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Inspired by camouflage-colored organisms, the development of bio-camouflage systems using electrochromic (EC) technology has gained significant interest. However, existing EC systems struggle with achieving a wide color gamut, noniridescent colors, and self-sustainability. Herein, a self-sustainable color-adaptive bio-camouflage system integrating EC and nanogenerator (NG) technologies, enabling environmental color adaptation, and thermal regulation without an external power source is proposed. The system is based on a zinc-anode EC device (ZECD) with an asymmetric structure, incorporating flexible tungsten oxide and vanadium oxide electrodes. During the EC process, tungsten oxide shifts between blue and transparent, allowing near-infrared thermal modulation, while the vanadium oxide transitions from yellow to transparent. This design enables reversible near-infrared modulation and noniridescent color conversion among black, blue, green, yellow, and transparent. For the self-sustainability of the system, an electromagnetic and triboelectric hybrid NG that collects biomechanical energy is developed. In a typical driven cycle, the integrated system transitions colors and achieves significant near-infrared spectral modulation, demonstrating environmental adaptability and thermal regulation. Experiments on human skin and simulated chameleon color changes further confirm the system's effectiveness. This work highlights the potential of integrating EC and NG technologies to advance color-adaptive camouflage systems, opening new an avenue for bio-camouflage design.
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The photocatalytic degradation of polychlorinated biphenyls (PCBs) is advancing, yet the efficiency of degradation within the visible spectral range continues to encounter significant challenges. In this study, two biochar-based organic semiconductor photocatalysts, Active Carbon@PTQ10 (5,8-Dibromo-6,7-difluoro-2-(2-hexyldecoxy)quinoxaline; trimethyl-(5-trimethylstannylthiophen-2-yl)stannane): ITIC-Th (Propanedinitrile,2,2'-[[6,6,12,12-tetrakis(5-hexyl-2-thienyl)-6,12-dihydrodithieno[2,3-d: 2',3'-d'] -s-indaceno[1,2-b:5,6-b'] dithiophene-2,8-diyl] bis[methylidyne(3-oxo-1H-indene-2,1(3H)-diylidene)]] bis-) (AC@PI) and Active Carbon@PTQ10: PC71BM (6,6)-phenyl C71 butyric acid methyl ester), were synthesized using a wide bandgap material, PTQ10, as the electron donor, along with a non-fullerene material, ITIC-Th, and a fullerene material, PC71BM, as the acceptors, respectively. Under optimized conditions, AC@PI degraded 93.4 % of 2,2 ',4,4 '-tetrachlorobiphenyl (PCB 47) within 60 min. By incorporating a non-fullerene acceptor (ITIC-Th), AC@PI exhibits a larger surface photopressure, a lower hole-electron transfer ratio, a broader absorption spectrum (400 - 1000 nm), and enhanced structural stability. AC@PI can generate photogenerated electrons and holes, as well as superoxide anions (O2-) and hydroxyl radicals (OH), through type II heterojunctions, which contributes to its exceptional properties. This study synthesized novel organic semiconductor catalysts that offer a green, efficient, and non-toxic method for the degradation of aromatic pollutants, such as polychlorinated biphenyls.
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Doping of ns2 metal ions as an energy transfer (ET) bridge can significantly elevate the photoluminescence properties. Nonetheless, the fundamental influence of ns2 metal ions on the local lattice structures remains unclear, hindering the advancement of functional materials. Herein, Sb3+ doped rare earth double perovskites is employed as a typical case to demonstrate this issue. It is found that the isoelectronic doping of Sb3+ ions not only enhances the ET efficiency but also changes their localized electronic and lattice structures. Both density functional theory (DFT) and Judd-Ofelt (J-O) theory calculations provide unambiguous evidence that the isoelectronic doping of Sb3+ ions enables a more localized charge density in the [LnCl6]3- (Ln: Lanthanide) octahedron and reduces the symmetry of the environment around the Ln3+, facilitating the radiative transition rates of Ln3+ while enhancing their ET efficiency. Compared with Cs2NaScCl6:Ln3+, the ET efficiency of Cs2NaScCl6:Sb3+/Ln3+ is enhanced by 1.5-fold, reaching up to 98.3%. To the best of available knowledge, this work is the first to unravel the intrinsic mechanism of enhanced ET process enabled by isoelectronic doping via DFT and J-O theory. This research sheds light on understanding the mechanism of photophysics and rational design of the functional perovskite materials.
