Organic Photovoltaic Stability: Understanding the Role of Engineering Exciton and Charge Carrier Dynamics from Recent Progress.

Benefiting from the synergistic development of material design, device engineering, and the mechanistic understanding of device physics, the certified power conversion efficiencies (PCEs) of single-junction non-fullerene organic solar cells (OSCs) have already reached a very high value of exceeding 19%. However, in addition to PCEs, the poor stability is now a challenging obstacle for commercial applications of organic photovoltaics (OPVs). Herein, recent progress made in exploring operational mechanisms, anomalous photoelectric behaviors, and improving long-term stability in non-fullerene OSCs are highlighted from a novel and previously largely undiscussed perspective of engineering exciton and charge carrier pathways. Considering the intrinsic connection among multiple temporal-scale photocarrier dynamics, multi-length scale morphologies, and photovoltaic performance in OPVs, this review delineates and establishes a comprehensive and in-depth property-function relationship for evaluating the actual device stability. Moreover, this review has also provided some valuable photophysical insights into employing the advanced characterization techniques such as transient absorption spectroscopy and time-resolved fluorescence imagings. Finally, some of the remaining major challenges related to this topic are proposed toward the further advances of enhancing long-term operational stability in non-fullerene OSCs.

Computational Design of Multiple Resonance-Type BN Molecules for Inverted Singlet and Triplet Excited States.

A computational design of linearly extended multiple resonance (MR)-type BN molecules based on DABNA-1 is proposed herein in the quest to find potential candidates that exhibit a negative singlet-triplet gap (ΔEST) and a large oscillator strength value. The impact of a proper account of the electron correlation in the lowest singlet and triplet excited states is systematically investigated by using double-hybrid functionals within the TD-DFT framework, as well as wavefunction-based methods (EOM-CCSD and SCS-CC2), since this contribution plays an essential role in driving the magnitude of the ΔEST in MR-TADF and inverted singlet-triplet gap compounds. Our results point out a gradual reduction of the ΔEST gap with respect to the increasing sum of the number of B and N atoms, reaching negative ΔEST values for some molecules as a function of their size. The double-hybrid functionals reproduce the gap with only slight deviation compared to available experimental data for DABNA-1, ν-DABNA, and mDBCz and nicely agree with high-level quantum mechanical methods (e.g., EOM-CCSD and SCS-CC2). Larger oscillator strengths are found compared to the azaphenalene-type molecules, also exhibiting the inversion of their singlet and triplet excited states. We hope this study can serve as a motivation for further design of the molecules showing negative ΔEST based on boron- and nitrogen-doped polyaromatic hydrocarbons.

Correlating Charge Transfer Dynamics with Interfacial Trap States in High-Efficiency Organic Solar Cells.

The charge transfer between the donor and acceptor determines the photogenerated carrier density in organic solar cells. However, a fundamental understanding regarding the charge transfer at donor/acceptor interfaces with high-density traps has not been fully addressed. Herein, a general correlation between trap densities and charge transfer dynamics is established by adopting a series of high-efficiency organic photovoltaic blends. It is found that the electron transfer rates are reduced with increased trap densities, while the hole transfer rates are independent of trap states. The local charges captured by traps can induce potential barrier formation around recombination centers, leading to the suppression of electron transfer. For the hole transfer process, the thermal energy provides a sufficient driving force, which ensures an efficient transfer rate. As a result, a 17.18% efficiency is obtained for PM6:BTP-eC9-based devices with the lowest interfacial trap densities. This work highlights the importance of interfacial traps in charge transfer processes and proposes an underlying insight into the charge transfer mechanism at nonideal interfaces in organic heterostructures.

Delayed fluorescence from inverted singlet and triplet excited states.

Hund's multiplicity rule states that a higher spin state has a lower energy for a given electronic configuration1. Rephrasing this rule for molecular excited states predicts a positive energy gap between spin-singlet and spin-triplet excited states, as has been consistent with numerous experimental observations over almost a century. Here we report a fluorescent molecule that disobeys Hund's rule and has a negative singlet-triplet energy gap of -11 ± 2 meV. The energy inversion of the singlet and triplet excited states results in delayed fluorescence with short time constants of 0.2 µs, which anomalously decrease with decreasing temperature owing to the emissive singlet character of the lowest-energy excited state. Organic light-emitting diodes (OLEDs) using this molecule exhibited a fast transient electroluminescence decay with a peak external quantum efficiency of 17%, demonstrating its potential implications for optoelectronic devices, including displays, lighting and lasers.

