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A new yellow-emitting quadrupolar donor–π–acceptor–π–donor (D–π–A–π–D) molecule compound has been synthesised featuring benzo-[1,2-c:4,5-c′]dithiophene-4,8-dione as the acceptor. This molecule was prepared for the purpose of elucidating the origins of the very low photoluminescence quantum yield encountered in its thermally activated delayed fluorescent (TADF) red-emitting isomer which used benzo-[1,2-b:4,5-b′]dithiophene-4,8-dione as the acceptor. The molecule was designed to circumvent the energy gap law, by having a wider HOMO–LUMO gap, while retaining a comparable singlet–triplet gap but ultimately demonstrates even weaker photoluminescence than the red isomer. It shows extremely fast intersystem crossing followed by rapid non-radiative decay and no observable TADF. The electronic structure of this new molecule has been studied using cyclic voltammatery alongside steady-state and transient optical spectroscopy, with observations underpinned by computational insights. To identify whether the observations made from the experimental results might be general properties of benzodithiophene-4,8-dione containing emitters, a computational study is extended to the four isomers of benzodithiophene-4,8-dione in comparison with 9,10-anthraquinone. The results suggest that the singlet and triplet manifolds of these systems are strongly coupled via spin–orbit interactions, and explain how the relative electron-accepting strength of these quinones arises from an interplay between the resonance gains or losses of the central benzene and fused thiophene rings upon photoexcitation. This provides valuable insights into the design principles required for efficient organic light-emitting materials. [ABSTRACT FROM AUTHOR]

The control of non-radiative losses in light-emitting diodes (LEDs) based on metal halide perovskites is crucial to improve device efficiency. Recent studies have shown a correlation between lattice strain and electron–hole recombination. To consolidate the concept, we investigate how external pressure (strain) affects the crystal structure, electronic properties, point defect concentration, and luminescence efficiency of CH3NH3PbBr3. Relativistic first-principles calculations reveal enhanced Rashba splitting and Schottky defect disorder under compression, which produce a pronounced decrease in the electroluminescence peak energy and intensity in operating CH3NH3PbBr3 LEDs. The resulting model sheds light on the factors underpinning the intricate strain–property relationships in soft crystalline semiconductors. [ABSTRACT FROM AUTHOR]

Hybrid small-molecule/quantum dot films have the potential to reduce thermalization losses in single-junction photovoltaics as photon multiplication devices. Here grazing incidence X-ray scattering, optical microscopy and IR fluorescence microscopy (probing materials at two distinct wavelengths), provide new insight into highly complex morphologies across nm and μm lengthscales to provide direct links between morphologies and photon multiplication performance. Results show that within the small molecule crystallites three different QD morphologies may be identified; (i) large quantum dot aggregates at the crystallite nucleus, (ii) relatively well-dispersed quantum dots and (iii) as aggregated quantum dots "swept" from the growing crystallite and that regions containing aggregate quantum dot features lead to relatively poor photon multiplication performance. These results establish how combinations of scattering and microscopy may be employed to reveal new insights into the structure and function of small molecule:quantum dot blends. [ABSTRACT FROM AUTHOR]

The unique synergy of properties offered by an efficient and processable near-infrared thermally activated delayed fluorescent (NIR TADF) dye could be transformative across research fields. Here, a solution-processable NIR TADF material is demonstrated (CAT-TPE). Good solubility is achieved through the use of a new tetraphenylethylene (TPE)-based triphenylamine electron donor. TADF is confirmed through variable temperature time-resolved measurements at a peak photoluminescence (PL) wavelength of 842 nm in a solution-processed film. An OLED with good roll-off characteristics for a solution-processed NIR TADF device is reported with electroluminescence λmax > 700 nm. CAT-TPE also demonstrates classic aggregation induced emission (AIE) behavior, being more emissive when aggregated than in solution with all PL > 700 nm. This work opens the door to the considerably enhanced structural diversity of solution-processable NIR TADF and will inform the design of future high efficiency AIE NIR TADF materials. [ABSTRACT FROM AUTHOR]

Halide double perovskites have gained significant attention, owing to their composition of low-toxicity elements, stability in air and long charge-carrier lifetimes. However, most double perovskites, including Cs2AgBiBr6, have wide bandgaps, which limits photoconversion efficiencies. The bandgap can be reduced through alloying with Sb3+, but Sb-rich alloys are difficult to synthesize due to the high formation energy of Cs2AgSbBr6, which itself has a wide bandgap. We develop a solution-based route to synthesize phase-pure Cs2Ag(SbxBi1−x)Br6 thin films, with the mixing parameter x continuously varying over the entire composition range. We reveal that the mixed alloys (x between 0.5 and 0.9) demonstrate smaller bandgaps than the pure Sb- and Bi-based compounds. The reduction in the bandgap of Cs2AgBiBr6 achieved through alloying (170 meV) is larger than if the mixed alloys had obeyed Vegard's law (70 meV). Through in-depth computations, we propose that bandgap lowering arises from the type II band alignment between Cs2AgBiBr6 and Cs2AgSbBr6. The energy mismatch between the Bi and Sb s and p atomic orbitals, coupled with their non-linear mixing, results in the alloys adopting a smaller bandgap than the pure compounds. Our work demonstrates an approach to achieve bandgap reduction and highlights that bandgap bowing may be found in other double perovskite alloys by pairing together materials forming a type II band alignment. [ABSTRACT FROM AUTHOR]

