High-Performance Poly(3-hexyl thiophene)-Based Organic Photovoltaics with Side-Chain Engineering of Core Units of Small Molecule Acceptors.

In this study, we synthesized a series of four large-band gap small molecule acceptors with side-chain engineering of the dithieno-pyrrolo-fused pentacyclic benzotriazole (BZTTP or Y1 core) or the fused-ring dithienothiophene-pyrrolobenzothiadiazole (TPBT or Y6 core) with difluoro-indene-dione (IO2F) or dichloro-indene-dione (IO2Cl) end groups to form Y1-IO2F, Y1-IO2Cl, Y6-IO2F, and Y6-IO2Cl acceptors, respectively, for blending with poly(3-hexyl thiophene) (P3HT) for bulk heterojunction organic photovoltaics. The complementary UV-vis absorption spectra of these small molecules and P3HT along with their offset energy bands allow broad absorption and effective electron transfer. Through synchrotron wide-angle X-ray scattering (WAXS) analyses and contact angle measurements, we found that the blend of the small molecule Y6-IO2F (having a TPBT core) and P3HT achieves an optimum morphology that balances their crystallinity and miscibility, among those of these four blends, leading to a substantial enhancement in the short-circuit current density and thus power conversion efficiency (PCE) in their devices. For example, the P3HT:Y6-IO2F (w/w: 1/1.2) device exhibited a champion PCE of 10.5% with a short current density (Jsc) value of 15.9 mA/cm2 as compared to the P3HT:Y1-IO2F device having a PCE of 2.2% with a Jsc value of 5.7 mA/cm2 because of the higher Y6-IO2F (with TPBT core) molecular packing that facilitated carrier transport in the devices. The enhanced thermal stability exhibited by the devices incorporating Y6-IO2F and Y6-IO2Cl, as compared to that of Y1-IO2F and Y1-IO2Cl devices, is also due to the more planar TPBT core structure, while the photostability of devices incorporating Y6-IO2Cl and Y1-IO2Cl is better than that of devices incorporating Y6-IO2F and Y1-IO2F, owing to more photostable chemical structures. These results present an outstanding performance for P3HT-based organic solar cells. Moreover, these small molecule blends are processed with an environmentally friendly solvent tetrahydrofuran, demonstrating both the sustainability and commercial viability of these types of organic photovoltaics.

Suppressing ion migration in metal halide perovskite via interstitial doping with a trace amount of multivalent cations.

Cations with suitable sizes to occupy an interstitial site of perovskite crystals have been widely used to inhibit ion migration and promote the performance and stability of perovskite optoelectronics. However, such interstitial doping inevitably leads to lattice microstrain that impairs the long-range ordering and stability of the crystals, causing a sacrificial trade-off. Here, we unravel the evident influence of the valence states of the interstitial cations on their efficacy to suppress the ion migration. Incorporation of a trivalent neodymium cation (Nd3+) effectively mitigates the ion migration in the perovskite lattice with a reduced dosage (0.08%) compared to a widely used monovalent cation dopant (Na+, 0.45%). The photovoltaic performances and operational stability of the prototypical perovskite solar cells are enhanced with a trace amount of Nd3+ doping while minimizing the sacrificial trade-off.

Configurable Organic Charge Carriers toward Stable Perovskite Photovoltaics.

Due to their solution processability and unique photoelectric characteristics, perovskite solar cells (PSCs) have shown considerable promise in the area of renewable energy. Although their power conversion efficiency (PCE) has risen from 3.8% to 25.7% in only a few years, their short lifetime and high material prices continue to be key roadblocks to commercial viability. Charge transporting materials (CTMs), such as hole/electron transporting materials, are critical components in PSCs because they not only govern hole or electron extraction and transporting from the perovskite layer to the electrodes but also protect the perovskite from direct contact with the ambient environment. CTMs are split into two types: inorganic CTMs (ICTMs) and organic CTMs (OCTMs). Because of their inexpensive prices, well-adjusted energy levels, and low temperature solution-processed features, OCTMs have been more frequently explored and employed than ICTMs. Various forms of OCTMs with more straightforward synthetic pathways and better performance have been thoroughly researched. Recent achievements in the development of OCTMs will be discussed and evaluated on a molecular level in this study, which will include a systematic categorization of OCTMs based on molecular functionalization techniques. In order to achieve highly efficient and stable PSCs, we will present insights on the structure-property relationship in the design of OCTMs as well as device stability. We hope that this analysis will serve as a comprehensive reference to molecular design guidelines for various types of OCTMs, spurring greater research toward designing highly efficient and OCTMs for stable PSCs.