Hydrothermal synthesis of water-soluble Mn- and Cu-doped CdSe quantum dots with multi-shell structures and their photoluminescence properties.

Optical properties of semiconductor quantum dots (QDs) can be tuned by doping with transition metal ions. In this study, water-soluble CdSe/ZnS:Mn/ZnS QDs with the core/shell/shell structure were synthesized through a hydrothermal method, in which the surface of the CdSe core was coated with a ZnS:Mn shell and ZnS capping shell. Herein, the CdSe core QDs were prepared first and then doped with Mn2+; therefore, the QD size and doping level could be controlled independently and interference from the self-purifying effect could be avoided. When CdSe cores with diameters less than 1.9 nm were used, Mn-related photoluminescence (PL) was observed as the main PL band, whereas the band-edge PL was mainly observed when larger CdSe cores were used. Furthermore, using ZnS:Cu as the doping shell layer, CdSe/ZnS:Cu/ZnS and ZnSe/ZnS:Cu/ZnS nanoparticles were successfully synthesized, and Cu-related PL was clearly observed. These results indicate that the core/shell/shell QD structure with doping in the shell layer is a versatile method for synthesizing doped QDs.

Designs and understanding of small molecule-based non-fullerene acceptors for realizing commercially viable organic photovoltaics.

Organic photovoltaics (OPVs) have emerged as a promising next-generation technology with great potential for portable, wearable, and transparent photovoltaic applications. Over the past few decades, remarkable advances have been made in non-fullerene acceptor (NFA)-based OPVs, with their power conversion efficiency exceeding 18%, which is close to the requirements for commercial realization. Novel molecular NFA designs have emerged and evolved in the progress of understanding the physical features of NFA-based OPVs in relation to their high performance, while there is room for further improvement. In this review, the molecular design of representative NFAs is described, and their blend characteristics are assessed via statistical comparisons. Meanwhile, the current understanding of photocurrent generation is reviewed along with the significant physical features observed in high-performance NFA-based OPVs, while the challenging issues and the strategic perspectives for the commercialization of OPV technology are also discussed.

Simple cubic self-assembly of PbS quantum dots by finely controlled ligand removal through gel permeation chromatography.

The geometry in self-assembled superlattices of colloidal quantum dots (QDs) strongly affects their optoelectronic properties and is thus of critical importance for applications in optoelectronic devices. Here, we achieve the selective control of the geometry of colloidal quasi-spherical PbS QDs in highly-ordered two and three dimensional superlattices: Disordered, simple cubic (sc), and face-centered cubic (fcc). Gel permeation chromatography (GPC), not based on size-exclusion effects, is developed to quantitatively and continuously control the ligand coverage of PbS QDs. The obtained QDs can retain their high stability and photoluminescence on account of the chemically soft removal of the ligands by GPC. With increasing ligand coverage, the geometry of the self-assembled superlattices by solution-casting of the GPC-processed PbS QDs changed from disordered, sc to fcc because of the finely controlled ligand coverage and anisotropy on QD surfaces. Importantly, the highly-ordered sc supercrystal usually displays unique superfluorescence and is expected to show high charge transporting properties, but it has not yet been achieved for colloidal quasi-spherical QDs. It is firstly accessible by fine-tuning the QD ligand density using the GPC method here. This selective formation of different geometric superlattices based on GPC promises applications of such colloidal quasi-spherical QDs in high-performance optoelectronic devices.

Electron spin resonance resolves intermediate triplet states in delayed fluorescence.

Molecular organic fluorophores are currently used in organic light-emitting diodes, though non-emissive triplet excitons generated in devices incorporating conventional fluorophores limit the efficiency. This limit can be overcome in materials that have intramolecular charge-transfer excitonic states and associated small singlet-triplet energy separations; triplets can then be converted to emissive singlet excitons resulting in efficient delayed fluorescence. However, the mechanistic details of the spin interconversion have not yet been fully resolved. We report transient electron spin resonance studies that allow direct probing of the spin conversion in a series of delayed fluorescence fluorophores with varying energy gaps between local excitation and charge-transfer triplet states. The observation of distinct triplet signals, unusual in transient electron spin resonance, suggests that multiple triplet states mediate the photophysics for efficient light emission in delayed fluorescence emitters. We reveal that as the energy separation between local excitation and charge-transfer triplet states decreases, spin interconversion changes from a direct, singlet-triplet mechanism to an indirect mechanism involving intermediate states.

Roles and Impacts of Ancillary Materials for Multi-Component Blend Organic Photovoltaics towards High Efficiency and Stability.

