GeSn Films Research Articles

Infrared optical properties of SiGeSn and GeSn layers grown by molecular beam epitaxy

The infrared optical properties of thick GeSn films (>500 nm) having 10% Sn concentration and of SiGeSn layers, utilized for the growth of strain-relieved, direct-gap GeSn films by molecular beam epitaxy, are investigated. Two growth methods are used: a graded-growth structure and a stepped-growth structure that help us to illustrate the properties of the GeSn and SiGeSn layers. Interestingly, there can be strong absorption in SiGeSn films throughout the infrared. We observe an increase in infrared absorption with increasing Sn concentration up to 21% Sn and in films, where the Sn is held constant at 18%, with increasing Si concentration up to 30%. Cavity effects in the infrared transmission measurement of stepped-growth structures are observed and associated with reflections at growth interfaces. Si–Si bond formation is proposed to occur at high Si concentrations in SiGeSn films, and the bandgap in SiGeSn films appears to decrease with increasing Si and Sn concentrations.

Development of GeSn epitaxial films with strong direct bandgap luminescence in the mid-wave infrared region using a commercial chemical vapor deposition reactor

Germanium tin (GeSn) is a material of interest for electronic and photonic device applications, but its development and commercialization have been limited by material quality issues and lack of availability from epitaxy suppliers. In this paper, we report initial studies in optimizing GeSn films deposited on a Ge buffer layer grown on 200-mm diameter silicon (Si) substrates with an ASM Epsilon 2000 chemical vapor deposition reactor designed for commercial production. Using a single-step growth process, a Sn content up to 22% near the surface of a GeSn film was achieved due to the increase in Sn incorporation via strain relaxation. A two-step growth process resulted in a bilayer structure with a nearly 100% relaxation on the first layer, followed by a higher quality GeSn layer with 18% Sn as evident by a high photoluminescence intensity emitting in the mid-wave infrared region at 3.2 μm at 20 K.

Remote plasma-enhanced chemical vapor deposition of GeSn on Si (100), Si (111), sapphire, and fused silica substrates

GeSn films were simultaneously deposited on Si (100), Si (111), c-plane sapphire (Al2O3), and fused silica substrates to investigate the impact of the substrate on the resulting GeSn film. The electronic, structural, and optical properties of these films were characterized by temperature-dependent Hall-effect measurements, x-ray diffractometry, secondary ion mass spectrometry, and variable angle spectroscopic ellipsometry. All films were polycrystalline with varying degrees of texturing. The film on Si (100) contained only GeSn (100) grains, 40.4 nm in diameter. The film deposited on Si (111) contained primarily GeSn (111) grains, 36.4 nm in diameter. Both films deposited on silicon substrates were fully relaxed. The layer deposited on Al2O3 contained primarily GeSn (111) grains, 41.3 nm in diameter. The film deposited on fused silica was not textured, and the average grain size was 35.0 nm. All films contained ∼5.6 at. % Sn throughout the layer, except for the film deposited on Al2O3, which contained 7.5% Sn. The films deposited on Si (111), Al2O3, and fused silica exhibit p-type conduction over the entire temperature range, 10–325 K, while the layer deposited on the Si (100) substrate shows a mixed conduction transition from p-type at low temperature to n-type above 220 K. From ∼175 to 260 K, both holes and electrons contribute to conduction. Texturing of the GeSn film on Si (100) was the only characteristic that set this film apart from the other three films, suggesting that something related to GeSn (100) crystal orientation causes this transition from p- to n-type conduction.

Development of aspect ratio trapping growth of GeSn on Si for midwave infrared applications

The development of all-group IV GeSn materials on Si substrates is of interest for monolithic midwave infrared (MWIR) silicon photonics. Despite their great potential, the growth of high crystalline quality materials is still challenging. The conventional growth of GeSn films on Si displays high densities of dislocations and, hence, large dark currents. We have examined a state-of-the-art lithographically defined aspect ratio trapping (ART) growth approach for threading dislocations (TDs) filtering in GeSn and demonstrated the selective growth in the holes embedded in the SiO2/Si(001) template. While an exceptionally low density of TDs was confirmed by transmission electron microscopy imaging, we find that Sn incorporation is strongly suppressed in the ART-grown structures. Nonetheless, these results provide a solid basis for further efforts to enhance the Sn fraction of the GeSn ART growth.

