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At least 37 records · Page 2

A monolithic lead sulfide-silicon MOS integrated-circuit structure

A technique is developed for directly integrating infrared photoconductive PbS detector material with MOS transistors. A layer of chromium, instead of aluminum, is deposited followed by a gold deposition in order to ensure device survival during the chemical deposition of the PbS. Among other devices, a structure was fabricated and evaluated in which the PbS was directly coupled to the gate of a PMOS. The external bias, load, and source resistors were connected and the circuit was operated as a source-follower amplifier. Radiometric evaluations were performed on a variety of different MOSFETs of different geometry. In addition, various detector elements were simultaneously fabricated to demonstrate small element capability, and it was shown that elements of 25 x 25 microns could easily be fabricated. Results of room temperature evaluations using a filtered 700 K black body source yielded a detectivity at peak wavelength of 10 to the 11th cm (root Hz)/W at 100 Hz chopping frequency.

Jhabvala, M. D.↗

Coupling of Infrared Active Colloidal Quantum Dots and Amorphous Selenium for Fast and Sensitive Photodetection

Colloidal quantum dot (CQD) based infrared (IR) photodetectors offer facile wavelength tunability in the IR and low-cost fabrication. However, owing to their large surface areas, CQDs intrinsically have significant surface traps critically affecting the speed of CQD photodetectors, typically mediated through tedious surface passivation efforts. In this report, an alternative strategy involving coupling of near-IR photoactive lead sulfide CQDs with a thermally evaporated amorphous selenium (a-Se) hole transport layer is proposed. By separating the detector into a photon absorbing CQD region and a charge transport a-Se region, the study takes advantage of the extremely low noise, predominantly hole-only transport process in a-Se. Here, a high 3 dB bandwidth of 2.5 MHz and a competitive specific detectivity of 2.5 × 10 11 Jones at room temperature are demonstrated at 980 nm. This report serves as a first demonstration of strong coupling between an IR active CQD absorber and a-Se, which paves the path to obtain fast and highly photoresponsive IR photodetection in the future.

36 MATERIALS SCIENCE↗

Tailoring the Surface of Metal Halide Perovskites to Enable the Atomic Layer Deposition of Metal Oxide Contacts

Replacing organic contact layers with inorganic counterparts, such as metal oxides, is one strategy for improving long-term device stability in metal halide perovskite solar cells. Often, the methods used to deposit metal oxide thin films are incompatible with metal halide perovskites, creating challenges for the fabrication of contacts above the perovskite absorber layer. In this study, we utilize a one-step, solution treatment of the top surface of Cs 0.25 FA 0.75 Pb(Br 0.20 I 0.80 ) 3 to create a thin (~1 nm) overlayer of lead sulfide (PbS) to protect the underlying perovskite during subsequent deposition. X-ray characterization of the surface region shows that the PbS overlayer limits undesirable changes to the perovskite structure and stoichiometry during atomic layer deposition (ALD) of SnO 2 . This protection enables ALD growth of SnO 2 electron contacts on top of the perovskite without an organic transport layer (e.g., C 60 ), resulting in a solar cell with a power conversion efficiency of 5.8%. This result is a marked improvement over devices with ALD SnO 2 grown directly on the perovskite without a PbS overlayer, which produce no power output. Furthermore, the interface characterization and device results in this study highlight some of the key challenges associated with ALD metal oxide growth on perovskite materials and can help inform the future design of inorganic contact layer deposition in solar photovoltaic technologies.