Organic photovoltaics (OPVs) are a promising next-generation photovoltaic technology with great potential for wearable and transparent device applications. Over the past decades, remarkable advances in device efficiency close to 20 % have been made for bulk heterojunction (BHJ)-based OPV devices with long-term stability, and room for further improvements still exists. In recent years, ancillary components have been demonstrated as effective in improving the photovoltaic performance of OPVs by controlling the optoelectronic and morphological properties of BHJ blends. Herein, an updated understanding of polymer-based blend OPVs is provided, and the role and impact of ancillary components in various blend systems are categorized and discussed. Lastly, a strategic perspective on the ancillary components of blend-based OPVs for commercialization is provided.

Improved Electroluminescence Performance of Perovskite Light-Emitting Diodes by a New Hole Transporting Polymer Based on the Benzocarbazole Moiety.

A new hole-transporting material, poly-2-(9H-carbazol-9-yl)-5-(4-vinylphenyl)-5H-benzo[b]carbazole (PBCZCZ), was developed for perovskite light-emitting diodes (PeLEDs). This polymer, which is based on the benzocarbazole moiety, has good solubility in common solvents and enabled the fabrication of highly efficient multilayer perovskite devices. It has excellent film morphology and a high hole mobility of 3.67 × 10-5 cm2 V-1 s-1, which made it possible to vary the device configuration. Green and sky-blue perovskite PeLEDs using PBCZCZ as the hole-transporting layer had current efficiencies and external quantum efficiencies (EQEs) of 43.90 cd A-1 and 8.67% for the green device and 9.07 cd A-1 and 4.04% for the sky-blue device, respectively. The EQE of the green PeLEDs was about 2.5 times higher and that of the sky-blue PeLEDs was about 3 times higher than the device made with the commercial HTL of poly(9-vinylcarbazole) (PVK). The operational device lifetimes of the green and sky-blue PeLEDs made with PBCZCZ were about 4.1 and 4.8 times higher than the PVK-containing device, respectively.

Controlling the dimension of the quantum resonance in CdTe quantum dot superlattices fabricated via layer-by-layer assembly.

In quantum dot superlattices, wherein quantum dots are periodically arranged, electronic states between adjacent quantum dots are coupled by quantum resonance, which arises from the short-range electronic coupling of wave functions, and thus the formation of minibands is expected. Quantum dot superlattices have the potential to be key materials for new optoelectronic devices, such as highly efficient solar cells and photodetectors. Herein, we report the fabrication of CdTe quantum dot superlattices via the layer-by-layer assembly of positively charged polyelectrolytes and negatively charged CdTe quantum dots. We can thus control the dimension of the quantum resonance by independently changing the distances between quantum dots in the stacking (out-of-plane) and in-plane directions. Furthermore, we experimentally verify the miniband formation by measuring the excitation energy dependence of the photoluminescence spectra and detection energy dependence of the photoluminescence excitation spectra.

Kinetic prediction of reverse intersystem crossing in organic donor-acceptor molecules.

Reverse intersystem crossing (RISC), the uphill spin-flip process from a triplet to a singlet excited state, plays a key role in a wide range of photochemical applications. Understanding and predicting the kinetics of such processes in vastly different molecular structures would facilitate the rational material design. Here, we demonstrate a theoretical expression that successfully reproduces experimental RISC rate constants ranging over five orders of magnitude in twenty different molecules. We show that the spin flip occurs across the singlet-triplet crossing seam involving a higher-lying triplet excited state where the semi-classical Marcus parabola is no longer valid. The present model explains the counterintuitive substitution effects of bromine on the RISC rate constants of previously unknown molecules, providing a predictive tool for material design.

Room-Temperature Phosphorescence from a Series of 3-Pyridylcarbazole Derivatives.

Exploration of pure metal-free organic molecules that exhibit strong room-temperature phosphorescence (RTP) is an emerging research topic. In this regard, unveiling the design principles for an efficient RTP molecule is an essential, but challenging, task. A small molecule is an ideal platform to precisely understand the fundamental role of each functional component because the parent molecule can be easily derivatized. Here, the RTP behaviors of a series of 3-pyridylcarbazole derivatives are presented. Experimental studies in combination with theoretical calculations reveal the crucial role of the n orbital on the central pyridine ring in the dramatic enhancement of the intersystem crossing between the charge-transfer-excited singlet state and the locally excited triplet states. Single-crystal X-ray crystallographic studies apparently indicate that both the pyridine ring and fluorine atom contribute to the enhancement of the RTP because of the restricted motion owing to weak C-H⋅⋅⋅N and H⋅⋅⋅F hydrogen-bonding interactions. The single crystal of the fluorine-substituted derivative shows an ultra-long phosphorescent lifetime (τP ) of 1.1 s and a phosphorescence quantum yield (ΦP ) of 1.2 %, whereas the bromine-substituted derivative exhibits τP of 0.15 s with a ΦP of 7.9 %. We believe that this work provides a fundamental and universal guideline for the generation of pure organic molecules exhibiting strong RTP.

