We describe an alternative strategy to the fabrication of Ge–Sn based materials on Si by using chlorogermane (GeH 3 Cl) instead of the specialty Ge hydrides (Ge 2 H 6 , Ge 3 H 8 , Ge 4 H 10 ) currently employed as ultra-low temperature sources of Ge. This simpler and potentially more practical chlorinated derivative is obtained in high yields and in research-grade purity by direct reactions of commercial GeH 4 and SnCl 4 and exhibits favorable physical and chemical properties that make it an effective source of Ge for a wide range of chemical vapor deposition (CVD) processing conditions. As a proof-of concept, we have employed GeH 3 Cl to demonstrate deposition of pure Ge and GeSn hetero-structures on large-area Si wafers, at conditions compatible with current specialty methods for next generation technologies but with higher deposition efficiency, ensuring an optimal use of the Ge feedstock. In the case of pure Ge, GeH 3 Cl has enabled growth of thick and uniform Ge layers with flat surfaces and relaxed microstructures at 330–360 °C, exhibiting lower residual doping than obtained by alternate Ge hydride methods. GeH 3 Cl allows for in situ doping with the same facility as the Ge hydrides, and this has enabled the design and fabrication of homo-structure pin photodetectors exhibiting low dark current densities and closer to ideal optical collection efficiencies when compared to devices produced by other Ge-on-Si approaches. In the case of GeSn, the high reactivity of GeH 3 Cl toward Sn hydrides has enabled the formation of mono-crystalline alloy layers at ultra-low temperatures between 200–300 °C and conditions akin to molecular beam epitaxy (MBE). Combined, these results suggest an intriguing potential for this new CVD process in the device-application space. The deployment of GeH 3 Cl as a highly reactive low-temperature Ge-source could not only improve on the current wasteful methods that use GeH 4 , but also eliminate the need for the higher-cost polygermanes.
more »
« less
Bending and precipitate formation mechanisms in epitaxial Ge-core/GeSn-shell nanowires
Core–shell Ge/GeSn nanowires provide a route to dislocation-free single crystal germanium-tin alloys with desirable light emission properties because the Ge core acts as an elastically compliant substrate during misfitting GeSn shell growth. However, the uniformity of tin incorporation during reduced pressure chemical vapor deposition may be limited by the kinetics of mass transfer to the shell during GeSn growth. The balance between Sn precursor flux and available surfaces for GeSn nucleation and growth determines whether defects are formed and their type. On the one hand, when the Sn precursor delivery is insufficient, local variations in Sn arrival rate at the nanowire surfaces during GeSn growth produce asymmetries in shell growth that induce wire bending. This inhomogeneous elastic dilatation due to the varying composition occurs via deposition of Sn-poor regions on some of the {112} sidewall facets of the nanowires. On the other hand, when the available nanowire surface area is insufficient to accommodate the arriving Sn precursor flux, Sn-rich precipitate formation results. Between these two extremes, there exists a regime of growth conditions and nanowire densities that permits defect-free GeSn shell growth.
more »
« less
- Award ID(s):
- 2003266
- NSF-PAR ID:
- 10353773
- Date Published:
- Journal Name:
- Nanoscale
- Volume:
- 13
- Issue:
- 41
- ISSN:
- 2040-3364
- Page Range / eLocation ID:
- 17547 to 17555
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Germanium alloyed with α-tin (GeSn) transitions to a direct bandgap semiconductor of significance for optoelectronics. It is essential to localize the carriers within the active region for improving the quantum efficiency in a GeSn based laser. In this work, epitaxial GeSn heterostructure material systems were analyzed to determine the band offsets for carrier confinement: (i) a 0.53% compressively strained Ge 0.97 Sn 0.03 /AlAs; (ii) a 0.81% compressively strained Ge 0.94 Sn 0.06 /Ge; and (iii) a lattice matched Ge 0.94 Sn 0.06 /In 0.12 Al 0.88 As. The phonon modes in GeSn alloys were studied using Raman spectroscopy as a function of Sn composition, that showed Sn induced red shifts in wavenumbers of the Ge–Ge longitudinal optical phonon mode peaks. The material parameter b representing strain contribution to Raman shifts of a Ge 0.94 Sn 0.06 alloy was determined as b = 314.81 ± 14 cm −1 . Low temperature photoluminescence measurements were performed at 79 K to determine direct and indirect energy bandgaps of E g,Γ = 0.72 eV and E g,L = 0.66 eV for 0.81% compressively strained Ge 0.94 Sn 0.06 , and E g,Γ = 0.73 eV and E g,L = 0.68 eV for lattice matched Ge 0.94 Sn 0.06 epilayers. Chemical effects of Sn atomic species were analyzed using X-ray photoelectron spectroscopy (XPS), revealing a shift in Ge 3d core level (CL) spectra towards the lower binding energy affecting the bonding environment. Large valence band offset of Δ E V = 0.91 ± 0.1 eV and conduction band offset of Δ E C,Γ–X = 0.64 ± 0.1 eV were determined from the Ge 0.94 Sn 0.06 /In 0.12 Al 0.88 As heterostructure using CL spectra by XPS measurements. The evaluated band offset was found to be of type-I configuration, needed for carrier confinement in a laser. In addition, these band offset values were compared with the first-principles-based calculated Ge/InAlAs band alignment, and it was found to have arsenic up-diffusion limited to 1 monolayer of epitaxial GeSn overlayer, ruling out the possibility of defects induced modification of band alignment. Furthermore, this lattice matched GeSn/InAlAs heterostructure band offset values were significantly higher than GeSn grown on group IV buffer/substrates. Therefore, a lattice matched GeSn/InAlAs material system has large band offsets offering superior carrier confinement to realize a highly efficient GeSn based photonic device.more » « less
-
Short-range atomic order in semiconductor alloys is a relatively unexplored topic that may promote design of new materials with unexpected properties. Here, local atomic ordering is investigated in Ge–Sn alloys, a group-IV system that is attractive for its enhanced optoelectronic properties achievable via a direct gap for Sn concentrations exceeding ≈10 at. %. The substantial misfit strain imposed on Ge–Sn thin films during growth on bulk Si or Ge substrates can induce defect formation; however, misfit strain can be accommodated by growing Ge–Sn alloy films on Ge nanowires, which effectively act as elastically compliant substrates. In this work, Ge core/Ge 1−x Sn x ( x ≈ 0.1) shell nanowires were characterized with extended x-ray absorption fine structure (EXAFS) to elucidate their local atomic environment. Simultaneous fitting of high-quality EXAFS data collected at both the Ge K-edge and the Sn K-edge reveals a large (≈ 40%) deficiency of Sn in the first coordination shell around a Sn atom relative to a random alloy, thereby providing the first direct experimental evidence of significant short-range order in this semiconductor alloy system. Comparison of path length data from the EXAFS measurements with density functional theory simulations provides alloy atomic structures consistent with this conclusion.more » « less
-
Solvents employed in the solution processing of metal halide perovskites are known to play a key role in defining the morphology and properties of the resulting thin film, and thus the performance of perovskite solar cell devices. Accurate metrics are needed that are capable of differentiating among candidates, finding solvents that adequately solubilize the various precursor species in solution and facilitate the nucleation and growth of these materials. Existing metrics such as the unsaturated Mayer bond order (UMBO) and the Gutmann donor number (DN) have been tested for lead iodide perovskite systems; but there has yet to be a comprehensive study on their transferability to lead-free perovskite solutions. We use ab initio methods (density functional theory) and regression analysis tools to study the usefulness of DN and BF 3 affinity scales in this regard. We compared the relative effectiveness of these scales to describe interactions between solvents and BX n perovskite salts of lead (Pb 2+ ), tin (Sn 2+ and Sn 4+ ), germanium (Ge 2+ ), bismuth (Bi 3+ ), and antimony (Sb 3+ and Sb 5+ ). The DN proved to be a better representation than the BF 3 of such interactions, reflecting the closer similarity of these species to the “parent” SbCl 5 Lewis acid than to BF 3 . In addition, we have uncovered the usefulness of the lithium cation affinity metric (LCA) to describe the strength of interactions between solvents and A-site cations ( e.g. Na + , K + , Rb + and Cs + ) in all-inorganic metal halide perovskite solutions. We find that the coordination strengths of solvents towards species in all-inorganic metal halide perovskite solutions are best described by two different metrics with distinct modes of action: DN differentiates among BX n salt complexes, and LCA among A-site cation species. This revelation can help guide the choice of solvent to optimize processing conditions. It also emphasizes the importance of selecting solvents whose DN and LCA optimize coordination to key Lewis acid species in all-inorganic perovskite solutions.more » « less
-
Vertically-aligned, high aspect ratio In InAsyP1-y, InxAl1-xAs, and core-shell InAsP-InP nanowires (NWs) are grown directly on two-dimensional (2-D) monolayer graphene via seed-free pseudo-van der Waals epitaxy (vdWE), as reported here for the first time. Growth is achieved using metalorganic chemical vapor deposition (MOCVD). By altering growth temperature and molar flow ratio of precursors, the composition Of InAsyP1-y NWs can be tuned within the 1 ≤ y ≤ 0.8 range. Similarly, by tuning the group-III precursor flow rates, InxAl1-x As composition can be modified in the range. NW morphology and NW array number density variances are measured for different ternary compositions as functions of precursor flow rates and growth temperature.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d1nr04220c
