Cluster-assembled Films Research Articles

Efficiency and controllability of stochastic boolean function generation by a random network of non-linear nanoparticle junctions

Amid efforts to address energy consumption in modern computing systems, one promising approach takes advantage of random networks of non-linear nanoscale junctions formed by nanoparticles as substrates for neuromorphic computing. These networks exhibit emergent complexity and collective behaviors akin to biological neural networks, characterized by self-organization, redundancy, and non-linearity. Based on this foundation, a generalization of n-inputs devices has been proposed, where the associated weights depend on all the input values. This model, called receptron, has demonstrated its capability to generate Boolean functions as output, representing a significant breakthrough in unconventional computing methods. In this work, we characterize and present two actual implementations of this paradigm. One approach leverages the nanoscale properties of cluster-assembled Au films, while the other utilizes the recently introduced Stochastic Resistor Network (SRN) model. We first provide a concise overview of the electrical properties of these systems, emphasizing the insights gained from the SRN regarding the physical processes within real nanostructured gold films at a coarse-grained scale. Furthermore, we present evidence indicating the minimum complexity level required by the SRN model to achieve a stochastic dynamics adequate to effectively model a novel component for logic systems. To support our argument that these systems are preferable to conventional random search algorithms, we discuss quantitative criteria based on Information-theoretic tools. This suggests a practical means to steer the stochastic dynamics of the system in a controlled way, thus focusing its random exploration where it is most useful.

The role of coalescence and ballistic growth on in-situ electrical conduction of cluster-assembled nanostructured Sn films

The electrical conduction of nanostructured Sn films assembled via Supersonic Cluster Beam Deposition is studied in-situ during film growth. The kinetic energy of Sn nanoparticles, in combination with low melting point of Sn, promotes coalescence phenomena, enabling the investigation of their impact on film morphology and on percolation threshold. A percolation threshold occurring at thicknesses much larger than the dimensions of Sn nanoparticles suggests that coalescence leads to the growth of disconnected, island-like structures. The deposition rate is found to influence coalescence dynamics during the early stages of film growth, allowing for the tuning of film microstructure from a more compact, island-like morphology to a more porous structure. The percolation threshold shifts accordingly from 24 nm to 3 nm film thickness. Upon completion of the percolation phase, film resistivity settles at values 2–3 orders of magnitude larger than that of bulk Sn, attributed to the nanogranular nature of cluster-assembled films. During the “3D conduction” phase, resistivity exhibits an increasing trend with thickness following a power law with an exponent value of 0.76–0.78. This behavior is attributed to the decrease in the density of interconnections between particles in the topmost layer during film growth, consistent with expectations in ballistic growth processes.

In Situ TEM Investigation of Thermally Induced Modifications of Cluster-Assembled Gold Films Undergoing Resistive Switching: Implications for Nanostructured Neuromorphic Devices

<i>In Situ</i> TEM Investigation of Thermally Induced Modifications of Cluster-Assembled Gold Films Undergoing Resistive Switching: Implications for Nanostructured Neuromorphic Devices

Intermediate tin oxide in stable core-shell structures by room temperature oxidation of cluster-assembled nanostructured Sn films

Room temperature oxidation of cluster-assembled nanostructured Sn films obtained by supersonic cluster beam deposition was investigated. Sn clusters smaller than about 10 nm are observed to be fully oxidized while in larger ones, as well as in Sn islands formed by clusters coalescence, completion of Cabrera-Mott process is prevented resulting in partial oxidation. Core-shell structures are therefore obtained, with shell thickness of about 4 nm. Core is composed by highly ordered, tetragonal β-tin, with micro-strain of 0.16 %, while shell is composed of tin oxides, where similar quantity of both Sn oxidation states Sn2+ and Sn4+ are observed, according to XPS. The presence in the samples of metallic tin, SnO, and SnO2 is confirmed by valence band photoelectron spectrum, whose components show edges at 0, 0.6, and 3.2 eV from Fermi level, respectively. Raman spectroscopy highlights the presence of Sn3O4 (short version of Sn2+2O2Sn4+O2), which confirms the spontaneous formation of this intermediate oxide. It is therefore proposed that an oxidation gradient Sn-SnO-Sn3O4-SnO2 characterizes core-shell system resulting from room temperature Cabrera-Mott oxidation of cluster-assembled nanostructured films.