Exciplex emissions derived from exceptionally long-distance donor and acceptor molecules.

Intermolecular electron-hole coupling in organic semiconductor excited states plays important roles in organic light-emitting diodes and organic photovoltaics, and the distance of the coupling is typically only on the order of a few nanometers. Here, we report exceptionally long-distance coupled exciplex emissions between electron-donor and electron-acceptor molecules even with a 70 nm-thick spacer layer. Donor/spacer (∼70 nm)/acceptor-type stacked films showed a low-energy band emission, which is not ascribed to the emission of the donor, spacer, and acceptor themselves, but well corresponds to the energy difference between the highest occupied molecular orbital of the donor and the lowest unoccupied molecular orbital of the acceptor. Delayed transient photoluminescence (PL) and electroluminescence (EL) decays and PL quenching by oxygen at the low-energy band were observed and are consistent with the characteristics of the exciplex species.

Study on the Cerebral Blood Flow Regulatory Features of Acupuncture at Acupoints of the Governor Vessel.

Background: Many studies to clarify the influences of acupuncture at different acupoints of various meridians on cerebral blood flow (CBF) were conducted in the past. However, the influences of acupuncture at the points of the Governor Vessel on CBF have not yet been studied tangibly. Objective: The purpose of this study was to investigate the influences of acupuncture at individual acupoints of the Governor Vessel on cerebral hemodynamic indices. Materials and Methods: Two hundred and seventy-nine patients with chronic cerebral circulation insufficiency (CCCI) were observed, using a cerebrovascular disease diagnosis system (CVD 3000, KCC, Pyongyang, Democratic People's Republic of Korea). Various hemodynamic indices-such as vascular compliance, hemodynamic resistance, and blood flow quantity-were compared before and after acupuncture at individual acupoints of the Governor Vessel. Results: The influences of the points of Governor Vessel on CBF were different from each other, and systemic specificity of the Governor Vessel did not emerge. The largest number of indices showed significant changes when GV 16 was punctured, and the effects of GV 16, GV 20, and GV 14 on the head and the neck were relatively better than those of the points on the trunk. Conclusions: The points on the head and the neck of the Governor Vessel improve CBF biphasic regulation relatively better than the points on the trunk.

Two-Dimensional Ca2Nb3O10 Perovskite Nanosheets for Electron Injection Layers in Organic Light-Emitting Devices.

We report in this article the application of calcium niobate (CNO) perovskite nanosheets for electron injection layers (EILs) in organic light-emitting devices (OLEDs). Four kinds of tetraalkylammonium hydroxides having different alkyl lengths were utilized as the exfoliation agents of a layered compound precursor HCa2Nb3O10 to synthesize CNO nanosheets, including tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide (TPAOH), and tetrabutylammonium hydroxide. CNO nanosheet EILs were applied in fluorescent poly[(9,9-di- n-octylfluorenyl-2,7-diyl)- alt-(benzo[2,1,3]thiadiazol-4,8-diyl)] (F8BT) organic light-emitting polymer-based devices. The effects of dispersion concentrations and alkyl chain length on the devices' performances were investigated. The results demonstrated that OLEDs' performances were related to the coverage ratio of the CNO nanosheets, their thicknesses, and their work function values. Among the four exfoliation agents, the device with CNO nanosheets exfoliated by TPAOH showed the lowest driving voltage. The OLEDs with the CNO nanosheet EILs showed lower driving voltages compared with the devices with conventional EIL material lithium 8-quinolate.

Conjugated Polyelectrolyte Blend with Polyethyleneimine Ethoxylated for Thickness-Insensitive Electron Injection Layers in Organic Light-Emitting Devices.

