Brain-like critical dynamics and long-range temporal correlations in percolating networks of silver nanoparticles and functionality preservation after integration of insulating matrix.

Random networks of nanoparticle-based memristive switches enable pathways for emulating highly complex and self-organized synaptic connectivity together with their emergent functional behavior known from biological neuronal networks. They therefore embody a distinct class of neuromorphic hardware architectures and provide an alternative to highly regular arrays of memristors. Especially, networks of memristive nanoparticles (NPs) poised at the percolation threshold are promising due to their capabilities of showing brain-like activity such as critical dynamics or long-range temporal correlation (LRTC), which are closely connected to the computational capabilities in biological neuronal networks. Here, we adapt this concept to networks of Ag-NPs poised at the electrical percolation threshold, where the memristive properties are governed by electro-chemical metallization. We show that critical dynamics and LRTC are preserved although the nature of individual memristive gaps throughout the network is fundamentally changed by filling the gaps with an insulating matrix. The results in this work generate important contributions towards the practical applicability of critical dynamics and LRTC in percolating NP networks by elucidating the consequences of NP network encapsulation, which is considered as an important step towards device integration.

Sparse CNT networks with implanted AgAu nanoparticles: A novel memristor with short-term memory bordering between diffusive and bipolar switching.

With this work we introduce a novel memristor in a lateral geometry whose resistive switching behaviour unifies the capabilities of bipolar switching with decelerated diffusive switching showing a biologically plausible short-term memory. A new fabrication route is presented for achieving lateral nano-scaled distances by depositing a sparse network of carbon nanotubes (CNTs) via spin-coating of a custom-made CNT dispersion. Electrochemical metallization-type (ECM) resistive switching is obtained by implanting AgAu nanoparticles with a Haberland-type gas aggregation cluster source into the nanogaps between the CNTs and shows a hybrid behaviour of both diffusive and bipolar switching. The resistance state resets to a high resistive state (HRS) either if the voltage is removed with a retention time in the second- to sub-minute scale (diffusive) or by applying a reverse voltage (bipolar). Furthermore, the retention time is positively correlated to the duration of the Set voltage pulse. The potential for low-voltage operation makes this approach a promising candidate for short-term memory applications in neuromorphic circuits. In addition, the lateral fabrication approach opens the pathway towards integrating sensor-functionality and offers a general starting point for the scalable fabrication of nanoscaled devices.

Revealing the growth of copper on polystyrene-block-poly(ethylene oxide) diblock copolymer thin films with in situ GISAXS.

Copper (Cu) as an excellent electrical conductor and the amphiphilic diblock copolymer polystyrene-block-poly(ethylene oxide) (PS-b-PEO) as a polymer electrolyte and ionic conductor can be combined with an active material in composite electrodes for polymer lithium-ion batteries (LIBs). As interfaces are a key issue in LIBs, sputter deposition of Cu contacts on PS-b-PEO thin films with high PEO fraction is investigated with in situ grazing-incidence small-angle X-ray scattering (GISAXS) to follow the formation of the Cu layer in real-time. We observe a hierarchical morphology of Cu clusters building larger Cu agglomerates. Two characteristic distances corresponding to the PS-b-PEO microphase separation and the Cu clusters are determined. A selective agglomeration of Cu clusters on the PS domains explains the origin of the persisting hierarchical morphology of the Cu layer even after a complete surface coverage is reached. The spheroidal shape of the Cu clusters growing within the first few nanometers of sputter deposition causes a highly porous Cu-polymer interface. Four growth stages are distinguished corresponding to different kinetics of the cluster growth of Cu on PS-b-PEO thin films: (I) nucleation, (II) diffusion-driven growth, (III) adsorption-driven growth, and (IV) grain growth of Cu clusters. Percolation is reached at an effective Cu layer thickness of 5.75 nm.

Tailoring the Optical Properties of Sputter-Deposited Gold Nanostructures on Nanostructured Titanium Dioxide Templates Based on In Situ Grazing-Incidence Small-Angle X-ray Scattering Determined Growth Laws.

