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Semiconductor nanowires have shown great potential for enabling ultra-compact lasers for integrated photonics platforms. Despite the impressive progress in developing nanowire lasers, their integration into Si photonics platforms remains challenging largely due to the use of III-V and II-VI semiconductors as gain media. These materials not only have high material costs, but also require inherently complex integration with Si-based fabrication processing, increasing overall costs and thereby limiting their large-scale adoption. Furthermore, these material-based nanowire lasers rarely emit above 2 um, which is a technologically important wavelength regime for various applications in imaging and quantum sensing. Recently, group-IV nanowires, particularly direct bandgap GeSn nanowires capable of emitting above 2 um, have emerged as promising cost-effective gain media for Si-compatible nanowire lasers, but there has been no successful demonstration of lasing from this seemingly promising nanowire platform. Herein, we report the experimental observation of lasing above 2 um from a single bottom-up grown GeSn nanowire. By harnessing strain engineering and optimized cavity designs simultaneously, the single GeSn nanowire achieves an amplified material gain that can sufficiently overcome minimized optical losses, resulting in a single-mode lasing with an ultra-low threshold of ~5.3 kW cm-2. Our finding paves the way for all-group IV mid-infrared photonic-integrated circuits with compact Si-compatible lasers for on-chip classical and quantum sensing and free-space communication., Comment: 24 pages, 4 figures

Due to their narrow band gap and compatibility with silicon processing, germanium-tin (Ge$_{1-x}$Sn$_x$) alloys are a versatile platform for scalable integrated mid-infrared photonics. These semiconductors are typically grown on silicon wafers using Ge as an interlayer. However, the large lattice mismatch in this heteroepitaxy protocol leads to the build-up of compressive strain in the grown layers. This compressive strain limits the material quality and its thermal stability besides expanding the band gap, thereby increasing the Sn content needed to cover a broader range in the mid-infrared. Released Ge$_{1-x}$Sn$_x$ membranes provide an effective way to mitigate these harmful effects of the epitaxial strain and control the band gap energy while enabling the hybrid integration onto different substrates. With this perspective, herein strain-relaxed Ge$_{0.89}$Sn$_{0.11}$ membranes are fabricated and subsequently transfer-printed with metal contacts to create multiple photodetectors in a single transfer step. The resulting photodetectors exhibit an extended photodetection cutoff reaching a wavelength of $3.1 \,\mu$m, coupled with a significant reduction in the dark current of two orders of magnitude as compared to as-grown photoconductive devices. The latter yields a reduced cutoff of $2.8 \,\mu$m due to the inherent compressive strain. Furthermore, the impact of chemical treatment and annealing on the device performance was also investigated showing a further reduction in the dark current. The demonstrated transfer printing, along with the use of an adhesive layer, would allow the transfer of multiple GeSn membranes onto virtually any substrate. This approach paves the way for scalable fabrication of hybrid optoelectronic devices leveraging the tunable band gap of Ge$_{1-x}$Sn$_x$ in the mid-wave infrared range.

There is an increasing need for silicon-compatible high bandwidth extended-short wave infrared (e-SWIR) photodetectors (PDs) to implement cost-effective and scalable optoelectronic devices. These systems are quintessential to address several technological bottlenecks in detection and ranging, surveillance, ultrafast spectroscopy, and imaging. In fact, current e-SWIR high bandwidth PDs are predominantly made of III-V compound semiconductors and thus are costly and suffer a limited integration on silicon besides a low responsivity at wavelengths exceeding $2.3 \,\mu$m. To circumvent these challenges, Ge$_{1-x}$Sn$_{x}$ semiconductors have been proposed as building blocks for silicon-integrated high-speed e-SWIR devices. Herein, this study demonstrates a vertical all-GeSn PIN PDs consisting of p-Ge$_{0.92}$Sn$_{0.08}$/i-Ge$_{0.91}$Sn$_{0.09}$/n-Ge$_{0.89}$Sn$_{0.11}$ and p-Ge$_{0.91}$Sn$_{0.09}$/i-Ge$_{0.88}$Sn$_{0.12}$/n-Ge$_{0.87}$Sn$_{0.13}$ heterostructures grown on silicon following a step-graded temperature-controlled epitaxy protocol. The performance of these PDs was investigated as a function of the device diameter in the $10-30 \,\mu$m range. The developed PD devices yield a high bandwidth of 12.4 GHz at a bias of 5V for a device diameter of $10 \,\mu$m. Moreover, these devices show a high responsivity of 0.24 A/W, a low noise, and a $2.8 \,\mu$m cutoff wavelength thus covering the whole e-SWIR range.

