Intrinsically stretchable organic photovoltaics by redistributing strain to PEDOT:PSS with enhanced stretchability and interfacial adhesion.

Intrinsically stretchable organic photovoltaics have emerged as a prominent candidate for the next-generation wearable power generators regarding their structural design flexibility, omnidirectional stretchability, and in-plane deformability. However, formulating strategies to fabricate intrinsically stretchable organic photovoltaics that exhibit mechanical robustness under both repetitive strain cycles and high tensile strains remains challenging. Herein, we demonstrate high-performance intrinsically stretchable organic photovoltaics with an initial power conversion efficiency of 14.2%, exceptional stretchability (80% of the initial power conversion efficiency maintained at 52% tensile strain), and cyclic mechanical durability (95% of the initial power conversion efficiency retained after 100 strain cycles at 10%). The stretchability is primarily realised by delocalising and redistributing the strain in the active layer to a highly stretchable PEDOT:PSS electrode developed with a straightforward incorporation of ION E, which simultaneously enhances the stretchability of PEDOT:PSS itself and meanwhile reinforces the interfacial adhesion with the polyurethane substrate. Both enhancements are pivotal factors ensuring the excellent mechanical durability of the PEDOT:PSS electrode, which further effectively delays the crack initiation and propagation in the top active layer, and enables the limited performance degradation under high tensile strains and repetitive strain cycles.

Waterproof and ultraflexible organic photovoltaics with improved interface adhesion.

Ultraflexible organic photovoltaics have emerged as a potential power source for wearable electronics owing to their stretchability and lightweight nature. However, waterproofing ultraflexible organic photovoltaics without compromising mechanical flexibility and conformability remains challenging. Here, we demonstrate waterproof and ultraflexible organic photovoltaics through the in-situ growth of a hole-transporting layer to strengthen interface adhesion between the active layer and anode. Specifically, a silver electrode is deposited directly on top of the active layers, followed by thermal annealing treatment. Compared with conventional sequentially-deposited hole-transporting layers, the in-situ grown hole-transporting layer exhibits higher thermodynamic adhesion between the active layers, resulting in better waterproofness. The fabricated 3 µm-thick organic photovoltaics retain 89% and 96% of their pristine performance after immersion in water for 4 h and 300 stretching/releasing cycles at 30% strain under water, respectively. Moreover, the ultraflexible devices withstand a machine-washing test with such a thin encapsulation layer, which has never been reported. Finally, we demonstrate the universality of the strategy for achieving waterproof solar cells.

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.

Dependence of Exciton Binding Energy on Bandgap of Organic Semiconductors.

Strongly bound excitons crucially affect the operation of organic optoelectronic devices. Nevertheless, precise experimental data on the exciton binding energy of organic semiconductors are lacking. In this study, we determine the exciton binding energy as the difference between the optical and transport bandgaps with a precision of 0.1 eV. In particular, electron affinities with a precision higher than 0.05 eV determined by low-energy inverse photoelectron spectroscopy allow us to determine the transport gap and the exciton binding energies with such high precision. Through a systematic comparison of a wide range of organic semiconductors, including 42 organic solar cell materials (15 nonfullerene acceptors, 4 fullerene acceptors, 13 low-bandgap polymers, 7 organic light-emitting diode materials, and 3 crystalline materials), we found that the exciton binding energy is one-quarter of the transport gap regardless of the materials. We interpret this unexpected relation from a hydrogen atom-like model, i.e., the quantized energy levels in a Coulomb potential between the positive and the negative charges.

Synthesis of 3,3'-dihydroxy-2,2'-diindan-1,1'-dione derivatives for tautomeric organic semiconductors exhibiting intramolecular double proton transfer.

