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Interfacing molecular machines to inorganic nanoparticles can, in principle, lead to hybrid nanomachines with extended functions. Here we demonstrate a ligand engineering approach to develop atomically precise hybrid nanomachines by interfacing gold nanoclusters with tetraphenylethylene molecular rotors. When gold nanoclusters are irradiated with near-infrared light, the rotation of surface-decorated tetraphenylethylene moieties actively dissipates the absorbed energy to sustain the photothermal nanomachine with an intact structure and steady efficiency. Solid-state nuclear magnetic resonance and femtosecond transient absorption spectroscopy reveal that the photogenerated hot electrons are rapidly cooled down within picoseconds via electron-phonon coupling in the nanomachine. We find that the nanomachine remains structurally and functionally intact in mammalian cells and in vivo. A single dose of near-infrared irradiation can effectively ablate tumours without recurrence in tumour-bearing mice, which shows promise in the development of nanomachine-based theranostics.
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Nanopartículas , Neoplasias , Estilbenos , Animales , Ratones , Fototerapia/métodos , Nanopartículas/química , Oro/química , MamíferosRESUMEN
The advancement of acceptors plays a pivotal role in determining photovoltaic performance. While previous efforts have focused on optimizing acceptor-donor-acceptor1-donor-acceptor (A-DA1-D-A)-typed acceptors by adjusting side chains, end groups, and conjugated extension of the electron-deficient central A1 unit, the systematic exploration of the impact of peripheral aryl substitutions, particularly with different electron groups, on the A1 unit and its influence on device performance is still lacking. In this study, three novel acceptors - QxTh, QxPh, and QxPy - with distinct substitutions on the quinoxaline (Qx) are designed and synthesized. Density functional theory (DFT) analyses reveal that QxPh, featuring a phenyl-substituted Qx, exhibits the smallest molecular binding energies and a tightest π···π stacking distance. Consequently, the PM6:QxPh device demonstrates a better power conversion efficiency (PCE) of 17.1% compared to the blends incorporating QxTh (16.4%) and QxPy (15.7%). This enhancement is primarily attributed to suppressed charge recombination, improved charge extraction, and more favorable molecular stacking and morphology. Importantly, introducing QxPh as a guest acceptor into the PM6:BTP-eC9 binary system yields an outstanding PCE of 19.5%, indicating the substantial potential of QxPh in advancing ternary device performance. The work provides deep insights into the expansion of high-performance organic photovoltaic materials through peripheral aryl substitution strategy.
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Designing and synthesizing narrow band gap acceptors that exhibit high photoluminescence quantum yield (PLQY) and strong crystallinity is a highly effective, yet challenging, approach to reducing non-radiative energy losses (âµEnr) and boosting the performance of organic solar cells (OSCs). We have successfully designed and synthesized an A-D-A type fused-ring electron acceptor, named DM-F, which features a planar molecular backbone adorned with bulky three-dimensional camphane side groups at its central core. These bulky substituents effectively hinder the formation of H-aggregates of the acceptors, promoting the formation of more J-aggregates and notably elevating the PLQY of the acceptor in the film. As anticipated, DM-F showcases pronounced near-infrared absorption coupled with impressive crystallinity. Organic solar cells (OSCs) leveraging DM-F exhibit a high EQEEL value and remarkably low âµEnr of 0.14â eV-currently the most minimal reported value for OSCs. Moreover, the power conversion efficiency (PCE) of binary and ternary OSCs utilizing DM-F has reached 16.16 % and 20.09 %, respectively, marking a new apex in reported efficiency within the OSCs field. In conclusion, our study reveals that designing narrow band gap acceptors with high PLQY is an effective way to reduce âµEnr and improve the PCE of OSCs.