Comparison of GeSn alloy films prepared by ion implantation and remote plasma-enhanced chemical vapor deposition methods

Thin films of germanium-tin (GeSn) alloy with Sn content well above its equilibrium solubility limit in Ge are produced using both remote plasma-enhanced chemical vapor deposition (RPECVD) directly on silicon substrates and ion implantation of Sn into Ge. For RPECVD, the growth temperature of 302 °C resulted in fully relaxed GeSn alloys with high defect density, principally threading dislocations related to the large lattice mismatch between Si and GeSn. For the implantation case, pulsed laser melting was used to melt and crystallize the GeSn layer on a time scale of a few tens of nanoseconds. The resulting GeSn layers were also relaxed and defective, presumably again as a result of lattice mismatch with the underlying Ge lattice. However, the nature of the defects was quite different to the RPECVD method, whereby the line defects were not threading dislocations but stackinglike defects, which developed into arrays of these defects in the high Sn content region close to the surface. For the purpose of comparing RPECVD and ion-implantation methods, alloy films of similar thickness (400–450 nm) and Sn content (4.5–6.5 at. %) were examined. Film parameters (thickness, Sn content, Sn solubility, and segregation), as well as film quality and defect structures, were examined for both fabrication methods using several analytical techniques. This comparison provided us with a better physical understanding of our GeSn films and will help inform future growth/fabrication strategies targeted at minimizing defects formed in the GeSn films for the realization of optoelectronic devices.

Algorithm-Based Linearly Graded Compositions of GeSn on GaAs (001) via Molecular Beam Epitaxy.

The growth of high-composition GeSn films in the future will likely be guided by algorithms. In this study, we show how a logarithmic-based algorithm can be used to obtain high-quality GeSn compositions up to 16% on GaAs (001) substrates via molecular beam epitaxy. Herein, we use composition targeting and logarithmic Sn cell temperature control to achieve linearly graded pseudomorph Ge1-xSnx compositions up to 10% before partial relaxation of the structure and a continued gradient up to 16% GeSn. In this report, we use X-ray diffraction, simulation, secondary ion mass spectrometry, and atomic force microscopy to analyze and demonstrate some of the possible growths that can be produced with the enclosed algorithm. This methodology of growth is a major step forward in the field of GeSn development and the first ever demonstration of algorithmically driven, linearly graded GeSn films.

Epitaxial twin coupled microstructure in GeSn films prepared by remote plasma enhanced chemical vapor deposition

Growth of GeSn films directly on Si substrates is desirable for integrated photonics applications since the absence of an intervening buffer layer simplifies device fabrication. Here, we analyze the microstructure of two GeSn films grown directly on (001) Si by remote plasma-enhanced chemical vapor deposition (RPECVD): a 1000 nm thick film containing 3% Sn and a 600 nm thick, 10% Sn film. Both samples consist of an epitaxial layer with nano twins below a composite layer containing nanocrystalline and amorphous. The epilayer has uniform composition, while the nanocrystalline material has higher levels of Sn than the surrounding amorphous matrix. These two layers are separated by an interface with a distinct, hilly morphology. The transition between the two layers is facilitated by formation of densely populated (111)-coupled nano twins. The 10% Sn sample exhibits a significantly thinner epilayer than the one with 3% Sn. The in-plane lattice mismatch between GeSn and Si induces a quasi-periodic misfit dislocation network along the interface. Film growth initiates at the interface through formation of an atomic-scale interlayer with reduced Sn content, followed by the higher Sn content epitaxial layer. A corrugated surface containing a high density of twins with elevated levels of Sn at the peaks begins forming at a critical thickness. Subsequent epitaxial breakdown at the peaks produces a composite containing high levels of Sn nanocrystalline embedded in lower level of Sn amorphous. The observed microstructure and film evolution provide valuable insight into the growth mechanism that can be used to tune the RPECVD process for improved film quality.

