Vacancy complexes in nonequilibrium germanium-tin 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

Pnictogens Allotropy and Phase Transformation during van der Waals Growth

Pnictogens have multiple allotropic forms resulting from their ns2 np3 valence electronic configuration, making them the only elemental materials to crystallize in layered van der Waals (vdW) and quasi-vdW structures throughout the group. Light group VA elements are found in the layered orthorhombic A17 phase such as black phosphorus, and can transition to the layered rhombohedral A7 phase at high pressure. On the other hand, bulk heavier elements are only stable in the A7 phase. Herein, we demonstrate that these two phases not only co-exist during the vdW growth of antimony on weakly interacting surfaces, but also undertake a spontaneous transformation from the A17 phase to the thermodynamically stable A7 phase. This metastability of the A17 phase is revealed by real-time studies unraveling its thickness-driven transition to the A7 phase and the concomitant evolution of its electronic properties. At a critical thickness of ~4 nm, A17 antimony undergoes a diffusionless shuffle transition from AB to AA stacked alpha-antimonene followed by a gradual relaxation to the A7 bulk-like phase. Furthermore, the electronic structure of this intermediate phase is found to be determined by surface self-passivation and the associated competition between A7- and A17-like bonding in the bulk. These results highlight the critical role of the atomic structure and interfacial interactions in shaping the stability and electronic characteristics of vdW layered materials, thus enabling a new degree of freedom to engineer their properties using scalable processes

Atomic-Scale Insights into Semiconductor Heterostructures: From Experimental Three-Dimensional Analysis of the Interface to a Generalized Theory of Interfacial Roughness Scattering

In this manuscript, we develop a generalized theory for the scattering process produced by interface roughness on charge carriers that is suitable for any semiconductor heterostructure. By exploiting our experimental insights into the three-dimensional atomic landscape of Ge/Ge-Si heterointerfaces obtained by atom probe tomography, we are able to define the full set of interface parameters relevant to the scattering potential, including both the in-plane and axial correlation inside real diffuse interfaces. Our experimental findings indicate a partial coherence of the interface roughness along the growth direction within the interfaces. We show that it is necessary to include this feature, previously neglected by theoretical models, when heterointerfaces characterized by finite interface widths are taken into consideration. To show the relevance of our generalized scattering model in the physics of semiconductor devices, we implement it in a nonequilibrium Green's function simulation platform to assess the performance of a Ge/Si-Ge-based terahertz quantum cascade laser

High-Quality n-Type Ge/SiGe Multilayers for THz Quantum Cascade Lasers

The exploitation of intersubband transitions in Ge/SiGe quantum cascade devices could pave the way towards the integration of THz light emitters into the silicon-based technology. Aiming at the realization of a Ge/SiGe Quantum Cascade Laser (QCL), we investigate optical and structural properties of n-type Ge/SiGe coupled quantum well systems. The samples have been investigated by means of X-ray diffraction, scanning transmission electron microscopy, atom probe tomography and Fourier Transform Infrared absorption spectroscopy to assess the growth capability with respect to QCL design requirements, carefully identified by means of modelling based on the non-equilibrium Green function formalism

Direct bandgap GeSn nanowires enabled with ultrahigh tension from harnessing intrinsic compressive strain

GeSn alloys are a promising emerging complementary metal–oxide–semiconductor compatible technology for applications in photonics and electronics. However, the unavoidable intrinsic compressive strain introduced during epitaxial growth has prevented researchers from pushing the performance of GeSn devices to the limit and realizing real-world applications. In this paper, we present a straightforward geometric strain-inversion technique that harnesses the harmful compressive strain to achieve beneficial tensile strain in GeSn nanowires, drastically increasing the directness of the band structure. We achieve 2.67% uniaxial tensile strain in 120 nm wide nanowires, surpassing other values reported thus far. Unique pseudo-superlattices comprising of indirect and direct bandgap GeSn are demonstrated in a single material only by applying a periodic tensile strain. Improved directness in tensile-strained GeSn significantly enhances the photoluminescence by a factor of 2.5. This work represents a way to develop scalable band-engineered GeSn nanowire devices with lithographic design flexibility. This technique can be potentially applied to any layer with an intrinsic compressive strain, creating opportunities for unique tensile strained materials with diverse electronic and photonic applications

Non-equilibrium induction of tin in germanium: towards direct bandgap Ge1−xSnx nanowires

The development of non-equilibrium group IV nanoscale alloys is critical to achieving new functionalities, such as the formation of a direct bandgap in a conventional indirect bandgap elemental semiconductor. Here, we describe the fabrication of uniform diameter, direct bandgap Ge1−xSnx alloy nanowires, with a Sn incorporation up to 9.2 at.%, far in excess of the equilibrium solubility of Sn in bulk Ge, through a conventional catalytic bottom-up growth paradigm using noble metal and metal alloy catalysts. Metal alloy catalysts permitted a greater inclusion of Sn in Ge nanowires compared with conventional Au catalysts, when used during vapour–liquid–solid growth. The addition of an annealing step close to the Ge-Sn eutectic temperature (230 °C) during cool-down, further facilitated the excessive dissolution of Sn in the nanowires. Sn was distributed throughout the Ge nanowire lattice with no metallic Sn segregation or precipitation at the surface or within the bulk of the nanowires. The non-equilibrium incorporation of Sn into the Ge nanowires can be understood in terms of a kinetic trapping model for impurity incorporation at the triple-phase boundary during growth

Catalyst composition and impurity-dependent kinetics of nanowire heteroepitaxy.

