RESUMEN
Lead-free halide double perovskite (HDP) Cs2AgBiBr6 has set a benchmark for research in HDP photoelectric applications due to its attractive optoelectronic properties. However, its narrow absorption range is a key limitation of this material. Herein, a novel dopant, palladium (Pd), is doped into Cs2AgBiBr6 and significantly extends the absorption to ≈1400 nm. Pd2+ ions are partially doped in the host lattice, most probably replacing Ag atoms and introducing a sub-bandgap state within the host bandgap, as indicated by the combination of spectroscopical measurements and theoretical calculations. Importantly, this sub-bandgap state extends the photoresponse of Cs2AgBiBr6 up to the NIR-II region of 1300 nm, setting a new record for HDPs. This work demonstrates a novel and efficient dopant for HDPs and highlights the effectiveness of employing a sub-bandgap to broaden the absorption of HDPs, shedding new light on tailoring large bandgap HDPs for NIR optoelectronic applications.
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Broadband photodetectors covering ultraviolet (UV) to near-infrared (NIR) wavelengths play an essential role in communications, imaging, and biosensing. Developing a single photodetector with a broadband optical response operating at room temperature can significantly reduce the complexity and cost of receiver systems for multispectral applications. In this work, utilizing the porous structure characteristics of Cs2AgBiBr6:Sn thin films, a self-powered detector with broad spectral response (UV-vis-NIR) was achieved by constructing an effective Cs2AgBiBr6:Sn/PDPP3T heterojunction. This photodetector possesses a broad response spectrum from 350 to 950 nm with an average detection rate exceeding 1011 Jones and maintains excellent photoelectric performance over two months. Sn2+ doping effectively reduces the bandgap of Cs2AgBiBr6, enhancing its near-infrared absorption and optimizing energy level alignment with conjugated polymer (diketopyrrolopyrrole-terthiophene, PDPP3T). More importantly, the porous structure derived from Sn doping significantly improves carrier extraction and transport under a near-infrared light response at the heterojunction interface. Utilizing its broad spectral response characteristics in the UV-vis-NIR range, a novel information transfer and encryption system employing full optical modulation has been realized within a single perovskite photodetector. This work provides a new approach to fabricating lead-free double perovskite broadband photodetectors with potential applications in photonic devices.
RESUMEN
An original molecular imprinting photoelectrochemical (PEC) sensor for sarcosine detection based on stable lead-free inorganic halide double perovskite Cs2AgBiBr6 is proposed. Cs2AgBiBr6 as a lead-free halide perovskite material possesses several positive optoelectronic properties for PEC analysis, such as long-lived component to the charge-carrier lifetime, and strong absorption of visible light. At the same time, two-dimensional materials also offer excellent electronic and mechanical properties; thus, Bi2O2S was used and combined with Cs2AgBiBr6 to provide a stable and large photocurrent, which also benefits from the stability of perovskite Cs2AgBiBr6. Based on this novel PEC assay, the detection range for sarcosine was between 0.005 and 5000 ng/mL with a low detection limit of 0.002 ng/mL. This work also improved the adhibition of metal halide perovskite in analytical chemistry field, providing a novel way for other small molecule detection.
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Halide perovskites have garnered significant attention for their unique optoelectronic properties in solar-to-fuel conversions. However, the efficiency of halide perovskites in the field of photocatalytic CO2 reduction is largely limited by serious charge recombination and a lack of efficient active sites. In this work, a rubidium (Rb) doped Cs2AgBiBr6 (Rb:CABB) hierarchical microsphere is developed for photocatalytic CO2 reduction. Experimental and theoretical analysis discloses that partially substituting Rb+ for Ag+ can effectively modulate the electronic structure of CABB, favoring charge separation and making adjacent Bi atoms an electron-rich active site. Further investigations indicated that Rb doping also reduces the energy barriers of the rate-determining step in CO2 reduction. As a result, Rb:CABB demonstrated an enhanced CO yield compared to its undoped counterpart. This work presents a promising approach to optimizing the electronic structures of photocatalysts and paving a new way for exploring halide perovskites for photocatalytic CO2 reduction.