We report morphological control with phenyl-C60-butyric acid methyl ester (PCBM) molecular aggregation for perovskite–PCBM bulk heterostructure (Pe–PCBM BHS) solar cells. Solar cells prepared via the Pe–PCBM BHS method exhibited a higher power conversion efficiency (PCE) of 18% than 11% from a device with a conventional planar heterojunction structure. The Pe–PCBM BHS can enhance device efficiency by improving electron transfer, shortening the electron transport length required for collection, and reducing the charge transfer resistance at the interface between the perovskite and PCBM through an increase of the perovskite crystal size and construction of a vertical perovskite–PCBM intermixing zone. To the best of our knowledge, the high PCE achieved by our Pe–PCBM BHS is the highest value to be reported in an inverted perovskite solar cell without buffer layers, such as metal oxides or low work function metals. [ABSTRACT FROM AUTHOR]

Artificial light harvesters require ordered arrangement of chromophores. We covalently attach three organic chromophore ligands to silicon dioxide nanoparticles. This allows us to study inter-ligand energy transfer when attached to SiO2 nanoparticles, creating a simple system with a large ratio of donors to acceptors. Using steady-state and transient spectroscopy measurements we quantify this energy transfer between ligands. We show a maximum transfer efficiency of 30% and measure the 2D diffusion length of anthracene carboxylic acid on SiO2 to be between 0.6 and 2.2 nm. [ABSTRACT FROM AUTHOR]

Employing the thiophene based quinone, benzo[1,2-b:4,5-b′]dithiophene-4,8-dione, as the electron-accepting moiety alongside N-phenylcarbazole donors to produce a donor–π–acceptor–π–donor (D–π–A–π–D) molecule has yielded a new red emitter displaying delayed fluorescence. This new molecule shows strongly (over 100 nm) red-shifted emission when compared to an anthraquinone based analogue. Cyclic voltammetry complemented by computational insights prove that this red-shift is due to the significantly stronger electron-accepting ability of the thiophene quinone compared to anthraquinone. Photophysical and computational studies of this molecule have revealed that while the presence of the thiophene containing acceptor facilitates rapid intersystem crossing which is comparable to anthraquinone analogues, the reverse intersystem crossing rate is slow and non-radiative decay is rapid which we can attribute to low-lying locally excited states. This limits the total photoluminescence quantum efficiency to less than 10% in both solution and the solid state. These results provide a useful example of how very minor structural variations can have a defining impact on the photophysical properties of new molecular materials. [ABSTRACT FROM AUTHOR]

Non-fullerene acceptors (NFAs) have recently outperformed their fullerene counterparts in binary bulk-heterojunction (BHJ) organic solar cells (OSCs). Further development of NFA OSCs may benefit other novel OSC device structures that alter or extend the standard BHJ concept. Here, we report such a new processing route that forms a BHJ-like morphology between sequentially processed polymer donor and NFA with high power conversion efficiencies in excess of 10%. Both devices show similar charge generation and recombination behaviours, supporting formation of similar BHJ active layers. We correlate the ∼30 meV smaller open-circuit voltage in sq-BHJ devices to more substantial non-radiative recombination by voltage loss analysis. We also determine the exciton diffusion length of benchmark polymer PBDB-T to be 10 ± 3 nm. Our results demonstrate high-efficiency OSC devices using sequential deposition method and provide new opportunities to further improve performance of state-of-the-art OSCs. [ABSTRACT FROM AUTHOR]

The performance of bulk heterojunction (BHJ) organic solar cells (OSCs) strongly depends on the intermolecular packing of donor:acceptor (D:A) molecules, as it directly influences the photo-physics and charge transfer properties of the blend. Intermolecular packing can be tuned by solvent additives and/or the chemical structure of molecules to optimize the performance of OSCs. Three high efficiency polymer:fullerene systems are investigated based on the donor polymers PCPDTBT, PTB7 and PTB7-Th (also known as PBDTTT-EFT). For the PCDPTBT:PC71BM system, we demonstrate that the use of the solvent additive diiodooctane (DIO) which is employed to optimize the solar cell efficiency actually increases interfacial disorder by 13 meV despite lowering bulk disorder by 35 meV. In contrast, the Urbach energy (bulk and interfacial charge transfer (CT) states) and reorganization energy (λ) are minimally influenced by the addition of DIO into PTB7:PC71BM & PTB7-Th:PC71BM devices, where PTB7-Th is a chemical analogue of PTB7. However, PTB7-Th devices show remarkably low voltage losses (∼100 meV) with respect to other systems studied here, suggesting a favorable energy landscape at the D:A interface for charge separation. Hence, optimizing the molecular structure of the donor polymer can help to overcome the voltage losses even when solvent additive treatment is applied. [ABSTRACT FROM AUTHOR]