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Carbamazepine, recognized as one of the most prevalent pharmaceuticals, has attracted considerable attention due to its potential impact on ecosystems and human health. In response, this work synthesized and characterized a novel environmentally friendly and cost-effective organic semiconductor photocatalyst PM6:Y6:ITCPTC loaded with coconut shell charcoal, and then investigated its performance for photocatalytic removal. Remarkably, carbamazepine demonstrated a photodegradation efficiency exceeding 99% within a mere 20 minutes of exposure to one sunlight intensity, and also showed good effectiveness under a low light intensity of 50 W. The catalyst exhibited exceptional reusability and stability, maintaining degradation efficiency between 95-99% over 25 cycles. The high photocatalytic activity of PM6:Y6:ITCPTC is primarily attributed to the incorporation of the third component (named ITCPTC), which enhances exciton dissociation and carrier transfer, generating superoxide radicals, electrons, and holes. Furthermore, the plausible degradation pathway of carbamazepine was proposed based on the measured intermediates and density functional theory calculations.
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Antimony selenosulfide (Sb2(S,Se)3) has obtained widespread concern for photovoltaic applications as a light absorber due to superior photoelectric features. Accordingly, various deposition technologies have been developed in recent years, especially hydrothermal deposition method, which has achieved a great success. However, device performances are limited with severe carrier recombination, relating to the quality of absorber and interfaces. Herein, bulk and interface defects are simultaneously suppressed by regulating heterogeneous nucleation kinetics with barium dibromide (BaBr2) introduction. In details, the Br adsorbs and dopes on the polar planes of cadmium sulfide (CdS) buffer layer, promoting the exposure of nonpolar planes of CdS, which facilitates the favorable growth of [hk1]-Sb2(S,Se)3 films possessing superior crystallinity and small interface defects. Additionally, the Se/S ratio is increased due to the replacement of S/Se by Br, causing a downshift of the Fermi levels with a benign band alignment and a shallow-level defect. Moreover, Ba2+ is located at grain boundaries by coordination with S and Se ions, passivating grain boundary defects. Consequently, the efficiency is increased from 7.70% to 10.12%. This work opens an avenue towards regulating the heterogeneous nucleation kinetics of Sb2(S,Se)3 film deposited via hydrothermal deposition approach to optimize its crystalline orientation and defect features.
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Lead-free double perovskites (DPs) have superior phase stability and optical properties, which make them competitive for future applications in illumination and displays. However, the preparation of DPs was mainly based on high-temperature heating and hydrochloric acid as a solvent to form powders, which increased the risk and cost of the preparation process and limited its further application. In this study, the growth of Cs2NaInCl6: Sb3+ DPs in polyvinylidene difluoride (PVDF) films was achieved using an in situ fabrication strategy with DMSO as the solvent. The prepared Cs2NaInCl6: Sb3+@PVDF composite films (CFs) can achieve a bright blue emission under 302 nm irradiation. To achieve the optimal luminescent performance of CFs, the photoluminescence (PL) intensity of Cs2NaInCl6: Sb3+@PVDF CFs under various in situ preparation conditions was compared. In addition, the photoluminescence quantum yield (PLQY) of CFs was increased from 0.72% to 83.77% by adjusting the doping amount of Sb3+, and the fluorescence lifetimes t1 and t2 were 131.08 and 1048.52 ns, respectively. Temperature-dependent PL spectroscopy and density functional theory (DFT) calculations indicate that these excellent optical properties are derived from the self-trapped excitons (STEs) at the [SbCl6]3- octahedron and [InCl6]3- octahedron connected via Cl-Na-Cl. The CFs also demonstrated excellent environmental stability, maintaining a relatively stable PL intensity even under conditions of water immersion, high temperatures, and ultraviolet (UV) radiation. Finally, we used the CFs to assemble a blue light-emitting device (LED), which showed good and stable blue emission performance at different currents. This work can provide a new idea for preparing DPs, which is conducive to promoting their commercial application in high-performance optoelectronic devices.