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Utilizing intermolecular hydrogen-bonding interactions stands for an effective approach in advancing the efficiency and stability of small-molecule acceptors (SMAs) for polymer solar cells. Herein, we synthesized three SMAs (Qo1, Qo2, and Qo3) using indeno[1,2-b]quinoxalin-11-one (Qox) as the electron-deficient group, with the incorporation of a methylation strategy. Through crystallographic analysis, it is observed that two Qox-based methylated acceptors (Qo2 and Qo3) exhibit multiple hydrogen bond-assisted 3D network transport structures, in contrast to the 2D transport structure observed in gem-dichlorinated counterpart (Qo4). Notably, Qo2 exhibits multiple and stronger hydrogen-bonding interactions compared with Qo3. Consequently, PM6 : Qo2 device realizes the highest power conversion efficiency (PCE) of 18.4 %, surpassing the efficiencies of devices based on Qo1 (15.8 %), Qo3 (16.7 %), and Qo4 (2.4 %). This remarkable PCE in PM6 : Qo2 device can be primarily ascribed to the enhanced donor-acceptor miscibility, more favorable medium structure, and more efficient charge transfer and collection behavior. Moreover, the PM6 : Qo2 device demonstrates exceptional thermal stability, retaining 82.8 % of its initial PCE after undergoing annealing at 65 °C for 250â hours. Our research showcases that precise methylation, particularly targeting the formation of intermolecular hydrogen-bonding interactions to tune crystal packing patterns, represents a promising strategy in the molecular design of efficient and stable SMAs.
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Phototheranostics have emerged as a promising subset of cancer theranostics owing to their potential to provide precise photoinduced diagnoses and therapeutic outcomes. However, the design of phototheranostics remains challenging due to the nature of tumors and their microenvironment, including limitations to the oxygen supply, high rates of recurrence and metastasis, and the immunosuppressive state of cancer cells. Here we report a dual-functional oxygen-independent phototheranostic agent, Ni-2, rationally designed to provide a near-infrared (NIR) photoactivated thermal- and hydroxyl radical (â¢OH)-enhanced photoimmunotherapeutic anticancer response. Under 880 nm laser irradiation, Ni-2 exhibited high photostability and excellent photoacoustic and photothermal effects with a photothermal conversion efficacy of 58.0%, as well as novel photoredox features that allowed the catalytic conversion of H2O2 to â¢OH upon photooxidation of Ni(II) to Ni(III). As a multifunctional photoagent, Ni-2 was found not only to inhibit tumor growth in a CT26 tumor-bearing mouse model but also to activate an immune response via a combination of photothermal- and H2O2-induced effects. When combined with an antiprogrammed death-ligand 1 (aPD-L1), Ni-2 treatment allowed for the suppression of distant tumor growth and cancer metastasis. Collectively, the present results provide support for the proposition that Ni-2 or its analogues could emerge as useful tools for photoimmunotherapy. They also highlight the potential of appropriately designed 3d transition metal complexes as "all- in-one" phototheranostics.
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Nanopartículas , Neoplasias , Ratones , Animales , Níquel , Peróxido de Hidrógeno , Nanomedicina Teranóstica/métodos , Fototerapia/métodos , Neoplasias/diagnóstico por imagen , Neoplasias/terapia , Oxígeno , Inmunoterapia , Línea Celular Tumoral , Microambiente TumoralRESUMEN
The research on perylene diimide (PDI) aggregates effectively promotes their applications in organic photovoltaic solar cells and fluorescent sensors. In this paper, a PDI fabricated with three peripheral PDI units (N, N'-bis(6-undecyl) perylene-3,4,9,10-bis(dicarboximide)) is investigated. The trimer shows different absorption and fluorescence properties due to hydrophobicity when dissolved in the mixed solvent of tetrahydrofuran (THF) and water. Through comprehensive analysis of the fluorescence lifetime and transient absorption spectroscopic results, we concluded that the trimer underwent different excited state kinetic pathways with different concentrations of water in THF. When dissolved in pure THF solvent, both the intramolecular charge-transfer and excimer states are formed. When the water concentration increases from 0 to 50% (v/v), the formation time of the excimer state and its structural relaxation time are prolonged, illustrating the arising of the intermolecular excimer state. It is interesting to determine that the probability of the intramolecular charge-transfer pathway will first decrease and then increase as the speed of intermolecular excimer formation slows down. The two inflection points appear when the water concentration is above 10% and 40%. The results not only highlight the importance of hydrophobicity on the aggregate properties of PDI multimers but also guide the further design of PDI-based organic photovoltaic solar cells.