RESUMEN
Recently, the lead-free double perovskite Cs2AgBiBr6has been considered as a promising candidate for next-generation nonvolatile memory and artificial synapse devices due to its high stability and low toxicity compared to its lead-based counterparts. In this work, we developed a simple and effective method to produce high-quality lead-free double perovskite Cs2AgBiBr6thin films without pinholes and particles by applying a low-pressure assisted method under ambient condition with a relative humidity (RH) of about 45%. The formation of pinholes and Ag precipitation in the perovskite Cs2AgBiBr6 films is effectively suppressed by the proper ratio of N,N-dimenthylformamide (DMF) mixed in dimethyl sulfoxide (DMSO) solvents. Furthermore, the grain size of the Cs2AgBiBr6films can be significantly increased by increasing the post-annealing temperature. Finally, a sandwiched structure memristor with an ITO/Cs2AgBiBr6/Ta configuration was successfully demonstrated, featuring ultralow operation voltage (VSetâ¼ 57 ± 23 mV,VResetâ¼ -692 ± 68 mV) and satisfactory memory window (the ratio ofRHRS/RLRSâ¼ 10 times), which makes it suitable for low-power consumption information storage devices.
RESUMEN
To address the toxicity and stability issues of traditional lead halide perovskite solar cells (PSCs), the development of lead-free PSCs, such as Cs2AgBiBr6 solar cells, is of great significance. However, due to the low defect formation energy of Cs2AgBiBr6, a large number of vacancies, including A-site vacancies and X-site vacancies, form during the fabrication process of the Cs2AgBiBr6 film, which seriously damage the performance of the devices. The traditional phenylethylammonium (PEA) cation, mainly focusing on passivating A-site vacancies, is incapable of reducing X-site vacancies and so results in a limited performance improvement in Cs2AgBiBr6 solar cells. Herein, inspired by the capability of the Lewis base to coordinate with metal cations, a series of N-heterocyclic amines are introduced to serve as a dual-site passivator, reducing A-site and X-site vacancies at the same time. The highest power conversion efficiency of modified Cs2AgBiBr6 solar cells has been increased 36% from 1.10 to 1.50%. Further investigation reveals that the higher electron density of additives would lead to a stronger interaction with metal cations like Ag+ and Bi3+, thus reducing more X-site defects and improving carrier dynamics. Our work provides a strategy for passivating perovskite with various kinds of defects and reveals the connection between the coordination capability of additives and device performance enhancement, which could be instructive in improving the performance of lead-free PSCs.
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Reversible optical property changes in lead-free perovskites have recently received great interest due to their potential applications in smart windows, sensors, data encryption, and various on-demand devices. However, it is challenging to achieve remarkable color changes in their thin films. Here, methylamine gas (CH3 NH2 , MA0 ) induced switchable optical bleaching of bismuth (Bi)-based perovskite films is demonstrated for the first time. By exposure to an MA0 atmosphere, the color of Cs2 AgBiBr6 (CABB) films changes from yellow to transparent, and the color of Cs3 Bi2 I9 (CBI) films changes from dark red to transparent. More interestingly, the underlying reason is found to be the interactions between MA0 and Bi3+ with the formation of an amorphous liquefied transparent intermediate phase, which is different from that of lead-based perovskite systems. Moreover, the generality of this approach is demonstrated with other amine gases, including ethylamine (C2 H5 NH2 , EA0 ) and butylamine (CH3 (CH2 )3 NH2 , BA0 ), and another compound, Cs3 Sb2 I9 , by observing a similar reversible optical bleaching phenomenon. The potential for the application of CABB and CBI films in switchable smart windows is investigated. This study provides valuable insights into the interactions between amine gases and lead-free perovskites, opening up new possibilities for high-efficiency optoelectronic and stimuli-responsive applications of these emerging Bi-based materials.
