Redox-driven conductance changes are critical processes in molecular- and coordination-complex-based memristive thin films and devices that are envisioned for neuromorphic technologies, but fundamental mechanisms of conductance switching are not fully understood. Here, we explore charge disproportionation (CD) processes in [RuIIL2](PF6)2 molecular systems that intrinsically involve interfragment charge transfer (IFCT). Using a combination of ab initio molecular dynamics simulation (AIMD), time-dependent density functional theory (TD-DFT), and density functional theory (DFT) calculations, we investigate the electron transfer mechanisms and the roles of temperature and cell volumetric expansion in facilitating the counterion movements and electronic transitions required for low-cost IFCT and charge redistribution. A detailed analysis of the density of states and TD-DFT calculations highlights that unpaired electrons play a crucial role in low-energy transitions, with the azo (N═N) groups of the ligand serving as the primary sites for electronic transport between molecular fragments, further stabilizing the asymmetric state. Localization of added electrons on azo ligands occurs with negligible change at the Ru centers, supported by atomic volume expansions up to +4.74 bohr3, and goes along with a progressive reduction of the HOMO–LUMO gap across redox states, suggesting enhanced conductivity. The TD-DFT analysis reveals a dominant IFCT excitation at 2082.76 nm in the doubly reduced (22) state, while a stabilization energy of 1.20 eV of the asymmetric (13) state relative to the symmetric (22) state is predicted by constrained DFT. Periodic DFT and AIMD simulations emulating a molecular film show that the stabilization of the asymmetric state, relative to a symmetric one, translates in net charge separation values (order of ∼0.33 e) that are strongly linked to increased counterion mobility (average counterion displacements exceeding 0.7 Å per atom during CD events) and the involvement of azo groups in electron redistribution. These findings, which align with previously reported experimental and computational data, provide key insights into the IFCT mechanisms and electronic transport facilitated by azo groups, with important implications for redox-driven memristive and neuromorphic technologies.
Publications
Mechanisms enabling reconfigurability and long-term retention in vanadium oxide electrochemical memory
August 6, 2025
Phase coexistence in nanoscale electrochemical random-access memory (ECRAM) has recently been demonstrated to enable both information storage and extraordinary reconfigurability. These proof-of-principle demonstrations have left the mechanistic details of such a process unresolved. Particularly, the mechanisms that stabilize the multiple phases, and the underlying processes behind sustained memory retention, remain unclear, and are necessary to design such devices. Here we report microscale ECRAM devices composed of VO𝑥, which enables us to directly probe the active region in an operando fashion using optical techniques. Using Raman mapping, we show the phase coexistence driven by the electrochemical injection of O vacancies to be spatially uniform (i.e., with no filaments). The stability was observed to be unusually long, with 1% loss over 14 years in ambient conditions. First-principles calculations of the oxygen vacancy formation energies in VO𝑥 further support the thermodynamic coexistence of multiple VO𝑥 phases and clarify the origin of the observed long-term retention in the ECRAM devices. Further, we demonstrate single devices that can be voltage programmed to exhibit synaptic, neuronal, and reconfigurable logic gate functionalities. Therefore, we not only uncover the phase coexistence mechanism that may help device design, but also demonstrate the circuit-level applications of reconfigurability.
Materials Selection Principles for Designing Electro-Thermal Neurons
Artificial neurons exhibiting volatile threshold switching and action potential-like oscillations are crucial for brain-inspired computing. While Complimentary Metal-Oxide-Semiconductor (CMOS)-based strategies require hundreds of transistors to simulate each neuron, neuronal oscillations arise spontaneously in individual electro-thermal devices due to nonlinearities like the Mott transition in VO2. Despite improved understanding of the physics, quantitative connections between neuronal performance and material properties remain under-explored, preventing predictive neuron design and rational materials selection. In this work, a physics-aware forward design methodology is developed for interrogating a wide palette of materials with properties varying by orders of magnitude, and their performance (high frequency, high dynamical reconfigurability and low power) under external circuit and device geometry constraints is assessed. The space of viable materials is identified to be much larger than previously recognized, with candidates from a range of materials classes, including Ge, GaP and MoS2. CMOS-compatible performance (such as 100 GHz oscillating frequencies) can be achieved with CMOS-compatible node sizes (≈10 nm). Finally, combinations of material properties yielding desired neuronal performance under uncertain design constraints are considered. This work solidifies forward design principles for electro-thermal neuron devices, a necessary pre-condition for inverse design from desired neuronal performance to required materials properties.
