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Colloidal nanocrystals (NCs) exhibit significant potential for photovoltaic bioelectronic interfaces because of their solution processability, tunable energy levels, and inorganic nature, lending them chemical stability. Silver bismuth sulfide (AgBiS2) NCs, free from toxic heavy-metal elements (e.g., Cd, Hg, and Pb), particularly offer an exceptional absorption coefficient exceeding 105 cm-1 in the near-infrared (NIR), surpassing many of their inorganic counterparts. Here, we integrated an ultrathin (24 nm) AgBiS2 NC layer into a water-stable photovoltaic bioelectronic device architecture that showed a high capacitive photocurrent of 2.3 mA·cm-2 in artificial cerebrospinal fluid (aCSF) and ionic charges over 10 µC·cm-2 at a low NIR intensity of 0.5 mW·mm-2. The device without encapsulation showed a halftime of 12.5 years under passive accelerated aging test and did not show any toxicity on neurons. Furthermore, patch-clamp electrophysiology on primary hippocampal neurons under whole-cell configuration revealed that the device elicited neuron firing at intensity levels more than an order of magnitude below the established ocular safety limits. These findings point to the potential of AgBiS2 NCs for photovoltaic retinal prostheses.
Assuntos
Bismuto , Neurônios , Sulfetos , Neurônios/citologia , Animais , Bismuto/química , Sulfetos/química , Sulfetos/efeitos da radiação , Raios Infravermelhos , Nanopartículas/química , Compostos de Prata/química , Prata/química , Ratos , Hipocampo/citologia , CamundongosRESUMO
Colloidal quantum dot (CQD) technology is considered the main contender toward a low-cost high-performance optoelectronic technology platform for applications in the short-wave infrared (SWIR) to enable 3D imaging, LIDAR night vision, etc. in the consumer electronics and automotive markets. In order to unleash the full potential of this technology, there is a need for a material that is environmentally friendly, thus RoHS compliant, and possesses adequate optoelectronic properties to deliver high-performance devices. InSb CQDs hold great potential in view of their RoHS-compliant nature andâin principleâfacile access to the SWIR. However, to date progress in realizing high-performance optoelectronic devices, including photodetectors (PDs), has been limited. Here, we have developed a synthesis method for producing size-tunable InSb CQDs with distinct excitonic peaks spanning a wide range from 900 to 1750 nm. To passivate the surface defects and enhance the photoluminescence (PL) efficiency of InSb CQDs, we further designed an InSb/InP core-shell structure. By employing the InSb/InP core-shell CQDs in a photodiode device stack, we report on robust InSb CQD SWIR photodetectors that exhibit an external quantum efficiency (EQE) of 25% at 1240 nm, a wide linear dynamic range exceeding 128 dB, a photoresponse time of 70 ns, and a specific detectivity of 4.4 × 1011 jones.
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Efficient charge-carrier transport is critical to the success of emergent semiconductors in photovoltaic applications. So far, disorder has been considered detrimental for charge-carrier transport, lowering mobilities, and causing fast recombination. This work demonstrates that, when properly engineered, cation disorder in a multinary chalcogenide semiconductor can considerably enhance the charge-carrier mobility and extend the charge-carrier lifetime. Here, the properties of AgBiS2 nanocrystals (NCs) are explored as a function of Ag and Bi cation-ordering, which can be modified via thermal-annealing. Local Ag-rich and Bi-rich domains formed during hot-injection synthesis are transformed to induce homogeneous disorder (random Ag-Bi distribution). Such cation-disorder engineering results in a sixfold increase in the charge-carrier mobility, reaching ≈2.7 cm2 V-1 s-1 in AgBiS2 NC thin films. It is further demonstrated that homogeneous cation disorder reduces charge-carrier localization, a hallmark of charge-carrier transport recently observed in silver-bismuth semiconductors. This work proposes that cation-disorder engineering flattens the disordered electronic landscape, removing tail states that would otherwise exacerbate Anderson localization of small polaronic states. Together, these findings unravel how cation-disorder engineering in multinary semiconductors can enhance the efficiency of renewable energy applications.
