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Stacking textured films on lattice-mismatched transparent conducting oxides via matched Voronoi cell of oxygen sublattice

Nature Materials volume 23, pages 383–390 (2024)Cite this article

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Abstract

Transparent conducting oxides are a critical component in modern (opto)electronic devices and solar energy conversion systems, and forming textured functional films on them is highly desirable for property manipulation and performance optimization. However, technologically important materials show varied crystal structures, making it difficult to establish coherent interfaces and consequently the oriented growth of these materials on transparent conducting oxides. Here, taking lattice-mismatched hexagonal α-Fe2O3 and tetragonal fluorine-doped tin oxide as the example, atomic-level investigations reveal that a coherent ordered structure forms at their interface, and via an oxygen-mediated dimensional and chemical-matching manner, that is, matched Voronoi cells of oxygen sublattices, [110]-oriented α-Fe2O3 films develop on fluorine-doped tin oxide. Further measurements of charge transport characteristics and photoelectronic effects highlight the importance and advantages of coherent interfaces and well-defined orientation in textured α-Fe2O3 films. Textured growth of lattice-mismatched oxides, including spinel Co3O4, fluorite CeO2, perovskite BiFeO3 and even halide perovskite Cs2AgBiBr6, on fluorine-doped tin oxide is also achieved, offering new opportunities to develop high-performance transparent-conducting-oxide-supported devices.

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Fig. 1: Structural measurements of α-Fe2O3 films deposited on FTO and fused silica glass.
Fig. 2: Dimensional matching of cations at the α-Fe2O3/FTO interface.
Fig. 3: Dimensional and chemical matching between α-Fe2O3(110) and SnO2(101).
Fig. 4: Out-of-plane conductivity in α-Fe2O3 films with [110] orientation and random orientation.
Fig. 5: Charge separation in α-Fe2O3 films with [110] orientation and random orientation.

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Data availability

All the relevant source data in this study are provided in the article and its Supplementary Information and are available from the corresponding authors upon request. Source data are provided with this paper.

Code availability

MTEX, a free MATLAB (R2018b) toolbox at https://mtex-toolbox.github.io/, is used to construct the pole figure and anisotropic electrical conductivity.

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Acknowledgements

We thank financial support from the National Science Fund for Distinguished Young Scholars (no. 22025202), National Key Research and Development Program of China (no. 2021YFA1502100), National Natural Science Foundation of China (nos. 51902153 and 51972165), Natural Science Foundation of Jiangsu Province of China (no. BK20202003), a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions and the program B for Outstanding PhD candidate of Nanjing University.

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Authors and Affiliations

  1. Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences, Nanjing University, Nanjing, People’s Republic of China

    Huiting Huang, Jun Wang, Minyue Zhao, Ningsi Zhang, Yingfei Hu, Jianyong Feng, Zhaosheng Li & Zhigang Zou

  2. Jiangsu Key Laboratory for Nano Technology, School of Physics, Nanjing University, Nanjing, People’s Republic of China

    Jun Wang, Yingfei Hu, Zhaosheng Li & Zhigang Zou

  3. State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, People’s Republic of China

    Yong Liu & Fengtao Fan

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Contributions

Z.L. supervised the project. J.F. and Z.L. conceived the research and designed the experiments. H.H., J.W. and M.Z. prepared the sample films, conducted the XRD characterization and analysed the pole figures. H.H., N.Z. and Y.H. measured and analysed the Raman spectra and TEM imaging. Y.L. and F.F. carried out the AFM characterization. H.H., Y.L. and F.F. analysed the I–V curves and photovoltages of the sample films. H.H., J.F. and Z.L. discussed and analysed the lattice-matching paradigm. H.H. and M.Z. designed the energy device setup. H.H. and J.F. wrote the manuscript. All authors contributed to the analysis of the experimental data and revised the paper.

Corresponding authors

Correspondence to Jianyong Feng or Zhaosheng Li.

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Nature Materials thanks Jagdish Narayan, Sheng Xu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Schematic illustration of structures and anisotropic electrical conductivities of (a) SnO2 and (b) α-Fe2O3.

The electrical conductivity along the trigonal axis/fourfold axis of α-Fe2O3/SnO2 (both denoted as \({\sigma }_{\perp (001)}\)) are served as the references based on literatures21,22. The anisotropic electrical conductivities are calculated in MTEX toolbox23.

Extended Data Fig. 2 Stacking of α-Fe2O3 (orange motifs) on SnO2 (blue motifs) at the sub-unit cell level.

Motifs of α-Fe2O3 (001) dimensionally match but chemically mismatch with those of SnO2 (101). While motifs of α-Fe2O3 (104) chemically match but dimensionally mismatch with those of SnO2 (101). Both dimensional and chemical matching are achieved between motifs of α-Fe2O3 (110) and SnO2 (101). Atomic arrangements of these models are shown in Supplementary Figs. 7–9.

Supplementary information

Supplementary Information

Supplementary Notes 1 and 2, Figs. 1–31 and Table 1.

Source data

Source Data Fig. 1

Statistical source data for Fig. 1.

Source Data Fig. 4

Statistical source data for Fig. 4.

Source Data Fig. 5

Statistical source data for Fig. 5.

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Huang, H., Wang, J., Liu, Y. et al. Stacking textured films on lattice-mismatched transparent conducting oxides via matched Voronoi cell of oxygen sublattice. Nat. Mater. 23, 383–390 (2024). https://doi.org/10.1038/s41563-023-01746-3

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