Advanced Materials最新文献

Self-assembled monolayers (SAMs) have precipitated a paradigm shift in the design of hole transport layers (HTLs) for p-i-n perovskite solar cells, emerging as the cornerstone of modern, high-efficiency devices. This review comprehensively charts the evolution of SAM-based HTLs from fundamental molecular-level insights to their pivotal role in commercial-scale applications and record-breaking perovskite/silicon tandem cells. We delve into the intricate structure-property-performance relationships that govern SAMs' function, examining how meticulous engineering of anchoring groups, π-bridges, and functional headgroups dictates critical features such as energy level alignment, interfacial defect passivation, and perovskite crystallization control. The discussion extends beyond champion efficiencies to critically assess the scalability of deposition techniques, the limitations of operational stability under real-world conditions, and the pathways for integration into tandem architectures. Furthermore, we highlight the transformative potential of machine learning in accelerating the discovery and optimization of next-generation SAM materials. Finally, we provide a forward-looking perspective on molecular design strategies required to overcome existing challenges and fully unlock SAM potential for stable, high-performance photovoltaics.

Quasi-2D metal halide perovskites (MHP) have emerged as promising candidates for light-emitting diodes (PeLEDs) due to their intrinsic advantages in color purity, bandgap tunability, and stability. The prime working principle realizing high radiative emission in quasi-2D MHP is the ultrafast, consecutive charge transfer (CT) process toward the low-bandgap crystallites across multiple quantum wells, called charge carrier funneling. Ironically, such a key process is intrinsically limited in the quasi-2D MHP by the molecular spacers, which have electronically insulating natures. To challenge this limit, herein, we explore the impact of a judiciously designed, stable, and conductive organic radical, (5H-pyrido[3,2-b]indole-2,6-dichlorophenyl)bis(2,4,6-trichlorophenyl)methyl as a molecular additive in the MHP matrix. It is found that the spatially delocalized singly occupied molecular orbital offers an electronic bridge accelerating interfacial CT and the carrier funneling by surface adsorption, thus maximizing radiation recombination yield. As a result, the radical-incorporating PeLEDs (peaking at ≈ 684 nm) achieve a remarkable external quantum efficiency of 26.8% with an operational half-lifetime of ≈ 340 min, ranking among the best deep-red devices reported to date. This work demonstrates that rational radical molecular design offers a powerful route to resolve intrinsic CT limitations in quasi-2D MHP, unlocking both high efficiency and long-term stability in next-generation PeLEDs.

The scalable fabrication of high-efficiency perovskite solar modules is critically challenged by the difficulty in controlling crystallization homogeneity and mitigating buried interfacial defects across large-area substrates. The commonly used dimethyl sulfoxide (DMSO) can induce heterogeneous nucleation and is prone to remain trapped within the films. Herein, diethyl sulfoxide (DESO) is introduced, a volatile Lewis acid-base additive that leverages steric hindrance effects from its branched-chain structure to achieve mild coordination with PbI₂. This structural feature reduces the binding energy between DESO and PbI₂, which avoid the formation of complex metastable intermediate phases. Moreover, the low binding energy of DESO enables its complete removal during vacuum quenching via rapid evaporation, effectively suppressing void formation at the buried interfaces during the subsequent annealing. The resultant perovskite films yield perovskite solar modules (PSMs) with power conversion efficiencies (PCEs) of 22.9% (11.2 cm², aperture area) and 20.8% (692 cm², aperture area) via scalable processes. These devices exhibit operational stability, retaining >96% of their initial PCE after 2000 h under continuous 1-sun illumination and >95% PCE following 2000 h damp-heat testing (85°C/85% RH).