Temperature-dependent morphology and composition of ultra-thin GeSn epilayers prepared by remote plasma enhanced chemical vapor deposition

Two distinct ultra-thin Ge1−xSnx (x ≤ 0.1) epilayers were deposited on (001) Si substrates at 457 and 313 °C through remote plasma-enhanced chemical vapor deposition. These films are considered potential initiation layers for synthesizing thick epitaxial GeSn films. The GeSn film deposited at 313 °C has a thickness of 10 nm and exhibits a highly epitaxial continuous structure with its lattice being compressed along the interface plane to coherently match Si without mismatch dislocations. The GeSn film deposited at 457 °C exhibits a discrete epitaxial island-like morphology with a peak height of ∼30 nm and full-width half maximum (FWHM) varying from 20 to 100 nm. GeSn islands with an FWHM smaller than 20 nm are defect free, whereas those exceeding 25 nm encompass nanotwins and/or stacking faults. The GeSn islands form two-dimensional modulated superlattice structures at the interface with Si. The GeSn film deposited at 457 °C possesses a lower Sn content compared to the one deposited at lower temperature. The potential impact of using these two distinct ultra-thin layers as initiation layers for the direct growth of thicker GeSn epitaxial films on (001) Si substrates is discussed.

Polycrystalline GeSn Films Grown by Hot Wire Chemical Vapor Deposition on SiO2/Si(001) Substrates

The conditions for the growth of polycrystalline GeSn films on SiO2/Si(001) substrates by hot wire chemical vapor deposition are determined for the first time. The effect of the introduction of Sn into the Ge lattice on the morphology, structure, and transport properties of films is studied. GeSn films obtained at 300 °C have a uniform surface with a roughness of less than 1.0 nm. It is shown that the introduction of 5% Sn allows, without the use of recrystallization annealing, to significantly increase the hole mobility of polycrystalline GeSn films from 20 to 60 cm2 V−1 × s−1. despite the small grain size of 35 nm. Such films are of great interest for creating thin‐film transistors for active matrices’ liquid crystal displays.

Mid-infrared emission of germanium-tin films produced by sputtering

In this work, the synthesis of germanium-tin (GeSn) films by magnetron sputtering is reported. A fractional factorial experiment was conducted; the varied factors were temperature, power applied to Ge target by a radio-frequency source, and power applied to the Sn target by a direct-current source. Vibrational modes, film composition, morphology, deposition rate, dark conductivity, Raman spectra, and Fourier-transform infrared (FTIR) spectra of the GeSn films were analyzed. Mid-infrared spectrum of emission and absorption was obtained by FTIR electroluminescence (EL) spectroscopy in the range of 400–4000cm−1, thermal emission was monitored by a FLIR camera in the range of 8–14μm, and power emitted from the GeSn films was measured in the range of 2.7–5.3μm by means of a InAsSb photodetector; results obtained by these approaches at room temperature and low-field bias were consistent. Sample Ge0.71Sn0.29 exhibited Ge Raman crystalline fraction of 85%; from FTIR EL spectrum were observed peaks of absorption located at 1084, and 606 cm−1 that was attributed to Si−Si bonds from the c-Si substrate, as well as broadband attenuation of 2% in the range of 1500−3500cm−1, this behavior was associated to the self-heating of this sample at 90 °C. Sample Ge0.3Sn0.7 showed Raman crystalline fraction of 16 and 22% for Ge and Sn, respectively; from FTIR EL spectrum were observed peaks of emission located at 2.74 μm (0.452 eV) and 6.66 μm (0.186 eV), as well as broadband emission in the range of 600–2000 cm−1 attributed to Planck’s law at a temperature of 45 °C; these results were correlated to the proper content of Ge and Sn, fluctuating current, and polymorphic morphology of this sample.

Growth of single-crystalline GeSn films with high-Sn content on InP substrates by sputtering and rapid thermal annealing

In this work, the polycrystalline GeSn film with Sn content of 25.3 % on InP is obtained by sputtering at room temperature and then rapid thermal annealing (RTA) at 300 ℃. The single-crystalline GeSn film with Sn content of 24.7 % on InP is obtained by sputtering at 200 ℃ and then RTA at 300 ℃. This indicates that the growth temperature is one of the key factors affecting the formation of single-crystalline films. The effects of the sputtering power and film thickness on the crystallization of the GeSn films are investigated. The competition between the spontaneous and substrate-induced crystallization of the films limits the preparation of single-crystalline GeSn films. The strain relaxation of the film (R = 69.3 %) is achieved by annealing. The device fabricated by the GeSn film exhibits a high response of 18.1 A/W @-1 V at room temperature with the 1550-nm-line excitation. These suggest that sputtering epitaxy can be an effective method for growing single-crystalline GeSn films with high-Sn content on InP substrates, which is of great significance for developing high-performance mid-infrared devices.

The growth of Ge and direct bandgap Ge1-xSnx on GaAs (001) by molecular beam epitaxy.