RESUMEN
Lead-free Cs2AgBiBr6 double perovskite has emerged as a promising new-generation photovoltaic, due to its non-toxicity, long carrier lifetime, and low exciton binding energies. However, the low power conversion efficiency, due to the high indirect bandgap (≈2 eV), is a challenge that must be overcome and acts as an obstacle to commercialization. Herein, to overcome the limitations through the light trapping strategy, we analyzed the performance evaluation via FDTD simulation when applying the moth-eye broadband antireflection (AR) layer on top of a Cs2AgBiBr6 double perovskite cell. A parabola cone structure was used as a moth-eye AR layer, and an Al2O3 (n: 1.77), MgF2 (n: 1.38), SiO2 (n: 1.46), and ZnO (n: 1.9) were selected as investigation targets. The simulation was performed assuming that the IQE was 100% and when the heights of Al2O3, MgF2, SiO2, and ZnO were 500, 350, 250, and 450 nm, which are the optimal conditions, respectively, the maximum short-circuit current density improved 41, 46, 11.7, and 15%, respectively, compared to the reference cell. This study is meaningful and innovative in analyzing how the refractive index of a moth-eye antireflection layer affects the light trapping within the cell under broadband illumination until the NIR region.
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Although lead-free double perovskites such as Cs2AgBiBr6 have been widely explored, they still remain a daunting challenge for the controlled synthesis of lead-free double perovskite nanocrystals with highly tunable morphology and band structure. Here, we report the controlled synthesis of lead-free double perovskite colloidal nanocrystals including Cs2AgBiBr6 and Cs2AgInxBi1-xBr6 via a facile wet-chemical synthesis method for the fabrication of high-performance nonvolatile resistive memory devices. Cs2AgBiBr6 colloidal nanocrystals with well-defined cuboidal, hexagonal, and triangular morphologies are synthesized through a facile wet-chemical approach by tuning the reaction temperature from 150 to 190 °C. Further incorporating indium into Cs2AgBiBr6 to synthesize alloyed Cs2AgInxBi1-xBr6 nanocrystals not only can induce the indirect-to-direct bandgap transition with enhanced photoluminescence but also can improve its structural stability. After optimizing the active layers and device structure, the fabricated Ag/polymethylene acrylate@Cs2AgIn0.25Bi0.75Br6/ITO resistive memory device exhibits a low power consumption (the operating voltage is â¼0.17 V), excellent cycling stability (>10â¯000 cycles), and good synaptic property. Our study would enable the facile wet-chemical synthesis of lead-free double perovskite colloidal nanocrystals in a highly controllable manner for the development of high-performance resistive memory devices.
RESUMEN
The stability and toxicity problems have haunted the development and applications of metal halide perovskite materials, for which the lead-free inorganic double perovskite Cs2AgBiBr6 has emerged as a promising substitute in recent years. However, poor film quality has severely limited its photovoltaic performance that could have been induced by some key factors such as high annealing temperature. Herein, we present a facile strategy to fabricate high-quality pinhole-free Cs2AgBiBr6 films with large grain sizes by introducing carbohydrazide (CBH) into the precursor. Detailed characterizations have shown that the carbonyl group (CâO) in CBH plays the critical role in coordinating with Ag+ and Bi3+ cations during the film formation process. As another consequence, the as-fabricated devices have exhibited significantly higher reproducibility for fabrication. By optimizing the amount of CBH, the power conversion efficiency (PCE) relatively increased 37 to 1.57%, which remained 95.0% in an ambient environment for a 1000-h test. Hopefully, this work could facilitate the current technologies in the exploration of high-performance lead-free perovskites such as Cs2AgBiBr6 and better understanding of the mechanism in the additive engineering as well.
