Plasmonic Properties of Silicon Nanocrystals Doped with Boron and Phosphorus

Degenerately doped silicon nanocrystals are appealing plasmonic materials due to silicon’s low cost and low toxicity. While surface plasmonic resonances of boron-doped and phosphorus-doped silicon nanocrystals were recently observed, there currently is poor understanding of the effect of surface conditions on their plasmonic behavior. Here, we demonstrate that phosphorus-doped silicon nanocrystals exhibit a plasmon resonance immediately after their synthesis but may lose their plasmonic response with oxidation. In contrast, boron-doped nanocrystals initially do not exhibit plasmonic response but become plasmonically active through postsynthesis oxidation or annealing. We interpret these results in terms of substitutional doping being the dominant doping mechanism for phosphorus-doped silicon nanocrystals, with oxidation-induced defects trapping free electrons. The behavior of boron-doped silicon nanocrystals is more consistent with a strong contribution of surface doping. Importantly, boron-doped silicon nanocrystals exhibit air-stable plasmonic behavior over periods of more than a year

Thermodynamic Driving Force in the Spontaneous Formation of Inorganic Nanoparticle Solutions

Nanoparticles are the bridge between the molecular and the macroscopic worlds. The growing number of commercial applications for nanoparticles spans from consumer products to new frontiers of medicine and next-generation optoelectronic technology. They are most commonly deployed in the form of a colloid, or “ink”, which are formulated with solvents, surfactants, and electrolytes to kinetically prevent the solid particulate phase from reaching the thermodynamically favored state of separate solid and liquid phases. In this work, we theoretically determine the thermodynamic requirements for forming a single-phase solution of spherical particles and engineer a model system to experimentally demonstrate the spontaneous formation of solutions composed of only solvent and bare inorganic nanoparticles. We show molecular interactions at the nanoparticle interface are the driving force in high-concentration nanoparticle solutions. The work establishes a regime where inorganic nanoparticles behave as molecular solutes as opposed to kinetically stable colloids, which has far-reaching implications for the future design and deployment of nanomaterial technologies

Thermodynamic Driving Force in the Spontaneous Formation of Inorganic Nanoparticle Solutions

Nanoparticles are the bridge between the molecular and the macroscopic worlds. The growing number of commercial applications for nanoparticles spans from consumer products to new frontiers of medicine and next-generation optoelectronic technology. They are most commonly deployed in the form of a colloid, or “ink”, which are formulated with solvents, surfactants, and electrolytes to kinetically prevent the solid particulate phase from reaching the thermodynamically favored state of separate solid and liquid phases. In this work, we theoretically determine the thermodynamic requirements for forming a single-phase solution of spherical particles and engineer a model system to experimentally demonstrate the spontaneous formation of solutions composed of only solvent and bare inorganic nanoparticles. We show molecular interactions at the nanoparticle interface are the driving force in high-concentration nanoparticle solutions. The work establishes a regime where inorganic nanoparticles behave as molecular solutes as opposed to kinetically stable colloids, which has far-reaching implications for the future design and deployment of nanomaterial technologies

Controlled Doping of Silicon Nanocrystals Investigated by Solution-Processed Field Effect Transistors

The doping of semiconductor nanocrystals (NCs), which is vital for the optimization of NC-based devices, remains a significant challenge. While gas-phase plasma approaches have been successful in incorporating dopant atoms into NCs, little is known about their electronic activation. Here, we investigate the electronic properties of doped silicon NC thin films cast from solution by field effect transistor analysis. We find that, analogous to bulk silicon, boron and phosphorus electronically dope Si NC thin films; however, the dopant activation efficiency is only ∼10^–2–10^–4. We also show that surface doping of Si NCs is an effective way to alter the carrier concentrations in Si NC films

Nonequilibrium-Plasma-Synthesized ZnO Nanocrystals with Plasmon Resonance Tunable via Al Doping and Quantum Confinement

Metal oxide semiconductor nanocrystals (NCs) exhibit localized surface plasmon resonances (LSPRs) tunable within the infrared (IR) region of the electromagnetic spectrum by vacancy or impurity doping. Although a variety of these NCs have been produced using colloidal synthesis methods, incorporation and activation of dopants in the liquid phase has often been challenging. Herein, using Al-doped ZnO (AZO) NCs as an example, we demonstrate the potential of nonthermal plasma synthesis as an alternative strategy for the production of doped metal oxide NCs. Exploiting unique, thoroughly nonequilibrium synthesis conditions, we obtain NCs in which dopants are not segregated to the NC surfaces and local doping levels are high near the NC centers. Thus, we achieve overall doping levels as high as 2 × 10²⁰ cm^–3 in NCs with diameters ranging from 12.6 to 3.6 nm, and for the first time experimentally demonstrate a clear quantum confinement blue shift of the LSPR energy in vacancy- and impurity-doped semiconductor NCs. We propose that doping of central cores and heavy doping of small NCs are achievable via nonthermal plasma synthesis, because chemical potential differences between dopant and host atomswhich hinder dopant incorporation in colloidal synthesisare irrelevant when NC nucleation and growth proceed via irreversible interactions among highly reactive gas-phase ions and radicals and ligand-free NC surfaces. We explore how the distinctive nucleation and growth kinetics occurring in the plasma influences dopant distribution and activation, defect structure, and impurity phase formation