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The gradual rise of personal healthcare awareness is accelerating the deployment of wearable sensors, whose ability of acquiring physiological vital signs depends on sensing materials. MXenes have distinct chemical and physical superiorities over other 2D nanomaterials for wearable sensors. This review presents a comprehensive summary of the latest advancements in MXenes-based materials for wearable physical sensors. It begins with an introduction to special structural features of MXenes for sensing performance, followed by an in-depth exploration of versatile functionalities. A detailed description of different sensing mechanisms is also included to illustrate the contribution of MXenes to the sensing performance and its improvement. In addition, the real-world applications of MXenes-based physical sensors for monitoring different physiological signs are included as well. The remaining challenges of MXenes-based materials for wearable physical sensors and their promising opportunities are finally narrated, in conjunction with a prospective for future development.
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Nanoestruturas , Dispositivos Eletrônicos Vestíveis , Humanos , Nanoestruturas/química , Monitorização Fisiológica/instrumentaçãoRESUMO
Transition metal (TM) ion doping in II-VI semiconductors can produce exciton magnetic polarons (EMPs) and localized EMPs containing longitudinal optical (LO) phonon coupling, which will be discussed in this paper. TM ion doping in II-VI semiconductors for a dilute magnetic semiconductor show emission via magnetic polarons (MPs) together with hot carrier effects that need to be understood via its optical properties. The high excitation power that is responsible for hot carrier effects suppresses the charge trapping effect in low exciton binding energy (8.12 meV) semiconductors, even at room temperature (RT). The large polaron radius exhibits strong interaction between the carrier and MP, resulting in anharmonicity effects, in which the side-band energy overtone to LO phonons. The photon-like polaritons exhibit polarized spin interactions with LO phonons that show strong spin-phonon polaritons at RT. The temperature-dependent photoluminescence spectra of Ni-doped ZnTe show free excitons (FX) and FXs interacting with 2LO phonon-spin interactions, corresponding to3T1(3F) â1T1(1G) and EMP peaks with ferromagnetically coupled Ni ions at3T1(3F) â1E(1G). In addition, other d-d transitions of single Ni ions (600-900 nm) appear at the low-energy side. RT energy shifts of 14-38 meV are observed due to localized states with density-of-states tails extending far into the bandgap-related spin-induced localization at the valence band. These results show spin-spin magnetic coupling and spin-phonon interactions at RT that open up a more realistic new horizon of optically controlled dilute magnetic semiconductor applications.
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Metal halide-based broadband near-infrared (NIR) luminescent materials face problems such as complicated preparation, high cost, low photoluminescence quantum yield, and high excitation energy. Here, incorporating Sb3+ and Br- into (C20H20P)2ZnCl4 crystals allowed for the achievement of efficient broadband near-infrared emission under 400 nm excitation while maintaining satisfactory environmental and thermal stability. The compounds exhibit a broad range of emission bands from 550 to 1050 nm, with a photoluminescence quantum yield of 93.57%. This is a groundbreaking achievement for organic-inorganic hybrid metal halide NIR luminescent materials. The near-infrared emission is suggested to originate from [SbX5]2-, as supported by the femtosecond transient absorption spectra and density-functional theory calculations. This phosphor-based NIR LEDs successfully demonstrate potential applications in night vision, medical imaging, information encryption, and anticounterfeiting.
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Lanthanide ions are commonly used as co-dopant ions for trap regulation in afterglow phosphors. However, rationally designing trap distribution to improve the afterglow performance remains challenging. Herein, the vacuum referred binding energy (VRBE) diagram was constructed to aid in the search for effective lanthanide ions to improve the near-infrared afterglow properties of ZnGa2O4:Cr3+. The constructed VRBE diagram indicates that Ln3+ (Ln = Sm, Yb, Tb) ions can create traps in ZnGa2O4, which is confirmed by the luminescence characterization. Results show that doping with Ln3+ (Ln = Sm, Yb, Tb) ions can significantly improve the afterglow intensity and duration of the phosphor due to the increased shallow trap density and trap depth. Among these samples, the Sm3+-doped sample exhibits the best afterglow properties. The afterglow enhancement mechanism by Ln3+ doping is discussed in detail. This work not only presents the lanthanide ions that can be used to regulate the trap distribution of ZnGa2O4:Cr3+ phosphors, but also provides new insights for the design of new afterglow phosphors with practical application value.