Shortwave infrared (SWIR) photodetectors are in high demand in modern applications, including night surveillance, biological imaging, and optical communication. Emerging organic semiconductors, featuring a tailorable spectral response and solution processability, open new avenues for SWIR light detection. However, SWIR organic photodetectors (OPDs) suffer from a scarcity of ultralow-bandgap organic semiconductors and low responsivity above 1000 nm. Here, we report a new electron-rich building block, thieno[3',2':4,5]cyclopenta[1,2-b]thieno[2,3-d]pyrrole (SNCS), that exhibits strong electron-donating ability. By applying acceptor-donor-acceptor and acceptor-quinoidal-donor-quinoidal-acceptor strategy, we developed two new nonfullerene acceptors: SNCS-4F and SNCSTT-4F. The latter, with thieno[3,4-b]thiophene moiety, exhibits strong SWIR absorption up to 1400 nm in thin films. The best-performing PTB7-Th:SNCSTT-4F-based OPD exhibits a record external quantum efficiency of 50.2%, a responsivity of 0.49 A W^-1 and remarkable specific detectivity of 4.47 × 10¹² Jones at 1200 nm under zero bias. This is the highest performance among reported SWIR organic photodiodes and is comparable with commercial InGaAs photodetectors. Ultraviolet photoelectron spectra, Mott-Schottky analysis and trap density of states analysis were applied to evaluate the OPDs' performances. Finally, we demonstrate that the OPDs can detect SWIR light with high sensitivity in photoplethysmography measurements and infrared audio communication applications.

Harnessing solar energy to produce value-added chemicals simultaneously requires the critical step of spatially separating redox processes. However, conventional photocatalysts remain fundamentally constrained by sluggish charge dynamics and irreversible recombination. Here, we propose an atomic-level interfacial shuttle mechanism in sub-nanometer gold cluster-anchored nickel manganite (H-NiMn₂O_4-β/Au_0.5 NCs), which couples dynamic electron-hole separation with Ni³⁺/Ni²⁺ redox cycling. Ultrafast transient absorption spectroscopy indicates electron transfer occurring within 3.06 ps, mediated by an Au-O-Ni coordination interface. In this system, Ni³⁺ functions as a transient electron trap, undergoing rapid reduction to Ni²⁺ and subsequently transferring electrons to adjacent Au clusters, accelerating charge kinetics by 22.16-fold. This atomic-scale electron relay selectively steers 2e^- oxygen reduction by balancing *OOH intermediate stabilization and desorption, yielding H₂O₂ at 1.00 mmol g^-1 h^-1. Simultaneously, hole accumulation on lattice oxygen drives α-H abstraction, enabling photooxidation of benzyl alcohol to benzaldehyde (14.59 mmol g^-1 h^-1). This work presents a dynamic dual-site catalysis model, offering atomic-level insight into interfacial charge management for solar-driven redox transformations.

All-solid-state lithium-sulfur batteries (ASSLSBs) hold great promise for next-generation electrochemical energy storage due to sulfur's high theoretical specific capacity and low cost. However, sluggish sulfur conversion kinetics and severe volume variations during cycling, as well as poor ionic percolation in composite cathodes, limit their practical viability. To overcome these challenges, we herein introduce solid electrolytes of nominal composition Li_{10.5- x}Si_1.5P_1.5S_{12- x}I_x (with x = 0, 0.2, 0.4), possessing high ionic conductivities of ≥ 7 mS cm^-1 at room temperature. We show that increasing iodine content alters the phase composition and triggers reversible redox activity in these materials. If implemented as catholytes, this enables very fast sulfur conversion kinetics, ultimately leading to ASSLSBs with exceptional performance. The cells achieve 86% sulfur utilization at a rate of C/2 and at 45°C and offer high-rate capability by delivering 1175 mAh g_sulfur ^-1 at 5C and 590 mAh g_sulfur ^-1 at 15C. Furthermore, the synergistic effects of ionic percolation and redox-activity enable record areal capacities up to 14 mAh cm^-2 with a sulfur loading of 10 mg cm^-2. Taken together, our findings provide new strategies for designing redox-active catholytes for application in advanced ASSLSBs and further strengthen the redox-mediating role of iodine therein.