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Achieving low-threshold infrared stimulated emission in solution-processed quantum dots is critical to enable real-life applications including photonic integrated circuits (PICs), LIDAR application, and optical telecommunication. However, realization of low threshold infrared gain is fundamentally challenging due to high degeneracy of the first emissive state (e.g., 8-fold) and fast Auger recombination. In this Letter, we demonstrate ultra-low-threshold infrared stimulated emission with an onset of 110 µJ cm-2 employing cascade charge transfer (CT) in Pb-chalcogenide colloidal quantum dot (CQD) solids. In doing so, we investigate this idea in two different architectures including a mixture of multiband gap CQDs and a layer-by-layer (LBL) configuration. Using transient absorption spectroscopy, we show ultrafast cascade CT from large band gap PbS CQD to small band gap PbS/PbSSe core/shell CQDs in LBL (â¼2 ps) and mixture (â¼9 ps) configurations. These results indicate the feasibility of using cascade CT as an efficient method to reduce the optical gain threshold in CQD solid films.
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Cs2TiBr6 stands as a promising Pb-free alternative perovskite material having demonstrated its potential in photovoltaics. However, it is considered to be highly unstable in air, hindering further improvements and raising concerns regarding its practical implementation. In this work, we report on a method to improve the stability of Cs2TiBr6 NCs using SnBr4 in a facile surface treatement.
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The use of colloidal quantum dots (CQDs) as a gain medium in infrared laser devices has been underpinned by the need for high pumping intensities, very short gain lifetimes, and low gain coefficients. Here, PbS/PbSSe core/alloyed-shell CQDs are employed as an infrared gain medium that results in highly suppressed Auger recombination with a lifetime of 485 ps, lowering the amplified spontaneous emission (ASE) threshold down to 300 µJ cm-2 , and showing a record high net modal gain coefficient of 2180 cm-1 . By doping these engineered core/shell CQDs up to nearly filling the first excited state, a significant reduction of optical gain threshold is demonstrated, measured by transient absorption, to an average-exciton population-per-dot ãNth ãg of 0.45 due to bleaching of the ground state absorption. This in turn have led to a fivefold reduction in ASE threshold at ãNth ãASE = 0.70 excitons-per-dot, associated with a gain lifetime of 280 ps. Finally, these heterostructured QDs are used to achieve near-infrared lasing at 1670 nm at a pump fluences corresponding to sub-single-exciton-per-dot threshold (ãNth ãLas = 0.87). This work brings infrared CQD lasing thresholds on par to their visible counterparts, and paves the way toward solution-processed infrared laser diodes.
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Low-cost, nontoxic, and earth-abundant photovoltaic materials are long-sought targets in the solar cell research community. Perovskite-inspired materials have emerged as promising candidates for this goal, with researchers employing materials design strategies including structural, dimensional, and compositional transformations to avoid the use of rare and toxic elemental constituents, while attempting to maintain high optoelectronic performance. These strategies have recently been invoked to propose Ti-based vacancy-ordered halide perovskites (A2TiX6; A = CH3NH3, Cs, Rb, or K; X = I, Br, or Cl) for photovoltaic operation, following the initial promise of Cs2SnX6 compounds. Theoretical investigations of these materials, however, consistently overestimate their band gaps, a fundamental property for photovoltaic applications. Here, we reveal strong excitonic effects as the origin of this discrepancy between theory and experiment, a consequence of both low structural dimensionality and band localization. These findings have vital implications for the optoelectronic application of these compounds while also highlighting the importance of frontier-orbital character for chemical substitution in materials design strategies.
