Nanoscience News (<front>)

High-brightness organic LED arrays are produced by direct vacuum deposition of the organic materials onto complementary metal–oxide–semiconductor (CMOS) backplanes produced in a commercial chip foundry. The composition of the foundry-provided aluminum anodes is analyzed by scanning transmission electron microscopy and their surface is pre-conditioned for optimal electrical contact by plasma treatment.

Direct deposition of organic light-emitting diodes (OLEDs) on silicon-based complementary metal–oxide–semiconductor (CMOS) chips has enabled self-emissive microdisplays with high resolution and fill-factor. Emerging applications of OLEDs in augmented and virtual reality (AR/VR) displays and in biomedical applications, e.g., as brain implants for cell-specific light delivery in optogenetics, require light intensities orders of magnitude above those found in traditional displays. Further requirements often include a microscopic device footprint, a specific shape and ultrastable passivation, e.g., to ensure biocompatibility and minimal invasiveness of OLED-based implants. In this work, up to 1024 ultrabright, microscopic OLEDs are deposited directly on needle-shaped CMOS chips. Transmission electron microscopy and energy-dispersive X-ray spectroscopy are performed on the foundry-provided aluminum contact pads of the CMOS chips to guide a systematic optimization of the contacts. Plasma treatment and implementation of silver interlayers lead to ohmic contact conditions and thus facilitate direct vacuum deposition of orange- and blue-emitting OLED stacks leading to micrometer-sized pixels on the chips. The electronics in each needle allow each pixel to switch individually. The OLED pixels generate a mean optical power density of 0.25 mW mm−2, corresponding to >40 000 cd m−2, well above the requirement for daylight AR applications and optogenetic single-unit activation in the brain.

Efficient and bright deep-red perovskite light-emitting diodes (LEDs) are achieved based on a lateral Cs4PbI6/FA x Cs1− x PbI3 (0D/3D) heterostructure, which can simultaneously reduce nonradiative recombination and enhance light extraction. This leads to deep-red perovskite LEDs with a record external quantum efficiency of 21% at a high current density of ≈200 mA cm−2.

Bright and efficient deep-red light-emitting diodes (LEDs) are important for applications in medical therapy and biological imaging due to the high penetration of deep-red photons into human tissues. Metal-halide perovskites have potential to achieve bright and efficient electroluminescence due to their favorable optoelectronic properties. However, efficient and bright perovskite-based deep-red LEDs have not been achieved yet, due to either Auger recombination in low-dimensional perovskites or trap-assisted nonradiative recombination in 3D perovskites. Here, a lateral Cs4PbI6/FA x Cs1− x PbI3 (0D/3D) heterostructure that can enable efficient deep-red perovskite LEDs at very high brightness is demonstrated. The Cs4PbI6 can facilitate the growth of low-defect FA x Cs1− x PbI3, and act as low-refractive-index grids, which can simultaneously reduce nonradiative recombination and enhance light extraction. This device reaches a peak external quantum efficiency of 21.0% at a photon flux of 1.75 × 1021 m−2 s−1, which is almost two orders of magnitude higher than that of reported high-efficiency deep-red perovskite LEDs. Theses LEDs are suitable for pulse oximeters, showing an error <2% of blood oxygen saturation compared with commercial oximeters.

Time-resolved microwave conductivity shows that the rate of photocatalytic hydrogen evolution by aqueous-soluble organic donor–acceptor nanoparticles is limited by charge concentration, and that nanoparticles have 3× more long-lived accumulated charges relative to bulk samples of the same material composition.

Time-resolved microwave conductivity is used to compare aqueous-soluble organic nanoparticle photocatalysts and bulk thin films composed of the same mixture of semiconducting polymer and non-fullerene acceptor molecule and the relationship between composition, interfacial surface area, charge-carrier dynamics, and photocatalytic activity is examined. The rate of hydrogen evolution reaction by nanoparticles composed of various donor:acceptor blend ratio compositions is quantitatively measured, and it is found that the most active blend ratio displays a hydrogen quantum yield of 0.83% per photon. Moreover, it is found that nanoparticle photocatalytic activity corresponds directly to charge generation, and that nanoparticles have 3× more long-lived accumulated charges relative to bulk samples of the same material composition. These results suggest that, under the current reaction conditions, with ≈3× solar flux, catalytic activity by the nanoparticles is limited by the concentration of electrons and holes in operando and not a finite number of active surface sites or the catalytic rate at the interface. This provides a clear design goal for the next generation of efficient photocatalytic nanoparticles.

