C. L. Senaratne

Compositional dependence of the direct and indirect band gaps in Ge1-ySny alloys from room temperature photoluminescence: Implications for the indirect to direct gap crossover in intrinsic and n-type materials

The compositional dependence of the lowest direct and indirect band gaps in Ge1−ySny alloys has been determined from room-temperature photoluminescence measurements. This technique is particularly attractive for a comparison of the two transitions because distinct features in the spectra can be associated with the direct and indirect gaps. However, detailed modeling of these room temperature spectra is required to extract the band gap values with the high accuracy required to determine the Sn concentration yc at which the alloy becomes a direct gap semiconductor. For the direct gap, this is accomplished using a microscopic model that allows the determination of direct gap energies with meV accuracy. For the indirect gap, it is shown that current theoretical models are inadequate to describe the emission properties of systems with close indirect and direct transitions. Accordingly, an ad hoc procedure is used to extract the indirect gap energies from the data. For y < 0.1 the resulting direct gap compositional dependence is given by ΔE0 = −(3.57 ± 0.06)y (in eV). For the indirect gap, the corresponding expression is ΔEind = −(1.64 ± 0.10)y (in eV). If a quadratic function of composition is used to express the two transition energies over the entire compositional range 0 y 1, the quadratic (bowing) coefficients are found to be b0 = 2.46 ± 0.06 eV (for E0) and bind = 1.03 ± 0.11 eV (for Eind). These results imply a crossover concentration yc = , much lower than early theoretical predictions based on the virtual crystal approximation, but in better agreement with predictions based on large atomic supercells.

Compositional dependence of the bowing parameter for the direct and indirect band gaps in Ge1−ySny alloys

Photoluminescence spectroscopy has been used to determine the direct gap E0 of Ge1−ySny alloys over a broad compositional range from pure Ge to Sn concentrations exceeding 10%. A fit of the compositional dependence of E0 using a standard quadratic expression is not fully satisfactory, revealing that the bowing parameter (quadratic coefficient) b0 is compositionally dependent. Excellent agreement with the data is obtained with b0(y) = (2.66 ± 0.09) eV − (5.4 ± 1.1)y eV. A theoretical model of the bowing is presented, which explains the strong compositional dependence of the bowing parameter and suggest a similar behavior for the indirect gap. Combining the model predictions with experimental data for samples with y ≤ 0.06, it is proposed that the bowing parameter for the indirect gap is bind(y) = (1.11 ± 0.07) eV − (0.78 ± 0.05)y eV. The compositional dependence of the bowing parameters shifts the crossover concentration from indirect to direct gap behavior to yc = 0.087, significantly higher than the valu...

Electroluminescence from GeSn heterostructure pin diodes at the indirect to direct transition

The emission properties of GeSn heterostructure pin diodes have been investigated. The devices contain thick (400–600 nm) Ge1−ySny i-layers spanning a broad compositional range below and above the crossover Sn concentration yc where the Ge1−ySny alloy becomes a direct-gap material. These results are made possible by an optimized device architecture containing a single defected interface thereby mitigating the deleterious effects of mismatch-induced defects. The observed emission intensities as a function of composition show the contributions from two separate trends: an increase in direct gap emission as the Sn concentration is increased, as expected from the reduction and eventual reversal of the separation between the direct and indirect edges, and a parallel increase in non-radiative recombination when the mismatch strains between the structure components is partially relaxed by the generation of misfit dislocations. An estimation of recombination times based on the observed electroluminescence intensi...

Ge1-ySny (y = 0.01-0.10) alloys on Ge-buffered Si: Synthesis, microstructure, and optical properties

Novel hydride chemistries are employed to deposit light-emitting Ge1-ySny alloys with y ≤ 0.1 by Ultra-High Vacuum Chemical Vapor Deposition (UHV-CVD) on Ge-buffered Si wafers. The properties of the resultant materials are systematically compared with similar alloys grown directly on Si wafers. The fundamental difference between the two systems is a fivefold (and higher) decrease in lattice mismatch between film and virtual substrate, allowing direct integration of bulk-like crystals with planar surfaces and relatively low dislocation densities. For y ≤ 0.06, the CVD precursors used were digermane Ge2H6 and deuterated stannane SnD4. For y ≥ 0.06, the Ge precursor was changed to trigermane Ge3H8, whose higher reactivity enabled the fabrication of supersaturated samples with the target film parameters. In all cases, the Ge wafers were produced using tetragermane Ge4H10 as the Ge source. The photoluminescence intensity from Ge1−ySny/Ge films is expected to increase relative to Ge1−ySny/Si due to the less def...

Non-radiative recombination in Ge1−ySny light emitting diodes: The role of strain relaxation in tuned heterostructure designs

This paper describes the properties of Ge1−ySny light emitting diodes with a broad range of Sn concentrations (y = 0.0–0.11). The devices are grown upon Si(100) platforms using ultra-low temperature deposition of highly reactive Ge and Sn hydrides. The device fabrication adopts two new photodiode designs which lead to optimized performance and enables a systematic study of the effects of strain relaxation on emission efficiency. In contrast with n-Ge/i-Ge1−ySny/p-Ge analogs, which in most cases contain two defected interfaces, our designs include a p-layer with composition Ge1−zSnz chosen to be z < y to facilitate light extraction, but with z close enough to y to guarantee no strain relaxation at the i/p interface. In addition, a Ge1−xSnx alloy is also used for the n layer, with compositions in the 0 ≤ x ≤ y range, so that defected and non-defected n/i interfaces can be studied. The electroluminescence spectra vs the Sn content y in the intrinsic layer of the diodes exhibit a monotonic shift in the emissi...