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Developing high performance, low-cost solid-state light emitters in the telecom wavelength bandwidth is of paramount importance for infrared light-based communications. Colloidal quantum dot (CQD) based light emitting diodes (LEDs) have shown tremendous advances in recent times through improvement in synthesis chemistry, surface property, and device structures. Despite the tremendous advancements of CQD based LEDs in the visible range with efficiency reaching theoretical limits, their short-wave infrared (SWIR) counterparts mainly based on lead chalcogenide CQDs, have shown lower performance (≈8%). Here the authors report on highly efficient SWIR CQD LEDs with a recorded EQE of 11.8% enabled by the use of a binary CQD matrix comprising QD populations of different bandgaps at the emission wavelength of 1550 nm. By further optimizing the optical out-coupling via the use of a hemispherical lens to reduce optical waveguide loss, the EQE of the LED increased to 18.6%. The CQD LED has an electrical bandwidth of 2 MHz, which motivated them to demonstrate its use in the first SWIR free-space optical transmission link based entirely on CQD technology (photodetector and light emitter) opening a new window of applications for CQD optoelectronics.
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Heavy-metal-free colloidal nanocrystals are gaining due attention as low-cost, semiconducting materials for solution-processed optoelectronic applications. One common limitation of such materials is their limited carrier transport and trap-assisted recombination, which impede the performance of thick photoactive layers. Here we mix small-size and large-size AgBiS2 nanocrystals to judiciously favour the band alignment in photovoltaic and photodetector devices. The absorbing layer of these devices is fabricated in a gradient fashion in order to maximise charge transfer and transport. We implement this strategy to fabricate mixed AgBiS2 thin film solar cells with a power conversion of 7.3%, which significantly surpasses the performance of previously reported devices based on single-batch AgBiS2 nanocrystals. Additionally, this approach allows us to fabricate devices using thicker photoactive layers that show lower dark currents and external quantum efficiencies exceeding 40% over a broad bandwidth - covering the visible and near infrared range beyond 1 µm, thus unleashing the potential of colloidal AgBiS2 nanocrystals in photodetector applications.
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Selective spectral detection of ultraviolet (UV) radiation is highly important across numerous fields from health and safety to industrial and environmental monitoring applications. Herein, a nontoxic, visible-blind, quantum dot (QD)-based sensing scheme that expands the spectral coverage of silicon complementary metal-oxide-semiconductor (CMOS) sensors into the UV, enabling efficient UV detection without affecting the sensor performance in the visible and UV-band discrimination, is reported. This scheme uses zinc magnesium oxide (ZnMgO) QDs with compositionally tunable absorption across UV and high photoluminescence quantum yield in the visible. The efficient luminescence and large Stokes shift of these QDs are exploited herein to act as an efficient downconverting material that enhances the UV sensitivity of Si-photodetectors (Si-PDs). A Si-PD integrated with the QDs results in a ninefold improvement in photoresponsivity from 0.83 to 7.5 mA W-1 at 260 nm. Leveraging the tunability of these QDs, a simple UV-band identification scheme is further reported, which uses two distinct-bandgap ZnMgO QDs stacked in a tandem architecture whose spectral emission color depends on the UV-band excitation light. The downconverting stack enables facile discrimination of UV light using a standard CMOS image sensor (camera) or by the naked eye and avoids the use of complex optics.
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Pb-chalcogenide colloidal quantum dots (CQDs) are attractive materials to be used as tuneable laser media across the infrared spectrum. However, excessive nonradiative Auger recombination due to the presence of trap states outcompetes light amplification by rapidly annihilating the exciton population, leading to high gain thresholds. Here, a binary blend is employed of CQDs and ZnO nanocrystals in order to passivate the in-gap trap states of PbS-CQD gain medium. Using transient absorption, a fivefold increase is measured in Auger lifetime demonstrating the suppression of trap-assisted Auger recombination. By doing so, a twofold reduction is achieved in amplified spontaneous emission (ASE) threshold. Finally, by integrating the proposed binary blend to a distributed feedback (DFB) resonator, single-mode lasing emission is demonstrated at 1650 nm with a linewidth of 1.23 nm (0.62 meV), operating at a low lasing threshold of ≈385 µJ cm-2 . The Auger suppression in this system has allowed to achieve unprecedented lasing emission stability for a CQD laser with recorded continuous operation of 5 h at room temperature and ambient conditions.
