From Impurity Doping to Metallic Growth in Diffusion Doping: Properties and Structure of Ag Doped InAs Nanocrystals

TL;DR

This study investigates Ag doping in InAs nanocrystals using diffusion methods, revealing a two-stage doping process and the formation of metallic structures beyond a solubility limit, which impacts their electronic properties.

Contribution

It introduces a detailed two-stage doping model for Ag in InAs nanocrystals, linking structural and electronic changes during doping.

Findings

Doping occurs in two stages: initial impurity substitution and subsequent metallic growth.

Impurities substitute In atoms near the surface until a solubility limit is reached.

Beyond the solubility limit, metallic structures form rapidly.

Abstract

Tuning of the electronic properties of pre-synthesized colloidal semiconductor nanocrystals (NCs) by doping plays a key role in the prospect of implementing them in printed electronics devices such as transistors, and photodetectors. While such impurity doping reactions have already been introduced, the understanding of the doping process, the nature of interaction between the impurity and host atoms, and the conditions affecting the solubility limit of impurities in nanocrystals are still unclear. Here, we used a post-synthesis diffusion based doping reaction to introduce Ag impurities into InAs NCs. Optical absorption spectroscopy along with analytical inductively coupled plasma mass-spectroscopy (ICP-MS) were used to present a two stage doping model consisting of a "doping region" and a "growth region", depending on the concentration of the impurities in the reaction vessel. X-ray absorption fine-structure (XAFS) spectroscopy was employed to determine the impurity location and correlate between the structural and electronic properties for different sizes of InAs NCs and dopant concentrations. The resulting structural model describes a heterogeneous system where the impurities initially dope the NC, by substituting for In atoms near the surface of the NC, until the "solubility limit" is reached, after which the rapid growth and formation of metallic structures are identified.