RESUMEN
Lead-free Cs2AgBiBr6 perovskites have emerged as a promising, non-toxic, and eco-friendly photovoltaic material with high structural stability and a long lifetime of carrier recombination. However, the poor-light harvesting capability of lead-free Cs2AgBiBr6 perovskites due to the large indirect band gap is a critical factor restricting the improvement of its power conversion efficiency, and little information is available about it. Therefore, this study focused on the plasmonic approach, embedded metallic nanospheres in Cs2AgBiBr6 perovskite solar cells, and quantitatively investigated their light-harvesting capability via finite-difference time-domain method. Gold and palladium were selected as metallic nanospheres and embedded in a 600 nm thick-Cs2AgBiBr6 perovskite layer-based solar cell. Performances, including short-circuit current density, were calculated by tuning the radius of metallic nanospheres. Compared to the reference devices with a short-circuit current density of 14.23 mA/cm2, when a gold metallic nanosphere with a radius of 140 nm was embedded, the maximum current density was improved by about 1.6 times to 22.8 mA/cm2. On the other hand, when a palladium metallic nanosphere with the same radius was embedded, the maximum current density was improved by about 1.8 times to 25.8 mA/cm2.
RESUMEN
Lead-free perovskites have attracted increasing attention because they can address the toxicity and instability problems inherent to lead-halide perovskites. Furthermore, the nonlinear optical (NLO) properties of lead-free perovskites are rarely explored. Herein, we report significant NLO responses and defect-dependent NLO behavior of Cs2AgBiBr6. Specifically, a thin film of pristine Cs2AgBiBr6 exhibits strong reverse saturable absorption (RSA), while a film of Cs2AgBiBr6 with defects (denoted as Cs2AgBiBr6(D)) shows saturable absorption (SA). The nonlinear absorption coefficients are ca. 4.0 × 104 cm GW-1 (515 nm laser excitation) and 2.6 × 104 cm GW-1 (800 nm laser excitation) for Cs2AgBiBr6 and -2.0 × 104 cm GW-1 (515 nm laser excitation) and -7.1 × 103 cm GW-1 (800 nm laser excitation) for Cs2AgBiBr6(D). The optical limiting threshold of Cs2AgBiBr6 is 8.1 × 10-4 J cm-2 (515 nm laser excitation). The samples show excellent long-term performance stability in air. The RSA of pristine Cs2AgBiBr6 correlates with excited-state absorption (515 nm laser excitation) and excited-state absorption following two-photon absorption (800 nm laser excitation), while the defects in Cs2AgBiBr6(D) strengthen the ground-state depletion and Pauli blocking, resulting in SA.
RESUMEN
The practical application of lead-free double perovskite Cs2 AgBiBr6 in photocatalytic H2 evolution is still restricted due to the low activity and poor stability. The rational design of lead-free halide double perovskites heterojunctions with efficient charge transfer and effective active sites is a potential route to achieve the ideal prospect. Herein, in this work an S-scheme heterojunction of Cs2 AgBiBr6 with enriched Br-vacancies and WO3 nanorods (VBr -Cs2 AgBiBr6 /WO3 ) obtaining excellent visible-light responsive photocatalytic H2 evolution performance and durable stability is reported. The S-scheme heterojunction driven by the unaligned Fermi levels of these two semiconductors ensures the efficient charge transfer at the interface, and density functional theory calculations reveal the enriched Br vacancies on Cs2 AgBiBr6 (022) surfaces introduced by atom thermal vibration provide effective active sites for hydrogen evolution. The optimized VBr -Cs2 AgBiBr6 /WO3 S-scheme photocatalyst exhibits the photocatalytic hydrogen evolution rate of 364.89 µmol g-1 h-1 which is 4.9-fold of bare VBr -Cs2 AgBiBr6 (74.44 µmol g-1 h-1 ) and presents long-term stability of 12 h continuous photocatalytic reaction. This work provides deep insights into the photocatalytic mechanism of VBr -Cs2 AgBiBr6 /WO3 S-scheme heterojunctions, which emerges a new strategy in the applications of perovskite-based photocatalysts.