The mechanisms and kinetics of axial Ge-Si nanowire heteroepitaxial growth based on the tailoring of the Au catalyst composition via Ga alloying are studied by environmental transmission electron microscopy combined with systematic ex situ CVD calibrations. The morphology of the Ge-Si heterojunction, in particular, the extent of a local, asymmetric increase in nanowire diameter, is found to depend on the Ga composition of the catalyst, on the TMGa precursor exposure temperature, and on the presence of dopants. To rationalize the findings, a general nucleation-based model for nanowire heteroepitaxy is established which is anticipated to be relevant to a wide range of material systems and device-enabling heterostructures.S.H. acknowledges funding from ERC grant InsituNANO (No. 279342). A.D.G. acknowledges funding from the Marshall Aid Commemoration Commission and the National Science Foundation. C.D. acknowledges funding from the Royal Society. A portion of the research was also performed using EMSL, a national scientific user facility sponsored by the Department of Energy’s (DOE) Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the U.S. DOE under Contract DE-AC05-76RL01830. We gratefully acknowledge the use of facilities within the LeRoy Eyring Center for Solid State Science at Arizona State University. This work was performed in part at CINT, a U.S. DOE, Office of Science User Facility. The research was funded in part by the Laboratory Directed Research and Development Program at LANL, an affirmative action equal opportunity employer operated by Los Alamos National Security, LLC, for the National Nuclear Security Administration of the U.S. DOE under Contract DE-AC52-06NA25396.This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Nano, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/nn402208p. Gamalski AD, Perea DE, Yoo J, Li N, Olszta MJ, Colby R, Schreiber DK, Ducati C, Picraux ST, Hofmann S, ACS Nano 2013, 7 (9), 7689–7697, doi:10.1021/nn402208

The Phenomenology of Ion Implantation-Induced Blistering and Thin-Layer Splitting in Compound Semiconductors

Hydrogen and/or helium implantation-induced surface blistering and layer splitting in compound semiconductors such as InP, GaAs, GaN, AlN, and ZnO are discussed. The blistering phenomenon depends on many parameters such as the semiconductor material, ion fluence, ion energy, and implantation temperature. The optimum values of these parameters for compound semiconductors are presented. The blistering and splitting processes in silicon have been studied in detail, motivated by the fabrication of the widely used silicon-on-insulator wafers. Hence, a comparison of the blistering process in Si and compound semiconductors is also presented. This comparative study is technologically relevant since ion implantation-induced layer splitting combined with direct wafer bonding in principle allows the transfer of any type of semiconductor layer onto any foreign substrate of choice-the technique is known as the ion-cut or Smart-Cut (TM) method. For the aforementioned compound semiconductors, investigations regarding layer transfer using the ion-cut method are still in their infancy. We report feasibility studies of layer transfer by the ion-cut method for some of the most important and widely used compound semiconductors. The importance of characteristic values for successful wafer bonding such as wafer bow and surface flatness as well as roughness are discussed, and difficulties in achieving some of these values are pointed out

Effect of hydrogen implantation on the mechanical properties of AlN throughout ion-induced splitting

The ability to transfer bulk quality III-N thin layers onto foreign platforms is a powerful strategy to enable high-efficiency and low-cost optoelectronic devices. Ion-cut using sub-surface defect engineering has been an effective process to split and transfer a variety of semiconductors. With this perspective, hydrogen-implanted AlN samples were annealed in air at temperatures ranging from 300°C to 600°C for 5 min to study the influence of pre-layer splitting treatments on the nanomechanical properties. There is a clear dependence of the hardness on implanted hydrogen implantation fluence. We observe that the as-implanted hardness increased from 18 GPa for the virgin reference sample to ∼25 GPa for the highest fluence of 3 × 1017 H cm-2 prior to annealing. In the case of reference single crystalline Si samples, a significant drop in the hardness and elastic modulus is observed in the H implantation-induced damage zone subsequent to thermal annealing , while for crystalline epitaxial AlN samples with 0.5 × 1017 and 2.0 × 1017 H implant fluences, the hardness increases and peaks until the thermal annealing temperature reaches 350°C and subsequently begins to drop thereafter for higher annealing temperatures. However, for the 1.0 × 1017 H implantation fluence the hardness continues to increase with increasing thermal annealing temperature