Engineering the structural and electrical interplay of nanostructured Au resistive switching networks by controlling the forming process

Networks of random-assembled gold clusters produced in the gas phase show resistive switching (RS) activity at room temperature and they are suitable for the fabrication of devices for neuromorphic data processing and classification. Fully connected cluster-assembled nanostructured Au films are characterized by a granular structure rich of interfaces, grain boundaries and crystalline defects. Here we report a systematic characterization of the electroforming process of the cluster-assembled films demonstrating how this process affects the interplay between the nano- and mesoscale film structure and the neuromorphic characteristics of the resistive switching activity. The understanding and the control of the influence of the resistive switching forming process on the organization of specific structures at different scales of the cluster-assembled films, provide the possibility to engineer random-assembled neuromorphic architectures for data processing task.

Energetically deposited cluster assembly of metallic glasses

Metallic glasses, prepared by rapid quenching and ball milling, have been studied extensively for decades. Nevertheless, they are not as well understood as crystalline materials in terms of structure and local atomic packing. The assembly of amorphous nanoclusters by energetic deposition has recently been shown as an alternative route to synthesize amorphous films. Furthermore, the local atomic structures of these cluster-assembled films were found to be different from that of the rapidly quenched metallic glass of the same composition. However, the underlying mechanisms, which result in these novel structures of the cluster-assembled films are hitherto unknown. An atomistic molecular dynamics study of the formation of Cu50Zr50 cluster-assembled metallic glass films is presented. Two amorphous phases are identified: one in the cores of the clusters, and the other in the continuous network of interfaces formed amongst the clusters. These two phases are chemically distinct from one other and also different from the rapidly quenched metallic glasses. An increased short-range order is observed in the interfaces, while the cores occupy lower energy states. The present results further demonstrate that the amorphous short- and medium-range orders of cluster-assembled glasses not only differ from rapidly quenched glass of the same macroscopic composition, but can be tailored by the variation of the deposition energy.

Cluster-Assembled Nanoporous Super-Hydrophilic Smart Surfaces for On-Target Capturing and Processing of Biological Samples for Multi-Dimensional MALDI-MS.

Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) on cluster-assembled super-hydrophilic nanoporous titania films deposited on hydrophobic conductive-polymer substrates feature a unique combination of surface properties that significantly improve the possibilities of capturing and processing biological samples before and during the MALDI-MS analysis without changing the selected sample target (multi-dimensional MALDI-MS). In contrast to pure hydrophobic surfaces, such films promote a remarkable biologically active film porosity at the nanoscale due to the soft assembling of ultrafine atomic clusters. This unique combination of nanoscale porosity and super-hydrophilicity provides room for effective sample capturing, while the hydrophilic-hydrophobic discontinuity at the border of the dot-patterned film acts as a wettability-driven containment for sample/reagent droplets. In the present work, we evaluate the performance of such advanced surface engineered reactive containments for their benefit in protein sample processing and characterization. We shortly discuss the advantages resulting from the introduction of the described chips in the MALDI-MS workflow in the healthcare/clinical context and in MALDI-MS bioimaging (MALDI-MSI).

Influence of the nanostructure on the electric transport properties of resistive switching cluster-assembled gold films

The use of Au clusters produced in the gas phase and deposited at low kinetic energy on a substrate allows the bottom-up fabrication of nanostructured metallic thin films with an extremely large number of interfaces, grain boundary junctions and crystal lattice defects. Cluster-assembled gold films exhibit non-ohmic electrical transport properties with a complex resistive switching behavior, exploring discrete resistance states which depend on their structural features (average thickness, resistance value reached on the percolation curve). Their electric conduction properties can be modelled in terms of complex networks of nanojunctions and used to perform binary classification of Boolean functions. The fabrication of devices based on cluster-assembled Au films and exploiting emergent complexity and collective phenomena requires a deep understanding of the influence of the nanoscale structure on the fundamental mechanisms of electrical conduction. Here we present a detailed study of the correlation between the nanostructure and the electrical properties of cluster-assembled gold films by a systematic characterization of the film growth from sub-monolayer to continuous layer beyond the electrical percolation threshold. The influence of different cluster size distributions on the onset of the electrical conduction and the role of defects is investigated by combining in situ and ex situ electrical and structural characterizations.

