Tunable surface plasmon resonance and enhanced electrical conductivity of in doped ZnO colloidal nanocrystals

We report a new synthesis process of colloidal indium (In) doped zinc oxide (ZIO) nanocrystals by a hot injection technique. By fine tuning the synthesis we reached the same nucleation temperature for indium oxide and zinc oxide which helped us to study a dopant precursor dependent In incorporation into the ZnO matrix by using different In sources. The dopant induced shape evolution changes the hexagonal pyramid structured ZnO to a platelet like structure upon 8% In doping. The introduction of trivalent In³⁺ into the ZnO lattice and consequent substitution of divalent Zn²⁺ generates free electrons in the conduction band which produces a plasmonic resonance in the infrared region. The electron concentration controls plasmon frequency as well as the band gap of host ZnO. The variation of the band gap and the modification of the conduction band have been explained by the Burstein-Moss effect and Mie's theory respectively. The In dopant changes the defect chemistry of pure ZnO nanocrystals which has been studied by photoluminescence and other spectroscopic measurements. The nanocrystals are highly stable in the organic medium and can be deposited as a crack free thin film on different substrates. Careful ligand exchange and thermal annealing of the spin cast film lead to a good conductive film (720 Ω per square to 120 Ω per square) with stable inherent plasmonic absorption in the infrared and 90% transmittance in the visible region. A temperature induced metal-semiconductor transition was found for doped ZnO nanocrystals. The transition temperature shifts to a lower temperature with increase of the doping concentration.