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The advancement of optoelectronic applications relies heavily on the development of high-performance photodetectors that are self-driven and capable of detecting a wide range of wavelengths. CsPbI3 nanorods (NRs), known for their outstanding optical and electrical properties, offer direct bandgap characteristics, high absorption coefficients, and long carrier diffusion lengths. However, challenges such as stability and limited photoluminescence quantum yield have impeded their widespread application. By integrating PbSe colloidal quantum dots (CQDs) with CsPbI3 NRs, the hybrid nanomaterial harnesses the benefits of each component, resulting in enhanced optoelectronic properties and device performance. In this work, a self-powered and broadband photodetector, ITO/ZnO/CsPbI3:PbSe/CuSCN/Au, is fabricated, in which CsPbI3 NRs are decorated with PbSe QDs as the photoactive layer, ZnO as the electron-transporting layer and CuSCN as the hole-transporting layer. The device performance is further improved through the incorporation of Cs2CO3 into the ZnO layer, resulting in an enhancement of its overall operational characteristics. As a result, a notable responsivity of 9.29 A W-1 and a specific detectivity of 3.17 × 1014 Jones were achieved. Certainly, the TCAD simulations closely correlate with our experimental data, facilitating a comprehensive exploration of the fundamental physical mechanisms responsible for the improved performance of these surface-passivated heterojunction photodetectors. This opens up exciting possibilities for substantial advancements in the realm of next-generation optoelectronic devices.
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Lead-free halide double perovskites (DPs) have become a research hotspot in the field of photoelectrons due to their unique optical properties and flexible compositional tuning. However, the reports on the optical properties of DPs primarily concentrate on the room temperature state and only exhibit single emission band. Here, we synthesized Cs2NaYCl6:Sb3+, Dy3+ DPs by a solvothermal method to realize white light emission with photoluminescence (PL) quantum yield as high as 70.7%. The energy-transfer process from self-trapped excitons (STEs) to Dy3+ ions was revealed by optical characterization and theoretical simulation calculations. Interestingly, we observed the double-emission from low-energy STE emission of Sb3+ ions and Dy3+ emission at low temperatures, and the double-emission is consistent with the asymmetric doublet feature of the 3P1 â 1S0 transition split into two minima. The PL spectra further showed that the fluorescence intensity ratios of Dy3+ ions at 580 and 680 nm were strongly temperature-dependent, and the relative sensitivity is up to 1.79% K-1 at 360 K. Moreover, the near-infrared and radiation luminescence properties indicated that the Cs2NaYCl6:Sb3+, Dy3+ DPs also have good prospects for night vision and radiation detection, as well as the great potential for applications in solid-state illumination and optical temperature measurement.
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Herein, a novel copper selenide/zinc selenide/Nitrogen-doped carbon (Cu2Se/ZnSe/NC) sphere was constructed via a combination of cation exchange, selenization and carbonization approaches with zinc-based metal-organic frameworks (ZIF-8) as precursor for sulfadiazine (SDZ) removal. Compared with the ZnSe/NC, the defective Cu2Se/ZnSe interface in the optimizing Cu-ZnSe/NC2 sample caused a remarkably improved adsorption performance. Notably, the adsorption capacity of 129.32 mg/g was better than that of mostly reported adsorbents for SDZ. And the adsorption referred to multiple-layer physical-chemical process that was spontaneous and exothermic. Besides, the Cu-ZnSe/NC2 displayed fast adsorption equilibrium of about 20 min and significant anti-interference ability for inorganic ions. Specially, the adsorbent possessed excellent stability and reusability, which could also be applied for rhodamine B (RhB), methylene blue (MB), and methyl orange (MO) dyes removal. Ultimately, the charge redistribution of Cu2Se/ZnSe interface greatly contributes the superior adsorption performance for SDZ, in which electrostatic attraction occupied extremely crucial status as compared to π-π electron-donor-acceptor (π-π EDA) interaction and hydrogen bonding (H-bonding), as revealed by the density function theory (DFT) calculations and experimental results. This study can provide a guideline for design of high-efficient adsorbent with interfacial charge redistribution.