To investigate potential applications of the 3,3'-dihydroxy-2,2'-biindan-1,1'-dione (BIT) structure as an organic semiconductor with intramolecular hydrogen bonds, a new synthetic route under mild conditions is developed based on the addition reaction of 1,3-dione to ninhydrin and the subsequent hydrogenation of the hydroxyl group. This route affords several new BIT derivatives, including asymmetrically substituted structures that are difficult to access by conventional high-temperature synthesis. The BIT derivatives exhibit rapid tautomerization by intramolecular double proton transfer in solution. The tautomerizations are also observed in the solid state by variable temperature measurements of X-ray diffractometry and magic angle spinning 13C solid-state NMR. Possible interplay between the double proton transfer and the charge transport is suggested by quantum chemical calculations. The monoalkylated BIT derivative with a lamellar packing structure suitable for lateral charge transport in films shows a hole mobility of up to 0.012 cm2 V-1 s-1 with a weak temperature dependence in an organic field effect transistor.

Tin Halide Perovskite Solar Cells with Open-Circuit Voltages Approaching the Shockley-Queisser Limit.

The power conversion efficiency of tin-based halide perovskite solar cells is limited by large photovoltage losses arising from the significant energy-level offset between the perovskite and the conventional electron transport material, fullerene C60. The fullerene derivative indene-C60 bisadduct (ICBA) is a promising alternative to mitigate this drawback, owing to its superior energy level matching with most tin-based perovskites. However, the less finely controlled energy disorder of the ICBA films leads to the extension of its band tails that limits the photovoltage of the resultant devices and reduces the power conversion efficiency. Herein, we fabricate ICBA films with improved morphology and electrical properties by optimizing the choice of solvent and the annealing temperature. Energy disorder in the ICBA films is substantially reduced, as evidenced by the 22 meV smaller width of the electronic density of states. The resulting solar cells show open-circuit voltages of up to 1.01 V, one of the highest values reported so far for tin-based devices. Combined with surface passivation, this strategy enabled solar cells with efficiencies of up to 11.57%. Our work highlights the importance of controlling the properties of the electron transport material toward the development of efficient lead-free perovskite solar cells and demonstrates the potential of solvent engineering for efficient device processing.

Synthesis of 2,5,8-Tris(1-phenyl-1H-benzo[d]imidazol-2-yl)benzo[1,2-b:3,4-b':5,6-b″] Trithiophenes and Their Spontaneous Orientation Polarization in Thin Films.

To investigate the relationship between molecular structures and spontaneous orientation polarization (SOP) in organic thin films, 2,5,8-tris(1-phenyl-1H-benzo[d]imidazol-2-yl)benzo[1,2-b:3,4-b':5,6-b″] trithiophene (TPBTT) and its ethyl derivative (m-ethyl-TPBTT) were synthesized. Variable angle spectroscopic ellipsometry and two-dimensional grazing-incidence wide-angle X-ray scattering showed that the vacuum-deposited films of TPBTT and m-ethyl-TPBTT had a higher degree of molecular orientation parallel to the substrate compared with that of prototypical 2,2',2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi) due to the larger π-conjugated benzotrithiophene core. However, TPBTT films showed a lower SOP of +54.4 mV/nm than did the TPBi film (+77.3 mV/nm), indicating that the molecular orientation alone did not determine the SOP. In contrast, m-ethyl-TPBTT showed a larger SOP of +104.0 mV/nm in the film. Quantum chemical calculations based on density functional theory suggested that the differences in the stable molecular conformation and the permanent dipole moments between TPBTT and m-ethyl-TPBTT caused the differences in SOP. These results suggest that the simultaneous control of the orientational order and conformation of the molecules is important to achieving a large SOP in films.

Synergistic Surface Modification of Tin-Lead Perovskite Solar Cells.

Interfaces in thin-film photovoltaics play a pivotal role in determining device efficiency and longevity. In this work, the top surface treatment of mixed tin-lead (≈1.26 eV) halide perovskite films for p-i-n solar cells is studied. Charge extraction is promoted by treating the perovskite surface with piperazine. This compound reacts with the organic cations at the perovskite surface, modifying the surface structure and tuning the interfacial energy level alignment. In addition, the combined treatment with C60 pyrrolidine tris-acid (CPTA) reduces hysteresis and leads to efficiencies up to 22.7%, with open-circuit voltage values reaching 0.90 V, ≈92% of the radiative limit for the bandgap of this material. The modified cells also show superior stability, with unencapsulated cells retaining 96% of their initial efficiency after >2000 h of storage in N2 and encapsulated cells retaining 90% efficiency after >450 h of storage in air. Intriguingly, CPTA preferentially binds to Sn2+ sites at film surface over Pb2+ due to the energetically favored exposure of the former, according to first-principles calculations. This work provides new insights into the surface chemistry of perovskite films in terms of their structural, electronic, and defect characteristics and this knowledge is used to fabricate state-of-the-art solar cells.