Stability-limiting heterointerfaces of perovskite photovoltaics.

Optoelectronic devices consist of heterointerfaces formed between dissimilar semiconducting materials. The relative energy-level alignment between contacting semiconductors determinately affects the heterointerface charge injection and extraction dynamics. For perovskite solar cells (PSCs), the heterointerface between the top perovskite surface and a charge-transporting material is often treated for defect passivation1-4 to improve the PSC stability and performance. However, such surface treatments can also affect the heterointerface energetics1. Here we show that surface treatments may induce a negative work function shift (that is, more n-type), which activates halide migration to aggravate PSC instability. Therefore, despite the beneficial effects of surface passivation, this detrimental side effect limits the maximum stability improvement attainable for PSCs treated in this way. This trade-off between the beneficial and detrimental effects should guide further work on improving PSC stability via surface treatments.

Near-Infrared Materials: The Turning Point of Organic Photovoltaics.

Near-infrared (NIR)-absorbing organic semiconductors have opened up many exciting opportunities for organic photovoltaic (OPV) research. For example, new chemistries and synthetical methodologies have been developed; especially, the breakthrough Y-series acceptors, originally invented by our group, specifically Y1, Y3, and Y6, have contributed immensely to boosting single-junction solar cell efficiency to around 19%; novel device architectures such as tandem and transparent organic photovoltaics have been realized. The concept of NIR donors/acceptors thus becomes a turning point in the OPV field. Here, the development of NIR-absorbing materials for OPVs is reviewed. According to the low-energy absorption window, here, NIR photovoltaic materials (p-type (polymers) and n-type (fullerene and nonfullerene)) are classified into four categories: 700-800 nm, 800-900 nm, 900-1000 nm, and greater than 1000 nm. Each subsection covers the design, synthesis, and utilization of various types of donor (D) and acceptor (A) units. The structure-property relationship between various kinds of D, A units and absorption window are constructed to satisfy requirements for different applications. Subsequently, a variety of applications realized by NIR materials, including transparent OPVs, tandem OPVs, photodetectors, are presented. Finally, challenges and future development of novel NIR materials for the next-generation organic photovoltaics and beyond are discussed.

Wide-Gap Perovskite via Synergetic Surface Passivation and Its Application toward Efficient Stacked Tandem Photovoltaics.

Superior bandgap tunability enables solution-processed halide perovskite a promising candidate for multi-junction photovoltaics (PVs). Particularly, optically coupling wide-gap perovskite by stacking with commercially available PVs such as silicon and CIGS (also known as 4-terminal tandem) simplifies the technology transfer process, and further advances the commercialization potential of perovskite technology. However, compared with matured PV materials and the phase-pure FAPbI3 , wide-gap perovskite still suffers from huge voltage deficits. Here, the authors take advantage of the synergetic effect behind a sequential fluoride and organic ammonium salt surface passivation strategy to control non-radiative energy losses, and obtained a 17.7% efficiency in infrared-transparent wide-gap perovskite solar cells (21.1% for opaque device), and achieved efficiencies of over 25% when stacked with commercial Si and CIGS products with original PCEs of 18-20% under a 4-terminal working condition.

Towards High-Performance Semitransparent Organic Photovoltaics: Dual-Functional p-Type Soft Interlayer.

Semitransparent organic photovoltaics (OPVs) have drawn significant attention for their promising potential in the field of building integrated photovoltaics such as energy-generating greenhouses. However, the conflict between the need to attain satisfying average visible transmittances for greenhouse applications and the need to maintain high power conversion efficiencies is limiting the commercialization of semitransparent OPVs. A major manifestation of this issue is the undermining of charge carrier extraction efficiency when opaque, visible-light-absorbing electrodes are substituted with semitransparent ones. Here, we incorporated a dual-function p-type compatible interlayer to modify the interface of the hole-transporting layer and the ultrathin electrode of the semitransparent devices. We find that the p-type interlayer not only enhances the charge carrier extraction of the electrode but also increases the light transmittance in the wavelength range of 400-450 nm, which covers most of the photosynthetic absorption spectrum. The modified semitransparent devices reach a power conversion efficiency of 13.7% and an average visible transmittance of 22.2%.

Performance-limiting formation dynamics in mixed-halide perovskites.