Cost-effective mid-wave infrared (MWIR) optoelectronic devices are of utmost importance to a plethora of applications such as night vision, thermal sensing, autonomous vehicles, free-space communication, and spectroscopy. To this end, leveraging the ubiquitous silicon-based processing has emerged as a powerful strategy that can be accomplished through the use of group IV germanium-tin (GeSn) alloys. Indeed, due to their compatibility with silicon and their tunable bandgap energy covering the entire MWIR range, GeSn semiconductors are frontrunner platforms for compact and scalable MWIR technologies. However, the GeSn large lattice parameter has been a major hurdle limiting the quality of GeSn epitaxy on silicon wafers. Herein, it is shown that sub-20 nm Ge nanowires (NWs) provide effective compliant substrates to grow Ge$_{1-x}$Sn$_{x}$ alloys with a composition uniformity over several micrometers with a very limited build-up of the compressive strain. Ge/Ge$_{1-x}$Sn$_{x}$ core/shell NWs with Sn content spanning the 6 to 18 at.$\%$ range are demonstrated and integrated in photoconductive devices exhibiting a high signal-to-noise ratio at room temperature and a tunable cutoff wavelength covering the 2.0 $\mu$m to 3.9 $\mu$m range. Additionally, the processed NW-based detectors were used in uncooled imagers enabling the acquisition of high-quality images under both broadband and laser illuminations without a lock-in technique.

Silicon-compatible short- and mid-wave infrared emitters are highly sought-after for on-chip monolithic integration of electronic and photonic circuits to serve a myriad of applications in sensing and communication. To address this longstanding challenge, GeSn semiconductors have been proposed as versatile building blocks for silicon-integrated optoelectronic devices. In this regard, this work demonstrates light-emitting diodes (LEDs) consisting of a vertical PIN double heterostructure p-Ge$_{0.94}$Sn$_{0.06}$/i-Ge$_{0.91}$Sn$_{0.09}$/n-Ge$_{0.95}$Sn$_{0.05}$ grown epitaxially on a silicon wafer using germanium interlayer and multiple GeSn buffer layers. The emission from these GeSn LEDs at variable diameters in the 40-120 $\mu$m range is investigated under both DC and AC operation modes. The fabricated LEDs exhibit a room temperature emission in the extended short-wave range centered around 2.5 $\mu$m under an injected current density as low as 45 A/cm$^2$. By comparing the photoluminescence and electroluminescence signals, it is demonstrated that the LED emission wavelength is not affected by the device fabrication process or heating during the LED operation. Moreover, the measured optical power was found to increase monotonically as the duty cycle increases indicating that the DC operation yields the highest achievable optical power. The LED emission profile and bandwidth are also presented and discussed.

CMOS-compatible short- and mid-wave infrared emitters are highly coveted for the monolithic integration of silicon-based photonic and electronic integrated circuits to serve a myriad of applications in sensing and communications. In this regard, a group IV germanium-tin (GeSn) material epitaxially grown on silicon (Si) emerges as a promising platform to implement tunable infrared light emitters. Indeed, upon increasing the Sn content, the bandgap of GeSn narrows and becomes direct, making this material system suitable for developing an efficient silicon-compatible emitter. With this perspective, microbridge PIN GeSn LEDs with a small footprint of $1,520$ $\mu$m$^2$ are demonstrated and their operation performance is investigated. The spectral analysis of the electroluminescence emission exhibits a peak at $2.31$ $\mu$m and it red-shifts slightly as the driving current increases. It is found that the microbridge LED operates at a dissipated power as low as $10.8$ W at room temperature and just $3$ W at $80$ K. This demonstrated low operation power is comparable to that reported for LEDs having a significantly larger footprint reaching $10^6$ $\mu$m$^2$. The efficient thermal dissipation of the current design helped to reduce the heat-induced optical losses, thus enhancing light emission. Further performance improvements are envisioned through thermal and optical simulations of the microbridge design. The use of GeSnOI substrate for developing a similar device is expected to improve optical confinement for the realization of electrically driven GeSn lasers.