The relationship between crystal packing motifs and optical properties of pure organic room temperature phosphorescent (ORTP) cocrystals with halogen bonding is investigated by comparing three different binary cocrystals. By designing ternary cocrystals based on the analysis, a highly efficient ORTP cocrystal with a PLQY of over 20% is achieved. To obtain insight into energy loss, the phosphorescent mechanism is discussed.

Recently, there has been intense interest in pure organic room-temperature phosphorescence (ORTP) from cocrystals composed of 1,4-diiodotetrafluorobenzene (DITFB) and a variety of polycyclic aromatic hydrocarbons (PAHs) or their derivatives. To expand the possibility of halogen bonding-based cocrystals, the relationship between the crystal packing motifs and ORTP characteristics in binary cocrystals composed of DITFB and PAHs of phenanthrene (Phen), chrysene (Chry), and pyrene (Pyr), respectively, is investigated. The σ-hole···π and π-hole···π interactions determine not only the crystal packing motifs but also photoluminescence quantum yields (PLQYs). The Phen-DITFB and Chry-DITFB binary cocrystals with σ-hole···π interactions show higher PLQY compared with the Pyr-DITFB binary cocrystal with π-hole···π interaction. Further, to clarify the effect of crystal structures on PLQY, ternary cocrystals are prepared by partially doping Pyr into Phen-DITFB. The crystal packing motif of the ternary cocrystal originates from a Phen-DITFB cocrystal with σ-hole···π interaction, and some of the Phen sites are randomly replaced with Pyr molecules. The ORTP emission is derived from Pyr. The maximum PLQY is >20% due to suppressing nonradiative decay by changing the crystal packing motif.

Fully solution-processed microcavities are demonstrated that allow realizing strong light–matter coupling with an organic semiconductor, all enabled by a versatile molecular hybrid material that permits the fabrication of dielectric mirrors with high-refractive-index contrast between constituting layers.

Planar microcavities with strong light–matter coupling, monolithically processed fully from solution, consisting of two polymer-based distributed Bragg reflectors (DBRs) comprising alternating layers of a high-refractive-index titanium oxide hydrate/poly(vinyl alcohol) hybrid material and a low-refractive-index fluorinated polymer are presented. The DBRs enclose a perylene diimide derivative (b-PDI-1) film positioned at the antinode of the optical mode. Strong light–matter coupling is achieved in these structures at the target excitation of the b-PDI-1. Indeed, the energy-dispersion relation (energy vs in-plane wavevector or output angle) in reflectance and the group delay of transmitted light in the microcavities show a clear anti-crossing—an energy gap between two distinct exciton-polariton dispersion branches. The agreement between classical electrodynamic simulations of the microcavity response and the experimental data demonstrates that the entire microcavity stack can be controllably produced as designed. Promisingly, the refractive index of the inorganic/organic hybrid layers used in the microcavity DBRs can be precisely manipulated between values of 1.50 to 2.10. Hence, microcavities with a wide spectral range of optical modes might be designed and produced with straightforward coating methodologies, enabling fine-tuning of the energy and lifetime of the microcavities‘ optical modes to harness strong light–matter coupling in a wide variety of solution processable active materials.

RAINBOW solar cells consist of two or more junctions placed next to each other and illuminated by spectrally spread sunlight. Guidelines for materials selection are given for this novel geometry through device simulations. Moreover, experimental efficiencies greater than 46% with respect to the best sub-cell are demonstrated for a monolithic two-junction device based on organic semiconducting absorbers.