As security threats continue to evolve, static physical unclonable function (PUF) systems are facing inherent limitations in their security sustainability. This growing demand for sustainable security is driving a paradigm shift toward dynamic and reconfigurable PUF systems. However, previous approaches relying on thermal treatments to reconstruct physical entities can be limited in practicality due to concerns over thermal stability and scalability. Here, we present an all-optical reconfigurable PUF that fills this unmet need through non-invasive and scalable optical techniques. To demonstrate this, we introduce a nanopatterning method that employs plasmonic coupling-induced sintering of optically trapped gold nanoparticles (AuNPs) to fabricate optical PUFs. The resulting PUFs, which leverage complex spatiospectral information, deliver practically sufficient security, outstanding encoding density, and robust resistance against machine learning-based modeling attacks. Furthermore, we validate the applicability of the proposed PUF system for anti-counterfeiting and traceability applications by implementing a lightweight authentication protocol that exhibits reliable performance. Lastly, we demonstrate that irreversible and on-demand reconfiguration through optothermal nudging of patterned AuNPs enables repeated generation of unpredictable and independent responses while maintaining consistent security. These demonstrations signify the potential of our all-optical approach as a promising pathway toward achieving sustainable hardware-based security.

Aqueous metal-selenium batteries (AMSeBs) have emerged as promising candidates for safe, cost-effective, and high-energy-density energy storage, yet their development is hindered by challenges spanning electrode stability, reaction reversibility, and electrolyte compatibility. This review systematically explores the thermodynamic and electrochemical landscape of AMSeBs, integrating theoretical analysis with experimental advances to establish a rational design framework. First, by evaluating key parameters, including electrode potentials, volume change rates, solubility of metal selenides, and energy metrics, we identify promising systems such as Zn-Se and Cu-Se, along with unexplored candidates like Fe-Se and Ga-Se. Second, selenium-based cathodes are categorized into three types, elemental Se & Se_xS_y composites, organic selenides, and transition metal selenides, with emphasis on multi-electron transfer mechanisms, particularly the six-electron Se⁴⁺/Se^2- redox pathway, which offers a route to overcome capacity limitations. Third, strategies for stabilizing metal anodes, expanding the electrochemical stability window of aqueous electrolytes, and mitigating shuttle effects are critically discussed. Finally, we outline future directions, including interface engineering, artificial intelligence-assisted material screening, and flexible device integration, providing a roadmap toward high-performance AMSeBs for next-generation energy storage applications.

Structured vortex beams have driven significant advances in multiplexing communication technologies and have been demonstrated experimentally in optics, electromagnetics, and airborne acoustics. However, the strong vibroacoustic coupling and high hydrostatic pressure hamper the experimental enhancement of acoustic information capacity in underwater communication via passively modulating coaxial beams. Here, we report the experimental realization of simultaneous information capacity enhancement and hybrid physical-computational camouflage in underwater free-space pressure-independent acoustic-vortex communication. Two inverse-designed free-flooded metasurfaces, with hydrostatically resilient stability and customized wave scattering characteristics, synthesize and demodulate experimentally coaxial vortex beams of different topological charges, enabling physically encrypted, port-to-port information transfer. A computational-mask encryption scheme further digitally conceals a plaintext image within two ciphertext bitstreams. Transmission of these ciphertexts through the synthesized hetero-order vortex beams experimentally confirms physical-computational anti-eavesdropping capabilities of the system. Our research charts an unprecedented path toward high-capacity, highly secure underwater acoustic communication technologies in the deep ocean.

Conventional cathodes of lithium battery relying on single storage mechanisms-whether intercalation or conversion-face intrinsic limitations in energy density and sluggish electrode kinetics. Hybrid systems combining both mechanisms offer promising pathways to transcend these constraints; yet, their dynamic interfacial synergies remain poorly deciphered at the nanoscale. This study employs multimodal in situ characterization (Electrochemical atomic force microscopy/Raman/Electrochemical impedance spectroscopy) to elucidate the dynamic synergy in TiS₂-S hybrid cathodes, revealing the concurrent interfacial evolution during cycling: nanoscale steps formation via Li-ion intercalation in the TiS₂-LiTiS₂ host and the phase transformation of S-Li₂S/Li₂S₂. Crucially, the TiS₂/LiTiS₂ serves as a bifunctional interface that not only contributes capacity but also mediates sulfide adsorption and catalyzes preferential edge-directed sulfide deposition. The partially delithiated Li_xTiS₂ enhances electronic conductivity, creating rapid electron transport that facilitates subsequent interfacial sulfide conversion reaction. The hybrid storage mechanism retains features characteristic of both S and TiS₂ storage mechanisms, yet manifests synergistic interfacial reconstruction rather than simple superposition, achieving enhanced reversibility, exceptional cycling stability, and superior rate capability.