Modeling charge transport in gold nanogranular films

Cluster-assembled metallic films show interesting electrical properties, both in the near-to-percolation regime, when deposited clusters do not form a complete layer yet, and when the film thickness is well above the electrical percolation threshold. Correctly estimating their electrical conductivity is crucial, but, particularly for the latter regime, standard theoretical tools are not quite adequate. We therefore developed a procedure based on an atomically informed mesoscopic model in which ab-initio estimates of electronic transport at the nanoscale are used to reconstruct the conductivity of nanogranular gold films generated by molecular dynamics. An equivalent resistor network is developed, appropriately accounting for ballistic transport. The method is shown to correctly capture the non-monotonic behavior of the conductivity as a function of the film thickness, namely a signature feature of nanogranular films.

A binary classifier based on a reconfigurable dense network of metallic nanojunctions

Major efforts to reproduce the brain performances in terms of classification and pattern recognition have been focussed on the development of artificial neuromorphic systems based on top-down lithographic technologies typical of highly integrated components of digital computers. Unconventional computing has been proposed as an alternative exploiting the complexity and collective phenomena originating from various classes of physical substrates. Materials composed of a large number of non-linear nanoscale junctions are of particular interest: these systems, obtained by the self-assembling of nano-objects like nanoparticles and nanowires, results in non-linear conduction properties characterized by spatiotemporal correlation in their electrical activity. This appears particularly useful for classification of complex features: nonlinear projection into a high-dimensional space can make data linearly separable, providing classification solutions that are computationally very expensive with digital computers. Recently we reported that nanostructured Au films fabricated from the assembling of gold clusters by supersonic cluster beam deposition show a complex resistive switching behaviour. Their non-linear electric behaviour is remarkably stable and reproducible allowing the facile training of the devices on precise resistive states. Here we report about the fabrication and characterization of a device that allows the binary classification of Boolean functions by exploiting the properties of cluster-assembled Au films interconnecting a generic pattern of electrodes. This device, that constitutes a generalization of the perceptron, can receive inputs from different electrode configurations and generate a complete set of Boolean functions of n variables for classification tasks. We also show that the non-linear and non-local electrical conduction of cluster-assembled gold films, working at room temperature, allows the classification of non-linearly separable functions without previous training of the device.

Nanostructure Determines the Wettability of Gold Surfaces by Ionic Liquid Ultrathin Films.

Ionic liquids are employed in energy storage/harvesting devices, in catalysis and biomedical technologies, due to their tunable bulk and interfacial properties. In particular, the wettability and the structuring of the ionic liquids at the interface are of paramount importance for all those applications exploiting ionic liquids tribological properties, their double layer organization at electrified interfaces, and interfacial chemical reactions. Here we report an experimental investigation of the wettability and organization at the interface of an imidazolium-based ionic liquid ([Bmim][NTf2]) and gold surfaces, that are widely used as electrodes in energy devices, electronics, fluidics. In particular, we investigated the role of the nanostructure on the resulting interfacial interactions between [Bmim][NTf2] and atom-assembled or cluster-assembled gold thin films. Our results highlight the presence of the solid-like structured ionic liquid domains extending several tens of nanometres far from the gold interfaces, and characterized by different lateral extension, according to the wettability of the gold nanostructures by the IL liquid-phase.

Micropatterning of Substrates for the Culture of Cell Networks by Stencil-Assisted Additive Nanofabrication.

The fabrication of in vitro neuronal cell networks where cells are chemically or electrically connected to form functional circuits with useful properties is of great interest. Standard cell culture substrates provide ensembles of cells that scarcely reproduce physiological structures since their spatial organization and connectivity cannot be controlled. Supersonic Cluster Beam Deposition (SCBD) has been used as an effective additive method for the large-scale fabrication of interfaces with extracellular matrix-mimicking surface nanotopography and reproducible morphological properties for cell culture. Due to the high collimation of SCBD, it is possible to exploit stencil masks for the fabrication of patterned films and reproduce features as small as tens of micrometers. Here, we present a protocol to fabricate micropatterned cell culture substrates based on the deposition of nanostructured cluster-assembled zirconia films by stencil-assisted SCBD. The effectiveness of this approach is demonstrated by the fabrication of micrometric patterns able to confine primary astrocytes. Calcium waves propagating in the astrocyte networks are shown.

Anomalous electrical conduction and negative temperature coefficient of resistance in nanostructured gold resistive switching films

We report the observation of non-metallic electrical conduction, resistive switching, and a negative temperature coefficient of resistance in nanostructured gold films above the electrical percolation and in strong-coupling regime, from room down to cryogenic temperatures (24 K). Nanostructured continuous gold films are assembled by supersonic cluster beam deposition of Au aggregates formed in the gas phase. The structure of the cluster-assembled films is characterized by an extremely high density of randomly oriented crystalline nanodomains, separated by grain boundaries and with a large number of lattice defects. Our data indicates that space charge limited conduction and Coulomb blockade are at the origin of the anomalous electrical behavior. The high density of extended defects and grain boundaries causes the localization of conduction electrons over the entire investigated temperature range.

