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conductive oxide
Mirco Bazzani, Andrea Neroni, Arrigo Calzolari, and Alessandra Catellani
Citation: Applied Physics Letters 98, 121907 (2011); doi: 10.1063/1.3567513
View online: http://dx.doi.org/10.1063/1.3567513
View Table of Contents: http://scitation.aip.org/content/aip/journal/apl/98/12?ver=pdfcov
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Received 18 November 2010; accepted 23 February 2011; published online 22 March 2011
We study the effects of aluminum doping on the electronic and optical properties of ZnO, via density
functional simulations. We discuss the bandstructure and absorption properties of Al:ZnO as a
function of the dopant concentration, and compare with recent experimental data. Our results
support the formation of a transparent conductive oxide compound up to an incorporation of Al of
about 3% in substitutional Zn sites. We propose an explanation to the observed degradation of
conductivity in terms of interstitial defects expected to occur at high doping concentrations, beyond
the Al solubility limit. 2011 American Institute of Physics. doi:10.1063/1.3567513
Doping of oxides is a complex problem:1 several efforts
have been conducted to understand and optimize doping of
these materials that suffer from volatility of oxygen, accompanied by large lattice anisotropy, responsible for inhomogeneous diffusion.2
Because of the coexistence of high conductivity and high
transparency in the visible region, the realization of transparent conductive oxides TCOs through doping has attracted
much interest for optoelectronic device applications, such as
solar cells and liquid crystal displays. Among all, it has been
recently proposed that aluminum-doped zinc oxide AZO
films can be the optimal choice as TCO layers in ZnO
nanowire-based solar cells.35 The optical, electrical, structural, and morphological properties of the TCO films are
essential in determining device performances. Yet the remarkable combination of conductivity in an albeit wide-gap
i.e., transparent material is not fully understood, along with
the effect of dopants on charge transport: these issues contrast with the standard classification between zero-gap conductive and finite-gap optical materials and are still the subject of intense debate.68 Furthermore, experimental data911
have shown nonmonotonic variations in the electronic properties of AZO films increasing dopant concentration: recent
transport measurements11 have revealed an unexpected deterioration of mobility beyond the Al solubility limit 3%.
Hence, a full understanding of the formation, stability, and
solubility properties of TCOs still constitutes a fundamental
challenge and a technological goal. First principles investigations offer the unique possibility of characterizing the optoelectronic properties of TCOs at an atomistic level, taking
directly into account the interplay between the electronic and
structural properties of the system.
In this paper we discuss the electronic and optical properties of AZO, by means of ab initio simulations. We first
discuss how doping affects the electronic properties of AZO
up to the experimental solubility limit 3%4%,10 presenting the details of neutral substitutional Aluminum at Zn sites
a
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98,is121907-1
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Bazzani et al.
(a)
(b)
(c)
Al tot
Al sub
Al int
ZnO
AZO 1.6% Substitutional
AZO 3.2% Substitutional
AZO 3.2% Interstitial
AZO 3.2% Cluster
EF
Energy
tot
Zn
O
Al
Im () (arbit. units)
121907-2
ZnO
Eg
AZO
E g+EBM
-3
-6
-2
-5
-1
-4
-3
-2
-1
Energy (eV)
FIG. 1. Color online Total and projected DOSs for a clean bulk ZnO, b
substitutional, and c interstitial AZO at 3.2% Al content. DOSs are aligned
at the EF vertical line, and normalized to the Zn 3d peak area. The gray
areas indicate the pristine ZnO gap. Inset zooms on the Al contributions
substitutional and interstitial around the gap.
Energy (eV)
121907-3
Bazzani et al.
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
167.205.22.105 On: Tue, 04 Mar 2014 06:58:25