aqueous solution processed transition-metal-doped ZnO as electron injection layers for efficient inverted organic light emitting diodes

Zinc oxide (ZnO) has attracted lots of attention to be used as interfacial materials in organic optoelectronic devices owing to its attractive properties. In this work, a series of transition-metal-doped ZnO thin films were prepared by using a facile aqueous solution process, thereafter these films were employed as electron injection layers (EILs) combined with the tris-(8-hydroxyquinoline) aluminum (Alq3) emitting layer to construct the inverted organic light-emitting diodes (IOLEDs). The transition-metal-doped ZnO EIL-based IOLEDs demonstrate markedly improved device performance compared to the reference neat ZnO EIL-based IOLED. However, different transition-metal ions have much different doping effect on the device performance. CoCl2 doped ZnO EIL based IOLED device possesss an optimal current efficiency of 5.52 cd A−1, which is increased about 40% compared to the device with the neat ZnO as EIL. The enhancement might be attributed to the increased electron mobility and favorable interfacial energy level alignment of the transition-metal doped ZnO EIL for more efficient electron injection. Our findings may provide a promising strategy to improve the electron injection properties of ZnO film in the OLED devices.

Electropolymerization and characterization of a new ambipolar perimidine polymer with a perylene core

We successfully synthesized a stable electroactive perinone polymer by electropolymerization from the mixture of syn- and anti- isomers (ratio 1:1) of 3,4:9,10-bis(1,8-naphthapyrimidine)-1,6,7,12-tetrakis(1,1,3,3-tetramethylobutylphenoxy)perylene (NPP). The polymer p(NPP) exhibited distinct redox process, with reduction at -1.20 V and oxidation at 0.60 V (vs. ferrocene/ferrocenium couple). Spectroscopic and computational analyses confirmed structural similarity of the polymer to its monomeric form, revealing a perimidine unit involved in electrocoupling. Our thorough investigations elucidated the redox reactions electrochemical mechanism within the polymer film, identifying predominantly deprotonated bis-perimidine segments contributing to oxidation peaks at 0.60 V and 0.68 V. Additionally, the perylenediamide core exhibits the reversible, multi-stage reduction process. Impedance analysis highlighted efficient n-doping-induced conductivity, suggesting application in organic optoelectronic devices. This work positions p(NPP) as a versatile ambipolar multiredox p- and n-type conductor, indicating a potential for expanding perinone-based perylene-diperimidine polymers for innovative electronics.

Highly reliable and stretchable OLEDs based on facile patterning method: toward stretchable organic optoelectronic devices

Stretchable displays attract significant attention because of their potential applications in wearable electronics, smart textiles, and human-conformable devices. This paper introduces an electrically stable, mechanically ultra-robust, and water-resistant stretchable OLED display (SOLED) mounted on a stress-relief pillar platform. The SOLED is fabricated on a thin, transparent polyethylene terephthalate (PET) film using conventional vacuum evaporation, organic-inorganic hybrid thin film encapsulation (TFE), and a nonselective laser patterning process. This simple and efficient process yields an OLED display with exceptional stretchability, reaching up to 95% strain and outstanding durability, enduring 100,000 stretch-release cycles at 50% strain. Operational lifetime and water-resistant storage lifetime measurements confirm that the TFE provides effective protection even after the nonselective laser patterning process. A 3 × 3 array SOLED display module mounted on a stress-relief pillar platform is successfully implemented, marking the first case of water-resistant display array operation in the field of SOLEDs. This work aims to develop practical stretchable displays by offering a reliable fabrication method and device design for creating mechanically robust and adaptable displays, potentially paving the way for future advances in human-conformable electronics and other innovative applications.

