Investigation of SiGeSn/GeSn/SiGeSn single quantum well with enhanced well emission.

In this work, a SiGeSn/GeSn/SiGeSn single quantum well was grown and characterized. The sample has a thicker GeSn well of 22nm compared to a previously reported 9nm well configuration. The thicker well leads to: (i) lowered ground energy level in Γ valley offering more bandgap directness; (ii) increased carrier density in the well; and (iii) improved carrier collection due to increased barrier height. As a result, significantly enhanced emission from the quantum well was observed. The strong photoluminescence (PL) signal allows for the estimation of quantum efficiency (QE), which was unattainable in previous studies. Using pumping-power-dependent PL spectra at 20K, the peak spontaneous QE and external QE were measured as 37.9% and 1.45%, respectively.

Optically pumped lasing at 3 µm from compositionally graded GeSn with tin up to 22.3.

The recent demonstration of the GeSn laser opened a promising route towards the monolithic integration of light sources on the Si platform. A GeSn laser with higher Sn content is highly desirable to enhance the emission efficiency and to cover longer wavelength. This Letter reports optically pumped edge-emitting GeSn lasers operating at 3 µm, whose device structure featured Sn compositionally graded with a maximum Sn content of 22.3%. By using a 1950-nm laser pumping in comparison with a 1064-nm pumping, the local heating and quantum defect were effectively reduced, which improved laser performance in terms of higher maximum lasing temperature and lower threshold.

Study of direct bandgap type-I GeSn/GeSn double quantum well with improved carrier confinement.

The GeSn-based quantum wells (QWs) have been investigated recently for the development of efficient GeSn emitters. Although our previous study indicated that the direct bandgap well with type-I band alignment was achieved, the demonstrated QW still has insufficient carrier confinement. In this work, we report the systematic study of light emission from the Ge0.91Sn0.09/Ge0.85Sn0.15/Ge0.91Sn0.09 double QW structure. Two double QW samples, with the thicknesses of Ge0.85Sn0.15 well of 6 and 19 nm, were investigated. Band structure calculations revealed that both samples feature type-I band alignment. Compared with our previous study, by increasing the Sn composition in GeSn barrier and well, the QW layer featured increased energy separation between the indirect and direct bandgaps towards a better direct gap semiconductor. Moreover, the thicker well sample exhibited improved carrier confinement compared to the thinner well sample due to lowered first quantized energy level in the Γ valley. To identify the optical transition characteristics, photoluminescence (PL) study using three pump lasers with different penetration depths and photon energies was performed. The PL spectra confirmed the direct bandgap well feature and the improved carrier confinement, as significantly enhanced QW emission from the thicker well sample was observed.

Study of a SiGeSn/GeSn/SiGeSn structure toward direct bandgap type-I quantum well for all group-IV optoelectronics.

A SiGeSn/GeSn/SiGeSn single quantum well structure was grown using an industry standard chemical vapor deposition reactor with low-cost commercially available precursors. The material characterization revealed the precisely controlled material growth process. Temperature-dependent photoluminescence spectra were correlated with band structure calculation for a structure accurately determined by high-resolution x-ray diffraction and transmission electron microscopy. Based on the result, a systematic study of SiGeSn and GeSn bandgap energy separation and barrier heights versus material compositions and strain was conducted, leading to a practical design of a type-I direct bandgap quantum well.

Systematic study of Si-based GeSn photodiodes with 2.6 µm detector cutoff for short-wave infrared detection.

Normal-incidence Ge1-xSnx photodiode detectors with Sn compositions of 7 and 10% have been demonstrated. Such detectors were based on Ge/Ge1-xSnx/Ge double heterostructures grown directly on a Si substrate via a chemical vapor deposition system. A temperature-dependence study of these detectors was conducted using both electrical and optical characterizations from 300 to 77 K. Spectral response up to 2.6 µm was achieved for a 10% Sn device at room temperature. The peak responsivity and specific detectivity (D*) were measured to be 0.3 A/W and 4 × 109 cmHz1/2W-1 at 1.55 µm, respectively. The spectral D* of a 7% Sn device at 77 K was only one order-of-magnitude lower than that of an extended-InGaAs photodiode operating in the same wavelength range, indicating the promising future of GeSn-based photodetectors.

Temperature dependent spectral response and detectivity of GeSn photoconductors on silicon for short wave infrared detection.

