Mid-infrared emission and absorption in strained and relaxed direct bandgap GeSn semiconductors

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

Strain engineering in Ge/GeSn core/shell nanowires

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

Decoupling the effects of composition and strain on the vibrational modes of GeSn

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

Combined Iodine- and Sulfur-based Treatments for an Effective Passivation of GeSn Surface

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

Mid-infrared top-gated Ge/Ge0.82_{0.82}Sn0.18_{0.18} nanowire phototransistors

Achieving high crystalline quality Ge$_{1-x}$Sn$_{x}$ semiconductors at Sn content exceeding 10\% is quintessential to implementing the long sought-after silicon-compatible mid-infrared photonics. Herein, by using sub-20 nm Ge nanowires as compliant growth substrates, Ge$_{1-x}$Sn$_{x}$ alloys with a Sn content of 18\% exhibiting a high composition uniformity and crystallinity along a few micrometers in the nanowire growth direction were demonstrated. The measured bandgap energy of the obtained Ge/Ge$_{0.82}$Sn$_{0.18}$ core/shell nanowires is 0.322 eV enabling the mid-infrared photodetection with a cutoff wavelength of 3.9 $\mu$m. These narrow bandgap nanowires were also integrated into top-gated field-effect transistors and phototransistors. Depending on the gate design, these demonstrated transistors were found to exhibit either ambipolar or unipolar behavior with a subthreshold swing as low as 228 mV/decade measured at 85 K. Moreover, varying the top gate voltage from -1 V to 5 V yields nearly one order of magnitude increase in the photocurrent generated by the nanowire phototransistor under a 2330 nm illumination. This study shows that the core/shell nanowire architecture with a super thin core not only mitigates the challenges associated with strain buildup observed in thin films but also provides a promising platform for all-group IV mid-infrared photonics and nanoelectronics paving the way toward sensing and imaging applications

500-period epitaxial Ge/Si0.18Ge0.82 multi-quantum wells on silicon

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

Extended-SWIR High-Speed All-GeSn PIN Photodetectors on Silicon

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

All-Group IV membrane room-temperature mid-infrared photodetector

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

Kinetic Control of Morphology and Composition in Ge/GeSn Core/Shell Nanowires

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