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In this work, inspired by the principles of a pressure cooker, we utilized a high-pressure method to address the processing challenges associated with high molecular weight polymers. Through this approach, we successfully dissolved high molecular weight D18 in chloroform at 100 °C within a pressure-tight vial. The increased steam pressure raised the boiling point and dissolving capacity of chloroform, enabling the creation of a hybrid film with superior properties, including more ordered molecular arrangement, increased crystallinity, extended exciton diffusion length, and improved phase morphology. Organic solar cells (OSCs) based on D18 : L8-BO prepared using this high-pressure method achieved an outstanding power conversion efficiency of 19.65 %, setting a new record for binary devices to date. Furthermore, this high-pressure method was successfully applied to fabricate OSCs based on other common systems, leading to significant enhancements in device performance. In summary, this research introduces a universal method for processing high molecular weight D18 materials, ultimately resulting in the highest performance reported for binary organic solar cells.
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Earth-abundant metal-based theranostics, agents that integrate diagnostic and therapeutic functions within the same molecule, may hold the key to the development of low-cost personalized medicines. Here, we report a set of O-linked nonaromatic benzitripyrrin (C^N^N^N) macrocyclic organonickel(II) complexes, Ni-1-4, containing strong σ-donating M-C bonds. Complexes Ni-1-4 are characterized by a square-planar coordination geometry as inferred from the structural studies of Ni-1. They integrate photothermal therapy, photothermal imaging, and photoacoustic imaging (PAI) within one system. This makes them attractive as potential phototheranostics. Relative to traditional Ni(II) porphyrins, such as F20TPP (tetrapentafluorophenylporphyrin), the lowest energy absorption of Ni-1 is shifted into the near infrared region, presumably as a consequence of Ni-C bonding. Ultrafast transient absorption spectroscopy combined with theoretical calculations revealed that, upon photoexcitation, a higher population of ligand-centered and 3MLCT states is seen in Ni-1 relative to NiTPBP (TPBP = 6,11,16,21-tetraphenylbenziporphyrin). Encapsulating Ni-1 in 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-2000] (DSPE-PEG2000) afforded nanoparticles, Ni-1@DSPE, displaying red-shifted absorption features, as well as good photothermal conversion efficiency (â¼45%) in aqueous media. Proof-of-principle experiments involving thrombus treatment were carried out both in vitro and in vivo. It was found that Ni-1@DSPE in combination with 785 nm photo-irradiation for 3 min (0.3 W/cm2) proved successful in removing blood clots from a mouse thrombus model as monitored by photoacoustic imaging (PAI). The present work highlights the promise of organonickel(II) complexes as potential theranostics and the benefits that can accrue from manipulating the excited-state features of early transition-metal complexes via, for example, interrupting π-conjugation pathways.
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Complejos de Coordinación , Nanopartículas , Elementos de Transición , Animales , Complejos de Coordinación/química , Ligandos , Metales/química , Ratones , Nanopartículas/químicaRESUMEN
Motivated by simplifying the synthesis of nonfullerene acceptor and establishing the relation between molecular structure and photovoltaic performance, two isomeric nonfused ring electron acceptors (o-TT-Cl and m-TT-Cl), whose properties can be adjusted by changing the side chains, are designed and synthesized with several high-yield steps. o-TT-Cl with V-shaped side chain induces a dominated J-aggregation and displays much better solubility and more ordered packing than m-TT-Cl with linear side chain. Thus, the o-TT-Cl-based blend film generates better phase morphology and charge transport than m-TT-Cl-based one. Finally, the power conversion efficiency of o-TT-Cl-based devices is 12.84%, which is much higher than that of m-TT-Cl-based ones (6.54%). This work highlights the importance of side chains engineering on improving photovoltaic performance of nonfused ring electron acceptors.
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Photodynamic therapy (PDT) is a non-invasive treatment modality against a range of cancers and nonmalignant diseases, however one must be aware of the risk of causing phototoxic reactions after treatment. We herein report a bioinspired design of next-generation photosensitizers (PSs) that not only effectively produce ROS but undergo fast metabolism after treatment to overcome undesirable side effects. We constructed a series of ß-pyrrolic ring-opening seco-chlorins, termed beidaphyrin (BP), beidapholactone (BPL), and their zinc(II) derivatives (ZnBP and ZnBPL), featuring intense near-infrared absorption and effective O2 photosensitization. Irradiation of ZnBPL led to a non-cytotoxic, metabolizable beidaphodiacetamide (ZnBPD) via in situ generated O2.- but not 1 O2 , as revealed by mechanistic studies including time-resolved absorption, kinetics, and isotope labeling. Furthermore, water-soluble ZnBPL showed an effective therapeutic outcome, fast metabolism, and negligible phototoxic reactions.