The GeSn direct gap material system, with Si complementary-metal-oxide semiconductor (CMOS) compatibility, presents a promising solution for direct incorporation of focal plane arrays with short wave infrared detection on Si. A temperature dependence study of GeSn photoconductors with 0.9, 3.2, and 7.0% Sn was conducted using both electrical and optical characterizations from 300 to 77 K. The GeSn layers were grown on Si substrates using a commercially available chemical vapor deposition reactor in a Si CMOS compatible process. Carrier activation energies due to ionization and trap states are extracted from the temperature dependent dark I-V characteristics. The temperature dependent spectral response of each photoconductor was measured, and a maximum long wavelength response to 2.1 µm was observed for the 7.0% Sn sample. The DC responsivity measured at 1.55 µm showed around two orders of magnitude improvement at reduced temperatures for all samples compared to room temperature measurements. The noise current and temperature dependent specific detectivity (D*) were also measured for each sample at 1.55 µm, and a maximum D* value of 1 × 10(9) cm·âˆšHz/W was observed at 77 K.

Impurity rejection in the crystallization of ABT-510 as a method to establish starting material specifications.

Understanding impurity rejection in a drug substance crystallization process is valuable for establishing purity specifications for the starting materials used in the process. Impurity rejection has been determined for all known ABT-510 impurities and for many of the reasonable & conceivable impurities. Based on this study, a very high purity specification (e.g., > 99.7%) can be set for ABT-510 with a high level of confidence.

Ge1-xSnx alloys: Consequences of band mixing effects for the evolution of the band gap Γ-character with Sn concentration.

In this work we study the nature of the band gap in GeSn alloys for use in silicon-based lasers. Special attention is paid to Sn-induced band mixing effects. We demonstrate from both experiment and ab-initio theory that the (direct) Γ-character of the GeSn band gap changes continuously with alloy composition and has significant Γ-character even at low (6%) Sn concentrations. The evolution of the Γ-character is due to Sn-induced conduction band mixing effects, in contrast to the sharp indirect-to-direct band gap transition obtained in conventional alloys such as Al1-xGaxAs. Understanding the band mixing effects is critical not only from a fundamental and basic properties viewpoint but also for designing photonic devices with enhanced capabilities utilizing GeSn and related material systems.

Molecular-based synthetic approach to new group IV materials for high-efficiency, low-cost solar cells and Si-based optoelectronics.

Ge(1-x-y)Si(x)Sn(y) alloys have emerged as a new class of highly versatile IR semiconductors offering the potential for independent variation of band structure and lattice dimension, making them the first practical group IV ternary system fully compatible with Si CMOS processing. In this paper we develop and apply new synthetic protocols based on designer molecular hydrides of Si, Ge, and Sn to demonstrate this concept from a synthesis perspective. Variation of the Si/Sn ratio in the ternary leads to an entirely new family of semiconductors exhibiting tunable direct band gaps (E(o)) ranging from 0.8 to 1.2 eV at a fixed lattice constant identical to that of Ge, as required for the design of high-efficiency multijunction solar cells based on group IV/III-V hybrids. As a proof-of-concept demonstration, we fabricated lattice-matched Si(100)/Ge/SiGeSn/InGaAs architectures on low-cost Si(100) substrates for the first time. These exhibit the required optical, structural, and thermal properties, thus representing a viable starting point en route to a complete four-junction photovoltaic device. In the context of Si-Ge-Sn optoelectronic applications, we show that Ge(1-x-y)Si(x)Sn(y) alloys serve as higher-gap barrier layers for the formation of light emitting structures based on Ge(1-y)Sn(y) quantum wells grown on Si.

Agglomerative crystallization of ABT-510 in a partially miscible solvent system.

A modification of wet agglomeration technique is developed and demonstrated by agglomerative crystallization process for a nonapeptide (ABT-510) to improve processing of needle like crystals. Our procedure involves exploiting partial miscibility of the crystallization solvent system for in situ generation of a wetting agent with suitable agglomerative properties. Experiences with ABT-510 show that a relatively small fraction of phase separation (1-5%) is needed to create enough wetting agent for effective agglomeration. Manipulations in the properties and quantity of the wetting agent easily achieved by modifying process trajectories in the solvent space lead to significant variations in agglomerative particle shapes. An optimal process trajectory is established by thorough evaluation of solid-liquid equilibria, liquid-liquid equilibria, properties of the wetting agent and agglomerative particle shape. Optimum antisolvent addition profile is also established and the process scaled up using suitable process analytical tools (PAT) to monitor for consistent performance. This optimally designed agglomerative crystallization process consistently lead to agglomeration of the particles just inside the biphasic solvent region. Extremely rapid crystal form conversion to the desired crystalline form is also observed in the vicinity of the biphasic solvent region, probably as a consequence of density fluctuations generated by the onset of solvent immiscibility.