36 MATERIALS SCIENCE↗

Ultrafast Symmetry Control in Photoexcited Quantum Dots

Symmetry control is essential for realizing unconventional properties, such as ferroelectricity, nonlinear optical responses, and complex topological order, thus it holds promise for the design of emerging quantum and photonic systems. Nevertheless, fast and reversible control of symmetry in materials remains a challenge, especially for nanoscale systems. Here, reversible symmetry changes are unveiled in colloidal lead chalcogenide quantum dots on picosecond timescales. Using a combination of ultrafast electron diffraction and total X-ray scattering, in conjunction with atomic-scale structural modeling and first-principles calculations, it is revealed that symmetry-broken lead sulfide quantum dots restore to a centrosymmetric phase upon photoexcitation. The symmetry restoration is driven by photoexcited electronic carriers, which suppress lead off-centering for about 100 ps. Furthermore, the change in symmetry is closely correlated with the electronic properties, and the bandgap transiently red-shifts in the symmetry-restored quantum dots. Overall, this study elucidates reversible symmetry changes in colloidal quantum dots, and more broadly defines a new methodology to optically control symmetry in nanoscale systems on ultrafast timescales.

36 MATERIALS SCIENCE↗

Growth of lead tin telluride crystals in gels

Improved gels and several geometries were investigated for use in growing crystals. The use of lead sulfide test crystals proved workable, but it was impossible to obtain and maintain a sufficiently concentrated telluride ion solution to successfully grow lead telluride crystals. It appears that oxygen in the solution is capable of oxidizing the telluride ion up to tellurium metal. The method may still be successful, but only if precautions are taken to eliminate dissolved oxygen from the gels and aqueous solutions and to maintain a suitable concentration of telluride, Te(2)-(aq.).

Barber, Patrick G.↗

Comparison of Carbon XANES Spectra from an Iron Sulfide from Comet Wild 2 with an Iron Sulfide Interplanetary Dust Particle

Among one of the first particles removed from the aerogel collector from the Stardust sample return mission was an approx. 5 micron sized iron sulfide. The majority of the spectra from 5 different sections of this particle suggests the presence of aliphatic compounds. Due to the heat of capture in the aerogel we initially assumed these aliphatic compounds were not cometary but after comparing these results to a heated iron sulfide interplanetary dust particle (IDP) we believe our initial interpretation of these spectra was not correct. It has been suggested that ice coating on iron sulfides leads to aqueous alteration in IDP clusters which can then lead to the formation of complex organic compounds from unprocessed organics in the IDPs similar to unprocessed organics found in comets [1]. Iron sulfides have been demonstrated to not only transform halogenated aliphatic hydrocarbons but also enhance the bonding of rubber to steel [2,3]. Bromfield and Coville (1997) demonstrated using Xray photoelectron spectroscopy that "the surface enhancement of segregated sulfur to the surface of sulfided precipitated iron catalysts facilitates the formation of a low-dimensional structure of extraordinary properties" [4]. It may be that the iron sulfide acts in some way to protect aliphatic compounds from alteration due to heat.

Wirick, S.↗

Temperature-Controlled Reversible Formation and Phase Transformation of 3D Nanocrystal Superlattices Through In Situ Small-Angle X-ray Scattering

For decades, the spontaneous organization of nanocrystals into superlattices has captivated the scientific community. However, achieving direct control over the formation of the superlattice and its phase transformations has proven to be a grand challenge, often resulting in the generation of multiple symmetries under the same experimental conditions. Here, we achieve direct control over the formation of the superlattice and its phase transformations by modulating the thermal energy of a nanocrystal dispersion without relying on solvent evaporation. In this study, we follow the temperature-dependent dynamics of the self-assembly process using synchrotron-based small-angle X-ray scattering. When cooled below –24.5 °C, lead sulfide nanocrystals form micrometer-sized three-dimensional phase-pure body-centered cubic superlattices. When cooled below –35.1 °C, these superlattices undergo a collective diffusionless phase transformation that yields denser body-centered tetragonal phases. These structural changes can be reversed by increasing the temperature of the dispersion and may lead to the direct modulation of the optical properties of these artificial solids.

36 MATERIALS SCIENCE↗

Interpretation of the Jupiter red spot. I.