RESUMEN
All-inorganic lead-free halide double perovskites have emerged as rising star photocatalysts to substitute the toxic lead-based hailed perovskites (LHPs) owing to their unique photophysical properties. Nevertheless, their photocatalytic activities toward CO2 reduction are still far from comparable with the LHPs, associated with severe charge recombination and sluggish surface catalytic reaction. Herein, a delicate 0D/2D heterojunction of Cs2AgBiBr6/Bi2WO6 (CABB/BWO) was assembled by in-situ growing cubic CABB nanocrystals on the flat surface of BWO nanosheets via a facile hot-injection method. Density functional theory (DFT) calculations disclose that the work function and Fermi level difference between CABB and BWO give rise to charge redistribution at the interface upon the formation of the heterojunction, creating an internal electric field (IEF). Upon light irradiation, the IEF enables the photogenerated electron transfer from BWO to CABB via direct Z-scheme electron transfer mode with striking spatial charge separation as verified by in-situ X-ray photoelectron (XPS) and electron spin resonance (ESR) spectra. Consequently, the CABB/BWO heterojunction realizes 7-fold higher photocatalytic activity than pristine CABB with significant electron consumption rate of 87.66 µmol g-1h-1 under simulated solar light (AM 1.5G).
RESUMEN
Lead-free inorganic Cs2AgBiBr6 double perovskites have emerged as promising materials in perovskite solar cells (PSCs) to tackle the inferior stability and toxicity issues of organic-inorganic hybrid PSCs. However, the power conversion efficiencies (PCEs) of Cs2AgBiBr6 solar cells are remarkably restricted by the intrinsic and extrinsic defects of Cs2AgBiBr6 films. More specifically, the fast crystallization process in the formation of Cs2AgBiBr6 films strongly prevents the homogeneous growth of perovskite crystals, leading to inferior Cs2AgBiBr6 film quality. This work introduces a facile strategy to retard the crystallization of Cs2AgBiBr6 perovskites by introducing Lewis base additives into the precursor solution. The incorporation of a strongly coordinated thiourea additive with a sulfur donor leads to the generation of a Lewis acid base adduct, which retards the crystallization process for Cs2AgBiBr6 crystals, improves the quality of the Cs2AgBiBr6 film, decreases the defect density and inhibits charge carrier recombination. After optimization, the cell delivers a superior PCE of 3.07%, surpassing that reported for most Cs2AgBiBr6-based solar cells in the literature, and exhibits outstanding stability with a PCE retention rate of 95% after 20 days of storage in air. This work provides an effective strategy for further improvements in the performance of inorganic lead-free Cs2AgBiBr6-based photovoltaic cells.
RESUMEN
Pb-free perovskite material is considered to be a promising material utilized in next-generation X-ray detectors due to its high X-ray absorption coefficient, decent carrier transport properties, and relatively low toxicity. However, the pixelation of the perovskite material with an industry-level photolithography processing method remains challenging due to its poor structural stability. Herein, we use Cs2AgBiBr6 perovskite material as the prototype and investigate its interaction with photolithographic polar solvents. Inspired by that, we propose a wafer-scale photolithography patterning method, where the pixeled perovskite array devices for X-ray detection are successfully prepared. The devices based on pixeled Pb-free perovskite material show a high detection sensitivity up to 19118 ± 763 µC Gyair-1 cm-2, which is comparable to devices with Pb-based perovskite materials and superior to the detection sensitivity (â¼20 µC Gyair-1 cm-2) of the commercial a-Se detector. After pixelation, the devices achieve an improved spatial resolution capacity with the spatial frequency from 2.7 to 7.8 lp mm-1 at modulation-transfer-function (MTF) = 0.2. Thus, this work may contribute to the development of high-performance array X-ray detectors based on Cs2AgBiBr6 perovskite material.
