Why is P-Type Conductivity Limited in Transparent Conducting Oxides?

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SUMMARY

The discussion centers on the limitations of p-type conductivity in transparent conducting oxides (TCOs), specifically due to the localization of holes at the valence band edge, which is influenced by oxygen-2p levels. Participants highlight that while strong ionic bonding contributes to this localization, methods such as selecting cations with closed d-shells (e.g., Cu+, Ag+, Au+) and employing tetrahedral coordination of oxygen can enhance co-valency and potentially improve conductivity. Additionally, the conversation points out that hole localization does not inherently limit p-type conductivity, as evidenced by self-trapping phenomena in perovskite oxides and rare-earth nickelates, which exhibit covalent bonding yet still allow for hole trapping.

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  • Understanding of semiconductor physics, particularly in relation to transparent conducting oxides (TCOs).
  • Familiarity with concepts of ionic and covalent bonding in materials science.
  • Knowledge of valence band structures and hole localization mechanisms.
  • Insight into perovskite oxides and their p-type conduction properties.
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  • Research the role of oxygen-2p levels in the electronic structure of TCOs.
  • Study the effects of cation selection on the conductivity of transparent conducting oxides.
  • Explore the phenomenon of hole self-trapping in perovskite oxides and its implications for conductivity.
  • Investigate the covalent character of metal-oxygen bonds in rare-earth nickelates and their impact on hole trapping.
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Materials scientists, semiconductor physicists, and engineers involved in the development and optimization of transparent conducting oxides and related materials.

bilalarif
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I was reading about semiconductor transparent conducting oxides and I found this why p-type conductivity is limited in TCOs. But I could not understand its meaning please someone explain me how the holes are localized at valance band edge and how dominated by oxygen- 2p levels?

''Owing to the strong ionic nature of metal-oxygen bonding, holes are typically localized at the valence band
edge, which is dominated by oxygen-2p levels therefore limiting p-type conduction. Two methods have been
suggested to enhance the co-valency between metal oxygen bonding, thereby limiting localization:1 choosing cations having closed d-shells of energy comparable to that of the oxygen-2p levels (i.e., Cu+, Ag+, and Au+, especially when found in linear coordination with oxygen2), and choosing a structure in which oxygen adopts tetrahedral coordination''
 
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I do not think this statement is very precise. If holes tend to be localized, they would be localized in a gap state close to but not right at the valence band edge. It is also not true that hole localization limits the p-type conductivity. Take for example p-type conduction in perovskite oxides. In many cases it proceeds via hole conduction and these holes are self-trapped on oxygen sites and are derived from 2p states of oxygen.

Could you cite the source paper of this statement?
 
I think the sentence highlighted in red encompasses too many information and in fact recent work on hole-self-trapping brought new insights beyond 2004 at the time of writing this paper. In fact even the concept that covalency of metal-oxygen bond reduces self-trapping is questionable. Take for example rare-earth nickelates. The bonding between Ni and O has a clear covalent character, in spite of this hole trapping on oxygen occurs.
 

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