Control over Memory Performance of Layer-by-Layer Assembled Metal Phthalocyanine Multilayers via Molecular-Level Manipulation

We herein report on the nonvolatile memory properties of iron phthalocyanine multilayers prepared using an electrostatic layer-by-layer assembly method. Cationic poly­(allylamine hydrochloride) (PAH) and anionic iron­(III) phthalocyanine-4, 4,′ 4″, 4′″-tetrasulfonic acid (Fe-TsPc) were alternately deposited onto quartz glass, indium tin oxide (ITO), or platinum-coated silicon substrates via electrostatic interactions. The electrochemical response of the PAH/Fe-TsPc, which was obtained from cyclic voltammograms (CV) in solution, indicated that redox reactions occurred at the phthalocyanine unit and at the metallic center. It was found that these redox reactions of the PAH/Fe-TsPc multilayer films in solution could be extended to resistive switching nonvolatile memory based on a charge trap/release mechanism in air. The PAH/Fe-TsPc multilayers sandwiched between the bottom (platinum) and top (Ag or tungsten) electrodes exhibited the characteristics of a resistive switching memory at a relatively low operating voltage of less than 2 V, with a switching speed of about 100 ns and an ON/OFF current ratio of ∼10³. Additionally, it is confirmed using kelvin probe force microscopy (KPFM) that the reversible resistance changes in the PAH/Fe-TsPc multilayers are mainly caused by the externally applied voltage as a result of the trapping and release of charges at redox sites within the Fe-TsPc. Furthermore, in the case where insulating layers of about 2 nm in thickness are inserted between adjacent Fe-TsPc layers, it is demonstrated that these devices can exhibit further improvements in memory performance (ON/OFF current ratio of ∼10⁶) and a lower power consumption in comparison with PAH/Fe-TsPc multilayers

Electrically Bistable Properties of Layer-by-Layer Assembled Multilayers Based on Protein Nanoparticles

Electrochemical properties of redox proteins, which can cause the reversible changes in the resistance according to their redox reactions in solution, are of the fundamental and practical importance in bioelectrochemical applications. These redox properties often depend on the chemical activity of transition metal ions as cofactors within the active sites of proteins. Here, we demonstrate for the first time that the reversible resistance changes in dried protein films based on ferritin nanoparticles can be caused by the externally applied voltage as a result of charge trap/release of Fe^III/Fe^II redox couples. We also show that one ferritin nanoparticle of about 12 nm size can be operated as a nanoscale-memory device, and furthermore the layer-by-layer assembled protein multilayer devices can be extended to bioinspired electronics with adjustable memory performance <i>via</i> molecular level manipulation

Hydrophobic Nanoparticle-Based Nanocomposite Films Using <i>In Situ</i> Ligand Exchange Layer-by-Layer Assembly and Their Nonvolatile Memory Applications

A robust method for preparing nanocomposite multilayers was developed to facilitate the assembly of well-defined hydrophobic nanoparticles (<i>i.e.</i>, metal and transition metal oxide NPs) with a wide range of functionalities. The resulting multilayers were stable in both organic and aqueous media and were characterized by a high NP packing density. For example, inorganic NPs (including Ag, Au, Pd, Fe₃O₄, MnO₂, BaTiO₃) dispersed in organic media were shown to undergo layer-by-layer assembly with amine-functionalized polymers to form nanocomposite multilayers while incurring minimal physical and chemical degradation of the inorganic NPs. In addition, the nanocomposite multilayer films formed onto flat and colloidal substrates could directly induce the adsorption of the electrostatically charged layers without the need for additional surface treatments. This approach is applicable to the preparation of electronic film devices, such as nonvolatile memory devices requiring a high memory performance (ON/OFF current ratio >10³ and good memory stability)