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Low cost, multinary colloidal quantum dots (QDs) based on environmentally friendly elements, with bright, narrow-width, tunable near-infrared (NIR) luminescence are promising alternatives to Cd and Pb chalcogenide QDs for in vivo bio-imaging, LED and sensing applications. Herein, we demonstrate Pb/Cd free solution-processed colloidal luminescent Ag2ZnSnS4-ZnS (AZTS-ZnS) core-shell QDs with precise control over the ZnS shell thickness and thereby its optical properties. Unlike indium based multinary (I-III-VI group) core-shell QDs these nanocrystals show a narrow photoluminescence (PL) full width at half maximum (fwhm) of 105-110 meV in the first NIR window. By monitoring the starting AZTS core size, we achieve tunable emission over a small NIR window in these QDs with the best PL quantum yield (PLQY) of 17.4%.
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Solid-state broadband light emitters in the visible have revolutionized today's lighting technology achieving compact footprints, flexible form factors, long lifetimes, and high energy saving, although their counterparts in the infrared are still in the development phase. To date, broadband emitters in the infrared have relied on phosphor-downconverted light emitters based on atomic optical transitions in transition metal or rare earth elements in the phosphor layer resulting in limited spectral bandwidths in the near-infrared and preventing their integration into electrically driven light-emitting diodes (LEDs). Herein, phosphor-converted LEDs based on engineered stacks of multi-bandgap colloidal quantum dots (CQDs) are reported as a novel class of broadband emitters covering a broad short-wave infrared (SWIR) spectrum from 1050-1650 nm with a full-width-half-maximum of 400 nm, delivering 14 mW of optical power with a quantum efficiency of 5.4% and power conversion efficiency of 13%. Leveraging the electrical conductivity of the CQD stacks, further, the first broadband SWIR-active LED is demonstrated, paving the way toward complementary metal-oxide-semiconductor integrated broadband emitters for on-chip spectrometers and low-cost volume manufacturing. SWIR spectroscopy is employed to illustrate the practical relevance of the emitters in food and material identification case studies.
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Materials with optical gain in the infrared are of paramount importance for optical communications, medical diagnostics, and silicon photonics. The current technology is based either on costly III-V semiconductors that are not monolithic to silicon CMOS technology or Er-doped fiber technology that does not make use of the full fiber transparency window. Colloidal quantum dots (CQDs) offer a unique opportunity as an optical gain medium in view of their tunable bandgap, solution processability, and CMOS compatibility. The 8-fold degeneracy of infrared CQDs based on Pb-chalcogenides has hindered the demonstration of low-threshold optical gain and lasing, at room temperature. We demonstrate room-temperature, infrared, size-tunable, band-edge stimulated emission with a line width of â¼14 meV. Leveraging robust electronic doping and charge-exciton interactions in PbS CQD thin films, we reach a gain threshold at the single exciton regime representing a 4-fold reduction from the theoretical limit of an 8-fold degenerate system, with a net modal gain in excess of 100 cm-1.
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Steady-state access to intraband transitions in colloidal quantum dots (CQDs), via doping, permits exploitation of the electromagnetic spectrum at energies below the band gap. CQD intraband optoelectronics allows envisaging cheap mid- and long-wavelength infrared photodetectors and light-emitting devices, which today employ epitaxial materials. As intraband devices start to emerge, thorough studies of the basic properties of intraband transitions in different CQD materials are needed to guide technological research. In this work, we investigate the size and temperature dependence of the intraband transition in heavily n-doped PbS quantum dot (QD) films. In the studied QD size range (5-8 nm), the intraband energy spans from 209 to 151 meV. We measure the intraband absorption coefficient of heavily doped PbS QD films to be around 2 × 104 cm-1, proving that intraband absorption is as strong as interband absorption. We demonstrate a negative dependence of the intraband energy with temperature, in contrast to the positive dependence of the interband transition. Also opposite to the interband case, the temperature dependence of the intraband energy increases with decreasing size, going from -29 µeV/K to -49 µeV/K in the studied size range.
