High-performance one-dimensional halide perovskite crossbar memristors and synapses for neuromorphic computing.

Despite impressive demonstrations of memristive behavior with halide perovskites, no clear pathway for material and device design exists for their applications in neuromorphic computing. Present approaches are limited to single element structures, fall behind in terms of switching reliability and scalability, and fail to map out the analog programming window of such devices. Here, we systematically design and evaluate robust pyridinium-templated one-dimensional halide perovskites as crossbar memristive materials for artificial neural networks. We compare two halide perovskite 1D inorganic lattices, namely (propyl)pyridinium and (benzyl)pyridinium lead iodide. The absence of conjugated, electron-rich substituents in PrPyr+ prevents edge-to-face type π-stacking, leading to enhanced electronic isolation of the 1D iodoplumbate chains in (PrPyr)[PbI3], and hence, superior resistive switching performance compared to (BnzPyr)[PbI3]. We report outstanding resistive switching behaviours in (PrPyr)[PbI3] on the largest flexible crossbar implementation (16 × 16) to date - on/off ratio (>105), long term retention (105 s) and high endurance (2000 cycles). Finally, we put forth a universal approach to comprehensively map the analog programming window of halide perovskite memristive devices - a critical prerequisite for weighted synaptic connections in artificial neural networks. This consequently facilitates the demonstration of accurate handwritten digit recognition from the MNIST database based on spike-timing-dependent plasticity of halide perovskite memristive synapses.

Photocatalysis Based on Metal Halide Perovskites for Organic Chemical Transformations.

Heterogeneous photocatalysts incorporating metal halide perovskites (MHPs) have garnered significant attention due to their remarkable attributes: strong visible-light absorption, tuneable band energy levels, rapid charge transfer, and defect tolerance. Additionally, the promising optical and electronic properties of MHP nanocrystals can be harnessed for photocatalytic applications through controlled crystal structure engineering, involving composition tuning via metal ion and halide ion variations, dimensional tuning, and surface chemistry modifications. Combination of perovskites with other materials can improve the photoinduced charge separation and charge transfer, building heterostructures with different band alignments, such as type-II, Z-scheme, and Schottky heterojunctions, which can fine-tune redox potentials of the perovskite for photocatalytic organic reactions. This review delves into the activation of organic molecules through charge and energy transfer mechanisms. The review further investigates the impact of crystal engineering on photocatalytic activity, spanning a diverse array of organic transformations, such as C-X bond formation (X = C, N, and O), [2 + 2] and [4 + 2] cycloadditions, substrate isomerization, and asymmetric catalysis. This study provides insights to propel the advancement of metal halide perovskite-based photocatalysts, thereby fostering innovation in organic chemical transformations.

One-Pot Synthesis and Structural Evolution of Colloidal Cesium Lead Halide-Lead Sulfide Heterostructure Nanocrystals for Optoelectronic Applications.

Heterostructures, combining perovskite nanocrystals (PNC) and chalcogenide quantum dots, could pave a path to optoelectronic device applications by enabling absorption in the near-infrared region, tailorable electronic properties, and stable crystal structures. Ideally, the heterostructure host material requires a similar lattice constant as the guest which is also constrained by the synthesis protocol and materials selectivity. Herein, we present an efficient one-pot hot-injection method to synthesize colloidal all-inorganic cesium lead halide-lead sulfide (CsPbX3 (X = Cl, Br, I)-PbS) heterostructure nanocrystals (HNCs) via the epitaxial growth of the perovskite onto the presynthesized PbS nanocrystals (NCs). Optical and structural characterization evidenced the formation of heterostructures. The embedding of PbS NCs into CsPbX3 perovskite allows the tuning of the absorption and emission from 400 to 1100 nm by tuning the size and composition of perovskite HNCs. The CsPbI3-PbS HNCs show enhanced stability in ambient conditions. The stability, tunable optical properties, and variable band alignments accessible in this system would have implications in the design of novel optoelectronic applications such as light-emitting diodes, photodetectors, photocatalysis, and photovoltaics.

Halide perovskite memristors as flexible and reconfigurable physical unclonable functions.

Physical Unclonable Functions (PUFs) address the inherent limitations of conventional hardware security solutions in edge-computing devices. Despite impressive demonstrations with silicon circuits and crossbars of oxide memristors, realizing efficient roots of trust for resource-constrained hardware remains a significant challenge. Hybrid organic electronic materials with a rich reservoir of exotic switching physics offer an attractive, inexpensive alternative to design efficient cryptographic hardware, but have not been investigated till date. Here, we report a breakthrough security primitive exploiting the switching physics of one dimensional halide perovskite memristors as excellent sources of entropy for secure key generation and device authentication. Measurements of a prototypical 1 kb propyl pyridinium lead iodide (PrPyr[PbI3]) weak memristor PUF with a differential write-back strategy reveals near ideal uniformity, uniqueness and reliability without additional area and power overheads. Cycle-to-cycle write variability enables reconfigurability, while in-memory computing empowers a strong recurrent PUF construction to thwart machine learning attacks.

Electrical and Plasmonic Properties of Ligand-Free Sn(4+) -Doped In2 O3 (ITO) Nanocrystals.

Sn(4+) -doped In2 O3 (ITO) is a benchmark transparent conducting oxide material. We prepared ligand-free but colloidal ITO (8 nm, 10 % Sn(4+) ) nanocrystals (NCs) by using a post-synthesis surface-modification reaction. (CH3 )3 OBF4 removes the native oleylamine ligand from NC surfaces to give ligand-free, positively charged NCs that form a colloidal dispersion in polar solvents. Both oleylamine-capped and ligand-free ITO NCs exhibit intense absorption peaks, due to localized surface plasmon resonance (LSPR) at around λ=1950 nm. Compared with oleylamine-capped NCs, the electrical resistivity of ligand-free ITO NCs is lower by an order of magnitude (≈35 mΩ cm(-1) ). Resistivity over a wide range of temperatures can be consistently described as a composite of metallic ITO grains embedded in an insulating matrix by using a simple equivalent circuit, which provides an insight into the conduction mechanism in these systems.