Complex electrical spiking activity in resistive switching nanostructured Au two-terminal devices

Networks of nanoscale objects are the subject of increasing interest as resistive switching systems for the fabrication of neuromorphic computing architectures. Nanostructured films of bare gold clusters produced in gas phase with thickness well beyond the electrical percolation threshold, show a non-ohmic electrical behavior and resistive switching, resulting in groups of current spikes with irregular temporal organization. Here we report the systematic characterization of the temporal correlations between single spikes and spiking rate power spectrum of nanostructured Au two-terminal devices consisting of a cluster-assembled film deposited between two planar electrodes. By varying the nanostructured film thickness we fabricated two different classes of devices with high and low initial resistance respectively. We show that the switching dynamics can be described by a power law distribution in low resistance devices whereas a bi-exponential behavior is observed in the high resistance ones. The measured resistance of cluster-assembled films shows a scaling behavior in the range of analyzed frequencies. Our results suggest the possibility of using cluster-assembled Au films as components for neuromorphic systems where a certain degree of stochasticity is required.

Switchable metal-insulator transition in core-shell cluster-assembled nanostructure films.

Fe/Fe3O4 core-shell-cluster-assembled nanostructured films were prepared using the low-energy cluster beam deposition technique. The temperature-dependent resistivity behaviors were investigated for the films with changing core-occupation ratio of clusters. Much interestingly and surprisingly, a switchable metal-insulator transition can be observed, featuring the rapid switching from the metal state to the insulation state and then back to the metal state, for films within a specific range of core-occupation ratio. Further, the resistivity change rate used to characterize the metal-insulator transition can reach as high as two orders of magnitude over a very narrow temperature region. The design of Fe/Fe3O4 core-shell clusters plays a decisive role in the mechanism of the switchable metal-insulator transition in these films. The assembled core-shell clusters in the films form current conduction channels that are switchable between the cores and shells of clusters as the temperature changes. The switching of the current conduction channels can be regulated by controlling the core-occupation ratios of clusters, which induce a switchable metal-insulator transition and can be verified by the effective medium theory over a specific core-occupation ratio range.

Quantitative characterization of the interfacial morphology and bulk porosity of nanoporous cluster-assembled carbon thin films

The deposition of nanoporous carbon thin films with well-controlled morphology, high surface area and porosity is of great interest for different applications requiring autonomous and portable electrochemical devices for energy conversion and storage. The engineering of this class of devices and the evaluation of their performances require the measurement of the porosity and surface area of the active carbon layers. The quantitative characterization of these parameters by gas adsorption techniques is hampered by the small amount of material usually available on a thin film.Here we report a method based on the use of atomic force microscopy (AFM) and nitrogen adsorption technique for the quantitative characterization of the specific surface area and porosity of nanoporous carbon films. In particular, we apply it to nanostructured carbon films fabricated by supersonic cluster beam deposition (SCBD), studying the evolution of their structural properties with film thickness. We exploited the characteristics of SCBD in terms of high-throughput, stability, and reproducibility to fabricate films with controlled nano and microstructure over large substrates compatible with the requirements of gas adsorption measurements. Our approach demonstrates that the combination of AFM and nitrogen adsorption technique provides the possibility of undertaking systematic quantitative characterization of the nano- and mesostructure of cluster-assembled carbon films and of their evolution, which can be easily applied to porous thin films fabricated by many different techniques.

Non-ohmic behavior and resistive switching of Au cluster-assembled films beyond the percolation threshold

Networks based on nanoscale resistive switching junctions are considered promising for the fabrication of neuromorphic computing architectures. To date random networks of nanowires, nanoparticles, and metal clusters embedded in a polymeric matrix or passivated by shell of ligands or oxide layers have been used to produce resistive switching systems. The strategies applied to tailor resistive switching behavior are currently based on the careful control of the volume fraction of the nanoscale conducting phase that must be fixed close to the electrical percolation threshold. Here, by blending laboratory and computer experiments, we demonstrate that metallic nanostructured Au films fabricated by bare gold nanoparticles produced in the gas phase and with thickness well beyond the electrical percolation threshold, show a non-ohmic electrical behavior and complex and reproducible resistive switching. We observe that the nanogranular structure of the Au films does not evolve with thickness: this introduces a huge number of defects and junctions affecting the electrical transport and causing a dynamic evolution of the nanoscale electrical contacts under the current flow. To uncover the origin of the resistive switching behavior in Au cluster-assembled films, we developed a simple computational model for determining the evolution of a model granular film under bias conditions. The model exploits the information provided by experimental investigation about the nanoscale granular morphology of real films. Our results show that metallic nanogranular materials have functional properties radically different from their bulk counterparts, in particular nanostructured Au films can be fabricated by assembling bare gold clusters which retain their individuality to produce an all-metal resistive switching system.