The LPL research programs on Jupiter include continuing photographic coverage of the planet in color and in several wavelength bands; IR image scans especially around 5 microns; medium and high-resolution spectral studies in the photographic and the lead-sulfide regions, with laboratory comparisons; photometric and polarimetric studies; far-IR measurements at high altitudes; chemical studies designed to match formation of Jovian cloud particles; and participation in the NASA Pioneer missions. Some preliminary interpretative remarks are given which are in part suggested by the remarkable IR spectra and IR images of the earth and Mars obtained at NASA-Goddard. This leads to a discussion of the Red Spot and the White Ovals.

Kuiper, G. P.↗

Tuning the Quantum Dot (QD)/Mediator Interface for Optimal Efficiency of QD-Sensitized Near-Infrared-to-Visible Photon Upconversion Systems

Lead sulfide (PbS) quantum dots (QDs) have shown promising performance as a sensitizer in infrared-to-visible photon upconversion systems. To investigate the key design rules, we compare three PbS-sensitized upconversion systems using three mediator molecules with the same tetracene triplet acceptor at different distances from the QD. Using transient absorption spectroscopy, we directly measure the triplet energy-transfer rates and efficiencies from the QD to the mediator and from the mediator to the emitter. With increasing distance between the mediator and PbS QD, the efficiency of the first triplet energy transfer from the QD to the mediator decreases because of a decrease in the rate of this triplet energy-transfer step, while the efficiency of the second triplet energy transfer from the mediator to the emitter increases because of a reduction in the QD-induced mediator triplet state decay. The latter effect is a result of the slow rate constant of the second triplet energy-transfer process, which is 3 orders of magnitude slower than the diffusion-limited value. The combined results lead to a net decrease of the steady-state upconversion quantum yield with distance, which could be predicted by our kinetic model. Our result shows that the QD/mediator interface affects both the first and second triplet energy transfer processes in the photon upconversion system, and the QD/mediator distance has an opposite effect on the efficiencies of the first and second triplet energy transfer. Lastly, these findings provide important insight for the further rational improvement of the overall efficiency of QD-based upconversion systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An artificial intelligence’s interpretation of complex high-resolution in situ transmission electron microscopy data

Complicated nano- and atomic-scale processes with sub-angstrom spatial resolution and millisecond time resolution visualized by in situ transmission electron microscopy (TEM) are often highly dynamical and time consuming to analyze and interpret. Here, we report how variational autoencoders (VAEs) can provide an artificial intelligence’s interpretation of high-resolution in situ TEM data by condensing and deconvoluting complicated atomic-scale dynamics into a latent space with reduced dimensionality. We designed a VAE model with high latent dimensions capable of deconvoluting information from complex high-resolution TEM data. We demonstrate how this model, with high latent dimensions trained on atomically resolved TEM images of lead sulfide (PbS) nanocrystals, is able to capture movements and perturbations of periodic lattices in both simulated and real in situ TEM data. Importantly, the VAE model shows the capability of detecting and deconvoluting dynamical nanoscale physical processes, such as the rotation of crystal lattices and intra-particle ripening during the annealing of semiconductor nanocrystals.

47 OTHER INSTRUMENTATION↗

Strong Structural and Electronic Coupling in Metavalent PbS Moiré Superlattices

Moiré superlattices are twisted bilayer materials in which the tunable interlayer quantum confinement offers access to new physics and novel device functionalities. Previously, moiré superlattices were built exclusively using materials with weak van der Waals interactions, and synthesizing moiré superlattices with strong interlayer chemical bonding was considered to be impractical. Here, in this study, using lead sulfide (PbS) as an example, we report a strategy for synthesizing moiré superlattices coupled by strong chemical bonding. We use water-soluble ligands as a removable template to obtain free-standing ultrathin PbS nanosheets and assemble them into direct-contact bilayers with various twist angles. Atomic-resolution imaging shows the moiré periodic structural reconstruction at the superlattice interface due to the strong metavalent coupling. Electron energy loss spectroscopy and theoretical calculations collectively reveal the twist-angle-dependent electronic structure, especially the emergent separation of flat bands at small twist angles. The localized states of flat bands are similar to well-arranged quantum dots, promising an application in devices. This study opens a new door to the exploration of deep energy modulations within moiré superlattices alternative to van der Waals twistronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The effect of water on colloidal quantum dot solar cells