Localized Conduction Channels in Memristors
Localized Conduction Channels in Memristors
December 19, 2024
Since the early 2000s, the impending end of Moore’s scaling, as the physical limits to shrinking transistors have been approached, has fueled interest in improving the functionality and efficiency of integrated circuits by employing memristors or two-terminal resistive switches. Formation (or avoidance) of localized conducting channels in many memristors, often called “filaments”, has been established as the basis for their operation. While we understand some qualitative aspects of the physical and thermodynamic origins of conduction localization, there are not yet quantitative models that allow us to predict when they will form or how large they will be. Here we compile observations and explanations of channel formation that have appeared in the literature since the 1930s, show how many of these seemingly unrelated pieces fit together, and outline what is needed to complete the puzzle. This understanding will be a necessary predictive component for the design and fabrication of post-Moore’s-era electronics.
Electrically-Driven Metal-Insulator Transitions Emerging from Localizing Current Density and Temperature
March 27, 2025
Negative differential resistance (NDR) is a key electronic response enabling two-terminal artificial neurons that can be achieved through different physical phenomena, including phase-homogeneous current density and temperature (electro-thermal) localizations and spatially-localized metal-insulator phase transitions (MITs). These two effects have been observed to occur sequentially in select electrically-biased transition metal oxides. However, it is unknown why and under what conditions localizing behaviors precede MITs, particularly as a function of device length scale. To this end, the interplay between phase-homogeneous electro-thermal localizations and MITs is investigated in a 3D multiphysics simulation of a lateral thin film device, using the material properties of the prototype MIT material VO2. These findings demonstrate that the MIT is nucleated through dynamically localizing current density and temperature. A critical device width (≈0.7 µm in this study) is identified, below which both the electrically-induced electro-thermal and phase inhomogeneities cease to appear. It is demonstrated that the formation of spatial inhomogeneities directly relates to device dimensions, and demonstrate the decoupling of NDR from the MIT through device scaling relationships. These results provide insight into the material phenomena underlying the material’s electrical responses, clarifying conditions under which spatial inhomogeneities form in electrically-biased MIT materials.
Memristors with Tunable Volatility for Reconfigurable Neuromorphic Computing
Neuromorphic computing promises an energy-efficient alternative to traditional digital processors in handling data-heavy tasks, primarily driven by the development of both volatile (neuronal) and nonvolatile (synaptic) resistive switches or memristors. However, despite their energy efficiency, memristor-based technologies presently lack functional tunability, thus limiting their competitiveness with arbitrarily programmable (general purpose) digital computers. This work introduces a two-terminal bilayer memristor, which can be tuned among neuronal, synaptic, and hybrid behaviors. The varying behaviors are accessed via facile control over the filament formed within the memristor, enabled by the interplay between the two active ionic species (oxygen vacancies and metal cations). This solution is unlike single-species ion migration employed in most other memristors, which makes their behavior difficult to control. By reconfiguring a single crossbar array of hybrid memristors, two different applications that usually require distinct types of devices are demonstrated – reprogrammable heterogeneous reservoir computing and arbitrary non-Euclidean graph networks. Thus, this work outlines a potential path toward functionally reconfigurable postdigital computers.