While multi-junction geometries have the potential to boost the efficiency of organic solar cells, the experimental gains yet obtained are still very modest. This work proposes an alternative spectral splitting device concept in which various individual semiconducting junctions with cascading bandgaps are laid side by side, thus the name RAINBOW. Each lateral sub-cell receives a fraction of the spectrum that closely matches the main absorption band of the given semiconductor. Here, simulations are used to identify the important material and device properties of each RAINBOW sub-cell. Using the resulting design rules, three systems are selected, with narrow, medium, and wide effective bandgaps, and their potential as sub-cells in this geometry is experimentally investigated. With the aid of a custom-built setup that generates spectrally spread sunlight on demand, the simulations are experimentally validated, showing that this geometry can lead to a reduction in thermalization losses and an improvement in light harvesting, which results in a relative improvement in efficiency of 46.6% with respect to the best sub-cell. Finally, a working proof-of-concept monolithic device consisting of two sub-cells deposited from solution on the same substrate is fabricated, thus demonstrating the feasibility and the potential of the RAINBOW solar cell concept.

2D polymer heterojunctions are formed using a novel templating technique and are investigated as photocatalysts for proton reduction. Templated materials showed improved charge separation and reduced trapped charges at the donor–acceptor interface, which results in hydrogen evolution rates of 3–9 times that of either individual semiconductor and the ability to produce hydrogen in combination with the oxidation of reversible redox mediators, as well as sacrificial electron donors.

2D polymers have emerged as one of the most promising classes of organic photocatalysts for solar fuel production due to their tunability, charge-transport properties, and robustness. They are however difficult to process and so there are limited studies into the formation of heterojunction materials incorporating these components. In this work, a novel templating approach is used to combine an imine-based donor polymer and an acceptor polymer formed through Knoevenagel condensation. Heterojunction formation is shown to be highly dependent on the topological match of the donor and acceptor polymers with the most active templated material found to be between three and nine times more active for photocatalysis than its constituent components. Transient absorption spectroscopy reveals that this improvement is due to faster charge separation and more efficient charge extraction in the templated heterojunction. The templated material shows a very high hydrogen evolution rate of >20 mmol h−1 m−2 with an ascorbic acid hole scavenger but also produces hydrogen in the presence of only water and a cobalt-based redox mediator. This suggests the improved charge-separation interface and reduced trapping accessed through this approach could be suitable for Z-scheme formation.

12-nm layers of silver deposited on the commercial optical adhesive NOA63 serve as ultrasmooth, haze-free transparent electrodes for optoelectronics that exhibit high resilience to bending. The electrodes may be readily patterned by selectively etching the NOA63 substrate with an oxygen plasma prior to metal deposition, with the silver forming continuous, conducting regions above unetched NOA63 and fragmented, highly insulating regions above etched NOA63.

Template-patterned, flexible transparent electrodes (TEs) formed from an ultrathin silver film on top of a commercial optical adhesive – Norland Optical Adhesive 63 (NOA63) – are reported. NOA63 is shown to be an effective base-layer for ultrathin silver films that advantageously prevents coalescence of vapor-deposited silver atoms into large, isolated islands (Volmer-Weber growth), and so aids the formation of ultrasmooth continuous films. 12 nm silver films on top of free-standing NOA63 combine high, haze-free visible-light transparency (T ≈ 60% at 550 nm) with low sheet-resistance (Rs${\mathcal{R}}_s$ ≈ 16 Ω sq−1), and exhibit excellent resilience to bending, making them attractive candidates for flexible TEs. Etching the NOA63 base-layer with an oxygen plasma before silver deposition causes the silver to laterally segregate into isolated pillars, resulting in a much higher sheet resistance (Rs${\mathcal{R}}_{s}$ > 8 × 106 Ω sq-1) than silver grown on pristine NOA63 . Hence, by selectively etching NOA63 before metal deposition, insulating regions may be defined within an otherwise conducting silver film, resulting in a differentially conductive film that can serve as a patterned TE for flexible devices. Transmittance may be increased (to 79% at 550 nm) by depositing an antireflective layer of Al2O3 on the Ag layer at the cost of reduced flexibility.

A machine-learning-driven high-throughput workflow for solution-processed organic solar cells is presented, identifying causal relationships between process conditions and active layer morphology, and between morphology and stability. Using only inexpensive and fast optical probes, quantitative structure–property relationships are obtained that improve the understanding and control of electrical performance degradation.

