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 intensities is found to be strongly correlated with the reverse-bias dark current measured in the same devices.

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 emission wavelength from 1550 nm to 2500 nm. On the other hand, the emission intensities show a complex dependence that cannot be explained solely on the basis of Sn concentrations. Detailed theoretical modeling of these intensities makes it possible to extract recombination lifetimes that are found to be more than three times longer in samples in which strain relaxation has not occurred at the n-i interface, demonstrating the existence of a large non-radiative contribution from the relaxation defects. This finding is particularly significant for direct gap diodes with y > 0.09, for which it is practically impossible to avoid strain relaxation in n-Ge/i-Ge1−ySny/p-Ge analogs. The new designs introduced here open the door to the fabrication of highly efficient electrically pumped systems for applications in future generations of integrated photonics.

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 architectures incorporating Ge1-xSnx intermediate layers (x ∼ 12% Sn) that served to mitigate the lattice mismatch with the Ge platform. This yielded fully coherent diode interfaces devoid of strain relaxation defects. The electrical measurements in this case revealed a sharp increase in reverse-bias dark currents by almost two orders of magnitude, in spite of the comparable crystallinity of the active layers. This observation is attributed to the enhancement of band-to-band tunneling when all the diode layers consist of direct gap materials and thus has implications for the design of light emitting diodes and lasers operating at desirable mid-IR wavelengths. Possible ways to engineer these diode characteristics and improve carrier confinement involve the incorporation of new barrier materials, in particular, ternary Ge1-x-ySixSny alloys. The possibility of achieving type-I structures using binary and ternary alloy combinations is discussed in detail, taking into account the latest experimental and theoretical work on band offsets involving such materials.

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.

Ge-Si based n-type films are synthesized using specially designed hydrides P(SiH 3 ) 3 , Ge 3 H 8 and Ge 4 H 10 for potential applications in next-generation CMOS technologies. The films are grown on Ge buffered Si(100) at 340 °C using two complementary methods. The first employs a gassource molecular epitaxy approach using Ge 4 H 10 to produce materials with P doping densities varying from 4 × 10 18 to a 3.5 × 10 19 cm −3 threshold. These materials are co-doped with Si concentrations ranging from 3 × 10 19 cm −3 to 3.5%, roughly in proportion with the amount of P(SiH 3 ) 3 used in the reactions. The second approach applies an alternative ultra-high vacuum chemical vapor deposition (UHV-CVD) technique and Ge 3 H 8 in place of Ge 4 H 10 to achieve ultra-high carrier concentrations up to ∼6 × 10 19 cm −3 . The Si content in this case is minimal-in the 2-6 × 10 19 cm −3 range-indicating that the growth mechanism allows only 'impurity' levels of Si to be incorporated. The active carrier densities in both cases closely reflect the absolute P content, indicating that the P atoms are mostly substitutional. The electron mobilities are significantly higher compared to state-of-the-art prototypes, probably due to superior microstructure and dearth of inactive donors in the lattice. P-I-N diodes fabricated using the P(SiH 3 ) 3 compound show I-V characteristics comparable to state-of-the-art results for Ge-on-Si devices and are virtually undistinguishable from similar diodes doped with the P(GeH 3 ) 3 precursor. These results confirm P(SiH 3 ) 3 as a viable CVD doping source that is practical from a process standpoint and therefore attractive for industrial scale-up.