Highly Efficient and Scalable p-i-n Perovskite Solar Cells Enabled by Poly-metallocene Interfaces.

Inverted p-i-n perovskite solar cells (PSCs) are easy to process but need improved interface characteristics with reduced energy loss to prevent efficiency drops when increasing the active photovoltaic area. Here, we report a series of poly ferrocenyl molecules that can modulate the perovskite surface enabling the construction of small- and large-area PSCs. We found that the perovskite-ferrocenyl interaction forms a hybrid complex with enhanced surface coordination strength and activated electronic states, leading to lower interfacial nonradiative recombination and charge transport resistance losses. The resulting PSCs achieve an enhanced efficiency of up to 26.08% for small-area devices and 24.51% for large-area devices (1.0208 cm2). Moreover, the large-area PSCs maintain >92% of the initial efficiency after 2000 h of continuous operation at the maximum power point under 1-sun illumination and 65 °C.

Charge Management Enables Efficient Spontaneous Chromatic Adaptation Bipolar Photodetector.

Solution-processed photodetectors have emerged as promising candidates for next-generation of visible-near infrared (vis-NIR) photodetectors. This is attributed to their ease of processing, compatibility with flexible substrates, and the ability to tune their detection properties by integrating complementary photoresponsive semiconductors. However, the limited performance continues to hinder their further development, primarily influenced by the difference of charge transport properties between perovskite and organic semiconductors. In this work, a perovskite-organic bipolar photodetectors (PDs) is introduced with multispectral responsivity, achieved by effectively managing charges in perovskite and a ternary organic heterojunction. The ternary heterojunction, incorporating a designed NIR guest acceptor, exhibits a faster charge transfer rate and longer carrier diffusion length than the binary heterojunction. By achieving a more balanced carrier dynamic between the perovskite and organic components, the PD achieves a low dark current of 3.74 nA cm-2 at -0.2 V, a fast response speed of <10 µs, and a detectivity of exceeding 1012 Jones. Furthermore, a bioinspired retinotopic system for spontaneous chromatic adaptation is achieved without any optical filter. This charge management strategy opens up possibilities for surpassing the limitations of photodetection and enables the realization of high-purity, compact image sensors with exceptional spatial resolution and accurate color reproduction.

Suppressing Oxidation at Perovskite-NiOx Interface for Efficient and Stable Tin Perovskite Solar Cells.

Inorganic nickel oxide (NiOx ) is an ideal hole transport material (HTM) for the fabrication of high-efficiency, stable, and large-area perovskite photovoltaic devices because of its low cost, stability, and ease of solution processing. However, it delivers low power conversion efficiency (PCE) in tin perovskite solar cells (TPSCs) compared to other organic HTMs. Here, the origin of hole transport barriers at the perovskite-NiOx interface is identified and a self-assembled monolayer interface modification is developed, through introducing (4-(7H-dibenzo[c,g]carbazol-7-yl)ethyl)phosphonic acid (2PADBC) into the perovskite-NiOx interface. The 2PADBC anchors undercoordinated Ni cations through phosphonic acid groups, suppressing the reaction of highly active Ni≥3+ defects with perovskites, while increasing the electron density and oxidation activation energy of Sn at the perovskite interface, reducing the interface nonradiative recombination caused by tetravalent Sn defects. The devices deliver significantly increased open-circuit voltage from 0.712 to 0.825 V, boosting the PCE to 14.19% for the small-area device and 12.05% for the large-area (1 cm2 ) device. In addition, the 2PADBC modification enhances the operational stability of NiOx -based TPSCs, maintaining more than 93% of their initial efficiency after 1000 h.

Stabilized hole-selective layer for high-performance inverted p-i-n perovskite solar cells.

P-i-n geometry perovskite solar cells (PSCs) offer simplified fabrication, greater amenability to charge extraction layers, and low-temperature processing over n-i-p counterparts. Self-assembled monolayers (SAMs) can enhance the performance of p-i-n PSCs but ultrathin SAMs can be thermally unstable. We report a thermally robust hole-selective layer comprised of nickel oxide (NiOx) nanoparticle film with a surface-anchored (4-(3,11-dimethoxy-7H-dibenzo[c,g]carbazol-7-yl)butyl)phosphonic acid (MeO-4PADBC) SAM that can improve and stabilize the NiOx/perovskite interface. The energetic alignment and favorable contact and binding between NiOx/MeO-4PADBC and perovskite reduced the voltage deficit of PSCs with various perovskite compositions and led to strong interface toughening effects under thermal stress. The resulting 1.53-electron-volt devices achieved 25.6% certified power conversion efficiency and maintained >90% of their initial efficiency after continuously operating at 65 degrees Celsius for 1200 hours under 1-sun illumination.

Green-solvent Processable Dopant-free Hole Transporting Materials for Inverted Perovskite Solar Cells.