Peripheral Selenium Modification of Multi‐Resonance Thermally Activated Delayed Fluorescence Molecules for High‐Performance Blue Organic Light‐Emitting Diodes

AbstractMulti‐resonance thermally activated delayed fluorescence (MR‐TADF) molecules have attracted much attention in the academia owing to their unique photoelectrical properties. However, MR‐TADF emitters usually show slow reverse intersystem crossing (RISC) rate, resulting in high efficiency roll‐off of organic light‐emitting diodes (OLEDs) and seriously limiting their further development. Here, a peripheral selenium (Se) modification is presented for MR‐TADF molecules to promote the RISC process while keeping the narrowband emission for high‐performance blue OLEDs. Compared to the parent molecules (NBN and tBuNBN), SeNBN and SetBuNBN exhibited narrower full‐width at half maximum (FWHM) value of 23 nm and more obvious delayed fluorescence properties with a high efficiency of delayed fluorescence up to 86%, shorter delayed lifetime of 2.4 µs as well as a faster RISC rate of 3.34×105 s−1. Therefore, high‐performance OLEDs based on these two Se modified MR‐TADF emitters are achieved with a high maximum external quantum efficiency (EQE) up to 25.5% and extremely suppressed efficiency roll‐offs of 3.9% at 100 cd m−2 and 24.4% at 1000 cd m−2. This work demonstrated that the introduction of peripheral Se atom can achieve high‐performance organic semiconductors with both narrowband emission and fast RISC rate constant for high‐performance organic optoelectronic devices.

Visualization of Nanocrystallites in Organic Semiconducting Blends Using Cryo-Electron Microscopy.

The efficiency of an organic solar cell is highly dependent on the complex, interpenetrating morphology, and molecular order within the composite phases of the bulk heterojunction (BHJ) blend. Both these microstructural aspects are strongly influenced by the processing conditions and chemical design of donor/acceptor materials. To establish improved structure-function relationships, it is vital to visualize the local microstructural order to provide specific local information about donor/acceptor interfaces and crystalline texture in BHJ blend films. The visualization of nanocrystallites, however, is difficult due to the complex semi-crystalline structure with few characterization techniques capable of visualizing the molecular ordering of soft materials at the nanoscale. Here, it is demonstrated how cryo-electron microscopy can be utilized to visualize local nanoscale order. This method is used to understand the distribution/orientation of crystallites in a BHJ blend. Long-range (>300nm) texturing of IEICO-4F crystallites oriented in an edge-on fashion is observed, which has not previously been observed for spin-coated materials. This approach provides a wealth of quantitative information about the texture and size of nanocrystallites, which can be utilized to understand charge generation and transport in organic film. This study guides tailoring the material design and processing conditions for high-performance organic optoelectronic devices.

Unveiling the Strain‐induced Microstructural Evolution and Morphology‐Stretchability Correlations of Intrinsically Stretchable Organic Photovoltaic Films

AbstractThe progress of stretchable and wearable photovoltaics relies heavily on intrinsically stretchable active layer films. Nevertheless, there is a paucity of research clarifying the connections between their microstructure, performance, and their adaptation to large strain in polymer electronic films. The current study utilizes multiple synchrotron X‐ray scattering methods to collectively examine the correlations between morphology and stretchability, as well as the microstructural evolution induced by stretching in three sample cases of highly stretchable ternary blend films. These blends contain over 30% by weight of a polymer elastomer, such as styrene‐ethylene‐butylene‐styrene block copolymer, integrated into the high‐performance polymer:nonfullerene small molecule mixture. Specifically, the real‐time microstructural changes of these durable organic photovoltaic films with elastomers are monitored when subjected to tensile stretching through in situ synchrotron X‐ray scattering. The experiments demonstrate that polymeric elastomers can effectively lower the degree of crystallinity in films and deform the crystallites of semiconductor molecules. The elastomeric component aids in stress dispersion during stretching, thereby improving the microstructural durability of blend films. This study provides new recommendations for advancing stretchable organic optoelectronic devices.