Electrostatic Double-Layer Interaction at the Surface of Rough Cluster-Assembled Films: The Case of Nanostructured Zirconia.

Here, we investigated the influence of the nanoscale surface morphology on the electrostatic double layer at corrugated surfaces in aqueous electrolytes. For this purpose, we have produced cluster-assembled nanostructured zirconium dioxide (ns-ZrO x, x ≈ 2) films with controlled morphological properties by supersonic cluster beam deposition (SCBD) and measured the double-layer interaction by atomic force microscopy with colloidal probes. SCBD allowed tuning the characteristic widths of the corrugated interface (root-mean-square roughness, correlation length) across a wide range of values, matching the width of the electrostatic double layer (Debye length) and the typical size of nanocolloids (proteins, enzymes, and catalytic nanoparticles). To accurately characterize the surface charge density in the high-roughness regime, we have developed a two-exponential model of the electrostatic force that explicitly includes roughness and better accounts for the roughness-induced amplification of the interaction. We were then able to observe a marked reduction of the isoelectric point of ns-ZrO x surfaces of increasing roughness. This result is in good agreement with our previous observations on cluster-assembled nanostructured titania films and demonstrates that the phenomenon is not limited to a specific material, but more generally depends on peculiar nanoscale morphological effects, related to the competition of the characteristic lengths of the system.

Growth Mechanism of Cluster-Assembled Surfaces: From Submonolayer to Thin-Film Regime

Nanostructured films obtained by the assembling of preformed atomic clusters are of strategic importance for a wide variety of applications. The deposition of clusters produced in the gas phase onto a substrate offers the possibility to control and engineer the structural and functional properties of the cluster-assembled films. To date the microscopic mechanisms underlying the growth and structuring of cluster-assembled films are poorly understood, and in particular the transition from the sub-monolayer to the thin film regime is experimentally unexplored. Here we report the systematic characterization by Atomic Force Microscopy of the evolution of the structural properties of cluster-assembled films deposited by Supersonic Cluster Beam Deposition. As a paradigm of nanostructured systems, we have focused our attention on cluster-assembled zirconia films, investigating the influence of the building blocks dimensions on the growth mechanisms and on the roughening of the thin films, following the growth process from the early stages of the sub-monolayer to the thin film regime. Our results demonstrate that the growth dynamics in the sub-monolayer regime determines different morphological properties of the cluster-assembled thin film. The evolution of roughness with the number of deposited clusters reproduces exactly the growth exponent of the ballistic deposition in the 2+1 model, from the sub-monolayer to the thin film regime.

Tailoring magnetic properties of Co nanocluster assembled films using hydrogen

Tailoring magnetic properties in nanocluster assembled cobalt (Co) thin films was achieved by admitting a small percentage of H2 gas (∼2%) into the Co gas phase cluster formation chamber prior to deposition. The oxygen content in the films is considerably reduced by the presence of hydrogen during the cluster formation, leading to enhanced magnetic interactions between clusters. Two sets of Co samples were fabricated, one without hydrogen gas and one with hydrogen gas. Magnetic properties of the non-hydrogenated and the hydrogen-treated Co nanocluster assembled films are comparatively studied using magnetic force microscopy and vibrating sample magnetometry. When comparing the two sets of samples the considerably larger coercive field of the H2-treated Co nanocluster film and the extended micrometer-sized magnetic domain structure confirm the enhancement of magnetic interactions between clusters. The thickness of the antiferromagnetic CoO layer is controlled with this procedure and modifies the exchange bias effect in these films. The exchange bias shift is lower for the H2-treated Co nanocluster film, which indicates that a thinner antiferromagnetic CoO reduces the coupling with the ferromagnetic Co. The hydrogen-treatment method can be used to tailor the oxidation levels thus controlling the magnetic properties of ferromagnetic cluster-assembled films.