Electrochemical gelation of quantum dots using non-noble metal electrodes at high oxidation potentials.

Relative to conventional chemical approaches, electrochemical assembly of metal chalcogenide nanoparticles enables the use of two additional levers for tuning the assembly process: electrode material and potential. In our prior work, oxidative and metal-mediated pathways for electrochemical assembly of metal chalcogenide quantum dots (QDs) into three-dimensional gel architectures were investigated independently by employing a noble-metal (Pt) electrode at relatively high potentials and a non-noble metal electrode at relatively low potentials, respectively. In the present work, we reveal competition between the two electrogelation pathways under the condition of high oxidation potentials and non-noble metal electrodes (including Ni, Co, Zn, and Ag), where both pathways are active.

Reversible Electrochemical Gelation of Metal Chalcogenide Quantum Dots.

The ability to dictate the assembly of quantum dots (QDs) is critical for their integration into solid-state electronic and optoelectronic devices. However, assembly methods that enable efficient electronic communication between QDs, facilitate access to the reactive surface, and retain the native quantum confinement characteristics of the QD are lacking. Here we introduce a universal and facile electrochemical gelation method for assembling metal chalcogenide QDs (as demonstrated for CdS, ZnS, and CdSe) into macroscale 3-D connected pore-matter nanoarchitectures that remain quantum confined and in which each QD is accessible to the ambient.

Effect of metal ion solubility on the oxidative assembly of metal sulfide quantum dots.

The versatility of the oxidative assembly method for the creation of 2D and 3D quantum dot (QD) architectures represents both an opportunity and a challenge as a method enabling controlled placement of chemically distinct QDs in multicomponent systems. The opportunity lies in the ability to independently tune the kinetics of the different components so that they are similar (leading to well-mixed systems) or different (enabling gradient or phase-segregated composites) using a wide range of variables; the challenge lies in understanding those variables and how their interplay affects the overall kinetics. Here, we show that the identity of the cation in the sulfide matrix (M = Cd vs Zn) plays a large role in the kinetics of assembly of mass spectrometry QDs, attributed to differences in solubility.

Exploiting kinetics for assembly of multicomponent nanoparticle networks with programmable control of heterogeneity.

Kinetic control of metal chalcogenide nanoparticle oxidative assembly is realized by varying the redox potential of the chalcogenide, structure (wurtzite vs. zinc blende), and ligand chain length. This knowledge is exploited to form two-component (ZnS + CdSe) hybrid aerogels with minimal heterobonding (phase-segregated) or maximal heterobonding (intimately mixed).