Understanding free-carrier accumulation in semiconductor nanomaterials : plasmonic behavior, charge storage energetics, and quantum confinement resilience of colloidal indium nitride nanocrystals

Summary

Heavily doped semiconductor nanocrystals (NCs) are promising materials that can reversibly and substantially store electrical charges. Indium nitride (InN) is a particularly interesting semiconductor material for studying charge storage processes. Colloidal InN NCs are spontaneously degenerately doped with carrier densities large enough to lead to strong localized surface plasmon resonances (LSPR) in the infrared (IR) part of the spectrum. Unfortunately, many fundamental quantities that... Show moreHeavily doped semiconductor nanocrystals (NCs) are promising materials that can reversibly and substantially store electrical charges. Indium nitride (InN) is a particularly interesting semiconductor material for studying charge storage processes. Colloidal InN NCs are spontaneously degenerately doped with carrier densities large enough to lead to strong localized surface plasmon resonances (LSPR) in the infrared (IR) part of the spectrum. Unfortunately, many fundamental quantities that ultimately control the behavior of colloidal InN NCs are currently unknown. In this thesis, we focused on advancing our current understanding of the properties of colloidal InN NCs, with special emphasis on the quantification of free electron density, the LSPR behavior, the charge storage ability, the screening effect on phonon behaviors and few other important fundamental quantities such as the electron effective mass, Fermi level, conduction band (CB) edge potential and IR transition oscillator strength.To understand the LSPR behavior of InN NCs, we first evaluated the free carrier density with a direct, model-independent quantification. We found that the number of free electrons per as-prepared InN NC is directly proportional to the NC volume, such that the free electron density is a size-independent quantity. Furthermore, we demonstrated that free electrons in InN NCs can be reversibly extracted with redox species, which leads to a direct way to manipulate the LSPR. Importantly, the LSPR energy in InN NCs barely shifts with free electron density, a behavior strikingly at odds with what is typically observed in other semiconductor plasmonic systems. These unusual plasmonic signatures are shown to arise from the nonparabolicity of the CB dispersion, which leads to a change in the electron effective mass with the number of free electrons per NC, thus mitigating the shift of LSPR in InN NCs.Consequently, we estimated the charge storage capability of InN NCs by pinning the chemical potential of InN NCs to redox-active molecular species. These studies directly yielded precise information on the Fermi level and on the chemical capacitance of InN NCs, which allowed the CB edge potential of InN NCs to be quantitatively determined for the first time. Surprisingly, the CB edge in InN NCs hardly showed any sign of quantum confinement effects, even for NCs sizes that were clearly smaller than the excitonic Bohr radius of InN. This "resilience to quantum confinement" effect was shown to also arise from the same nonparabolic dispersion effects described above.In addition, the light harvesting ability of free electrons in InN NCs was evaluated by calculating the molar absorptivity per free electron. This value directly yielded the optical oscillator strength of LSPR. We found that optical oscillator strength (per free electron) is independent of NC.Finally, the effects of free electrons on lattice vibrations were also explored. We demonstrated that free electrons weakened the A1(LO) phonon mode by screening the Coulombic restoring force induced by the lattice distortion. The A1(LO) mode frequency red-shifted linearly with the increasing free electron density. This relationship provided a fast way to estimate free electron density of InN NCs by measuring Raman spectroscopy. Show less