Abstract

Transparent conducting oxides (TCOs), with high optical transparency (≥85%) and low electrical resistivity (10−4 Ω·cm) are used in a wide variety of commercial devices. There is growing interest in replacing conventional TCOs such as indium tin oxide with lower cost, earth abundant materials. In the current study, we dope Zr into thin ZnO films grown by atomic layer deposition (ALD) to target properties of an efficient TCO. The effects of doping (0–10 at.% Zr) were investigated for ~100 nm thick films and the effect of thickness on the properties was investigated for 50–250 nm thick films. The addition of Zr4+ ions acting as electron donors showed reduced resistivity (1.44 × 10−3 Ω·cm), increased carrier density (3.81 × 1020 cm−3), and increased optical gap (3.5 eV) with 4.8 at.% doping. The increase of film thickness to 250 nm reduced the electron carrier/photon scattering leading to a further reduction of resistivity to 7.5 × 10−4 Ω·cm and an average optical transparency in the visible/near infrared (IR) range up to 91%. The improved n-type properties of ZnO: Zr films are promising for TCO applications after reaching the targets for high carrier density (>1020 cm−3), low resistivity in the order of 10−4 Ω·cm and high optical transparency (≥85%).

Highlights

  • Doped zinc oxide is of interest as a transparent conductive oxide (TCO), due to its low resistivity (ď10 ́3 Ωcm), high transparency (>80%) and wide bandgap (3.37 eV [1])

  • The reported electrical and optical properties for doped ZnO are being improved by using different dopants in order to compete with indium tin oxide (ITO), which has a resistivity in the order of 10 ́4 Ωcm and transparency ě85% [21]

  • atomic layer deposition (ALD) grown ZnO: Zr films showed that doping offers control over resistivity reduction up to 4.8 at.% due to the extra ions offered by the substitution of Zr4` to Zn2`

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Summary

Introduction

Doped zinc oxide is of interest as a transparent conductive oxide (TCO), due to its low resistivity (ď10 ́3 Ωcm), high transparency (>80%) and wide bandgap (3.37 eV [1]). The reported electrical and optical properties for doped ZnO are being improved by using different dopants in order to compete with ITO, which has a resistivity in the order of 10 ́4 Ωcm and transparency ě85% [21]. Zirconium was chosen as the dopant in the current work due to its abundance, comparable ionic size to Zn and because it can potentially act as double donor providing up to two extra free electrons per ion when substituted for Zn2` [22]. Al can sit in interstitial positions in ZnO due to its small ionic radius [24], which can have the side effect of reducing interstitial Zn defects that act as native donors This is avoided if the dopant ions are comparable in size to Zn ions as the dopant can readily sit on Zn sites, which is the case with Zr4`. The current study builds up on this study by exploring how the Zr doping incorporated in the lattice, identifies possible causes of the carrier density decrease at high doping, investigates the doping effect on the grain growth, and examines the reason for the optical gap increase after doping

Experimental Section
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