Wide-bandgap (WBG) mixed-halide perovskites as the front cell absorber are accomplishing perovskite-based tandem solar cells with over 29% power conversion efficiency. However, their large voltage deficits limit their ultimate performance. Only a handful of studies probe the fundamental mechanisms underlying the voltage deficits, which remain an unsolved challenge in the field. In this study, we investigate the formation dynamics and defect physics of WBG mixed-halide perovskites in contrast with their corresponding triiodide-based perovskites. Our results show that the inclusion of bromide introduced a halide homogenization process that occurs during the perovskite growth stage from an initial bromide-rich phase toward the final target stoichiometry. We further elucidated a physical model that correlates the role of bromide with the formation dynamics, defect physics, and eventual optoelectronic properties of the film. This work provides a fundamental and unique perspective toward understanding the performance-limiting factors affecting WBG mixed-halide perovskites.

Surface Reconstruction of Halide Perovskites During Post-treatment.

Postfabrication surface treatment strategies have been instrumental to the stability and performance improvements of halide perovskite photovoltaics in recent years. However, a consensus understanding of the complex reconstruction processes occurring at the surface is still lacking. Here, we combined complementary surface-sensitive and depth-resolved techniques to investigate the mechanistic reconstruction of the perovskite surface at the microscale level. We observed a reconstruction toward a more PbI2-rich top surface induced by the commonly used solvent isopropyl alcohol (IPA). We discuss several implications of this reconstruction on the surface thermodynamics and energetics. Particularly, our observations suggest that IPA assists in the adsorption process of organic ammonium salts to the surface to enhance their defect passivation effects.

Chlorinated Spiroconjugated Fused Extended Aromatics for Multifunctional Organic Electronics.

The synthesis of a new molecule, SFIC-Cl, is reported, which features enhanced π-electron delocalization by spiroconjugation and narrowed bandgap by chlorination. SFIC-Cl is integrated into a single-crystal transistor (OFET) and organic light-emitting diode (OLED). The material demonstrates remarkable transport abilities across various solution-processed OFETs and retains efficient radiance in a near-infrared OLED emitting light at 700 nm. Furthermore, the intermolecular multi-dimensional connection of SFIC-Cl enables the fabrication of a single-component large-area (2 × 2 cm2 ) near-infrared OLED by spin-coating. The SFIC-Cl-acceptor-based solar cell shows excellent power conversion efficiency of 10.16% resulting from the broadened and strong absorption and well-matched energy levels. The study demonstrates that chlorinated spiroconjugated fused systems offer a novel direction toward the development of high-performance organic semiconductor materials for hybrid organic electronic devices.

Reconfiguring the band-edge states of photovoltaic perovskites by conjugated organic cations.

The band edges of metal-halide perovskites with a general chemical structure of ABX3 (A, usually a monovalent organic cation; B, a divalent cation; and X, a halide anion) are constructed mainly of the orbitals from B and X sites. Hence, the structural and compositional varieties of the inorganic B-X framework are primarily responsible for regulating their electronic properties, whereas A-site cations are thought to only help stabilize the lattice and not to directly contribute to near-edge states. We report a π-conjugation-induced extension of electronic states of A-site cations that affects perovskite frontier orbitals. The π-conjugated pyrene-containing A-site cations electronically contribute to the surface band edges and influence the carrier dynamics, with a properly tailored intercalation distance between layers of the inorganic framework. The ethylammonium pyrene increased hole mobilities, improved power conversion efficiencies relative to that of a reference perovskite, and enhanced device stability.

Molecular Interaction Regulates the Performance and Longevity of Defect Passivation for Metal Halide Perovskite Solar Cells.

Defect passivation constitutes one of the most commonly used strategies to fabricate highly efficient perovskite solar cells (PSCs). However, the durability of the passivation effects under harsh operational conditions has not been extensively studied regardless of the weak and vulnerable secondary bonding between the molecular passivation agents and perovskite crystals. Here, we incorporated strategically designed passivating agents to investigate the effect of their interaction energies on the perovskite crystals and correlated these with the performance and longevity of the passivation effects. We unraveled that the passivation agents with a stronger interaction energy are advantageous not only for effective defect passivation but also to suppress defect migration. The prototypical PSCs treated with the optimal passivation agent exhibited superior performance and operational stability, retaining 81.9 and 85.3% of their initial performance under continuous illumination or nitrogen at 85 °C after 1008 h, respectively, while the reference device completely degraded during that time. This work provides important insights into designing operationally durable defect passivation agents for perovskite optoelectronic devices.