Impact of Narrowing Density of States in Semiconducting Polymers on Performance of Organic Field-Effect Transistors.

To improve the performance of organic field-effect transistors (OFETs) employing π-conjugated polymers, a basic understanding of the relationships between the material properties and device characteristics is crucial. Although the density of states (DOS) distribution is one of the essential material properties of semiconducting polymers, insights into how the DOS shape affects the mobility (µ), subthreshold swing (S), and contact resistance (RC ) in OFETs remain lacking. In this study, by combining sensitive DOS measurements and multilayered OFET structures, it is experimentally demonstrated that narrower DOS widths in the polymer channels lead to higher µ, smaller S, and lower RC . By contrast, variation of the DOS in the bulk layer does not affect the performance. These results demonstrate a direct relationship between the polymer properties and OFET performance and highlight the importance of controlling the DOS width in π-conjugated polymers.

A Universal Surface Treatment for p-i-n Perovskite Solar Cells.

Perovskite interfaces critically influence the final performance of the photovoltaic devices. Optimizing them by reducing the defect densities or improving the contact with the charge transporting material is key to further enhance the efficiency and stability of perovskite solar cells. Inverted (p-i-n) devices can particularly benefit here, as evident from various successful attempts. However, every reported strategy is adapted to specific cell structures and compositions, affecting their robustness and applicability by other researchers. In this work, we present the universality of perovskite top surface post-treatment with ethylenediammonium diiodide (EDAI2) for p-i-n devices. To prove it, we compare devices bearing perovskite films of different composition, i.e., Sn-, Pb-, and mixed Sn-Pb-based devices, achieving efficiencies of up to 11.4, 22.0, and 22.9%, respectively. A careful optimization of the EDAI2 thickness indicates a different tolerance for Pb- and Sn-based devices. The main benefit of this treatment is evident in the open-circuit voltage, with enhancements of up to 200 mV for some compositions. In addition, we prove that this treatment can be successfully applied by both wet (spin-coating) and dry (thermal evaporation) methods, regardless of the composition. The versatility of this treatment makes it highly appealing for industrial application, as it can be easily adapted to specific processing requirements. We present a detailed experimental protocol, aiming to provide the community with an easy, universal perovskite post-treatment method for reliably improving the device efficiency, highlighting the potential of interfaces for the field.

Tuning Molecular Conformations to Enhance Spontaneous Orientation Polarization in Organic Thin Films.

Three isomeric derivatives of 2,2',2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi) bearing ethyl groups on the N-phenyl moieties were synthesized to elucidate the effects of intramolecular interactions on spontaneous orientation polarization (SOP) in thin films. The films of the TPBi derivatives displayed enhanced SOP with a surface potential change of up to 1.8 times that for TPBi, and the p-substituted derivative exhibited the largest potential change reported to date (+141.0 mV/nm). Density functional theory calculations and single-crystal structure analysis suggest that the introduction of the ethyl groups switched the stable molecular conformation from C1 to C3 symmetry. Through analysis of the structural anisotropy in the films by spectral ellipsometry and two-dimensional (2D) grazing-incidence wide-angle X-ray scattering, we conclude that the conformational change of the molecules was the major factor underlying the SOP enhancement.

Essential Role of Triplet Diradical Character for Large Magnetoresistance in Quinoidal Organic Semiconductor with High Electron Mobility.