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Neoplasias , Fotoquimioterapia , Porfirinas , Humanos , Neoplasias/tratamiento farmacológico , Fármacos Fotosensibilizantes/farmacología , Fármacos Fotosensibilizantes/uso terapéutico , Porfirinas/farmacología , Porfirinas/uso terapéuticoRESUMEN
Phototheranostics constitute an emerging cancer treatment wherein the core diagnostic and therapeutic functions are integrated into a single photosensitizer (PS). Achieving the full potential of this modality requires being able to tune the photosensitizing properties of the PS in question. Structural modification of the organic framework represents a time-honored strategy for tuning the photophysical features of a given PS system. Here we report an easy-to-implement metal selection approach that allows for fine-tuning of excited-state energy dissipation and phototheranostics functions as exemplified by a set of lanthanide (Ln = Gd, Yb, Er) carbazole-containing porphyrinoid complexes. Femto- and nanosecond time-resolved spectroscopic studies, in conjunction with density functional theory calculations, revealed that the energy dissipation pathways for this set of PSs are highly dependent on the energy gap between the lowest triplet excited state of the ligand and the excited states of the coordinated Ln ions. The Yb complex displayed a balance of deactivation mechanisms that made it attractive as a potential combined photoacoustic imaging and photothermal/photodynamic therapy agent. It was encapsulated into mesoporous silica nanoparticles (MSN) to provide a biocompatible construct, YbL@MSN, which displays a high photothermal conversion efficiency (η = 45%) and a decent singlet oxygen quantum yield (ΦΔ = 31%). Mouse model studies revealed that YbL@MSN allows for both photoacoustic imaging and synergistic photothermal- and photodynamic-therapy-based tumor reduction in vivo. Our results lead us to suggest that metal selection represents a promising approach to fine-tuning the excited state properties and functional features of phototheranostics.
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Elementos de la Serie de los Lantanoides/uso terapéutico , Neoplasias/tratamiento farmacológico , Fotoquimioterapia , Fármacos Fotosensibilizantes/uso terapéutico , Nanomedicina Teranóstica , Animales , Elementos de la Serie de los Lantanoides/química , Ratones , Nanopartículas/química , Neoplasias/diagnóstico por imagen , Fármacos Fotosensibilizantes/química , Dióxido de Silicio/químicaRESUMEN
Restricted by the energy-gap law, state-of-the-art organic solar cells (OSCs) exhibit relatively low open-circuit voltage (VOC) because of large nonradiative energy losses (ΔEnonrad). Moreover, the trade-off between VOC and external quantum efficiency (EQE) of OSCs is more distinctive; the power conversion efficiencies (PCEs) of OSCs are still <15% with VOCs of >1.0 V. Herein, the electronic properties and aggregation behaviors of non-fullerene acceptors (NFAs) are carefully considered and then a new NFA (Z19) is delicately designed by simultaneously introducing alkoxy and phenyl-substituted alkyl chains to the conjugated backbone. Z19 exhibits a hypochromatic-shifted absorption spectrum, high-lying lowest unoccupied molecular orbital energy level and ordered 2D packing mode. The D18:Z19-based blend film exhibits favorable phase separation with face-on dominated molecular orientation, facilitating charge transport properties. Consequently, D18:Z19 binary devices afford an exciting PCE of 19.2% with a high VOC of 1.002 V, surpassing Y6-2O-based devices. The former is the highest PCE reported to date for OSCs with VOCs of >1.0 V. Moreover, the ΔEnonrad of Z19- (0.200 eV) and Y6-2O-based (0.155 eV) devices are lower than that of Y6-based (0.239 eV) devices. Indications are that the design of such NFA, considering the energy-gap law, could promote a new breakthrough in OSCs.