A comprehensive understanding of the charge generation mechanism in organic solar cells is critical for further improvement of device performance. Currently, the origin and magnitude of the coulombic binding energy of the charge-transfer state (CTS), an intermediate state which is fundamental for the charge separation process, are still under debate. Here, we propose a new approach for determining the dissociation energy of localised CTSs for a range of devices with different alignments of molecular energy levels (tuned by chemical modifications of fullerene) and disorder (adjusted by the blend composition) using temperature-dependent pump-push photocurrent spectroscopy. We observe that the dissociation of localised CTSs from initial excitation is a temperature-dependent process, and we determined the binding energy of these CTSs by measuring a single activation energy over a wide temperature range. We propose a simple qualitative picture to explain the observation, based on the split between the bound CTSs and free charges. In all the material systems studied here, the activation energy falls within the range of 90 ± 50 meV (corresponding to ∼1 nm separation of an electron–hole pair). Surprisingly, the binding energy does not depend on the material composition or the driving energy (∼150 meV variation) for charge separation. In contrast, the number of formed bound states and their following recombination dynamics are material- and nanomorphology-sensitive. Such observations in the studied benchmark polymer:fullerene systems reveal unexpected similarities in the energetics of CTSs formed in different electronic environments. This makes our results of general importance for understanding the photophysics at the heterojunction interface and for further development of organic photovoltaics. [ABSTRACT FROM AUTHOR]

We demonstrate the enhanced performance of perovskite light-emitting diodes (PeLEDs) using a solution-processable MoO3 and PEDOT:PSS (PEDOT:MoO3) composite layer as the hole transport layer (HTL). The PEDOT:MoO3 composite layer presents improved hole injection through a reduction in the contact barrier between the HTL and the CH3NH3PbBr3 layer and enhanced crystallinity of the perovskite film. The optimized PeLEDs with the PEDOT:MoO3 composite film showed enhanced external quantum efficiency (EQE) and maximum luminous efficiency, compared to a PeLED using a pristine PEDOT:PSS layer. [ABSTRACT FROM AUTHOR]

Recent experiments by Rao et al. (Nature, 2013, 500, 435–439) indicate that recombination of triplet charge-separated states is suppressed in organic polymer–fullerene based bulk-heterojunction (BHJ) photovoltaic cells exhibiting a high degree of crystallinity in the fullerene phase relative to systems with more disorder. In this paper, we use a series of Frenkel-exciton lattice models to rationalize these results in terms of wave-function localization, interface geometry, and density of states. In one-dimensional co-linear and co-facial models of the interface, increasing local energetic disorder in one phase localizes the interfacial triplet charge-transfer (3CT) states and increases the rate at which these states relax to form lower-energy triplet excitons. In two dimensional BHJ models, energetic disorder within the fullerene phase plays little role in further localizing states pinned to the interface. However, inhomogeneous broadening introduces strong coupling between the interfacial 3CT and nearby fullerene triplet excitons and can enhance the decay of these states in systems with higher degrees of energetic disorder. [ABSTRACT FROM AUTHOR]

We report the performance and photophysics of a low band-gap diketopyrrolopyrrole-based copolymer used in bulk heterojunction devices in combination with PC71BM. We show that the short lifetime of photogenerated excitons in the polymer constitutes an obstacle towards device efficiency by limiting the diffusion range of the exciton to the donor–acceptor heterojunction. We employ ultrafast transient-probe and fluorescence spectroscopy techniques to examine the excited state loss channels inside the devices. We use the high boiling point solvent additive 1,8-diiodooctane (DIO) to study the photoexcited state losses in different blend morphologies. The solvent additive acts as a compatibiliser between the donor and the acceptor material and leads to smaller domain sizes, higher charge formation yields and increased device efficiency. [ABSTRACT FROM AUTHOR]

Correction for ‘Efficient non-fullerene organic solar cells employing sequentially deposited donor–acceptor layers’ by Jiangbin Zhang et al., J. Mater. Chem. A, 2018, 6, 18225–18233. [ABSTRACT FROM AUTHOR]

Artificial light harvesters require ordered arrangement of chromophores. We covalently attach three organic chromophore ligands to silicon dioxide nanoparticles. This allows us to study inter-ligand energy transfer when attached to SiO2 nanoparticles, creating a simple system with a large ratio of donors to acceptors. Using steady-state and transient spectroscopy measurements we quantify this energy transfer between ligands. We show a maximum transfer efficiency of 30% and measure the 2D diffusion length of anthracene carboxylic acid on SiO2 to be between 0.6 and 2.2 nm.

The photo- and electroluminescence properties of a series of novel, heteroleptic, mer-cyclometallated iridium complexes have been fine-tuned from green to blue by changing the substituents on the pyridyl ring of the phenylpyridyl ligand. The X-ray crystal structures of two Ir-based triazolyl complexes are reported.