Electron injection layers (EILs) based on a simple polymer blend of polyethyleneimine ethoxylated (PEIE) and poly[(9,9-bis(3'-(( N, N-dimethyl)- N-ethylammonium)-propyl)-2,7-fluorene)- alt-2,7-(9,9-dioctylfluorene)] (PFN-Br) can suppress the dependence of organic light-emitting device (OLED) performance on thickness variation compared with single PEIE or PFN-Br EILs. PEIE and PFN-Br were compatible with each other and PFN-Br uniformly mixed in the PEIE matrix. PFN-Br in PEIE formed more fluorene-fluorene pairs than PFN-Br alone. In addition, PEIE:PFN-Br blends reduced the work function (WF) substantially compared with single PEIE or PFN-Br polymer. PEIE:PFN-Br blends were applied to EILs in fluorescent polymer-based OLEDs. Optimized PEIE:PFN-Br blend EIL-based devices presented lower driving voltages and smaller dependences of device performance on EIL thickness than single PEIE or PFN-Br-based devices. These improvements were attributed to electron-transporting fluorene moieties, increased fluorene-fluorene pairs working as channels of electron transport, and the large WF reduction effect of PEIE:PFN-Br blends.

Air-Stable and High-Performance Solution-Processed Organic Light-Emitting Devices Based on Hydrophobic Polymeric Ionic Liquid Carrier-Injection Layers.

A lot of research, mostly using electron-injection layers (EILs) composed of alkali-metal compounds has been reported with a view to increase the efficiency of solution-processed organic light-emitting devices (OLEDs). However, these materials have intractable properties, such as a strong affinity for moisture, which cause the degradation of OLEDs. Consequently, optimal EIL materials should exhibit high electron-injection efficiency as well as be stable in air. In this study, polymer light-emitting devices (PLEDs) based on the commonly used yellow-fluorescence-emitting polymer F8BT, which utilize poly(diallyldimethylammonium)-based polymeric ionic liquids, are experimentally and analytically investigated. As a result, the optimized PLED employing an EIL comprising poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (poly(DDA)TFSI), which is expected to display good moisture resistance because of water repellency of fluorocarbon groups, exhibits excellent storage stability in air and electroluminescence performance with a low turn-on voltage of 2.01 V, maximum external quantum efficiency of 9.00%, current efficiency of 30.1 cd A-1 , and power efficiency of 32.4 lm W-1 . The devices with poly(DDA)TFSI show one of the highest efficiencies as compared to the reported standard PLEDs. Moreover, poly(DDA)TFSI is applied as a hole-injection layer (HIL). The optimized PLED using poly(DDA)TFSI as the HIL exhibits performances comparable to those of a device that uses a conventional poly(3,4-ethylenedioxy-thiophene):poly(4-styrenesulfonate) HIL.

Post-Treatment-Free Solution-Processed Reduced Phosphomolybdic Acid Containing Molybdenum Oxide Units for Efficient Hole-Injection Layers in Organic Light-Emitting Devices.

We report the development of solution-processed reduced phosphomolybdic acid (rPMA) containing molybdenum oxide units for post-treatment-free hole-injection layers (HILs) in organic light-emitting devices (OLEDs). The physical and chemical properties of rPMA, including its structure, solubility in several solvents, film surface roughness, work function, and valence states, were investigated. The formation of gap states just below the Fermi level of rPMA was observed. Without any post-treatment after the formation of rPMA films, OLEDs employing rPMA as an HIL exhibited a very low driving voltage and a high luminous efficiency. The low driving voltage was attributed to the energy level alignment between the gap states formed by reduction and the HOMO level of the hole-transport layer material N,N'-bis(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine.

A Series of Lithium Pyridyl Phenolate Complexes with a Pendant Pyridyl Group for Electron-Injection Layers in Organic Light-Emitting Devices.

We report a new series of lithium pyridyl phenolate complexes with a pendant pyridyl group, Li2BPP, Li3BPP, and Li4BPP, in which the pendant pyridines are substituted at the 2-, 3-, and 4-positions, respectively. The most important difference between these complexes is their molecular planarity; Li3BPP and Li4BPP adopt twisted bipyridine structures, whereas Li2BPP adopts a planar structure owing to the steric hindrance and chelating effect of bipyridine on the Li core. The planar structure leads to crystallization through π-π stacking interactions, and the small differences in the molecular structures of the pendant pyridine rings cause drastic differences in the physical properties of thin solid films of these complexes. We applied these complexes as electron-injection layers (EILs) in Ir(ppy)3-based organic light-emitting devices. When thin EILs were used, Li3BPP and Li4BPP afforded lower driving voltages than Li2BPP; the order of the driving voltages followed the order of their electron affinity values. Moreover, the dependence of driving voltage on the EIL thickness was investigated for each complex. Among the three LiBPP derivatives, Li2BPP-based devices showed almost negligible EIL thickness dependence, which may be attributable to the high crystallinity of Li2BPP. All LiBPP-based devices also showed higher stability than conventional 8-quinolinolato lithium-based devices.