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Large-area printing fabrication is a distinctive feature of organic solar cells (OSCs). However, the advance of upscalable fabrication is challenged by the thickness of organic active layers considering the importance of both exciton dissociation and charge collection. In this work, a bulk-heterojunction-buried (buried-BHJ) structure is introduced by sequential deposition to realize efficient exciton dissociation and charge collection, thereby contributing to efficient OSCs with 500 nm thick active layers. The buried-BHJ distributes donor and acceptor phases in the vertical direction as charge transport channels, while numerous BHJ interfaces are buried in each phase to facilitate exciton dissociation simultaneously. It is found that buried-BHJ configurations possess efficient exciton dissociation and rapid charge transport, resulting in reduced recombination losses. In comparison with traditional structures, the buried-BHJ structure displays a decent tolerance to film thickness. In particular, a power conversion efficiency of 16.0% is achieved with active layers at a thickness of 500 nm. To the best of the authors' knowledge, this represents the champion efficiency of thick film OSCs.
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In this study, three nonfused-ring electron acceptors (2TT, 2TT-C6-F, and 2TT-C11-F) with the same steric hindrance groups (2,4,6-tripropylbenzene) are designed and synthesized and the impact of electron-withdrawing and lateral alkyl side chains on the performance of binary and ternary organic solar cells (OSCs) is explored. For the binary OSCs, 2TT-C11-F with IC-2F terminal groups and lateral undecyl side chains display a red shifted absorption spectrum and suitable energy levels, and the corresponding blend film exhibits appropriate phase separation and crystallinity. Thus, binary OSCs based on 2TT-C11-F achieve an impressive power conversion efficiency of 13.03%, much higher than the efficiencies of those based on 2TT (9.68%) and 2TT-C6-F (12.11%). In the ternary OSCs, 2TT with CC terminal groups and lateral hexyl side chains exhibit complementary absorption and cascade energy levels with a host binary system (D18:BTP-eC9-4F). Hence, the ternary OSCs based on 2TT achieve a remarkable efficiency of 19.39%, ranking among the highest reported values. The research yields comprehensive 2TT-series nonfused-ring electron acceptors, demonstrating their great potential for the fabrication of high-performance binary and ternary OSCs.
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High-performance organic solar cells often rely on halogen-containing solvents, which restrict the photovoltaic industry. Therefore, it is imperative to develop efficient organic photovoltaic materials compatible with halogen-free solvents. Herein, a series of benzo[a]phenazine (BP)-core-based small-molecule acceptors (SMAs) achieved through an isomerization chlorination strategy is presented, comprising unchlorinated NA1, 10-chlorine substituted NA2, 8-chlorine substituted NA3, and 7-chlorine substituted NA4. Theoretical simulations highlight NA3's superior orbit overlap length and tight molecular packing, attributed to interactions between the end group and BP unit. Furthermore, NA3 demonstrates dense 3D network structures and a record electronic coupling of 104.5 meV. These characteristics empower the ortho-xylene (o-XY) processed PM6:NA3 device with superior power conversion efficiency (PCE) of 18.94%, surpassing PM6:NA1 (15.34%), PM6:NA2 (7.18%), and PM6:NA4 (16.02%). Notably, the significantly lower PCE in the PM6:NA2 device is attributed to excessive self-aggregation characteristics of NA2 in o-XY. Importantly, the incorporation of D18-Cl into the PM6:NA3 binary blend enhances crystallographic ordering and increases the exciton diffusion length of the donor phase, resulting in a ternary device efficiency of 19.75% (certified as 19.39%). These findings underscore the significance of incorporating new electron-deficient units in the design of efficient SMAs tailored for environmentally benign solvent processing of OSCs.
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Incorporating sulfur atoms into photosensitizers (PSs) has been well-established to populate triplet states and increase singlet oxygen (1O2) production when exposed to light. In this work, we found that progressive thiolation of porphyrin ß-periphery does promote intersystem crossing (ISC) between triplets and singlets, as seen in the excited state dynamics in dichloromethane or PS nanoparticles in water. However, in the latter case, more sulfur substitution deactivates 1O2 photosensitization, in contrast to the expected trend observed in dichloromethane. This observation was further supported by photocytotoxicity studies, where 1O2 photosensitization was switched off in living cells and multicellular spheroids despite being switched on in in vivo mice models. To understand the inconsistency, we performed molecular dynamics simulation and time-dependent density functional theory calculations to investigate possible aggregation and related excited states. We found that the extent of thiolation could regulate molecular packing inside nanoparticles, which gradually lowers the energy levels of triplet states even lower than that of 1O2 and, in turn, alters their energy dissipation pathways. Therefore, this study provides new insights into the design of metal-free PSs and sheds light on the excited state dynamics in aqueous media beyond the molecular level.
