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Title: Zirconium doped zinc oxide thin films deposited by atomic layer deposition
Author: Herodotou, Stephania
ISNI:       0000 0004 5352 0317
Awarding Body: University of Liverpool
Current Institution: University of Liverpool
Date of Award: 2015
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Doped zinc oxide is of interest as a transparent conductive oxide (TCO), due to the abundance of its major constituents, its low resistivity, high transparency and wide bandgap. The current work focuses on the properties required for TCO applications including resistivity of ≤10-3 Ω•cm, carrier density of ≥1020 cm-3, and transparency >80% in the visible light. Zirconium (Zr4+) was chosen as the dopant in the current work due to its abundance, comparable ionic size to Zn and because it can act as a double donor providing up to two extra free electrons per ion when substituted for Zn2+. The doping process can be controlled using atomic layer deposition (ALD), with the doped films resulting in an increased conductivity. The films in the current work resulted in a minimum resistivity of 1.44×10-3 Ω•cm and maximum carrier density of 3.81×1020 cm-3 for films <100 nm thickness, having 4.8 at.% Zr concentration. The resistivity was further reduced after reducing the interfacial and grain boundary scattering (i.e. increase grain size), by increasing the overall film thickness. The resistivity of 7.5×10-4 Ω•cm, carrier mobility of 19.6 cm2V‒1s-1 and carrier density of 4.2×1020 cm-3 were measured for a 250 nm thick film with 4.8 at.% doping. The tuning of the carrier density via doping offers control over the optical gap due to the net effect of Burstein-Moss effect and bandgap renormalisation. This resulted to an increase of the optical gap from 3.2 eV for the un-doped ZnO to 3.5 eV for 4.8 at.% Zr-doped films. The average optical transparency in the visible/near IR range was as high as 91% for 4.8 at.% doped films. The thickness increase also resulted in a grain orientation shift from perpendicular to the substrate (i.e. polar c-plane orientation) to parallel (i.e. non-polar m-plane) due to the strain increase that forced the films to grow at a low strain energy direction. This offers the possibility of growing non-polarised films that show no piezoelectric field charge observed in polar oriented films. Therefore, controlling the grain size through the number of ALD cycles can effectively result in mobility and preferred orientation control, while the doping concentration controls the resistivity, optical bandgap and transparency of the films.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Q Science (General) ; T Technology (General)