Ge$_{1-x}$Sn$_x$ semiconductors hold the premise for large-scale, monolithic mid-infrared photonics and optoelectronics. However, despite the successful demonstration of several Ge$_{1-x}$Sn$_x$-based photodetectors and emitters, key fundamental properties of this material system are yet to be fully explored and understood. In particular, little is known about the role of the material properties in controlling the recombination mechanisms and their consequences on the carrier lifetime. Evaluating the latter is in fact fraught with large uncertainties that are exacerbated by the difficulty to investigate narrow bandgap semiconductors. To alleviate these limitations, herein we demonstrate that the radiative carrier lifetime can be obtained from straightforward excitation power- and temperature- dependent photoluminescence measurements. To this end, a theoretical framework is introduced to simulate the measured spectra by combining the band structure calculations from the k.p theory and the envelope function approximation (EFA) to estimate the absorption and spontaneous emission. Based on this model, the temperature-dependent emission from Ge$_{0.83}$Sn$_{0.17}$ samples at a biaxial compressive strain of $-1.3\%$ was investigated. The simulated spectra reproduce accurately the measured data thereby enabling the evaluation of the steady-state radiative carrier lifetimes, which are found in the 3-22 ns range for temperatures between 10 and 300 K at an excitation power of 0.9 kW/cm$^2$. For a lower power of 0.07 kW/cm$^2$, the obtained lifetime has a value of 1.9 ns at 4 K. The demonstrated approach yielding the radiative lifetime from simple emission spectra will provide valuable inputs to improve the design and modeling of Ge$_{1-x}$Sn$_x$-based devices.

The short-wave infrared (SWIR) is an underexploited portion of the electromagnetic spectrum in metasurface-based nanophotonics despite its strategic importance in sensing and imaging applications. This is mainly attributed to the lack of material systems to tailor light-matter interactions in this range. Herein, we address this limitation and demonstrate an all-dielectric silicon-integrated metasurface enabling polarization-induced Fano resonance control at SWIR frequencies. The platform consists of a two-dimensional Si/GeSn core/shell nanowire array on a silicon wafer. By tuning the light polarization, we show that the metasurface reflectance can be efficiently engineered due to Fano resonances emerging from the electric and magnetic dipoles competition. The interference of optically induced dipoles in high-index nanowire arrays offers additional degrees of freedom to tailor the directional scattering and the flow of light while enabling sharp polarization-modulated resonances. This tunability is harnessed in nanosensors yielding an efficient detection of 10^{-2} changes in the refractive index of the surrounding medium.

Ge/SiGe multi-quantum well heterostructures are highly sought-after for silicon-integrated optoelectronic devices operating in the broad range of the electromagnetic spectrum covering infrared to terahertz wavelengths. However, the epitaxial growth of these heterostructures at a thickness of a few microns has been a challenging task due the lattice mismatch and its associated instabilities resulting from the formation of growth defects. To elucidates these limits, we outline herein a process for the strain-balanced growth on silicon of 11.1 nm/21.5 nm Ge/Si0.18Ge0.82 superlattices (SLs) with a total thickness of 16 {\mu}m corresponding to 500 periods. Composition, thickness, and interface width are preserved across the entire SL heterostructure, which is an indication of limited Si-Ge intermixing. High crystallinity and low defect density are obtained in the Ge/Si0.18Ge0.82 layers, however, the dislocation pile up at the interface with the growth substate induces micrometer-longs cracks on the surface. This eventually leads to significant layer tilt in the strain-balanced SL and in the formation of millimeter-long, free-standing flakes. These results confirm the local uniformity of structural properties and highlight the critical importance of threading dislocations in shaping the wafer-level stability of thick multi-quantum well heterostructures required to implement effective silicon-compatible Ge/SiGe photonic devices.

