Probing Ge-Induced Strain and Emission in Rutile Sn <sub> 1– <i>x</i> </sub> Ge <sub> <i>x</i> </sub> O <sub>2</sub> Nanocrystals

Rutile-phase GeO<sub>2</sub> and its alloys, such as Sn<sub><i>x</i></sub>Ge<sub>1-<i>x</i></sub>O<sub>2</sub>, are promising semiconductors due to their ultrawide-bandgaps (4.4-4.7 eV), high carrier mobilities, ambipolar dopability, and excellent thermal conductivity. However, GeO<sub>2</sub> preferentially crystallizes in the α-quartz phase under ambient conditions, limiting the exploration of its rutile form. Alloying with rutile SnO<sub>2</sub> offers a route to stabilize this metastable phase. Here, we report the nanoscale characterization of rutile-Sn<sub><i>x</i></sub>Ge<sub>1-<i>x</i></sub>O<sub>2</sub> nanocrystals grown on Zn<sub>2</sub>GeO<sub>4</sub> nanowires, achieving Ge incorporation well beyond its solubility limit while preserving the rutile structure. Exploiting advanced X-ray nanoprobe techniques, we achieve a correlative view of the composition, structure, and optical properties within individual Sn<sub><i>x</i></sub>Ge<sub>1-<i>x</i></sub>O<sub>2</sub> nanostructures. Our results reveal preferential Ge accumulation along the faceted sides, generating local strain gradients without disrupting the rutile phase. Spatially resolved luminescence measurements show enhanced defect-related orange emission (∼2.1 eV) at the faceted nanocrystal edges. First-principles calculations confirm that while Ge incorporation modulates the bandgap of the alloy, the primary factors governing luminescence are the presence of oxygen vacancies and the increased surface-to-volume ratio at the crystallite edges. These findings establish a robust multimodal nanoscale approach for characterizing and engineering next-generation oxide nanomaterials with tunable optoelectronic properties.

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Journal
ACS Applied Materials & Interfaces
Published
2025-11-20
DOI
https://doi.org/10.1021/acsami.5c12549
Primary Topic
Semiconductor materials and devices
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article
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article

Probing Ge-Induced Strain and Emission in Rutile Sn 1– x Ge x O 2 Nanocrystals

Jaime Dolado, Sandra Benter, Ruth Martínez-Casado, Gema Martínez‐Criado et al.
ACS Applied Materials & Interfaces
Semiconductor materials and devices
article

Probing Ge-Induced Strain and Emission in Rutile Sn 1– x Ge x O 2 Nanocrystals

Jaime Dolado, Sandra Benter, Ruth Martínez-Casado, Gema Martínez‐Criado, Ana M. Sánchez, P. Hidalgo, Edoardo Zatterin, Bianchi Méndez, Tobias Urs Schülli, Steven A. Hindsmarsh
article en

Abstract

Rutile-phase GeO<sub>2</sub> and its alloys, such as Sn<sub><i>x</i></sub>Ge<sub>1-<i>x</i></sub>O<sub>2</sub>, are promising semiconductors due to their ultrawide-bandgaps (4.4-4.7 eV), high carrier mobilities, ambipolar dopability, and excellent thermal conductivity. However, GeO<sub>2</sub> preferentially crystallizes in the α-quartz phase under ambient conditions, limiting the exploration of its rutile form. Alloying with rutile SnO<sub>2</sub> offers a route to stabilize this metastable phase. Here, we report the nanoscale characterization of rutile-Sn<sub><i>x</i></sub>Ge<sub>1-<i>x</i></sub>O<sub>2</sub> nanocrystals grown on Zn<sub>2</sub>GeO<sub>4</sub> nanowires, achieving Ge incorporation well beyond its solubility limit while preserving the rutile structure. Exploiting advanced X-ray nanoprobe techniques, we achieve a correlative view of the composition, structure, and optical properties within individual Sn<sub><i>x</i></sub>Ge<sub>1-<i>x</i></sub>O<sub>2</sub> nanostructures. Our results reveal preferential Ge accumulation along the faceted sides, generating local strain gradients without disrupting the rutile phase. Spatially resolved luminescence measurements show enhanced defect-related orange emission (∼2.1 eV) at the faceted nanocrystal edges. First-principles calculations confirm that while Ge incorporation modulates the bandgap of the alloy, the primary factors governing luminescence are the presence of oxygen vacancies and the increased surface-to-volume ratio at the crystallite edges. These findings establish a robust multimodal nanoscale approach for characterizing and engineering next-generation oxide nanomaterials with tunable optoelectronic properties.

ACS Applied Materials & InterfacesVol. 17(48)
Universidad Complutense de Madrid (ES), Consejo Superior de Investigaciones Científicas (ES), European Synchrotron Radiation Facility (FR), University of Warwick (GB), Unidades Centrales Científico-Técnicas (ES), Instituto de Ciencia de Materiales de Madrid (ES), Material Physics Center (ES)
Openalex Percentile: Top 65%
Semiconductor materials and devices
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