Gold/titanium dioxide (Au/TiO2) nanohybrid materials have been widely applied in various fields because of their outstanding optical and photocatalytic performance. By state-of-the-art polymer templating, it is possible to make uniform nanostructured TiO2 layers with potentially large-scale processing methods. We use customized polymer templating to achieve TiO2 nanostructures with different morphologies. Au/TiO2 hybrid thin films are fabricated by sputter deposition. An in-depth understanding of the Au morphology on the TiO2 templates is achieved with in situ grazing-incidence small-angle X-ray scattering (GISAXS) during the sputter deposition. The resulting Au nanostructure is largely influenced by the TiO2 template morphology. Based on the detailed understanding of the Au growth process, characteristic distances can be selected to achieve tailored Au nanostructures at different Au loadings. For selected sputter-deposited Au/TiO2 hybrid thin films, the optical response with a tailored localized surface plasmon resonance is demonstrated.

Enhancing Reliability of Studies on Single Filament Memristive Switching via an Unconventional cAFM Approach.

Memristive devices are highly promising for implementing neuromorphic functionalities in future electronic hardware, and direct insights into memristive phenomena on the nanoscale are of fundamental importance to reaching this. Conductive atomic force microscopy (cAFM) has proven to be an essential tool for probing memristive action locally on the nanoscale, but the significance of the acquired data frequently suffers from the nonlocality associated with the thermal drift of the tip in ambient conditions. Furthermore, comparative studies of different configurations of filamentary devices have proven to be difficult, because of an immanent variability of the filament properties between different devices. Herein, these problems are addressed by constraining the memristive action directly at the apex of the probe through functionalization of a cAFM tip with an archetypical memristive stack, which is comprised of Ag/Si3N4. The design of such functionalized cantilevers (entitled here as "memtips") allowed the capture of the long-term intrinsic current response, identifying temporal correlations between switching events, and observing emerging spiking dynamics directly at the nanoscale. Utilization of an identical memtip for measurements on different counter electrodes made it possible to directly compare the impact of different device configurations on the switching behavior of the same filament. Such an analytical approach in ambient conditions will pave the way towards a deeper understanding of filamentary switching phenomena on the nanoscale.

Real-time insight into nanostructure evolution during the rapid formation of ultra-thin gold layers on polymers.

Ultra-thin metal layers on polymer thin films attract tremendous research interest for advanced flexible optoelectronic applications, including organic photovoltaics, light emitting diodes and sensors. To realize the large-scale production of such metal-polymer hybrid materials, high rate sputter deposition is of particular interest. Here, we witness the birth of a metal-polymer hybrid material by quantifying in situ with unprecedented time-resolution of 0.5 ms the temporal evolution of interfacial morphology during the rapid formation of ultra-thin gold layers on thin polystyrene films. We monitor average non-equilibrium cluster geometries, transient interface morphologies and the effective near-surface gold diffusion. At 1 s sputter deposition, the polymer matrix has already been enriched with 1% gold and an intermixing layer has formed with a depth of over 3.5 nm. Furthermore, we experimentally observe unexpected changes in aspect ratios of ultra-small gold clusters growing in the vicinity of polymer chains. For the first time, this approach enables four-dimensional insights at atomic scales during the gold growth under non-equilibrium conditions.

Diffusive Memristive Switching on the Nanoscale, from Individual Nanoparticles towards Scalable Nanocomposite Devices.

Nanoscale memristive phenomena are of great interest not only to miniaturize devices and improve their performance but also to understand the details of the underlying mechanism. Herein, we utilize conductive atomic force microscopy (C-AFM) as a non-invasive method to examine the nanoscale memristive properties of individual noble metal alloy nanoparticles that are sparsely encapsulated in a thin SiO2 dielectric matrix. The measurement of current-voltage hysteresis loops at the level of individual nanoparticles, enabled by the nanoscopic contact area of the C-AFM tip, indicates reliable memristive switching for several hours of continuous operations. Alongside the electrical characterization on the nanoscale, the method of C-AFM offers the potential for in situ monitoring of long term operation induced morphological alterations and device failure, which is demonstrated at the example of nanoparticle-based devices with additional Cr wetting layer. The application of alloy nanoparticles as reservoir for mobile silver species effectively limits the formation of stable metallic filaments and results in reproducible diffusive switching characteristics. Notably, similar behaviour is encountered on macroscopic nanocomposite devices, which incorporate multiple stacks of nanoparticles and offer a high design versatility to tune switching properties and engineer scalable memristive devices with diffusive switching characteristics. No additional forming step is required for the operation of the presented alloy nanoparticle based memristive devices, which renders them very attractive for applications.