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The creation of white and multicoloured 3D-printed objects with high color fidelity via powder sintering processes is currently limited by discolouration from thermal sensitizers used in the printing process. Here, we circumvent this problem by using switchable, photochromic tungsten oxide nanoparticles, which are colorless even at high concentrations. Upon ultraviolet illumination, the tungsten oxide nanoparticles can be reversibly activated, making them highly absorbing in the infrared. Their strong infrared absorption upon activation renders them efficient photothermal sensitizers that can act as fusing agents for polymer powders in sintering-based 3D printing. The WO3 nanoparticles show fast activation times, and when mixed with polyamide powders, they exhibit a heating-to-color-change ratio greatly exceeding other sensitizers in the literature. Upon mixing with colored inks, powders containing WO3 display identical coloration to a pristine powder. This demonstrates the potential of WO3, and photochromic nanoparticles in general as a new class of material for advanced manufacturing.
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Two major challenges exist before colloidal nanocrystal solar cells can take their place in the market: So far, these devices are based on Pb/Cd-containing nanocrystals, and second, the synthesis of these nanocrystals takes place in an inert atmosphere at elevated temperatures due to the use of air-sensitive chemicals. In this report, a room-temperature, ambient-air synthesis for nontoxic AgBiS2 nanocrystals is presented. As this method utilizes stable precursors, the need for the use of a protective environment is eliminated, enabling the large-scale production of AgBiS2 nanocrystals. The production cost of AgBiS2 NCs at room temperature and under ambient conditions reduces by â¼60% compared to prior reports based on hot injection, and the solar cells made of these nanocrystals yield a promising power conversion efficiency (PCE) of 5.5%, the highest reported to date for a colloidal nanocrystal material free of Pb or Cd synthesized at room temperature and under ambient conditions.
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By combining X-ray absorption fine structure and X-ray diffraction measurements with density functional and molecular dynamics simulations, we study the structure of a set of AgxBi1-xS2 nanoparticles, a materials system of considerable current interest for photovoltaics. An apparent contradiction between the evidence provided by X-ray absorption and diffraction measurements is solved by means of the simulations. We find that disorder in the cation sublattice induces strong local distortions, leading to the appearance of short Ag-S bonds, the overall lattice symmetry remaining close to hexagonal.
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Optical sensing in the mid- and long-wave infrared (MWIR, LWIR) is of paramount importance for a large spectrum of applications including environmental monitoring, gas sensing, hazard detection, food and product manufacturing inspection, and so forth. Yet, such applications to date are served by costly and complex epitaxially grown HgCdTe quantum-well and quantum-dot infrared photodetectors. The possibility of exploiting low-energy intraband transitions make colloidal quantum dots (CQD) an attractive low-cost alternative to expensive low bandgap materials for infrared applications. Unfortunately, fabrication of quantum dots exhibiting intraband absorption is technologically constrained by the requirement of controlled heavy doping, which has limited, so far, MWIR and LWIR CQD detectors to mercury-based materials. Here, we demonstrate intraband absorption and photodetection in heavily doped PbS colloidal quantum dots in the 5-9 µm range, beyond the PbS bulk band gap, with responsivities on the order of 10-4 A/W at 80 K. We have further developed a model based on quantum transport equations to understand the impact of electron population of the conduction band in the performance of intraband photodetectors and offer guidelines toward further performance improvement.
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Lead sulphide (PbS) nanocrystals (NCs) are promising materials for low-cost, high-performance optoelectronic devices. So far, PbS NCs have to be first synthesized with long-alkyl chain organic surface ligands and then be ligand-exchanged with shorter ligands (two-steps) to enable charge transport. However, the initial synthesis of insulated PbS NCs show no necessity and the ligand-exchange process is tedious and extravagant. Herein, we have developed a direct one-step, scalable synthetic method for iodide capped PbS (PbS-I) NC inks. The estimated cost for PbS-I NC inks is decreased to less than 6 $·g-1, compared with 16 $·g-1 for conventional methods. Furthermore, based on these PbS-I NCs, photodetector devices show a high detectivity of 1.4 × 1011 Jones and solar cells show an air-stable power conversion efficiency (PCE) up to 10%. This scalable and low-cost direct preparation of high-quality PbS-I NC inks may pave a path for the future commercialization of NC based optoelectronics.