Investigation of GeSn Strain Relaxation and Spontaneous Composition Gradient for Low-Defect and High-Sn Alloy Growth.

Recent development of group-IV alloy GeSn indicates its bright future for the application of mid-infrared Si photonics. Relaxed GeSn with high material quality and high Sn composition is highly desirable to cover mid-infrared wavelength. However, its crystal growth remains a great challenge. In this work, a systematic study of GeSn strain relaxation mechanism and its effects on Sn incorporation during the material growth via chemical vapor deposition was conducted. It was discovered that Sn incorporation into Ge lattice sites is limited by high compressive strain rather than historically acknowledged chemical reaction dynamics, which was also confirmed by Gibbs free energy calculation. In-depth material characterizations revealed that: (i) the generation of dislocations at Ge/GeSn interface eases the compressive strain, which offers a favorably increased Sn incorporation; (ii) the formation of dislocation loop near Ge/GeSn interface effectively localizes defects, leading to the subsequent low-defect grown GeSn. Following the discovered growth mechanism, a world-record Sn content of 22.3% was achieved. The experiment result shows that even higher Sn content could be obtained if further continuous growth with the same recipe is conducted. This report offers an essential guidance for the growth of high quality high Sn composition GeSn for future GeSn based optoelectronics.

Ether-like Si-Ge hydrides for applications in synthesis of nanostructured semiconductors and dielectrics.

Hydrolysis reactions of silyl-germyl triflates are used to produce ether-like Si-Ge hydride compounds including H(3)SiOSiH(3) and the previously unknown O(SiH(2)GeH(3))(2). The structural, energetic and vibrational properties of the latter were investigated by experimental and quantum chemical simulation methods. A combined Raman, infrared and theoretical analysis indicated that the compound consists of an equal mixture of linear and gauche isomers in analogy to the butane-like H(3)GeSiH(2)SiH(2)GeH(3) with an exceedingly small torsional barrier of approximately 0.2 kcal mol(-1). This is also corroborated by thermochemistry simulations which indicate that the energy difference between the isomers is less than 1 kcal mol(-1). Proof-of-principle depositions of O(SiH(2)GeH(3))(2) at 500 degrees C on Si(100) yielded nearly stoichiometric Si(2)Ge(2)O materials, closely reflecting the composition of the molecular core. A complete characterization of the film by RBS, XTEM, Raman and IR ellipsometry revealed the presence of Si(0.30)Ge(0.70) quantum dots embedded within an amorphous matrix of Si-Ge-O suboxide, as required for the fabrication of high performance nonvolatile memory devices. The use of readily available starting materials coupled with facile purification and high yields also makes the above molecular approach an attractive synthesis route to H(3)SiOSiH(3) with industrial applications in the formation of Si-O-N high-k gate materials in high-mobility SiGe based transistors.

ClnH6-nSiGe compounds for CMOS compatible semiconductor applications: synthesis and fundamental studies.

We describe the synthesis of a new family of chlorinated Si-Ge hydrides based on the formula ClnH6-nSiGe. Selectively controlled chlorination of H3SiGeH3 is provided by reactions with BCl3 to produce ClH2SiGeH3 (1) and Cl2HSiGeH3 (2). This represents a viable single-step route to the target compounds in commercial yields for semiconductor applications. The built-in Cl functionalities are specifically designed to facilitate selective growth compatible with CMOS processing. Higher order polychlorinated derivatives such as Cl2SiHGeH2Cl (3), Cl2SiHGeHCl2 (4), ClSiH2GeH2Cl (5), and ClSiH2GeHCl2 (6) have also been produced for the first time leading to a new class of highly reactive Si-Ge compounds that are of fundamental and practical interest. Compounds 1-6 are characterized by physical and spectroscopic methods including NMR, FTIR, and mass spectroscopy. The results combined with first principles density functional theory are used to elucidate the structural, thermochemical, and vibrational trends throughout the general sequence of ClnH6-nSiGe and provide insight into the dependence of the reaction kinetics on Cl content in the products. The formation of 1 was also demonstrated by an alternative route based on the reaction of (SO3CF3)SiH2GeH3 and CsCl. Depositions of 1 and 2 at very low temperatures (380-450 degrees C) produce near stoichiometric SiGe films on Si exhibiting monocrystalline microstructures, smooth and continuous surface morphologies, reduced defect densities, and unusual strain properties.