Enabling High-Performance Tandem Organic Photovoltaic Cells by Balancing the Front and Rear Subcells.

In tandem organic photovoltaics, the front subcell is based on large-bandgap materials, whereas the case of the rear subcell is more complicated. The rear subcell is generally composed of a narrow-bandgap acceptor for infrared absorption but a large-bandgap donor to realize a high open-circuit voltage. Unfortunately, most of the ultraviolet-visible part of the photons are absorbed by the front subcell; as a result, in the rear subcell, the number of excitons generated on large-bandgap donors will be reduced significantly. This reduces the (photo) conductivity and finally limits the hole-transporting property of the rear subcell. In this work, a simple and effective way is proposed to resolve this critical issue. To ensure sufficient photogenerated holes in the rear subcell, a small amount of an infrared-absorbing polymer donor as a third component is introduced, which provides a second hole-generation and transporting mechanism to minimize the aforementioned detrimental effects. Finally, the short-circuit current density of the two-terminal tandem organic photovoltaic is significantly enhanced from 10.3 to 11.7 mA cm-2 (while retaining the open-circuit voltage and fill factor) to result in an enhanced power conversion efficiency of 15.1%.

Transparent Hole-Transporting Frameworks: A Unique Strategy to Design High-Performance Semitransparent Organic Photovoltaics.

Thanks to the nature of molecular orbitals, the absorption spectra of organic semiconductors are not continuous like those in traditional inorganic semiconductors, which offers a unique application of organic photovoltaics (OPVs): semitransparent OPVs. Recently, the exciting progress of materials design has promoted the development of semitransparent OPVs. However, in the perspective of device engineering, almost all reported works reduce the thickness of back/reflected electrode to obtain high average visible transmittance (AVT), which is a trade-off between power conversion efficiency (PCE) and the transmittance of the whole solar spectrum (visible and infrared), and therefore limit the further development. Herein, a unique strategy of "transparent hole-transporting frameworks" is proposed. A hole-transporting large-bandgap polymer (poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine (PTAA)) is employed to partially replace polymer donors in the active layer of PBDB-T/Y1. PTAA is a p-type polymer with a large bandgap of 2.9 eV; the partial substitution of PBDB-T by PTAA reduces the absorption of the active layer only in the visible region, keeping the hole-transporting pathways as well as the optimized film morphology. As a result, semitransparent OPVs with PCEs of 12% and AVTs of 20% are achieved, both on rigid and flexible substrates. To demonstrate the generality, this strategy is also used in three different active layers.

Efficient Flexible Inorganic Perovskite Light-Emitting Diodes Fabricated with CsPbBr3 Emitters Prepared via Low-Temperature in Situ Dynamic Thermal Crystallization.

The present study systematically investigates the morphology and crystallization process of inorganic CsPbBr3 perovskite layer films fabricated by thermal coevaporation in conjunction with continuous low-temperature thermal annealing to promote in situ dynamic thermal crystallization. The results confirm for the first time that both the crystal grain size and the compactness of the CsPbBr3 films can be tuned during the thermal coevaporation fabrication process via in situ dynamic thermal crystallization. The performance of the PeLEDs employing the CsPbBr3 films as the emitter layer is investigated in detail with respect to the substrate temperature and deposition rate employed during deposition of the CsPbBr3 film. This study provides guidelines for developing suitable film production processes and highlights future challenges that must be addressed to facilitate the commercial development of large-area, uniform, and flexible perovskite-based optoelectronic devices.

A Polymerization-Assisted Grain Growth Strategy for Efficient and Stable Perovskite Solar Cells.

Intrinsically, detrimental defects accumulating at the surface and grain boundaries limit both the performance and stability of perovskite solar cells. Small molecules and bulkier polymers with functional groups are utilized to passivate these ionic defects but usually suffer from volatility and precipitation issues, respectively. Here, starting from the addition of small monomers in the PbI2 precursor, a polymerization-assisted grain growth strategy is introduced in the sequential deposition method. With a polymerization process triggered during the PbI2 film annealing, the bulkier polymers formed will be adhered to the grain boundaries, retaining the previously established interactions with PbI2 . After perovskite formation, the polymers anchored on the boundaries can effectively passivate undercoordinated lead ions and reduce the defect density. As a result, a champion power conversion efficiency (PCE) of 23.0% is obtained, together with a prolonged lifetime where 85.7% and 91.8% of the initial PCE remain after 504 h continuous illumination and 2208 h shelf storage, respectively.