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This study reports the successful design and synthesis of two novel polymerized nonfused ring electron acceptors, P-2BTh and P-2BTh-F, derived from the high-performance nonfused ring electron acceptor, 2BTh-2F. Prepared via Stille polymerization, these polymers feature thiophene and fluorinated thiophene as π-bridge units. Notably, P-2BTh-F, with difluorothiophene as the π-bridge, exhibits a more planar backbone and red-shifted absorption spectrum compared with P-2BTh. When employed in organic solar cells (OSCs) with PBDB-T as the donor material, P-2BTh-F-based devices demonstrate an outstanding power conversion efficiency (PCE) of over 11%, exceeding the 8.7% achieved by P-2BTh-based devices. Furthermore, all-polymer solar cells utilizing PBDB-T:P-2BTh-F exhibit superior storage stability. Additionally, P-2BTh-F was explored as a functional additive in a high-performance binary system, enhancing stability while maintaining comparable PCE (19.45%). This strategy offers a cost-effective approach for fabricating highly efficient and stable binary and ternary organic solar cells, opening new horizons for cost-effective and durable solar cell development.
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Three nonfused ring electron acceptors (NFREAs), namely, 3TT-C2-F, 3TT-C2-Cl, and 3TT-C2, are purposefully designed and synthesized with the concept of halogenation. The incorporation of F or/and Cl atoms into the molecular structure (3TT-C2-F and 3TT-C2-Cl) enhances the π-π stacking, improves electron mobility, and regulates the nanofiber morphology of blend films, thus facilitating the exciton dissociation and charge transport. In particular, blend films based on D18:3TT-C2-F demonstrate a high charge mobility, an extended exciton diffusion distance, and a well-formed nanofiber network. These factors contribute to devices with a remarkable power conversion efficiency of 17.19%, surpassing that of 3TT-C2-Cl (16.17%) and 3TT-C2 (15.42%). To the best of knowledge, this represents the highest efficiency achieved in NFREA-based devices up to now. These results highlight the potential of halogenation in NFREAs as a promising approach to enhance the performance of organic solar cells.
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CsPbBr3-Pb4S3Br2 Janus nanocrystals (NCs) are the only nanomaterial where the epitaxial structure of perovskite and chalcogenide materials has been realized at the nanoscale, but their exciton dynamics mechanism has not yet been thoroughly investigated or applied in photodetection applications. This work reports an attractive device performance of perovskite photoconductors based on epitaxial CsPbBr3-Pb4S3Br2 Janus NCs, as well as the carrier relaxation and transfer mechanism of the heterojunction. By a combination of transient optical absorption and quantum dynamics simulation, it is demonstrated that the photogenerated holes on CsPbBr3 can be successfully extracted by Pb4S3Br2, while the hole transfer proceeds about three times faster than energy loss and remains "hot" for about 300 fs. This feature has favorable effects on long-range charge separation and transport; therefore, the Janus NCs photoconductors exhibit an exceptional responsivity of 34.0 A W-1 and specific detectivity of 1.26 × 1014 Jones.
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Molecular dopants can effectively improve the performance of organic solar cells (OSCs). Here, PM6/BTP-eC9-4Cl-based OSCs are fabricated by a layer-by-layer (LbL) deposition method, and the electron acceptor BTP-eC9-4Cl layer is properly doped by n-type dopant benzyl viologen (BV) or [4-(1,3-dimethyl-2,3-dihydro-1H-benzoimidazol-2-yl)phenyl]dimethyl-amine (N-DMBI-H). The power conversion efficiency (PCE) of OSCs increases from 16.80 to 17.61 or 17.84% when the acceptor layer is doped by BV (0.01 wt %) or N-DMBI-H (0.01 wt %), respectively. At the optimal doping concentration, the device exhibits more balanced charge transport, fewer bimolecular recombinations, faster charge separation and transfer, and better stability. This doping strategy has good universality; when the acceptor layer L8-BO of LbL OSCs is doped by 0.01 wt % BV or 0.01 wt % N-DMBI-H, the PCE increases from 17.49 to 18.35 or 18.25%, respectively. All in all, our studies have demonstrated that the doping strategy is effective in enhancing the performance of OSCs.