The near-bandgap optical properties of Ge1-xSnx alloys were characterized by photovoltage spectroscopy and spectral ellipsometry measurements. Contributions of Urbach tailing as well as direct and indirect optical transitions were observed. The compositional dependence of direct bandgaps of strained GeSn films grown on a Ge buffered Si substrate was studied for up to 15% Sn content. The contribution to the photovoltage spectra of Ge1-xSnx alloys (x < 6%) from indirect optical transitions was observed at lower energies than from direct bandgaps. Using bowing parameters, a correlation was detected between calculated and measured indirect and direct bandgaps at 82 K. As the Sn content was increased, the difference between the energies of the indirect and direct bandgaps decreased, resulting in a smaller contribution of the indirect transitions due to competition with direct transitions and Urbach tails. Two sublayers with different Sn content, strain values and bandgaps were observed for samples with x ~12%. The results indicated that strain relaxation in films with thicknesses exceeding a critical value occurs via formation of a Sn-rich top layer with higher direct bandgap. These findings have important implications when designing IR photodetectors or solar cells.
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This content will become publicly available on November 14, 2024
Colloidal Synthesis of Homogeneous Ge1-x-ySiySnx Nanoalloys with Composition-Tunable Visible to Near IR Optical Properties
Group IV alloy nanocrystals (NCs) are a class of direct energy gap semiconductors that show high elemental abundance, low to non-toxicity, and composition-tunable absorption and emission properties. These properties have distinguished Ge1-xSnx NCs as an intriguing material for near-infrared (IR) optical studies. Achieving a material with efficient visible emission requires a modified class of Group IV alloys and the computational studies suggest that this can be achieved with Ge1-x-ySiySnx NCs. Herein, we report a colloidal strategy for the synthesis of bulk-like (10.3 ± 2.5 – 25.5 ± 5.3 nm) and quantum-confined (3.2 ± 0.6 – 4.2 ± 1.1 nm) Ge1-x-ySiySnx alloys that show strong size confinement effects and composition-tunable visible to near IR absorption and emission properties. This synthesis produces a homogeneous alloy with diamond cubic Ge structure and tunable Si (0.9 – 16.1%) and Sn (1.8 – 14.9%) compositions, exceeding the equilibrium solubility of Sn (<1%) in crystalline Si and Ge. Raman spectra of Ge1-x-ySiySnx alloys show a prominent redshift of the Ge-Ge peak and the emergence of a Ge-Si peak with increasing Si/Sn, suggesting the growth of homogeneous alloys. The smaller Ge1-x-ySiySnx NCs exhibit absorption onsets from 1.21 to 1.94 eV for x = 1.8 – 6.8% and y = 0.9 – 16.1% compositions, which are blueshifted from those reported for Ge1-x-ySiySnx bulk alloy films and Ge1-xSnx alloy NCs, indicating the influence of Si incorporation and strong size confinement effects. Solid-state photoluminescence (PL) spectra reveal core-related PL maxima from 1.77 – 1.97 eV in agreement with absorption onsets, consistent with the energy gaps calculated for ~3–4 nm alloy NCs. With facile low-temperature solution synthesis and direct control over physical properties, this methodology presents a noteworthy advancement in the synthesis of bulk-like and quantum-confined Ge1-x-ySiySnx alloys as versatile materials for future optical and electronic studies.
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- Award ID(s):
- 2211606
- NSF-PAR ID:
- 10513376
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Chemistry of Materials
- Volume:
- 35
- Issue:
- 21
- ISSN:
- 0897-4756
- Page Range / eLocation ID:
- 9007 to 9018
- Subject(s) / Keyword(s):
- Quantum dots, Gi/Ge/Sn alloys
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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