Organic solar cells (OSCs) now approach power conversion efficiencies of 20%. However, in order to enter mass markets, problems in upscaling and operational lifetime have to be solved, both concerning the connection between processing conditions and active layer morphology. Morphological studies supporting the development of structure–process–property relations are time-consuming, complex, and expensive to undergo and for which statistics, needed to assess significance, are difficult to be collected. This work demonstrates that causal relationships between processing conditions, morphology, and stability can be obtained in a high-throughput method by combining low-cost automated experiments with data-driven analysis methods. An automatic spectral modeling feeds parametrized absorption data into a feature selection technique that is combined with Gaussian process regression to quantify deterministic relationships linking morphological features and processing conditions with device functionality. The effect of the active layer thickness and the morphological order is further modeled by drift–diffusion simulations and returns valuable insight into the underlying mechanisms for improving device stability by tuning the microstructure morphology with versatile approaches. Predicting microstructural features as a function of processing parameters is decisive know-how for the large-scale production of OSCs.

Semiconducting polymer nanoparticles (SPNs) are a promising tool for theranostic applications. Here, a method of imparting colloidal stability, low-protein fouling, and high circulation efficiencies onto SPNs is described via a one-step, postpolymerization reaction. This method can also afford azide-functionalized SPNs, which allows for subsequent “click” reactions to achieve specific human epidermal growth factor receptor 2 (HER2) targeting in vitro and in vivo.

Semiconducting polymer nanoparticles (SPNs) are explored for applications in cancer theranostics because of their high absorption coefficients, photostability, and biocompatibility. However, SPNs are susceptible to aggregation and protein fouling in physiological conditions, which can be detrimental for in vivo applications. Here, a method for achieving colloidally stable and low-fouling SPNs is described by grafting poly(ethylene glycol) (PEG) onto the backbone of the fluorescent semiconducting polymer, poly(9,9′-dioctylfluorene-5-fluoro-2,1,3-benzothiadiazole), in a simple one-step substitution reaction, postpolymerization. Further, by utilizing azide-functionalized PEG, anti-human epidermal growth factor receptor 2 (HER2) antibodies, antibody fragments, or affibodies are site-specifically “clicked” onto the SPN surface, which allows the functionalized SPNs to specifically target HER2-positive cancer cells. In vivo, the PEGylated SPNs are found to have excellent circulation efficiencies in zebrafish embryos for up to seven days postinjection. SPNs functionalized with affibodies are then shown to be able to target HER2 expressing cancer cells in a zebrafish xenograft model. The covalent PEGylated SPN system described herein shows great potential for cancer theranostics.

Tin oxide as electron transport layer in organic solar cells (OSCs) can promote high device performance and stability. However, the poor quality of the material and of the interface with the organic layer often limits its potential. This work demonstrates that high-quality tin oxide can be grown by atomic layer deposition, for the fabrication of OSCs with outstanding performance.

Transport layers are of outmost importance for thin-film solar cells, determining not only their efficiency but also their stability. To bring one of these thin-film technologies toward mass production, many factors besides efficiency and stability become important, including the ease of deposition in a scalable manner and the cost of the different material's layers. Herein, highly efficient organic solar cells (OSCs), in the inverted structure (n-i-p), are demonstrated by using as electron transport layer (ETL) tin oxide (SnO2) deposited by atomic layer deposition (ALD). ALD is an industrial grade technique which can be applied at the wafer level and also in a roll-to-roll configuration. A champion power conversion efficiency (PCE) of 17.26% and a record fill factor (FF) of 79% are shown by PM6:L8-BO OSCs when using ALD-SnO2 as ETL. These devices outperform solar cells with SnO2 nanoparticles casted from solution (PCE 16.03%, FF 74%) and also those utilizing the more common sol–gel ZnO (PCE 16.84%, FF 77%). The outstanding results are attributed to a reduced charge carrier recombination at the interface between the ALD-SnO2 film and the active layer. Furthermore, a higher stability under illumination is demonstrated for the devices with ALD-SnO2 in comparison with those utilizing ZnO.