A diradicaloid molecule with high semiconducting performance is synthesized based on the quinoidal benzo[1,2-b:4,5-b']dithiophene structure. The diradical character is investigated by quantum chemical calculations and variable temperature electron spin resonance. The diode devices based on this molecule show a large change in electric current in magnetic fields below 100 mT with a strong dependence on the measurement temperatures; as the population of the triplet diradicals increases at high temperatures, the magnetoconductance (MC) values increase. As a result, a MC of -19.4% is achieved at 120 °C, which is the largest negative MC observed for organic molecules to date. In contrast, a smaller diradicaloid molecule based on quinoidal thieno[3,2-b]thiophene without thermally accessible triplet state shows no MC, indicating the essential role of the triplet diradicals. The strong correlation between the MC and the triplet diradical concentrations suggests that the charge conduction in the diradicaloid is suppressed through a spin-blocking mechanism, which can be controlled through the magnetic modulation of the hyperfine fields. The compound forms high-crystallinity thin films and has high monopolar electron transport in organic field-effect transistors, with an average mobility of 1.01 cm2 V-1 s-1 for edge-cast films.

Ultrathin and Efficient Organic Photovoltaics with Enhanced Air Stability by Suppression of Zinc Element Diffusion.

Ultrathin (thickness less than 10 µm) organic photovoltaics (OPVs) can be applied to power soft robotics and wearable electronics. In addition to high power conversion efficiency, stability under various environmental stresses is crucial for the application of ultrathin OPVs. In this study, the authors realize highly air-stable and ultrathin (≈3 µm) OPVs that possess high efficiency (15.8%) and an outstanding power-per-weight ratio of 33.8 W g-1 . Dynamic secondary-ion mass spectrometry is used to identify Zn diffusion from the electron transport layer zinc oxide (ZnO) to the interface of photoactive layer; this diffusion results in the degradation of the ultrathin OPVs in air. The suppression of the Zn diffusion by a chelating strategy results in stable ultrathin OPVs that maintain 89.6% of their initial efficiency after storage for 1574 h in air at room temperature under dark conditions and 92.4% of their initial efficiency after annealing for 172 h at 85 °C in air under dark conditions. The lightweight and stable OPVs also possess excellent deformability with 87.3% retention of the initial performance after 5000 cycles of a compressing-stretching test with 33% compression.

Reduction of Electric Current Loss by Aggregation-Induced Molecular Alignment of a Non-Fullerene Acceptor in Organic Photovoltaics.

Y6 is a recently developed non-fullerene electron acceptor (NFA) with dithienothiophen[3.2-b]-pyrrolobenzothiadiazole as the central unit and improves the performance of organic photovoltaics (OPVs) in combination with many electron-donor polymers. Although Y6 has desirable electronic properties for OPVs, the origin of its superiority as an acceptor is unclear. This study empirically investigates why Y6 is an excellent acceptor by comparing Y6 with F8IC, an analogue with a similar electronic structure, in bulk heterojunction (BHJ) OPVs with various electron-acceptor concentrations. The difference in the performance between Y6 and F8IC appears only at high concentrations, suggesting that it originates from the aggregation structures of the NFAs in the BHJs. Electric current loss analysis reveals that the exciton loss and non-geminate recombination are suppressed more strongly in Y6 OPVs than in F8IC OPVs. Variable angle spectroscopic ellipsometry shows that Y6 molecules align in the in-plane direction at high concentrations, contributing to the high charge generation rate via efficient exciton collection.

Triphenyleno[1,2-c:7,8-c']bis([1,2,5]thiadiazole) as a V-Shaped Electron-Deficient Unit to Construct Wide-Bandgap Amorphous Polymers for Efficient Organic Solar Cells.

The backbone shape of semiconducting polymers strongly affects their electronic properties and morphologies in films, yet the conventional design principle for building blocks focuses on using linear main chains to maintain high crystallinity. Here, we developed a V-shaped unit, triphenyleno[1,2-c:7,8-c']bis([1,2,5]thiadiazole) (TPTz), featuring two 1,2,5-thiadiazole rings fused to a triphenylene core with strong electron-withdrawing properties and an extended conjugation plane. We used TPTz to prepare a highly soluble copolymer, PTPTz-indacenodithiophene (IDT), which exhibited a wide bandgap of 1.94 eV and energy levels suitable for the donor polymer in organic solar cells (OSCs) in combination with non-fullerene acceptors. Despite the amorphous nature of the polymer film, single-junction OSCs with PTPTz-IDT:Y6 as the active layer achieved a power conversion efficiency of 10.4% (JSC = 19.8 mA cm-2; VOC = 0.80 V; fill factor = 0.66), which is the highest value reported for a single-junction OSC with IDT-based donor polymers. This work demonstrates that TPTz is a promising electron-acceptor unit for developing functional polymers with zigzag structures.