The monolithic integration of extended short-wave infrared (e-SWIR) photodetectors (PDs) on silicon is highly sought-after to implement manufacturable, cost-effective sensing and imaging technologies. With this perspective, GeSn PIN PDs have been the subject of extensive investigations because of their bandgap tunability and silicon compatibility. However, due to growth defects, these PDs suffer a relatively high dark current density as compared to commercial III-V PDs. Herein, we elucidate the mechanisms governing the dark current in $2.6 \, \mu$m GeSn PDs at a Sn content of $10$ at.%. It was found that in the temperature range of $293 \, $K -- $363 \,$K and at low bias, the diffusion and Shockley-Read-Hall (SRH) leakage mechanisms dominate the dark current in small diameter ($20 \, \mu$m) devices, while combined SRH and trap assisted tunneling (TAT) leakage mechanisms are prominent in larger diameter ($160 \, \mu$m) devices. However, at high reverse bias, TAT leakage mechanism becomes dominant regardless of the operating temperature and device size. The effective non-radiative carrier lifetime in these devices was found to reach $\sim 300$ -- $400$ ps at low bias. Owing to TAT leakage current, however, this lifetime reduces progressively as the bias increases.

Recent development on Ge$_{1-x}$Sn$_x$ nanowires with high Sn content, beyond its solid solubility limit, make them attractive for all group-IV Si-integrated infrared photonics at nanoscale. Herein, we report a chemical vapour deposition-grown high Sn-content Ge-Ge$_{0.92}$Sn$_{0.08}$ core-shell based single nanowire photodetector operating at the optical communication wavelength of 1.55 $\mu$m. The atomic concentration of Sn in nanowires has been studied using X-ray photoelectron and Raman spectroscopy data. A metal-semiconductor-metal based single nanowire photodetector, fabricated via electron beam lithography process, exhibits significant room-temperature photoresponse even at zero bias. In addition to the high-crystalline quality and identical shell composition of the nanowire, the efficient collection of photogenerated carriers under an external electric field result in the superior responsivity and photoconductive gain as high as ~70.8 A/W and ~57, respectively at an applied bias of -1.0 V. The extra-ordinary performance of the fabricated photodetector demonstrates the potential of GeSn nanowires for future Si CMOS compatible on-chip optical communication device applications., Comment: 16 pages, 4 figures, Supplementary material (2 Figures, 2 tables)

The quiet quantum environment of holes in solid-state devices has been at the core of increasingly reliable architectures for quantum processors and memories.1-6 However, due to the lack of scalable materials to properly tailor the valence band character and its energy offsets, the precise engineering of light-hole (LH) states remains a serious obstacle toward coherent photon-spin interfaces needed for a direct mapping of the quantum information encoded in photon flying qubits to stationary spin processor.4-9 Herein, to alleviate this long-standing limitation we demonstrate an all-group IV low-dimensional system consisting of highly tensile strained germanium quantum well grown on silicon allowing new degrees of freedom to control and manipulate the hole states. Wafer-level, high bi-isotropic in-plane tensile strain ($>1\%$) is achieved using strain-engineered, metastable germanium-tin alloyed buffer layers yielding quantum wells with LH ground state, high $g$-factor anisotropy, and a tunable splitting of the hole subbands. The epitaxial heterostructures display sharp interfaces with sub-nanometer broadening and show room-temperature excitonic transitions that are modulated and extended to the mid-wave infrared by controlling strain and thickness. This ability to engineer quantum structures with LH selective confinement and controllable optical response enables manufacturable silicon-compatible platforms relevant to integrated quantum communication and sensing technologies.

The prospect of GeSn semiconductors for silicon-integrated infrared optoelectronics brings new challenges related to the metastability of this class of materials. As a matter of fact, maintaining a reduced thermal budget throughout all processing steps of GeSn devices is essential to avoid possible material degradation. This constraint is exacerbated by the need for higher Sn contents along with an enhanced strain relaxation to achieve efficient mid-infrared devices. Herein, as a low thermal budget solution for post-epitaxy processing, we elucidate the effects of laser thermal annealing (LTA) on strain-relaxed Ge$_{0.89}$Sn0$_{.11}$ layers and Ni-Ge$_{0.89}$Sn0$_{.11}$ contacts. Key diffusion and recrystallization processes are proposed and discussed in the light of systematic microstructural studies. LTA treatment at a fluence of 0.40 J/cm2 results in a 200-300 nm-thick layer where Sn atoms segregate toward the surface and in the formation of Sn-rich columnar structures in the LTA-affected region. These structures are reminiscent to those observed in the dislocation-assisted pipe-diffusion mechanism, while the buried GeSn layers remain intact. Moreover, by tailoring the LTA fluence, the contact resistance can be reduced without triggering phase separation across the whole GeSn multi-layer stacking. Indeed, a one order of magnitude decrease in the Ni-based specific contact resistance was obtained at the highest LTA fluence, thus confirming the potential of this method for the functionalization of direct bandgap GeSn materials.