The commercialization of perovskite solar cells (PVSCs) urgently requires the development of green-solvent processable dopant-free hole transporting materials (HTMs). However, strong intermolecular interactions that ensure high hole mobility always compromise the solubility and film-forming ability in green solvents. Herein, we show a simple but effective design strategy to solve this trade-off, that is, constructing star-shaped D-A-D structure. The resulting HTMs (BTP1-2) can be processed by green solvent of 2-methylanisole (2MA), a kind of food additive, and show high hole mobility and multiple defect passivation effects. An impressive efficiency of 24.34 % has been achieved for 2MA-processed BTP1 based inverted PVSCs, the highest value for green-solvent processable HTMs so far. Moreover, it is manifested that the charge separation of D-A type HTMs at the photoinduced excited state can help to passivate the defects of perovskites, indicating a new HTM design insight.

Backbone Engineering Enables Highly Efficient Polymer Hole-Transporting Materials for Inverted Perovskite Solar Cells.

The interface and crystallinity of perovskite films play a decisive role in determining the device performance, which is significantly influenced by the bottom hole-transporting material (HTM) of inverted perovskite solar cells (PVSCs). Herein, a simple design strategy of polymer HTMs is reported, which can modulate the wettability and promote the anchoring by introducing pyridine units into the polyarylamine backbone, so as to realize efficient and stable inverted PVSCs. The HTM properties can be effectively modified by varying the linkage sites of pyridine units, and 3,5-linked PTAA-P1 particularly demonstrates a more regulated molecular configuration for interacting with perovskites, leading to highly crystalline perovskite films with uniform back contact and reduced defect density. Dopant-free PTAA-P1-based inverted PVSCs have realized remarkable efficiencies of 24.89% (certified value: 24.50%) for small-area (0.08 cm2 ) as well as 23.12% for large-area (1 cm2 ) devices. Moreover, the unencapsulated device maintains over 93% of its initial efficiency after 800 h of maximum power point tracking under simulated AM 1.5G illumination.

An asymmetric 2,3-fluoranthene imide building block for regioregular semiconductors with aggregation-induced emission properties.

For organic semiconductors, the development of electron-deficient building blocks has lagged far behind that of the electron-rich ones. Moreover, it remains a significant challenge to design organic molecules with efficient charge transport and strong solid-state emission simultaneously. Herein, we describe a facile synthetic route toward a new π-acceptor imide building block, namely 2,3-fluoranthene imide, based on which four regioregular small molecules (F1-F4) are synthesized by tuning the imide orientations and the central linkage bridges. All molecules exhibit attractive aggregation-induced emission (AIE) characteristics with strong far-red emission in the powder state, and F3 shows the highest photoluminescence quantum yield of 5.9%. F1 and F3 with a thiophene bridge present an obvious p-type characteristic, while for F3 with an outward imide orientation, the maximum hole mobility from a solution-processed field-effect transistor (FET) device reaches 0.026 cm2 V-1 s-1, being ∼104 times higher than the value of F1 with an inward imide orientation. By using a fluorinated thiophene bridge, the resulting F2 and F4 can be turned into n-type semiconductors, showing an electron mobility of ∼1.43 × 10-4 and ∼3.34 × 10-5 cm2 V-1 s-1, respectively. Our work not only demonstrates that asymmetric 2,3-fluoranthene imide is a promising building block for constructing organic materials with high carrier mobility and strong solid-state emission, but also highlights the importance of regioregular structures in the materials' properties.

Recent advances in developing high-performance organic hole transporting materials for inverted perovskite solar cells.

Inverted perovskite solar cells (PVSCs) have recently made exciting progress, showing high power conversion efficiencies (PCEs) of 25% in single-junction devices and 30.5% in silicon/perovskite tandem devices. The hole transporting material (HTM) in an inverted PVSC plays an important role in determining the device performance, since it not only extracts/transports holes but also affects the growth and crystallization of perovskite film. Currently, polymer and self-assembled monolayer (SAM) have been considered as two types of most promising HTM candidates for inverted PVSCs owing to their high PCEs, high stability and adaptability to large area devices. In this review, recent encouraging progress of high-performance polymer and SAM-based HTMs is systematically reviewed and summarized, including molecular design strategies and the correlation between molecular structure and device performance. We hope this review can inspire further innovative development of HTMs for wide applications in highly efficient and stable inverted PVSCs and the tandem devices.

Efficient Inverted Perovskite Solar Cells with Low Voltage Loss Achieved by a Pyridine-Based Dopant-Free Polymer Semiconductor.

Currently, the performance improvement for inverted perovskite solar cells (PVSCs) is mainly limited by the high open circuit voltage (VOC ) loss caused by detrimental non-radiative recombination (NRR) processes. Herein, we report a simple and efficient way to simultaneously reduce the NRR processes inside perovskites and at the interface by rationally designing a new pyridine-based polymer hole-transporting material (HTM), PPY2, which exhibits suitable energy levels with perovskites, high hole mobility, effective passivation of the uncoordinated Pb2+ and iodide defects, as well as the capability of promoting the formation of high-quality polycrystalline perovskite films. In absence of any dopants, the inverted PVSCs using PPY2 as the HTM deliver an encouraging PCE up to 22.41 % with a small VOC loss (0.40 V), among the best device performances for inverted PVSCs reported so far. Furthermore, PPY2-based unencapsulated devices show an excellent long-term photostability, and over 97 % of its initial PCE can be maintained after one sun constant illumination for 500 h.