Surface‐Initiated Living Self‐Assembly of Polythiophene‐Based Conjugated Block Copolymer into Erect Micellar Brushes

AbstractNanostructured conjugated polymers are of widespread interest due to their broad applications in organic optoelectronic devices, biomedical sensors and other fields. However, the alignment of conjugated nanostructures perpendicular to a surface remains a critical challenge. Herein, we report a facile method to directly self‐assemble a poly(3‐(2‐ethylhexyl)thiophene), P3EHT‐based block copolymer into densely aligned micellar brushes through surface‐initiated living crystallization‐driven self‐assembly. The presence of an ethyl pendant on the side group intrinsically moderates the crystallization rate of the polythiophene main chains, and hence favors the controlled living growth of long conjugated fibers and the subsequent fabrication of conjugated micellar brushes. The corona of the micellar brush can be further decorated with platinum nanoparticles, which enables the formation of erect nanoarrays with heights up to 2700 nm in the dried state. This also renders the micellar brush catalytically active toward hydrogen evolution reaction, which shows a low overpotential of 27 mV at 10 mA cm−2. Notably, the P3EHT‐based micellar brush can simultaneously grow with polyferrocenyldimethylsilane, PFS‐based micellar brush on the same surface without any significant interference between the two systems. Thus, these two micellar brushes can be patterned through site‐selective immobilization of two types of seeds followed by independent living self‐assembly.

Surface-Initiated Living Self-Assembly of Polythiophene-Based Conjugated Block Copolymer into Erect Micellar Brushes.

Nanostructured conjugated polymers are of widespread interest due to their broad applications in organic optoelectronic devices, biomedical sensors and other fields. However, the alignment of conjugated nanostructures perpendicular to a surface remains a critical challenge. Herein, we report a facile method to directly self-assemble a poly(3-(2-ethylhexyl)thiophene), P3EHT-based block copolymer into densely aligned micellar brushes through surface-initiated living crystallization-driven self-assembly. The presence of an ethyl pendant on the side group intrinsically moderates the crystallization rate of the polythiophene main chains, and hence favors the controlled living growth of long conjugated fibers and the subsequent fabrication of conjugated micellar brushes. The corona of the micellar brush can be further decorated with platinum nanoparticles, which enables the formation of erect nanoarrays with heights up to 2700 nm in the dried state. This also renders the micellar brush catalytically active toward hydrogen evolution reaction, which shows a low overpotential of 27 mV at 10 mA cm-2 . Notably, the P3EHT-based micellar brush can simultaneously grow with polyferrocenyldimethylsilane, PFS-based micellar brush on the same surface without any significant interference between the two systems. Thus, these two micellar brushes can be patterned through site-selective immobilization of two types of seeds followed by independent living self-assembly.

Comprehensive analysis of DFT-3C methods with B3LYP and experimental data to model optoelectronic properties of tetracene

Modern computational chemistry methods aid experimentalists in scrutinizing molecular systems for organic optoelectronic device fabrication. They are also helpful for device engineering, such as choosing metals for contact fabrication without sophisticated instrumentation. The B3LYP functional with 6-31G(d,p) or 6-311G(d,p) basis set is a widely used method in this regard. Recently, many upgraded methods, such as the three-fold corrected composite scheme (3C), have been reported to offer cost-effectiveness and better accuracy than the B3LYP. This is particularly interesting from a materials engineering point of view as these methods offer the possibility of rapidly screening the materials prior to the experimental analysis. In order to evaluate their suitability towards organic optoelectronic systems, in this work, we have used three composite schemes, namely B97-3C, PBEh-3C and HF-3C, along with B3LYP and the experimental data. The well-studied tetracene system is considered for the analysis, and different optoelectronic properties such as bandgap, reorganization energy, and absorption maximum are calculated theoretically and compared with the experimental data. The results indicate that though slightly expensive, B3LYP performs better than the 3C methods. Of the three, only PBEh-3C performs on par with B3LYP in accuracy and time. A note of caution is that these results should be inferred as this level of theory is adequate for the screening and modeling optoelectronic systems rather than a potential computational chemistry method.