Group IV Ge1-xSnx semiconductors hold the premise of enabling broadband silicon-integrated infrared optoelectronics due to their tunable bandgap energy and directness. Herein, we exploit these attributes along with the enhanced lattice strain relaxation in Ge/Ge0.92Sn0.08 core-shell nanowire heterostructures to implement highly responsive, room-temperature short-wave infrared nanoscale photodetectors. Atomic-level studies confirm the uniform shell composition and its higher crystallinity with respect to thin films counterparts. The demonstrated Ge/Ge0.92Sn0.08 p-type field-effect nanowire transistors exhibit superior optoelectronic properties achieving simultaneously a relatively high mobility, a high ON/OFF ratio, and a high responsivity, in addition to a broadband absorption in the short-wave infrared range. Indeed, the reduced bandgap of the Ge0.92Sn0.08 shell yields an extended cutoff wavelength of 2.1 um, with a room-temperature responsivity reaching 2.7 A/W at 1550 nm. These results highlight the potential of Ge/Ge1-xSnx core/shell nanowires as silicon-compatible building blocks for nanoscale integrated infrared photonics., Comment: 22 pages, 4 figures, 1 Tables, 5 Supplementary information Figures

GeSn alloys have been regarded as a potential lasing material for a complementary metal-oxide-semiconductor (CMOS)-compatible light source. Despite their remarkable progress, all GeSn lasers reported to date have large device footprints and active areas, which prevent the realization of densely integrated on-chip lasers operating at low power consumption. Here, we present a 1D photonic crystal (PC) nanobeam with a very small device footprint of 7 ${\mu}m^2$ and a compact active area of ~1.2 ${\mu}m^2$ on a high-quality GeSn-on-insulator (GeSnOI) substrate. We also report that the improved directness in our strain-free nanobeam lasers leads to a lower threshold density and a higher operating temperature compared to the compressive strained counterparts. The threshold density of the strain-free nanobeam laser is ~18.2 kW cm$^{ -2}$ at 4 K, which is significantly lower than that of the unreleased nanobeam laser (~38.4 kW cm$^{ -2}$ at 4 K). Lasing in the strain-free nanobeam device persists up to 90 K, whereas the unreleased nanobeam shows a quenching of the lasing at a temperature of 70 K. Our demonstration offers a new avenue towards developing practical group-IV light sources with high-density integration and low power consumption., Comment: 14 pages, 6 figures

This work unravels the atomic details of the interaction of solute atoms with nanoscale crystalline defects. The complexity of this phenomenon is elucidated through detailed atom probe tomographic investigations on epitaxially-strained, compositionally metastable, semiconductor alloys. Subtle variations are uncovered in the concentration and distribution of solute atoms surrounding dislocations, and their dynamic evolution is highlighted. The results demonstrate that crystal defects, such as dislocations, are instrumental in initiating the process of phase separation in strained metastable layers. Matrix regions, close to the dislocations, show clear signs of compositional degradation only after a relatively short time from disrupting the local equilibrium. The solute concentration as well as the density of non-random atomic clusters increases while approaching a dislocation from the surrounding matrix region. In parallel, far from a dislocation the lattice remains intact preserving the metastable structure and composition uniformity. At advanced stages of phase separation, the matrix outside the dislocation reaches the equilibrium concentration, while dislocations act as vehicles of mass-transport, providing fast diffusive channels for solute atoms to reach the surface. Besides, the number of atomic clusters almost doubles and the number of atoms per cluster increases steadily, moving along a dislocation towards the surface. In addition to understanding the atomic features involved in the phase separation of strained metastable alloys, the work also illustrates the thermodynamic and kinetic behavior of solute atoms in the vicinity of a nanoscale defect and describe quantitatively the key processes, thus providing the empirical input to improve the atomic models and simulations.