Tunable stochastic memristors for energy-efficient encryption and computing
Information security and computing, two critical technological challenges for post-digital computation, pose opposing requirements – security (encryption) requires a source of unpredictability, while computing generally requires predictability. Each of these contrasting requirements presently necessitates distinct conventional Si-based hardware units with power-hungry overheads. This work demonstrates Cu0.3Te0.7/HfO2 (‘CuTeHO’) ion-migration-driven memristors that satisfy the contrasting requirements. Under specific operating biases, CuTeHO memristors generate truly random and physically unclonable functions, while under other biases, they perform universal Boolean logic. Using these computing primitives, this work experimentally demonstrates a single system that performs cryptographic key generation, universal Boolean logic operations, and encryption/decryption. Circuit-based calculations reveal the energy and latency advantages of the CuTeHO memristors in these operations. This work illustrates the functional flexibility of memristors in implementing operations with varying component-level requirements.
Mott neurons with dual thermal dynamics for spatiotemporal computing
Heat dissipation is a natural consequence of operating any electronic system. In nearly all computing systems, such heat is usually minimized by design and cooling. Here, we show that the temporal dynamics of internally produced heat in electronic devices can be engineered to both encode information within a single device and process information across multiple devices. In our demonstration, electronic NbOx Mott neurons, integrated on a flexible organic substrate, exhibit 18 biomimetic neuronal behaviours and frequency-based nociception within a single component by exploiting both the thermal dynamics of the Mott transition and the dynamical thermal interactions with the organic substrate. Further, multiple interconnected Mott neurons spatiotemporally communicate purely via heat, which we use for graph optimization by consuming over 106 times less energy when compared with the best digital processors. Thus, exploiting natural thermal processes in computing can lead to functionally dense, energy-efficient and radically novel mixed-physics computing primitives.
True random number generation using the spin crossover in LaCoO3
While digital computers rely on software-generated pseudo-random number generators, hardware-based true random number generators (TRNGs), which employ the natural physics of the underlying hardware, provide true stochasticity, and power and area efficiency. Research into TRNGs has extensively relied on the unpredictability in phase transitions, but such phase transitions are difficult to control given their often abrupt and narrow parameter ranges (e.g., occurring in a small temperature window). Here we demonstrate a TRNG based on self-oscillations in LaCoO3 that is electrically biased within its spin crossover regime. The LaCoO3 TRNG passes all standard tests of true stochasticity and uses only half the number of components compared to prior TRNGs. Assisted by phase field modeling, we show how spin crossovers are fundamentally better in producing true stochasticity compared to traditional phase transitions. As a validation, by probabilistically solving the NP-hard max-cut problem in a memristor crossbar array using our TRNG as a source of the required stochasticity, we demonstrate solution quality exceeding that using software-generated randomness.
Axon-like active signal transmission
Axon-like Active Signal Transmission
September 11, 2024
Any electrical signal propagating in a metallic conductor loses amplitude due to the natural resistance of the metal. Compensating for such losses presently requires repeatedly breaking the conductor and interposing amplifiers that consume and regenerate the signal. This century-old primitive severely constrains the design and performance of modern interconnect-dense chips1. Here we present a fundamentally different primitive based on semi-stable edge of chaos (EOC)2,3, a long-theorized but experimentally elusive regime that underlies active (self-amplifying) transmission in biological axons4,5. By electrically accessing the spin crossover in LaCoO3, we isolate semi-stable EOC, characterized by small-signal negative resistance and amplification of perturbations6,7. In a metallic line atop a medium biased at EOC, a signal input at one end exits the other end amplified, without passing through a separate amplifying component. While superficially resembling superconductivity, active transmission offers controllably amplified time-varying small-signal propagation at normal temperature and pressure, but requires an electrically energized EOC medium. Operando thermal mapping reveals the mechanism of amplification—bias energy of the EOC medium, instead of fully dissipating as heat, is partly used to amplify signals in the metallic line, thereby enabling spatially continuous active transmission, which could transform the design and performance of complex electronic chips.