Self-Assembled Au Nanoelectrodes: Enabling Low-Threshold-Voltage HfO2-Based Artificial Neurons.

Filamentary-type resistive switching devices, such as conductive bridge random-access memory and valence change memory, have diverse applications in memory and neuromorphic computing. However, the randomness in filament formation poses challenges to device reliability and uniformity. To overcome this issue, various defect engineering methods have been explored, including doping, metal nanoparticle embedding, and extended defect utilization. In this study, we present a simple and effective approach using self-assembled uniform Au nanoelectrodes to controll filament formation in HfO2 resistive switching devices. By concentrating the electric field near the Au nanoelectrodes within the BaTiO3 matrix, we significantly enhanced the device stability and reduced the threshold voltage by up to 45% in HfO2-based artificial neurons compared to the control devices. The threshold voltage reduction is attributed to the uniformly distributed Au nanoelectrodes in the insulating matrix, as confirmed by COMSOL simulation. Our findings highlight the potential of nanostructure design for precise control of filamentary-type resistive switching devices.

Self-Assembled Complex Three-Phase Core-Shell Nanostructure of Au-CoFe2-TiN with a Magneto-Optical Coupling Effect.

Nanostructured plasmonic-magnetic metamaterials have gained great research interest due to their enhanced magneto-optical coupling effects. Here, we report a complex three-phase nanocomposite design combining ferromagnetic CoFe2 with plasmonic TiN and Au as a multifunctional hybrid metamaterial using either a cogrowth or a templated method. Via the first method of cogrowing three phases, three different morphologies of Au-CoFe2 core-shell nanopillars were formed in the TiN matrix. Via the second method of sequential deposition of a TiN-Au seed layer and a TiN-CoFe2 layer, highly ordered and uniform single-type core-shell nanopillars (i.e., the CoFe2 shell with a Au core) form in the TiN matrix. Both cogrowth and templated growth TiN-CoFe2-Au hybrid systems exhibit excellent epitaxial quality, hyperbolic dispersion, magnetic anisotropy, and a magneto-optical coupling effect. This study provides an effective approach for achieving highly uniform multiphase vertically aligned nanocomposite structures with well-integrated optical, magnetic, and coupling properties.

Thin-film design of amorphous hafnium oxide nanocomposites enabling strong interfacial resistive switching uniformity.

A design concept of phase-separated amorphous nanocomposite thin films is presented that realizes interfacial resistive switching (RS) in hafnium oxide-based devices. The films are formed by incorporating an average of 7% Ba into hafnium oxide during pulsed laser deposition at temperatures ≤400°C. The added Ba prevents the films from crystallizing and leads to ∼20-nm-thin films consisting of an amorphous HfOx host matrix interspersed with ∼2-nm-wide, ∼5-to-10-nm-pitch Ba-rich amorphous nanocolumns penetrating approximately two-thirds through the films. This restricts the RS to an interfacial Schottky-like energy barrier whose magnitude is tuned by ionic migration under an applied electric field. Resulting devices achieve stable cycle-to-cycle, device-to-device, and sample-to-sample reproducibility with a measured switching endurance of ≥104 cycles for a memory window ≥10 at switching voltages of ±2 V. Each device can be set to multiple intermediate resistance states, which enables synaptic spike-timing-dependent plasticity. The presented concept unlocks additional design variables for RS devices.

Abnormal in-plane epitaxy and formation mechanism of vertically aligned Au nanopillars in self-assembled CeO2-Au metamaterial systems.

Metamaterials present great potential in the applications of solar cells and nanophotonics, such as super lenses and other meta devices, owing to their superior optical properties. In particular, hyperbolic metamaterials (HMMs) with exceptional optical anisotropy offer improved manipulation of light-matter interactions as well as a divergence in the density of states and thus show enhanced performances in related fields. Recently, the emerging field of oxide-metal vertically aligned nanocomposites (VANs) suggests a new approach to realize HMMs with flexible microstructural modulations. In this work, a new oxide-metal metamaterial system, CeO2-Au, has been demonstrated with variable Au phase morphologies from nanoparticle-in-matrix (PIM), nanoantenna-in-matrix, to VAN. The effective morphology tuning through deposition background pressure, and the corresponding highly tunable optical performance of three distinctive morphologies, were systematically explored and analyzed. A hyperbolic dispersion at high wavelength has been confirmed in the nano-antenna CeO2-Au thin film, proving this system as a promising candidate for HMM applications. More interestingly, a new and abnormal in-plane epitaxy of Au nanopillars following the large mismatched CeO2 matrix instead of the well-matched SrTiO3 substrate, was discovered. Additionally, the tilting angle of Au nanopillars, α, has been found to be a quantitative measure of the balance between kinetics and thermodynamics during the depositions of VANs. All these findings provide valuable information in the understanding of the VAN formation mechanisms and related morphology tuning.

