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Advancement of resistive random access memory (ReRAM) requires fully understanding the various complex, defect-mediated transport mechanisms to further improve performance. Although thin-film oxide materials have been extensively studied, the switching properties of nanoparticle assemblies remain underexplored due to difficulties in fabricating ordered structures. Here, we employ a simple flow coating method for the facile deposition of highly ordered HfO 2 nanoparticle nanoribbon assemblies. The resistive switching character of nanoribbons was determined to correlate directly with the organic capping layer length of their constituting HfO 2 nanoparticles, using oleic acid, dodecanoic acid, and undecenoic acid as model nanoparticle ligands. Through a systematic comparison of the forming process, operating set/reset voltages, and resistance states, we demonstrate a tunable resistive switching response by varying the ligand type, thus providing a base correlation for solution-processed ReRAM device fabrication.

Ligand exchange is a crucial step between nanocrystal synthesis and nanocrystal application. Although colloidal stability and ligand exchange in nonpolar media are readily established, the exchange of native, hydrophobic ligands with polar ligands is less systematic. In this paper, we present a versatile ligand exchange strategy for the phase transfer of carboxylic acid capped HfO2 and ZrO2 nanocrystals to various polar solvents, based on small amino acids as the incoming ligand. To gain insight in the fundamental mechanism of the exchange, we study this system with a combination of FTIR, zeta potential measurements, and solution (1)H NMR techniques. The detection of surface-associated, small ligands with solution NMR proves challenging in this respect. Tightly bound amino acids are undetectable, but their existence can be proven through displacement with other ligands in titration experiments. Alternatively, we find that methyl moieties belonging to bound species can circumvent these limitations because of their more favorable relaxation properties as a result of internal mobility. As such, our results are not limited to amino acids but to any short-chained ligand and will therefore facilitate the rigorous investigation and understanding of various ligand exchange processes.

In this work, ZrO2 nanocrystals (NCs) are synthesized via a solvothermal treatment in benzyl alcohol, which is an established method for the synthesis of many metal oxide nanocrystals. We found that the use of microwave heating allows for a reduction in reaction time from 2 days in the autoclave to merely 4 h in the microwave. Furthermore, we were able to tune the crystallographic phase from pure cubic to pure monoclinic zirconia by changing the reaction mechanism through the use of a different zirconium precursor. Via GC-MS measurements, we found that the release of a strong acid during synthesis controls the key mechanism behind the control over crystal phase formation. The as-synthesized ZrO2 NCs (cubic or monoclinic) are small in size (3-10 nm), yet aggregated. However, aggregate-free NCs are generated through a surface-functionalization with carboxylic acid ligands, providing stabilization in apolar solvents via steric hindrance. Solution (1)H NMR was used to study the details of this post-modification step and the surface chemistry of the resulting aggregate-free NCs. This led to the conclusion that not only a different crystal structure but also a different surface chemistry is obtained, depending on the precursor composition.

We synthesized HfO2 nanocrystals from HfCl4 using a surfactant-free solvothermal process in benzyl alcohol and found that the resulting nanocrystals could be transferred to nonpolar media using a mixture of carboxylic acids and amines. Using solution (1)H NMR, FTIR, and elemental analysis, we studied the details of the transfer reaction and the surface chemistry of the resulting sterically stabilized nanocrystals. As-synthesized nanocrystals are charge-stabilized by protons, with chloride acting as the counterion. Treatment with only carboxylic acids does not lead to any binding of ligands to the HfO2 surface. On the other hand, we find that the addition of amines provides the basic environment in which carboxylic acids can dissociate and replace chloride. This results in stable, aggregate-free dispersions of HfO2 nanocrystals, sterically stabilized by carboxylate ligands. Moreover, titrations with deuterated carboxylic acid show that the charge on the carboxylate ligands is balanced by coadsorbed protons. Hence, opposite from the X-type/nonstoichiometric nanocrystals picture prevailing in literature, one should look at HfO2/carboxylate nanocrystals as systems where carboxylic acids are dissociatively adsorbed to bind to the nanocrystals. Similar results were obtained with ZrO2 NCs. Since proton accommodation on the surface is most likely due to the high Brønsted basicity of oxygen, our model could be a more general picture for the surface chemistry of metal oxide nanocrystals with important consequences on the chemistry of ligand exchange reactions.