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Plenty of exotic phenomena in moiré superlattices arise from the emergence of flatbands, but their significance could be diminished by structural disorders that will significantly alter flatbands. Thus, unveiling the effects of disorder on moiré flatbands is crucial. In this work, we explore the disorder effects on two sets of flatbands in silicon-based mismatched moiré superlattices, where the level of disorder is controlled by varying the magnitude of random perturbations of the locations of silicon strips. The results reveal that, after ensemble averaging, the average spectral positions of the four flatbands exhibit stability despite variations in the degree of disorder. However, the δ-like density of states (DOS) related to flatbands in the perfect superlattice evolves into a finite-width envelope of high DOS. By increasing the level of disorder, the width of the DOS envelope increases accordingly. Particularly, we observe a fascinating contrast: the width of bandgap flatbands saturates after initial growth, while the width of dispersive-band-crossed flatbands exhibits a linear increase versus the disorder. This unveils fundamental differences in how flatbands respond to structural imperfections, offering crucial insights into their perturbation characteristics within moiré superlattices. Our work offers new perspectives on flatbands in partially disordered moiré superlattices.
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Rare-earth halide double perovskites (DPs) have attracted extensive attention due to their excellent optoelectronic performance. However, the correlation between luminescence performance, crystal structure, and temperature, as well as the inherent energy transfer mechanism, is not well understood. Herein, Lanthanide ions (Ln3+: Nd3+ or Dy3+) as the co-dopants are incorporated into Sb3+ doped Cs2NaYbCl6 DPs to construct energy transfer (ET) models to reveal the effects of temperature and energy levels of rare earth on luminescence and ET. The different excited state structures of Sb3+-Ln3+ doped Cs2NaYbCl6 DPs at different temperatures and relative positions of energy levels of rare earth synergistically determine the physical processes of luminescence. These multi-mode luminescent materials exhibit good performance in anti-counterfeiting, NIR imaging, and temperature sensing. This work provides new physical insights into the effects of temperature and energy levels of rare earth on the energy transfer mechanism and related photophysical process.
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The host lattice environments of Sb3+ has a great influence on its photophysical properties. Here, we synthesized three zero-dimensional organic metal halides of (TPA)2SbCl5 (1), Sb3+-doped (TPA)SnCl5(H2O)·2H2O (Sb3+-2), and Sb3+-doped (TPA)2SnCl6 (Sb3+-3). Compared with the intense orange emission of 1, Sb3+-3 has smaller lattice distortion, thus effectively suppressing the exciton transformation from singlet to triplet self-trapped exciton (STE) states, which makes Sb3+-3 has stronger singlet STE emission and further bring a white emission with a photoluminescence quantum efficiency (PLQE) of 93.4%. Conversely, the non-emission can be observed in Sb3+-2 even though it has a similar [SbCl5]2- structure to 1, which should be due to its indirect bandgap characteristics and the effective non-radiative relaxation caused by H2O in the lattice. Interestingly, the non-emission of Sb3+-2 can convert into the bright emission of Sb3+-3 under TPACl DMF solution treatment. Meanwhile, the white emission under 315 nm excitation of Sb3+-3 can change into orange emission upon 365 nm irradiation, and the luminescence can be further quenched by the treatment of HCl. Therefore, a triple-mode reversible luminescence switch of off-onI-onII-off can be achieved. Finally, we demonstrated the applications of Sb3+-doped compounds in single-component white light illumination, latent fingerprint detection, fluorescent anti-counterfeiting, and information encryption.
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All-inorganic lead halide perovskites and quantum dots (QDs) have gained significant attention since their emergence, owing to their immense potential for applications in optoelectronic devices. Here, enhanced-performance broadband photodetectors based on the bulk-heterostructure of a CsPbBr3 perovskite and PbS colloidal quantum dots (CQDs) are presented, and 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM]BF4) ionic liquids as a dual-purpose additive were introduced in the blended film to regulate the surface of QDs by facilitating surface passivation, adjusting energy levels, and coupling with longer alkyl chains as compared to iodide ions (I-). As a result, a superior-quality bulk-heterostructure based photodetector with long-term stability was obtained, showing outstanding performance in photodetection across the visible to near-infrared wavelength range, demonstrating a high photoresponsivity of 22.4 A W-1 with a response time of 16.2 ms and a specific detectivity of 1.58 × 1014 Jones under 405 nm illumination. Thus, this work provides a novel modification strategy for PbS:CsPbBr3 as a promising material for novel optoelectronics.
