More Like this

1. Local ordering in Ge/Ge–Sn semiconductor alloy core/shell nanowires revealed by extended x-ray absorption fine structure (EXAFS)

   https://doi.org/10.1063/5.0136746  

   Lentz, J. Zach; Woicik, J. C.; Bergschneider, Matthew; Davis, Ryan; Mehta, Apurva; Cho, Kyeongjae; McIntyre, Paul C. (February 2023, Applied Physics Letters)

   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
2. Lattice matched GeSn/InAlAs heterostructure: role of Sn in energy band alignment, atomic layer diffusion and photoluminescence

   https://doi.org/10.1039/d3tc01018j  

   Karthikeyan, Sengunthar; Joshi, Rutwik; Zhao, Jing; Bodnar, Robert J.; Magill, Brenden A.; Pleimling, Yannick; Khodaparast, Giti A.; Hudait, Mantu K. (June 2023, Journal of Materials Chemistry C)

   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
3. Ultra-low temperature synthesis of Ge-based optical materials and devices on Si using GeH ₃ Cl

   https://doi.org/10.1039/d2tc02862j  

   Zhang, Aixin; Mircovich, Matthew A.; Ringwala, Dhruve A.; Poweleit, Christian D.; Roldan, Manuel A.; Menéndez, José; Kouvetakis, John (September 2022, Journal of Materials Chemistry C)

   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
4. Self-Assembled InAsP and lnAlAs Nanowires on Graphene Via Pseudo-Van Der Waals Epitaxy

   https://doi.org/10.1109/NANO.2018.8626308  

   Baboli, Mohadeseh A.; Slocum, Michael A.; Giussani, Alessandro; Hubbard, Seth M.; Mohseni, Parsian K. (July 2018, 2018 IEEE 18th International Conference on Nanotechnology (IEEE-NANO))

   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
5. Substrate Orientation Mediated Epitaxial GeSn Optoelectronic Materials

   Hudait, M K; Karthikeyan, S; Johnston, S; Joshi, R; Priya, D; Laha, A; Mahapatra, S (October 2023, Conference presentation (6th Tri-Service GeSn Conference))

   Researchers have been aggressively investigating group-IV (Ge, SiGeSn, GeSn) optoelectronic materials to realize tunable wavelength lasers, photodetectors, and transistors. By exploiting strain and bandgap engineering of these materials via choice of substrate orientation and intelligent buffer engineering as well as precise control of Sn alloy composition during material synthesis, it will offer widespread device applications. There is an opportunity to improve the device-level quality of GeSn material systems along with higher Sn incorporation that face growth challenges during epitaxy. The current research work presents the substrate orientation and misorientation (100)/2˚, (100)/6˚, (110), (111) mediated epitaxial GeSn and Ge optoelectronic materials synthesized via MBE and analyzed using several analytical tools. X-ray analysis demonstrated high quality GeSn materials with less broadening and good symmetricity on (100) compared to (110) GeSn materials. Minority carrier lifetimes of these GeSn epilayers were extracted as > 400 ns for the (100) substrate misoriented by 6˚ towards [110] direction. Raman spectroscopy measurements were performed to study the vibrational properties, where the LO phonon wavenumber shifts at ωLO = 301.11 ± 0.8 cm¬–1 from (100)/2˚, (100)/6˚ and (110) oriented GeSn epilayers that were synthesized in equivalent growth conditions. Cross-sectional TEM of (100)/2˚ GeSn sample was performed that revealed good quality GeSn material on GaAs. Elimination of the interfaced electronic dipole charge effects, that destabilize the group-IV/group III-V heterointerface and further layer growths, is attributed to aid in achieving superior quality GeSn epitaxial materials over a (100) substrate that is misoriented by 6˚ towards the [110] direction. This substrate offcut will enable to annihilate antiphase domains due to polar-on-non-polar epitaxial growth, which further reduce non-radiative recombination centers in GeSn material. Hence, growth of GeSn material on misoriented (100) substrate offers two-fold benefits: (i) reduced active defects at the GeSn/III-V heterointerface, and (ii) self-annihilation of the antiphase domain boundaries for enhancing the efficiency of optical devices. 

   more » « less