Almost all surfaces sensitive to the ambient environment are covered by water, whereas the impacts of water on surface-dominated colloidal quantum dot (CQD) semiconductor electronics have rarely been explored. Here, strongly hydrogen-bonded water on hydroxylated lead sulfide (PbS) CQD is identified. The water could pilot the thermally induced evolution of surface chemical environment, which significantly influences the nanostructures, carrier dynamics, and trap behaviors in CQD solar cells. The aggravation of surface hydroxylation and water adsorption triggers epitaxial CQD fusion during device fabrication under humid ambient, giving rise to the inter-band traps and deficiency in solar cells. To address this problem, meniscus-guided-coating technique is introduced to achieve dense-packed CQD solids and extrude ambient water, improving device performance and thermal stability. Our works not only elucidate the water involved PbS CQD surface chemistry, but may also achieve a comprehensive understanding of the impact of ambient water on CQD based electronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Overcoming efficiency and cost barriers for large-area quantum dot photovoltaics through stable ink engineering

The bottom-up construction of electronics from colloidal quantum dots (CQDs) could innovate nanotechnology manufacturing through printing. However, the unstable and expensive semiconductive CQD inks make the scaling up of CQD electronics challenging. Here, in this study, we develop a strategy for engineering the solution chemistry of lead sulfide (PbS) CQD inks prepared from a low-cost direct synthesis method. By creating an iodine-rich environment in weakly coordinating solvents, we convert the iodoplumbates into functional anions, which condense into a robust surface shell. The fully charged electrostatic surface layer prevents aggregation and epitaxial fusion of CQDs, yielding stable inks. By eliminating the fusion-induced inter-band states, we print a compact CQD film with uniformity in three dimensions, flattened energy landscape and improved carrier transport. We achieved a certified efficiency of 13.40% on 0.04 cm 2 cells, with a 300-fold increase in active area, scaling up to a 12.60 cm 2 module with a certified efficiency of 10%.

14 SOLAR ENERGY↗

Hydrothermal Liquefaction of Structurally Diverse Lignins: Insights into Biocrude Yield, Fuel Properties, and Reaction Mechanisms

Lignin holds significant promise as a feedstock for biocrude production via hydrothermal liquefaction (HTL). Although lignin HTL has been widely studied, the specific depolymerization pathways associated with distinct lignin structures remain largely unexplored. This study investigates the HTL of four structurally diverse lignins: alkaline (AL), dealkaline (DAL), organosolv (OL), and lignosulfonate (LS) across 270–310 °C to elucidate structure-specific mechanisms governing biocrude yield and composition. AL and OL achieved the highest yields (16.8 ± 0.3% and 16.8 ± 2.5%), with AL-derived biocrude showing the highest carbon content (70.2 ± 0.0%) and HHV (31.0 ± 0.2 MJ/kg). In contrast, DAL and LS produced lower yields and inferior fuel quality due to higher sulfur content and lower carbon enrichment. The structures of AL and DAL, containing fewer methoxy groups, produced guaiacol-rich biocrudes (46.6% and 69.5%). Methylation in AL formed alkyl guaiacols and veratroles, while DAL favored side-chain oxidation. OL retained complex structures, forming syringols and desaspidinol, which contributed to heavier biocrude compounds. Sulfonate groups in LS were stabilized mostly as sulfides, leading to elevated sulfur content. These findings provide mechanistic insight into how lignin structure governs HTL behavior, enabling targeted control of biocrude yield and quality for renewable fuel production.

biocrude↗