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For applications in magneto-electronic devices, diluted magnetic semiconductors (DMSs) usually exhibit spin-dependent coupling and induced ferromagnetism at high Curie temperatures. The processes behind the behavior of optical emission and ferromagnetism, which can be identified by complicated microstructural and chemical characteristics, are still not well understood. In this study, the impact of Al co-doping on the electronic, optical, and magnetic properties of Ni(II) doped ZnO monolayers has been investigated using first principles calculations. Ferromagnetism in the co-doped monolayer is mainly triggered by the exchange coupling between the electrons provided by Al co-doping and Ni(II)-dstates; therefore, the estimated Curie temperature is greater than room temperature. The spin-spin couplings in mono-doped and co-doped monolayers were explained using the band-coupling mechanism. Based on the optical study, we observed that the Ni-related absorption peak occurred at 2.13-2.17 eV, showing a redshift as Ni concentrations increased. The FM coupling between Ni ions in the co-doped monolayer may be responsible for the reduction in the fundamental band gap seen with Al co-doping. We observed peaks in the near IR and visible regions of the co-doped monolayer, which improve the optoelectronic device's photovoltaic performance. Additionally, the correlation between optical characteristics and spin-spin couplings has been studied. We found that the Ni(II)'sd-dtransition bands or fundamental band gap in the near configuration undergoes a significant shift in response to AFM and FM coupling, whereas in the far configuration, they have a negligible shift due to the paramagnetic behavior of the Ni ions. These findings suggest that the magnetic coupling in DMS may be utilized for controlling the optical characteristics.
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Organic-inorganic metal halides have become one of the most promising materials in the next generation of optoelectronic applications due to their high charge carrier mobility and tunable band gaps. In this study, Sb:PA6InCl9 and Sb:PA4NaInCl8 single crystals were prepared through evaporation crystallization, respectively. Due to the different degrees of lattice distortions, the highly efficient yellow emission in Sb:PA6InCl9 at 610 nm and the green emission in Sb:PA4NaInCl8 at 545 nm were achieved by regulation of the excited state, respectively. By introducing additional sodium ions in the post-treatment, we found that the zero-dimensional Sb:PA6InCl9 could rapidly convert into a two-dimensional layered structure of Sb:PA4NaInCl8, thus resulting in a novel green/yellow emission switch. This work guides the structural and performance control of organic-inorganic hybrid In-based metal halides and offers broad prospects for luminescent switching in anticounterfeiting applications.
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Recently, photodetectors based on perovskite nanoplatelets (NPLs) have attracted considerable attention in the visible spectral region owing to their large absorption cross-section, high exciton binding energy, excellent charge transfer properties, and appropriate flexibility. However, their stability and performance are still challenging for perovskite NPL photodetectors. Here, a surface engineering strategy to enhance the optical stability of blue-light CsPbBr3 NPLs by acetylenedicarboxylic acid (ATDA) treatment has been developed. ATDA has strong binding capacity and a short chain length, which can effectively passivate defects and significantly improve the photoluminescence quantum efficiency, stability, and carrier mobility of NPLs. As a result, ATDA-treated CsPbBr3 NPLs exhibit improved optical properties in both solutions and films. The NPL solution maintains high PL performance even after being heated at 80 °C for 2 h, and the NPL film remains nondegradable after 4 h of exposure to ultraviolet irradiation. Especially, photodetectors based on the treated CsPbBr3 NPL films demonstrate exceptional performance, especially when the detectivity approaches up to 9.36 × 1012 Jones, which can be comparable to the best CsPbBr3 NPL photodetectors ever reported. More importantly, the assembled devices demonstrated high stability (stored in an air environment for more than 30 days), significantly exceeding that of untreated NPLs.