Synthesis of butane-like SiGe hydrides: enabling precursors for CVD of Ge-rich semiconductors.

The synthesis of butane-like (GeH(3))(2)(SiH(2))(2) (1), (GeH(3))(2)SiH(SiH(3)) (2), and (GeH(3))(2)(SiH(2)GeH(2)) (3) Si-Ge hydrides with applications in low-temperature synthesis of Ge-rich Si(1-x)Ge(x) optoelectronic alloys has been demonstrated. The compositional, vibrational, structural, and thermochemical properties of these compounds were studied by FTIR, multinuclear NMR, mass spectrometry, Rutherford backscattering, and density functional theory (DFT) simulations. The analyses indicate that the linear (GeH(3))(2)(SiH(2))(2) (1) and (GeH(3))(2)(SiH(2)GeH(2)) (3) compounds exist as a mixture of the classic normal (n) and gauche (g) conformational isomers which do not seem to interconvert at 22 degrees C. The conformational proportions in the samples were determined using a new fitting procedure, which combines calculated molecular spectra to reproduce those observed by varying the global intensity, frequency scale, and admixture coefficients of the individual conformers. The (GeH(3))(2)(SiH(2))(2) (1) species was then utilized to fabricate Si(0.50)Ge(0.50) semiconductor alloys reflecting exactly the Si/Ge content of the precursor. Device quality layers were grown via gas source MBE directly on Si(100) at unprecedented low temperatures 350-450 degrees C and display homogeneous compositional and strain profiles, low threading dislocation densities, and atomically planar surfaces. Low energy electron microscopy (LEEM) analysis has demonstrated that the precursor is highly reactive on Si(100) surfaces, with H(2) desorption kinetics comparable to those of Ge(2)H(6), despite the presence of strong Si-H bonds in the molecular structure.

Synthesis and fundamental studies of (H3Ge)xSiH4-x molecules: precursors to semiconductor hetero- and nanostructures on Si.

The synthesis of the entire silyl-germyl sequence of molecules (H(3)Ge)(x)SiH(4)(-)(x) (x = 1-4) has been demonstrated. These include the previously unknown (H(3)Ge)(2)SiH(2), (H(3)Ge)(3)SiH, and (H(3)Ge)(4)Si species as well as the H(3)GeSiH(3) analogue which is obtained in practical high-purity yields as a viable alternative to disilane and digermane for semiconductor applications. The molecules are characterized by FTIR, multinuclear NMR, mass spectrometry, and Rutherford backscattering. The structural, thermochemical, and vibrational properties are studied using density functional theory. A detailed comparison of the experimental and theoretical data is used to corroborate the synthesis of specific molecular structures. The (H(3)Ge)(x)SiH(4)(-)(x) family of compounds described here is not only of intrinsic molecular interest but also provides a unique route to a new class of Si-based semiconductors including epitaxial layers and coherent islands (quantum dots), with Ge-rich stoichiometries SiGe, SiGe(2), SiGe(3), and SiGe(4) reflecting the Si/Ge content of the corresponding precursor. The layers grow directly on Si(100) at unprecedented low temperatures of 300-450 degrees C and display homogeneous compositional and strain profiles, low threading defect densities, and atomically planar surfaces circumventing entirely the need for conventional graded compositions or lift-off technologies. The activation energies of all Si-Ge hydride reactions on Si(100) (E(a) approximately 1.5-2.0 eV) indicate high reactivity profiles with respect to H(2) desorption, consistent with the low growth temperatures of the films. The quantum dots are obtained exclusively at higher temperatures (T > 500 degrees C) and represent a new family of Ge-rich compositions with narrow size distribution, defect-free microstructures, and homogeneous, precisely tuned elemental content at the atomic level.