Stretchable Imagers

In article number 2304048, Teppei Araki, Kou Li, Daichi Suzuki, Daichi Suzuki, Yukio Kawano, Tsuyoshi Sekitani, and co-workers review trends and technologies regarding stretchable imagers that are attached to an arbitrary surface and remotely acquire signals with minimal mechanical stress. The fusion of broadband photodetectors and stretchable packaging enables internal evaluations for health conditions and abnormalities of targeted living bodies and various objects.

Colloidal Quantum Dot Light-Emitting Diodes

Colloidal quantum dots light-emitting diodes (QLEDs) have attracted tremendous attention for display applications. To guide the pathway towards successful commercialization, Changhee Lee and co-workers review representative research trends, progress, and challenges of QLEDs in the categories of material synthesis, device engineering, and fabrication methods. More details can be found in article number 2212220.

This review overviews approaches to find an optimal perovskite cavity patterning method, including indirect patterning, bottom-up patterning, top-down patterning, and top-down controlled bottom-up patterning. Fundamental mechanisms behind various emission behaviors in perovskite thin films and cavities are also compared and contrasted.

Hybrid metal-halide perovskites (MHPs) have shown remarkable optoelectronic properties as well as facile and cost-effective processability. With the success of MHP solar cells and light-emitting diodes, MHPs have also exhibited great potential as gain media for on-chip lasers. However, to date, stable operation of optically pumped MHP lasers and electrically driven MHP lasers—an essential requirement for MHP laser's insertion into chip-scale photonic integrated circuits—is not yet demonstrated. The main obstacles include the instability of MHPs in the atmosphere, rudimentary MHP laser cavity patterning methods, and insufficient understanding of emission mechanisms in MHP materials and cavities. This review aims to provide a detailed overview of different strategies to improve the intrinsic properties of MHPs in the atmosphere and to establish an optimal MHP cavity patterning method. In addition, this review discusses different emission mechanisms in MHP materials and cavities and how to distinguish them.

To guide the pathway toward the commercialization of quantum dot light-emitting diodes (QLEDs), representative research trends, progress, and challenges of QLEDs in the categories of material synthesis, device engineering, and fabrication methods are reviewed to specify the current status and development direction. Furthermore, brief insights into the factors to be considered when realizing active matrix QLED displays are provided.

Colloidal quantum dots (QDs) exhibit tremendous potential in display technologies owing to their unique optical properties, such as size-tunable emission wavelength, narrow spectral linewidth, and near-unity photoluminescence quantum yield. Significant efforts in academia and industry have achieved dramatic improvements in the performance of quantum dot light-emitting diodes (QLEDs) over the past decade, primarily owing to the development of high-quality QDs and optimized device architectures. Moreover, sophisticated patterning processes have also been developed for QDs, which is an essential technique for their commercialization. As a result of these achievements, some QD-based display technologies, such as QD enhancement films and QD-organic light-emitting diodes, have been successfully commercialized, confirming the superiority of QDs in display technologies. However, despite these developments, the commercialization of QLEDs is yet to reach a threshold, requiring a leap forward in addressing challenges and related problems. Thus, representative research trends, progress, and challenges of QLEDs in the categories of material synthesis, device engineering, and fabrication method to specify the current status and development direction are reviewed. Furthermore, brief insights into the factors to be considered when conducting research on single-device QLEDs are provided to realize active matrix displays. This review guides the way toward the commercialization of QLEDs.

Flexible and stretchable organic transistors for biosensing are comprehensively reviewed, with detailed discussions on advanced functionalization strategies and the wide applications of organic transistors in wearable, implantable, and portable electronics, as well as neuromorphic biointerfaces. Special attention is paid to the innovations in stretchable devices and emerging e-skin and smart textiles. The remaining challenges and future opportunities are discussed.

Flexible and stretchable biosensors can offer seamless and conformable biological–electronic interfaces for continuously acquiring high-fidelity signals, permitting numerous emerging applications. Organic thin film transistors (OTFTs) are ideal transducers for flexible and stretchable biosensing due to their soft nature, inherent amplification function, biocompatibility, ease of functionalization, low cost, and device diversity. In consideration of the rapid advances in flexible-OTFT-based biosensors and their broad applications, herein, a timely and comprehensive review is provided. It starts with a detailed introduction to the features of various OTFTs including organic field-effect transistors and organic electrochemical transistors, and the functionalization strategies for biosensing, with a highlight on the seminal work and up-to-date achievements. Then, the applications of flexible-OTFT-based biosensors in wearable, implantable, and portable electronics, as well as neuromorphic biointerfaces are detailed. Subsequently, special attention is paid to emerging stretchable organic transistors including planar and fibrous devices. The routes to impart stretchability, including structural engineering and material engineering, are discussed, and the implementations of stretchable organic transistors in e-skin and smart textiles are included. Finally, the remaining challenges and the future opportunities in this field are summarized.