Dopant-Free Crossconjugated Hole-Transporting Polymers for Highly Efficient Perovskite Solar Cells.

Currently, there are only very few dopant-free polymer hole-transporting materials (HTMs) that can enable perovskite solar cells (PVSCs) to demonstrate a high power conversion efficiency (PCE) of greater than 20%. To address this need, a simple and efficient way is developed to synthesize novel crossconjugated polymers as high performance dopant-free HTMs to endow PVSCs with a high PCE of 21.3%, which is among the highest values reported for single-junction inverted PVSCs. More importantly, rational understanding of the reasons why two isomeric polymer HTMs (PPE1 and PPE2) with almost identical photophysical properties, hole-transporting ability, and surface wettability deliver so distinctly different device performance under similar device fabrication conditions is manifested. PPE2 is found to improve the quality of perovskite films cast on top with larger grain sizes and more oriented crystallization. These results help unveil the new HTM design rules to influence the perovskite growth/crystallization for improving the performance of inverted PVSCs.

A structure-property study of fluoranthene-cored hole-transporting materials enables 19.3% efficiency in dopant-free perovskite solar cells.

To date, most of the prevailing organic hole-transporting materials (HTMs) used in perovskite solar cells (PVSCs), such as spiro-OMeTAD and PTAA, generally require a sophisticated doping process to ensure their reasonable hole-transporting properties. Unfortunately, the employed dopants/additives and the associated oxidation reactions have been shown to deteriorate the long-term device stability seriously. The exploitation of efficient and stable dopant-free HTMs is thus strongly desired for PVSCs. However, effective molecular design strategies for dopant-free HTMs are still lacking. Thus far, only a few of them yielded comparable performance to their doped counterparts, while their synthetic costs are still high. In this work, a new class of cost-effective small molecule dopant-free HTMs have been developed using readily available fluoranthene as the structural framework. The structure-property correlation of the fluoranthene-based HTMs was carefully investigated by tuning their structural geometry (linear vs. branched), connection between electron-donating and electron-withdrawing moieties (single bond vs. ethylene), and the substitution position of the methoxy side-groups (para- vs. meta-). As a result, the optimized molecule, FBA3, was demonstrated to serve as an efficient dopant-free HTM in a conventional PVSC to deliver an impressive power conversion efficiency of 19.27%, representing one of the best cost-effective dopant-free organic HTMs reported thus far.

Fluoranthene-based dopant-free hole transporting materials for efficient perovskite solar cells.

Significant efforts have been devoted to developing new dopant-free hole transporting materials (HTMs) for perovskite solar cells (PVSCs). Fluoranthene is one typical cyclopentene-fused polycyclic aromatic hydrocarbon with a rigid planarized structure, and thus could be an ideal building block to construct dopant-free HTMs, which have not been reported yet. Here, we report a new and simple synthetic method to prepare unreported 2,3-dicyano-fluoranthene through a Diels-Alder reaction between dibenzofulvene and tetracyanoethylene, and demonstrate that it can serve as an efficient electron-withdrawing unit for constructing donor-acceptor (D-A) type HTMs. This novel building block not only endows the resulting molecules with suitable energy levels, but also enables highly ordered and strong molecular packing in solid states, both of which could facilitate hole extraction and transport. Thus with dopant-free HTMs, impressive efficiencies of 18.03% and 17.01% which are associated with enhanced stability can be achieved based on conventional n-i-p and inverted p-i-n PVSCs respectively, outperforming most organic dopant-free HTMs reported so far.

An ESIPT fluorescent probe sensitive to protein α-helix structures.

A large majority of membrane proteins have one or more transmembrane regions consisting of α-helices. Membrane protein levels differ from one type of cell to another, and the expression of membrane proteins also changes from normal to diseased cells. For example, prostate cancer cells have been reported to have downregulated expression of membrane proteins, including zinc transporters, compared with normal prostate cells. These reports inspired us to design a fluorescence probe sensitive to protein α-helical structures to discriminate individual prostate cancer cells from normal ones. A benzazole derivative ( in this study) was observed to emit strong fluorescence resulting from an excited-state intramolecular proton transfer (ESIPT) in protein α-helical environments. The intensity of ESIPT fluorescence of was observed to be positively correlated with the α-helix content of proteins. The molecular docking simulation suggested that it had low energy for the binding of to proteins when the binding sites were localized within the α-helical regions of protein via H-bonds. Furthermore, was found to be localized in cell membranes through binding to transmembrane α-helical regions of membrane proteins, and was capable of probing differences in the α-helix contents of membrane proteins between normal and cancerous prostate cells through changes in the ESIPT emission intensity. These results indicated that could distinguish individual prostate cancer cells from normal ones, as the changes in the ESIPT fluorescence intensity of could reflect the regulation in expression of the membrane proteins including zinc transporters. This recognition strategy of individual prostate cancer cells might contribute to early diagnosis techniques for prostate cancer.