GeSn alloys are promising candidates for complementary metal-oxide-semiconductor (CMOS)-compatible, tunable lasers. Relaxation of residual compressive strain in epitaxial GeSn has recently shown promise in improving the lasing performance. However, the suspended device configuration that has thus far been introduced to relax the strain is destined to limit heat dissipation, thus hindering the device performance. Herein, we demonstrate that strain-free GeSn microdisk laser devices fully released on Si outperform the canonical suspended devices. This approach allows to simultaneously relax the limiting compressive strain while offering excellent thermal conduction. Optical simulations confirm that, despite a relatively small refractive index contrast between GeSn and Si, optical confinement in strain-free GeSn optical cavities on Si is superior to that in conventional strain-free GeSn cavities suspended in the air. Moreover, thermal simulations indicate a negligible temperature increase in our device. Conversely, the temperature in the suspended devices increases substantially reaching, for instance, 120 K at a base temperature of 75 K under the employed optical pumping conditions. Such improvements enable increasing the operation temperature by ~40 K and reducing the lasing threshold by 30%. This approach lays the groundwork to implement new designs in the quest for room temperature GeSn lasers on Si., Comment: 16 pages, 7 figures

A true monolithic infrared photonics platform is within reach if strain and bandgap energy can be independently engineered in SiGeSn semiconductors. Herein, we investigate the structural and optoelectronic properties of a 1.5 {\mu}m-thick Si0.06Ge0.90Sn0.04 layer that is nearly lattice-matched to a Ge on Si substrate. Atomic-level studies demonstrate high crystalline quality and uniform composition and show no sign of short-range ordering and clusters. Room temperature spectroscopic ellipsometry and transmission measurements show direct bandgap absorption at 0.83 eV and a reduced indirect bandgap absorption at lower energies. Si0.06Ge0.90Sn0.04 photoconductive devices operating at room temperature exhibit dark current and spectral responsivity (1 A/W below 1.5 {\mu}m wavelengths) similar to Ge on Si devices, with the advantage of a near-infrared band gap tunable by alloy composition. These results underline the relevance of SiGeSn semiconductors in implementing a group IV material platform for silicon-integrated infrared optoelectronics.

GeSn alloys are metastable semiconductors that have been proposed as building blocks for silicon-integrated short-wave and mid-wave infrared photonic and sensing platforms. Exploiting these semiconductors requires, however, the control of their epitaxy and their surface chemistry to reduce non-radiative recombination that hinders the efficiency of optoelectronic devices. Herein, we demonstrate that a combined sulfur- and iodine-based treatments yields effective passivation of Ge and Ge0.9Sn0.1 surfaces. X-ray photoemission spectroscopy and in situ spectroscopic ellipsometry measurements were used to investigate the dynamics of surface stability and track the reoxidation mechanisms. Our analysis shows that the largest reduction in oxide after HI treatment, while HF+(NH4)2S results in a lower re-oxidation rate. A combined HI+(NH4)2S treatment preserves the lowest oxide ratio <10 % up to 1 hour of air exposure, while less than half of the initial oxide coverage is reached after 4 hours. These results highlight the potential of S- and I-based treatments in stabilizing the GeSn surface chemistry thus enabling a passivation method that is compatible with materials and device processing.

(Si)GeSn semiconductors are finally coming of age after a long gestation period. The demonstration of device quality epi-layers and quantum-engineered heterostructures has meant that tunable all-group IV Si-integrated infrared photonics is now a real possibility. Notwithstanding the recent exciting developments in (Si)GeSn materials and devices, this family of semiconductors is still facing serious limitations that need to be addressed to enable reliable and scalable applications. The main outstanding challenges include the difficulty to grow high crystalline quality layers and heterostructures at the desired Sn content and lattice strain, preserve the material integrity during growth and throughout device processing steps, and control doping and defect density. Other challenges are related to the lack of optimized device designs and predictive theoretical models to evaluate and simulate the fundamental properties and performance of (Si)GeSn layers and heterostructures. This Perspective highlights key strategies to circumvent these hurdles and bring this material system to maturity to create far-reaching new opportunities for Si-compatible infrared photodetectors, sensors, and emitters for applications in free-space communication, infrared harvesting, biological and chemical sensing, and thermal imaging.