Over the past 3 years, remarkable advancements in organic solar cells have emerged, propelled by the introduction of Y6—an innovative A-DA′D-A type small molecule non-fullerene acceptor in 2019. This review provides a critical discussion of the current knowledge about the structural and physical properties of the PM6:Y6 material combination in relation to its photovoltaic performance.

Over the past three years, remarkable advancements in organic solar cells (OSCs) have emerged, propelled by the introduction of Y6—an innovative A-DA'D-A type small molecule non-fullerene acceptor (NFA). This review provides a critical discussion of the current knowledge about the structural and physical properties of the PM6:Y6 material combination in relation to its photovoltaic performance. The design principles of PM6 and Y6 are discussed, covering charge transfer, transport, and recombination mechanisms. Then, the authors delve into blend morphology and degradation mechanisms before considering commercialization. The current state of the art is presented, while also discussing unresolved contentious issues, such as the blend energetics, the pathways of free charge generation, and the role of triplet states in recombination. As such, this review aims to provide a comprehensive understanding of the PM6:Y6 material combination and its potential for further development in the field of organic solar cells. By addressing both the successes and challenges associated with this system, this review contributes to the ongoing research efforts toward achieving more efficient and stable organic solar cells.

Intermolecular heteroatom interactions are well-known phenomena in organic charge transfer salts and are responsible for bulk metallic conductivity and even superconductivity. In this review, it is seen that the same interactions can be applied in organic semiconductors to increase bulk dimensionality through intermolecular contacts, and control molecular conformation through intramolecular interactions.

The field of synthetic metals is, and remains, highly influential for the development of organic semiconductor materials. Yet, with the passing of time and the rapid development of conjugated materials in recent years, the link between synthetic metals and organic semiconductors is at risk of being forgotten. This review reflects on one of the key concepts developed in synthetic metals – heteroatom interactions. The application of this strategy in recent organic semiconductor materials, small molecules and polymers, is highlighted, with analysis of X-ray crystal structures and comparisons with model systems used to determine the influence of these non-covalent short contacts. The case is made that the wide range of effective heteroatom interactions and the high performance that has been achieved in devices from organic solar cells to transistors is testament to the seeds sown by the synthetic metals research community.

The fusion of optical devices capable of detecting a wide range of wavelengths with stretchable packaging enables internal evaluations for health conditions and abnormalities of targeted living bodies and various objects without experiencing mechanical stress from an arbitrary surface. This review introduces the trends and detailed techniques of materials, electronics packaging, and remote imaging systems.

The integration of flexible electronics with optics can help realize a powerful tool that facilitates the creation of a smart society wherein internal evaluations can be easily performed nondestructively from the surface of various objects that is used or encountered in daily lives. Here, organic-material-based stretchable optical sensors and imagers that possess both bending capability and rubber-like elasticity are reviewed. The latest trends in nondestructive evaluation equipment that enable simple on-site evaluations of health conditions and abnormalities are discussed without subjecting the targeted living bodies and various objects to mechanical stress. Real-time performance under real-life conditions is becoming increasingly important for creating smart societies interwoven with optical technologies. In particular, the terahertz (THz)-wave region offers a substance- and state-specific fingerprint spectrum that enables instantaneous analyses. However, to make THz sensors accessible, the following issues must be addressed: broadband and high-sensitivity at room temperature, stretchability to follow the surface movements of targets, and digital transformation compatibility. The materials, electronics packaging, and remote imaging systems used to overcome these issues are discussed in detail. Ultimately, stretchable optical sensors and imagers with highly sensitive and broadband THz sensors can facilitate the multifaceted on-site evaluation of solids, liquids, and gases.