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.

Ion-Mediated Recombination Dynamics in Perovskite-Based Memory Light-Emitting Diodes for Neuromorphic Control Systems.

Neuromorphic devices can help perform memory-heavy tasks more efficiently due to the co-localization of memory and computing. In biological systems, fast dynamics are necessary for rapid communication, while slow dynamics aid in the amplification of signals over noise and regulatory processes such as adaptation- such dual dynamics are key for neuromorphic control systems. Halide perovskites exhibit much more complex phenomena than conventional semiconductors due to their coupled ionic, electronic, and optical properties which result in modulatable drift, diffusion of ions, carriers, and radiative recombination dynamics. This is exploited to engineer a dual-emitter tandem device with the requisite dual slow-fast dynamics. Here, a perovskite-organic tandem light-emitting diode (LED) capable of modulating its emission spectrum and intensity owing to the ion-mediated recombination zone modulation between the green-emitting quasi-2D perovskite layer and the red-emitting organic layer is introduced. Frequency-dependent response and high dynamic range memory of emission intensity and spectra in a LED are demonstrated. Utilizing the emissive read-out, image contrast enhancement as a neuromorphic pre-processing step to improve pattern recognition capabilities is illustrated. As proof of concept using the device's slow-fast dynamics, an inhibition of the return mechanism is physically emulated.

Reversible Photochromism in ⟨110⟩ Oriented Layered Halide Perovskite.

Extending halide perovskites' optoelectronic properties to stimuli-responsive chromism enables switchable optoelectronics, information display, and smart window applications. Here, we demonstrate a band gap tunability (chromism) via crystal structure transformation from three-dimensional FAPbBr3 to a ⟨110⟩ oriented FAn+2PbnBr3n+2 structure using a mono-halide/cation composition (FA/Pb) tuning. Furthermore, we illustrate reversible photochromism in halide perovskite by modulating the intermediate n phase in the FAn+2PbnBr3n+2 structure, enabling greater control of the optical band gap and luminescence of a ⟨110⟩ oriented mono-halide/cation perovskite. Proton transfer reaction-mass spectroscopy carried out to precisely quantify the decomposition product reveals that the organic solvent in the film is a key contributor to the structural transformation and, therefore, the chromism in the ⟨110⟩ structure. These intermediate n phases (2 ≤ n ≤ ∞) stabilize in metastable states in the FAn+2PbnBr3n+2 system, which is accessible via strain or optical or thermal input. The structure reversibility in the ⟨110⟩ perovskite allowed us to demonstrate a class of photochromic sensors capable of self-adaptation to lighting.

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.

Field-Driven Athermal Activation of Amorphous Metal Oxide Semiconductors for Flexible Programmable Logic Circuits and Neuromorphic Electronics.

Despite extensive research, large-scale realization of metal-oxide electronics is still impeded by high-temperature fabrication, incompatible with flexible substrates. Ideally, an athermal treatment modifying the electronic structure of amorphous metal oxide semiconductors (AMOS) to generate sufficient carrier concentration would help mitigate such high-temperature requirements, enabling realization of high-performance electronics on flexible substrates. Here, a novel field-driven athermal activation of AMOS channels is demonstrated via an electrolyte-gating approach. Facilitating migration of charged oxygen species across the semiconductor-dielectric interface, this approach modulates the local electronic structure of the channel, generating sufficient carriers for charge transport and activating oxygen-compensated thin films. The thin-film transistors (TFTs) investigated here depict an enhancement of linear mobility from 51 to 105.25 cm2 V-1 s-1 (ionic-gated) and from 8.09 to 14.49 cm2 V-1 s-1 (back-gated), by creating additional oxygen vacancies. The accompanying stochiometric transformations, monitored via spectroscopic measurements (X-ray photoelectron spectroscopy) corroborate the detailed electrical (TFT, current evolution) parameter analyses, providing critical insights into the underlying oxygen-vacancy generation mechanism and clearly demonstrating field-induced activation as a promising alternative to conventional high-temperature annealing strategies. Facilitating on-demand active programing of the operation modes of transistors (enhancement vs depletion), this technique paves way for facile fabrication of logic circuits and neuromorphic transistors for bioinspired computing.