Single-Step Fabrication of Au-Fe-BaTiO3 Nanocomposite Thin Films Embedded with Non-Equilibrium Au-Fe Alloyed Nanostructures.

Nanocomposite thin film materials present great opportunities in coupling materials and functionalities in unique nanostructures including nanoparticles-in-matrix, vertically aligned nanocomposites (VANs), and nanolayers. Interestingly the nanocomposites processed through a non-equilibrium processing method, e.g., pulsed laser deposition (PLD), often possess unique metastable phases and microstructures that could not achieve using equilibrium techniques, and thus lead to novel physical properties. In this work, a unique three-phase system composed of BaTiO3 (BTO), with two immiscible metals, Au and Fe, is demonstrated. By adjusting the deposition laser frequency from 2 Hz to 10 Hz, the phase and morphology of Au and Fe nanoparticles in BTO matrix vary from separated Au and Fe nanoparticles to well-mixed Au-Fe alloy pillars. This is attributed to the non-equilibrium process of PLD and the limited diffusion under high laser frequency (e.g., 10 Hz). The magnetic and optical properties are effectively tuned based on the morphology variation. This work demonstrates the stabilization of non-equilibrium alloy structures in the VAN form and allows for the exploration of new non-equilibrium materials systems and their properties that could not be easily achieved through traditional equilibrium methods.

Double-Exchange Bias Modulation under Horizontal and Perpendicular Field Directions by 3D Nanocomposite Design.

Exchange bias (EB) presents the interfacial coupling between ferromagnetic (FM) and antiferromagnetic (AFM) phases, which could be applied for high-density data storage and magnetic recording. In thin films, the EB effect could be realized in either a FM/AFM multilayer structure or a FM/AFM vertically aligned nanocomposite (VAN) form, which allows the interfacial coupling tuning along the horizontal or perpendicular directions, respectively. Here, to combine the schemes of multilayer and VAN structures, a new 3D nanocomposite has been designed, which is La0.7Sr0.3MnO3 (LSMO)/NiO VAN layers with inserted LSMO or NiO layers. Such a 3D nanocomposite structure provides a great platform to tailor the EB effect along both horizontal and perpendicular directions. Specifically, the sample with a NiO interlayer exhibits the highest EB field (HEB) of 350 Oe and 475 Oe under in-plane and out-of-plane field, respectively. Furthermore, the HEB value and Curie temperature (Tc) can be tuned by different 3D nanostructures. This work demonstrates the double EB modulation with the designed 3D nanostructures as a new route toward advanced magnetic data storage and spintronic devices.

Creating Ferromagnetic Insulating La0.9Ba0.1MnO3 Thin Films by Tuning Lateral Coherence Length.

In this work, heteroepitaxial vertically aligned nanocomposite (VAN) La0.9Ba0.1MnO3 (LBMO)-CeO2 films are engineered to produce ferromagnetic insulating (FMI) films. From combined X-ray photoelectron spectroscopy, X-ray diffraction, and electron microscopy, the elimination of the insulator-metal (I-M) transition is shown to result from the creation of very small lateral coherence lengths (with the corresponding lateral size ∼ 3 nm (∼7 u.c.)) in the LBMO matrix, achieved by engineering a high density of CeO2 nanocolumns in the matrix. The small lateral coherence length leads to a shift in the valence band maximum and reduction of the double exchange (DE) coupling. There is no "dead layer" effect at the smallest achieved lateral coherence length of ∼3 nm. The FMI behavior obtained by lateral dimensional tuning is independent of substrate interactions, thus intrinsic to the film itself and hence not related to film thickness. The unique properties of VAN films give the possibility for multilayer spintronic devices that can be made without interface degradation effects between the layers.

Vertically aligned nanocomposite (BaTiO3)0.8 : (La0.7Sr0.3MnO3)0.2 thin films with anisotropic multifunctionalities.

A new two-phase BaTiO3 : La0.7Sr0.3MnO3 nanocomposite system with a molar ratio of 8 : 2 has been grown on single crystal SrTiO3 (001) substrates using a one-step pulsed laser deposition technique. Vertically aligned nanocomposite thin films with ultra-thin La0.7Sr0.3MnO3 pillars embedded in the BaTiO3 matrix have been obtained and the geometry of the pillars varies with deposition frequency. The room temperature multiferroic properties, including ferromagnetism and ferroelectricity, have been demonstrated. Anisotropic ferromagnetism and dielectric constants have been observed, which can be tuned by deposition frequencies. The tunable anisotropic optical properties originated from the conducting pillars in the dielectric matrix structure, which cause different electron transport paths. In addition, tunable band gaps have been discovered in the nanocomposites. This multiferroic and anisotropic system has shown its great potentials towards multiferroics and non-linear optics.