Frustrated incomplete donor ionization in ultra-low resistivity germanium films

The relationship between carrier concentration and donor atomic concentration has been determined in n-type Ge films doped with P. The samples were carefully engineered to minimize non-active dopant incorporation by using specially designed P(SiH3)3 and P(GeH3)3 hydride precursors. The in situ nature of the doping and the growth at low temperatures, facilitated by the Ge3H8 and Ge4H10 Ge sources, promote the creation of ultra-low resistivity films with flat doping profiles that help reduce the errors in the concentration measurements. The results show that Ge deviates strongly from the incomplete ionization expected when the donor atomic concentration exceeds Nd = 1017 cm−3, at which the energy separation between the donor and Fermi levels ceases to be much larger than the thermal energy. Instead, essentially full ionization is seen even at the highest doping levels beyond the solubility limit of P in Ge. The results can be explained using a model developed for silicon by Altermatt and coworkers, provided...

Direct gap Ge1-ySny alloys: Fabrication and design of mid-IR photodiodes

Chemical vapor deposition methods were developed, using stoichiometric reactions of specialty Ge3H8 and SnD4 hydrides, to fabricate Ge1-ySny photodiodes with very high Sn concentrations in the 12%–16% range. A unique aspect of this approach is the compatible reactivity of the compounds at ultra-low temperatures, allowing efficient control and systematic tuning of the alloy composition beyond the direct gap threshold. This crucial property allows the formation of thick supersaturated layers with device-quality material properties. Diodes with composition up to 14% Sn were initially produced on Ge-buffered Si(100) featuring previously optimized n-Ge/i-Ge1-ySny/p-Ge1-zSnz type structures with a single defected interface. The devices exhibited sizable electroluminescence and good rectifying behavior as evidenced by the low dark currents in the I-V measurements. The formation of working diodes with higher Sn content up to 16% Sn was implemented by using more advanced n-Ge1-xSnx/i-Ge1-ySny/p-Ge1-zSnz architectu...

Electroluminescence from Ge1−ySny diodes with degenerate pn junctions

The light emission properties of GeSn pn diodes were investigated as a function of alloy composition and doping levels. Very sharp interfaces between contiguous ultra-highly doped p- and n-layers were obtained using in situ doping with B2H6 and P(SiH3)3 in a chemical vapor deposition environment, yielding nearly ideal model systems for systematic studies. Changes in the doping levels and layer Sn concentrations are shown to greatly affect the electroluminescence spectra. This sensitivity should make it possible to optimize the emission efficiency for these structures in the interesting quasi-direct regime, for which direct gap luminescence is observed due to the proximity of the conduction band quasi-Fermi level to the minimum of the conduction band at the center of the Brillouin zone. Such structures represent the basic building block of Ge-based electrically pumped lasers.

Ge1−x−ySixSny light emitting diodes on silicon for mid-infrared photonic applications

This paper reports initial the demonstration of prototype Ge1−x−ySixSny light emitting diodes with distinct direct and indirect edges and high quality I-V characteristics. The devices are fabricated on Si (100) wafers in heterostructure pin geometry [n-Ge/i-Ge1−x−ySixSny/p-Ge(Sn/Si)] using ultra low-temperature (T < 300 °C) depositions of the highly reactive chemical sources Si4H10, Ge4H10, Ge3H8, and SnD4. The Sn content in the i-Ge1−x−ySixSny layer was varied from ∼3.5% to 11%, while the Si content was kept constant near 3%. The Si/Sn amounts in the p-layer were selected to mitigate the lattice mismatch so that the top interface grows defect-free, thereby reducing the deleterious effects of mismatch-induced dislocations on the optical/electrical properties. The spectral responsivity plots of the devices reveal sharp and well-defined absorption edges that systematically red-shift in the mid-IR from 1750 to 2100 nm with increasing Sn content from 3.5% to 11%. The electroluminescence spectra reveal strong ...

Ultralow Resistivity Ge: Sb heterostructures on Si Using Hydride Epitaxy of Deuterated Stibine and Trigermane

The nonconventional deuterated stibine (SbD3) compound has been used for the first time in combination with trigermane (Ge3H8) to produce hyper-doped Ge-on-Si films with carrier concentrations n > 10(20) cm(-3) and record-low resistivities ρ = 1.8 × 10(-4) Ω cm. The growth takes place on Ge and Ge1-xSix buffered Si(100) wafers at ultralow temperatures (∼330 °C) at which Sb diffusion is negligible, leading to extremely flat atomic profiles of the constituents. The Sb substitution in the Ge lattice is determined by RBS channeling and corroborated by high-resolution XRD, which also reveal a systematic increase in lattice constant vs concentration, as expected due to the incorporation of the larger Sb. High-resolution TEM illustrates defect-free monocrystalline structures with device-quality morphologies. The electrical characteristics of the samples are measured using Hall effect and resistivity measurements combined with contactless infrared ellipsometry and are found to be consistent with an extrapolation of the bulk Ge:Sb properties to the high carrier concentrations achieved in our films. The Sb/Ge ratio in the doped layers is approximately the same as that in the precursor reaction mixture, indicating a highly efficient Sb incorporation afforded by the compatible reactivity of the molecules employed in this study. The resultant films are attractive for next generation germanium technologies that require low-resistance n+ junctions or a Fermi level that approaches the direct gap minimum in the conduction band, which drastically enhances the optical emission efficiency of n-type Ge.