Strain engineering has been a ubiquitous paradigm to tailor the electronic band structure and harness the associated new or enhanced fundamental properties in semiconductors. In this regard, semiconductor membranes emerged as a versatile class of nanoscale materials to control lattice strain and engineer complex heterostructures leading to the development of a variety of innovative applications. Herein we exploit this quasi-two-dimensional platform to tune simultaneously the lattice parameter and bandgap energy in group IV GeSn semiconductor alloys. As Sn content is increased to reach a direct band gap, these semiconductors become metastable and typically compressively strained. We show that the release and transfer of GeSn membranes lead to a significant relaxation thus extending the absorption wavelength range deeper in the mid-infrared. Fully released Ge$_{0.83}$Sn$_{0.17}$ membranes were integrated on silicon and used in the fabrication of broadband photodetectors operating at room temperature with a record wavelength cutoff of 4.6 $\mu$m, without compromising the performance at shorter wavelengths down to 2.3 $\mu$m. These membrane devices are characterized by two orders of magnitude reduction in dark current as compared to devices processed from as-grown strained epitaxial layers. The latter exhibit a content-dependent, shorter wavelength cutoff in the 2.6-3.5 $\mu$m range, thus highlighting the role of lattice strain relaxation in shaping the spectral response of membrane photodetectors. This ability to engineer all-group IV transferable mid-infrared photodetectors lays the groundwork to implement scalable and flexible sensing and imaging technologies exploiting these integrative, silicon-compatible strained-relaxed GeSn membranes.

By independently engineering strain and composition, this work demonstrates and investigates direct band gap emission in the mid-infrared range from GeSn layers grown on silicon. We extend the room-temperature emission wavelength above ~4.0 {\mu}m upon post-growth strain relaxation in layers with uniform Sn content of 17 at.%. The fundamental mechanisms governing the optical emission are discussed based on temperature-dependent photoluminescence, absorption measurements, and theoretical simulations. Regardless of strain and composition, these analyses confirm that single-peak emission is always observed in the probed temperature range of 4-300 K, ruling out defect- and impurity-related emission. Moreover, carrier losses into thermally-activated non-radiative recombination channels are found to be greatly minimized as a result of strain relaxation. Absorption measurements validate the direct band gap absorption in strained and relaxed samples at energies closely matching photoluminescence data. These results highlight the strong potential of GeSn semiconductors as versatile building blocks for scalable, compact, and silicon-compatible mid-infrared photonics and quantum opto-electronics.

Controlling the growth kinetics from the vapor phase has been a powerful paradigm enabling a variety of metastable epitaxial semiconductors such as Sn-containing group IV semiconductors (Si)GeSn. In addition to its importance for emerging photonic and optoelectronic applications, this class of materials is also a rich platform to highlight the interplay between kinetics and thermodynamic driving forces during growth of strained, nonequilibrium alloys. Indeed, these alloys are inherently strained and supersaturated in Sn and thus can suffer instabilities that are still to be fully elucidated. In this vein, in this work the atomic-scale microstructure of Ge0.82Sn0.18 is investigated at the onset of phase separation as the epitaxial growth aborts. In addition to the expected accumulation of Sn on the surface leading to Sn-rich droplets and sub-surface regions with the anticipated equilibrium Sn composition of 1.0at.%, the diffusion of Sn atoms also yields conspicuous Sn-decorated filaments with nonuniform Sn content in the range of ~1 to 11at.% . The latter are attributed to the formation and propagation of dislocations, facilitating the Sn transport toward the surface through pipe diffusion. Furthermore, the interface between the Sn droplet and GeSn shows a distinct, defective layer with Sn content of ~22at.%. This layer is likely formed by the expelled excess equilibrium Ge as the Sn solidifies, and its content seems to be a consequence of strain minimization between tetragonal Sn-rich and cubic Ge-rich equilibrium phases. The elucidation of these phenomena is crucial to understand the stability of GeSn semiconductors and control their epitaxial growth at a uniform composition., Comment: Submitted to Crystal Growth & Design. 20 pages. 5 figures