Steric Impediment of Ion Migration Contributes to Improved Operational Stability of Perovskite Solar Cells.

The operational instability of perovskite solar cells (PSCs) is known to mainly originate from the migration of ionic species (or charged defects) under a potential gradient. Compositional engineering of the "A" site cation of the ABX3 perovskite structure has been shown to be an effective route to improve the stability of PSCs. Here, the effect of size-mismatch-induced lattice distortions on the ion migration energetics and operational stability of PSCs is investigated. It is observed that the size mismatch of the mixed "A" site composition films and devices leads to a steric effect to impede the migration pathways of ions to increase the activation energy of ion migration, which is demonstrated through multiple theoretical and experimental evidence. Consequently, the mixed composition devices exhibit significantly improved thermal stability under continuous heating at 85 °C and operational stability under continuous 1 sun illumination, with an extrapolated lifetime of 2011 h, compared to the 222 h of the reference device.

Gelatin methacryloyl-based tactile sensors for medical wearables.

Gelatin methacryloyl (GelMA) is a widely used hydrogel with skin-derived gelatin acting as the main constituent. However, GelMA has not been used in the development of wearable biosensors, which are emerging devices that enable personalized healthcare monitoring. This work highlights the potential of GelMA for wearable biosensing applications by demonstrating a fully solution-processable and transparent capacitive tactile sensor with microstructured GelMA as the core dielectric layer. A robust chemical bonding and a reliable encapsulation approach are introduced to overcome detachment and water-evaporation issues in hydrogel biosensors. The resultant GelMA tactile sensor shows a high-pressure sensitivity of 0.19 kPa-1 and one order of magnitude lower limit of detection (0.1 Pa) compared to previous hydrogel pressure sensors owing to its excellent mechanical and electrical properties (dielectric constant). Furthermore, it shows durability up to 3000 test cycles because of tough chemical bonding, and long-term stability of 3 days due to the inclusion of an encapsulation layer, which prevents water evaporation (80% water content). Successful monitoring of various human physiological and motion signals demonstrates the potential of these GelMA tactile sensors for wearable biosensing applications.

Surface-2D/Bulk-3D Heterophased Perovskite Nanograins for Long-Term-Stable Light-Emitting Diodes.

Although metal halide perovskite (MHP) light-emitting diodes (LEDs) have demonstrated great potential in terms of electroluminescence efficiency, the operational stability of MHP LEDs currently remains the biggest bottleneck toward their practical usage. Well-confined excitons/charge carriers in a dielectric/quantum well based on conventional spatial or potential confinement approaches substantially enhance radiative recombination in MHPs, but an increased surface-to-volume ratio and multiphase interfaces likely result in a high degree of surface or interface defect states, which brings about a critical environmentally/operationally vulnerable point on LED stability. Here, an effective solution is suggested to mitigate such drawbacks using strategically designed surface-2D/bulk-3D heterophased MHP nanograins for long-term-stable LEDs. The 2D surface-functionalized MHP renders significantly reduced trap density, environmental stability, and an ion-migration-immune surface in addition to a fast radiative recombination owing to its spatially and potentially confined charge carriers, simultaneously. As a result, heterophased MHP LEDs show substantial improvement in operational lifetime (T50 : >200 h) compared to conventional pure 3D or quasi-2D counterparts (T50 : < 0.2 h) as well as electroluminescence efficiency (surface-2D/bulk-3D: ≈7.70 ph per el% and pure 3D: ≈0.46 ph per el%).

Constructive molecular configurations for surface-defect passivation of perovskite photovoltaics.

Surface trap-mediated nonradiative charge recombination is a major limit to achieving high-efficiency metal-halide perovskite photovoltaics. The ionic character of perovskite lattice has enabled molecular defect passivation approaches through interaction between functional groups and defects. However, a lack of in-depth understanding of how the molecular configuration influences the passivation effectiveness is a challenge to rational molecule design. Here, the chemical environment of a functional group that is activated for defect passivation was systematically investigated with theophylline, caffeine, and theobromine. When N-H and C=O were in an optimal configuration in the molecule, hydrogen-bond formation between N-H and I (iodine) assisted the primary C=O binding with the antisite Pb (lead) defect to maximize surface-defect binding. A stabilized power conversion efficiency of 22.6% of photovoltaic device was demonstrated with theophylline treatment.