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A neuromorphic visual system integrating optoelectronic synapses to perform the in-sensor computing is triggering a revolution due to the reduction of latency and energy consumption. Here it is demonstrated that the dwell time of photon-generated carriers in the space-charge region can be effectively extended by embedding a potential well on the shoulder of Schottky energy barrier. It permits the nonlinear interaction of photocurrents stimulated by spatiotemporal optical signals, which is necessary for in-sensor reservoir computing (RC). The machine vision with the sensor reservoir constituted by designed self-powered Au/P(VDF-TrFE)/Cs2 AgBiBr6 /ITO devices is competent for both static and dynamic vision tasks. It shows an accuracy of 99.97% for face classification and 100% for dynamic vehicle flow recognition. The in-sensor RC system takes advantage of near-zero energy consumption in the reservoir, resulting in decades-time lower training costs than a conventional neural network. This work paves the way for ultralow-power machine vision using photonic devices.
RESUMEN
High-density Cs2AgBiBr6 films with uniform grains were prepared by a simple one-step and low-temperature sol-gel method on indium tin oxide (ITO) substrates. An explicit tristate bipolar resistance switching behavior was observed in the Pt/Cs2 AgBiBr6/ITO/glass devices under irradiation of 10 mW/cm2 (445 nm). This behavior was stable over 1200 s. The maximum ratio of the high and low resistance states was about 500. Based on the analysis of electric properties, valence variation and absorption spectra, the resistive switching characteristics were attributed to the trap-controlled space charge-limited current mechanism due to the bromine vacancies in the Cs2AgBiBr6 layer. On the other hand, it is suggested that the ordering of the Schottky-like barrier located at Pt/Cs2AgBiBr6 affects the three-state resistance switching behavior under light irradiation. The ability to adjust the photoelectrical properties of Cs2AgBiBr6-based resistive switching memory devices is a promising strategy to develop high-density memory.
RESUMEN
Recently, the effect of dimensional control on the optoelectronic performance of two-dimensional (2D)/three-dimensional (3D) single perovskites has been confirmed. However, how the dimensional change affects the photoelectric properties of 2D/3D all-inorganic double perovskites remains unclear. In this study, we present a detailed theoretical research on a comparison between the optoelectronic properties of 3D all-inorganic double perovskite Cs2AgBiBr6and recently reported 2D all-inorganic double perovskite Cs4AgBiBr8with Ruddlesden-Popper (RP) structure based on density functional theory calculations. The results demonstrate the charge carrier mobility and absorption coefficients in the visible spectrum of Cs4AgBiBr8(2D) is poorer than Cs2AgBiBr6(3D). Moreover, the value of exciton-binding energy for 2D RP all-inorganic double perovskite Cs4AgBiBr8(720 meV) is 3 times larger than that of 3D all-inorganic double perovskite Cs2AgBiBr6(240 meV). Our works indicate that Cs4AgBiBr8(2D) is a promising material for luminescent device, while Cs2AgBiBr6(3D) may be suitable for photovoltaic applications. This study provides a theoretical guidance for the understanding of 2D RP all-inorganic double perovskite with potential applications in photo-luminescent devices.
RESUMEN
The lead-free double perovskite has been proven to be one of the promising alternatives to solve the stability and toxicity problems of lead-based organic-inorganic hybrid perovskite solar cells. Here, high-quality Cs2AgBiBr6 double perovskite films with large grains and smooth surface have been prepared through a sequential-vapor-deposition method, and a low-cost and eco-friendly Cu2O film with a suitable energy level and good electrical properties was prepared as an efficient hole transport layer by vacuum vapor deposition for the first time. The Cu2O-based devices achieve a champion power conversion efficiency increasing from 1.03 to 1.52% and an enhancement of photovoltage from 1.083 to 1.198 V compared with their organic counterparts. More importantly, the Cu2O-based devices have excellent stability; they maintained the initial 96% efficiency under environmental conditions after 33 days of unpackaged storage. These results also point out the direction for the further development of these new promising perovskite solar cells.