Mechanism of charge accumulation of poly(heptazine imide) gel.

Photo-stimuli response in materials is a fascinating feature with many potential applications. A photoresponsive gel of poly(heptazine imide), PHI, termed PHIG, exhibits photochromism, photoconductivity, and photo-induced charge accumulation, and is generated using ionic liquids and PHI. Although there are several examples of ionic liquid gels that exhibit photochromism and photoconductivity, this is the first report of an ionic liquid gel that exhibits both these properties as well as charge accumulation. We conducted experimental and theoretical investigations to understand the mechanism of the photostimulus response of PHIG, especially charge accumulation. The proposed model explains both the mechanism of charge accumulation and dark photocatalysis by PHI and provides new concepts in the field of photofunctional materials.

Highly Sensitive Evaluation of Density of States in Molecular Semiconductors by Photoelectron Yield Spectroscopy in Air.

Despite the critical importance of the density of states (DOS) to the electrical properties of molecular semiconductors, there are few reliable measurement methods for the DOS, especially for the edge regions with low DOS that determine the charge conduction. Here, we evaluate the DOS for occupied states with high sensitivity (down to 10-5 relative to the peak maxima) using a commercially available photoelectron yield spectroscopy (PYS) system operated in air. The conduction edges of the DOS for both the semiconducting polymers and molecules are expressed as a single Gaussian with no gap states with one exception. There are subtle differences in the widths of the Gaussian for the DOS edges between the surface of the polymer films and the interface with the substrate, which result in the large difference in the lateral charge carrier mobilities at each interface. The charge carrier mobilities of the semiconducting polymers have a correlation with the widths of the DOS. PYS in air is a powerful tool for studying the relationship among the structure and electronic and electrical properties of molecular semiconductors.

Inversion of Circular Dichroism Signals in Chiral Polythiophene Films Induced by End-On-Oriented Surface-Segregated Monolayers.

A chiral polythiophene surfactant based on poly(3-(S)-2-methylbutylthiophene) ((S)-P3MBT) with a semifluoroalkyl group at one end of the main chain was synthesized and used to form surface-segregated monolayers (SSMs). Films of pure (S)-P3MBT mainly adopted the edge-on orientation, whereas (S)-P3MBT films with a SSM of the polymer surfactant (S)-P3MBT-F17 contained a large proportion of end-on-oriented polythiophene, both at the surface and inside the films. The thin films with the SSM showed circular dichroism signals, with the sign opposite to those observed in (S)-P3MBT films. These findings suggest that the orientation-controlled SSM layers induced changes in the packing of the polymer aggregates in the films, resulting in a dramatic change in the excitonic interactions of the chiral semiconducting polymers.

Immobilization of Ethynyl-π-Extended Electron Acceptors with Amino-Terminated SAMs by Catalyst-Free Click Reaction.

Surface modification of SiO2 using a catalyst-free quantitative reaction between an amine and an ethynyl-π-extended naphthalenediimide was investigated. A post-reaction method, in which the catalyst-free reaction was performed at the surface after the formation of amino-terminated self-assembled monolayers (SAMs), resulted in dense, uniform modification of the SiO2 surface with the naphthalenediimide molecules. Both X-ray reflectivity and angle-resolved X-ray photoemission spectroscopy showed consistent results for the layer thickness and density. In contrast, a pre-reaction method, in which an amino-silane and the ethynyl-π-extended naphthalenediimide reacted first and then formed a SAM, afforded a sparse SAM on the SiO2 surface, probably due to the steric hindrance of the naphthalenediimide moieties. The in situ decoration of the SiO2 surface by a catalyst-free quantitative reaction offers a facile route for modifying surface properties with various π-conjugated molecules suitable for many applications.