The growth of Sn-rich group-IV semiconductors at the nanoscale provides new paths for understanding the fundamental properties of metastable GeSn alloys. Here, we demonstrate the effect of the growth conditions on the morphology and composition of Ge/GeSn core/shell nanowires by correlating the experimental observations with a theoretical interpretation based on a multi-scale approach. We show that the cross-sectional morphology of Ge/GeSn core/shell nanowires changes from hexagonal to dodecagonal upon increasing the supply of the Sn precursor. This transformation strongly influences the Sn distribution as a higher Sn content is measured under the {112} growth front. Ab-initio DFT calculations provide an atomic-scale explanation by showing that Sn incorporation is favored at the {112} surfaces, where the Ge bonds are tensile-strained. A phase-field continuum model was developed to reproduce the morphological transformation and the Sn distribution within the wire, shedding light on the complex growth mechanism and unveiling the relation between segregation and faceting. The tunability of the photoluminescence emission with the change in composition and morphology of the GeSn shell highlights the potential of the core/shell nanowire system for opto-electronic devices operating at mid-infrared wavelengths.

Strain engineering in Sn-rich group IV semiconductors is a key enabling factor to exploit the direct band gap at mid-infrared wavelengths. Here, we investigate the effect of strain on the growth of GeSn alloys in a Ge/GeSn core/shell nanowire geometry. Incorporation of Sn content in the 10-20 at.% range is achieved with Ge core diameters ranging from 50nm to 100nm. While the smaller cores lead to the formation of a regular and homogeneous GeSn shell, larger cores lead to the formation of multi-faceted sidewalls and broadened segregation domains, inducing the nucleation of defects. This behavior is rationalized in terms of the different residual strain, as obtained by realistic finite element method simulations. The extended analysis of the strain relaxation as a function of core and shell sizes, in comparison with the conventional planar geometry, provides a deeper understanding of the role of strain in the epitaxy of metastable GeSn semiconductors.

Understanding the nature and behavior of vacancy-like defects in epitaxial GeSn metastable alloys is crucial to elucidate the structural and optoelectronic properties of these emerging semiconductors. The formation of vacancies and their complexes is expected to be promoted by the relatively low substrate temperature required for the epitaxial growth of GeSn layers with Sn contents significantly above the equilibrium solubility of 1 at.%. These defects can impact both the microstructure and charge carrier lifetime. Herein, to identify the vacancy-related complexes and probe their evolution as a function of Sn content, depth-profiled pulsed low-energy positron annihilation lifetime spectroscopy and Doppler broadening spectroscopy were combined to investigate GeSn epitaxial layers with Sn content in the 6.5-13.0 at.% range. The samples were grown by chemical vapor deposition method at temperatures between 300 and 330 {\deg}C. Regardless of the Sn content, all GeSn samples showed the same depth-dependent increase in the positron annihilation line broadening parameters, which confirmed the presence of open volume defects. The measured average positron lifetimes were the highest (380-395 ps) in the region near the surface and monotonically decrease across the analyzed thickness, but remain above 350 ps. All GeSn layers exhibit lifetimes that are 85 to 110 ps higher than the Ge reference layers. Surprisingly, these lifetimes were found to decrease as Sn content increases in GeSn layers. These measurements indicate that divacancies are the dominant defect in the as-grown GeSn layers. However, their corresponding lifetime was found to be shorter than in epitaxial Ge thus suggesting that the presence of Sn may alter the structure of divacancies. Additionally, GeSn layers were found to also contain a small fraction of vacancy clusters, which become less important as Sn content increases.

We report on the behavior of Ge-Ge, Ge-Sn, Sn-Sn like and disorder-activated vibrational modes in GeSn semiconductors investigated using Raman scattering spectroscopy. By using an excitation wavelength close to E1 gap, all modes are clearly resolved and their evolution as a function of strain and Sn content is established. In order to decouple the individual contribution of content and strain, the analysis was conducted on series of pseudomorphic and relaxed epitaxial layers with a Sn content in the 5-17at.% range. All vibrational modes were found to display the same qualitative behavior as a function of content and strain, viz. a linear downshift as the Sn content increases or the compressive strain relaxes. Simultaneously, Ge-Sn and Ge-Ge peaks broaden, and the latter becomes increasingly asymmetric. This asymmetry, coupled with the peak position, is exploited in an empirical method to accurately quantify the Sn composition and lattice strain from Raman spectra.