Germanium tin (GeSn) is a tuneable narrow bandgap material, which has shown remarkable promise for the industry of near- and mid-infrared technologies for high efficiency photodetectors and laser devices. Its synthesis is challenged by the lattice mismatch between the GeSn alloy and the substrate on which it is grown, sensitively affecting its crystalline and optical qualities. In this article, we investigate the growth of Ge and GeSn on GaAs (001) substrates using two different buffer layers consisting of Ge/GaAs and Ge/AlAs via molecular beam epitaxy. The quality of the Ge layers was compared using X-ray diffraction, atomic force microscopy, reflection high-energy electron diffraction, and photoluminescence. The characterization techniques demonstrate high-quality Ge layers, including atomic steps, when grown on either GaAs or AlAs at a growth temperature between 500-600 °C. The photoluminescence from the Ge layers was similar in relative intensity and linewidth to that of bulk Ge. The Ge growth was followed by the growth of GeSn using a Sn composition gradient and substrate gradient approach to achieve GeSn films with 9 to 10% Sn composition. Characterization of the GeSn films also indicates high-quality gradients based on X-ray diffraction, photoluminescence, and energy-dispersive X-ray spectroscopy measurements. Finally, we were able to demonstrate temperature-dependent PL results showing that for the growth on Ge/GaAs buffer, the direct transition has shifted past the indirect transition to a longer wavelength/lower energy suggesting a direct bandgap GeSn material.

Impact of Sn incorporation on sputter epitaxy of GeSn

Epitaxial growth of high-quality low tin content germanium (GeSn) alloy is demonstrated by sputter deposition. Adding several percent of Sn during simultaneous sputter deposition significantly improved the crystallographic structure of the GeSn alloy, leading to intense photoluminescence even at room temperature. Dislocation-free single-crystal GeSn films were formed on a Ge(100) substrate under tuned growth conditions, that is, an Sn/Ge flux ratio of 6.2% and deposition temperature of 500 °C, in which compositional gradation of the Sn content in the film thickness direction spontaneously formed. The growth mechanisms are discussed based on growth kinetics and Sn diffusion on the growing surface.

SiGeSn buffer layer for the growth of GeSn films

Inclusion of Si atoms to the growth surface during the molecular beam epitaxy of Ge and Sn to form a SiGeSn alloy was identified as a reactive surface species and as a means to compensate strain, which allowed for the subsequent growth of GeSn alloys with high Sn content. The development of a SiGeSn virtual substrate having a 15% Sn concentration and lattice parameter larger than 5.72 Å is demonstrated, using atomic force microscopy, x-ray reciprocal space mapping, and transmission electron microscopy, as a method for the direct growth of thick (>500 nm) fully relaxed GeSn alloys with greater than 10% Sn. This buffer layer enables the monolithic integration of GeSn with silicon for optoelectronic applications, as the SiGeSn virtual substrate allows for selective chemical etching of GeSn, which is important for device fabrication.

Remote plasma-enhanced chemical vapor deposition of GeSn on Si: Material and defect characterization

Germanium–tin (GeSn) alloys at sufficiently high Sn concentration, above several atomic percent, are the only group IV semiconductor exhibiting a direct bandgap and have generated much recent interest for optoelectronic applications into the mid-infrared region. Because the large lattice mismatch between GeSn and Si results in considerable strain for thin layers and a high defect density for thicker strain-relaxed layers, most reported GeSn growths incorporate a Ge buffer layer rather than depositing directly on Si substrates. Published reports of GeSn growth directly on Si utilize specialized precursors such as higher order germanes (Ge2H6, Ge3H8, or Ge4H10) or SnD4. In this paper, we report GeSn films with up to 10.6% Sn grown directly on Si substrates by remote plasma-enhanced chemical vapor deposition using GeH4 and SnCl4 precursors. These alloys have been characterized in detail using x-ray diffraction (XRD), transmission electron microscopy (TEM), and Rutherford backscattering spectrometry with channeling (RBS-C), as well as Raman spectroscopy (RS) and optical microscopy. The films studied are almost fully relaxed, with small residual strain observed, particularly in thinner films, and contain a high interface density of misfit dislocations that increases with Sn concentration. The defect density decreases toward the surface. Good agreement is found between the various characterization methods for the Sn content (XRD and RBS-C), lattice parameter measurement (XRD and TEM), and defect characterization (RBS-C, TEM, and RS). Such characterization of GeSn grown directly on Si substrates is essential to allow growth parameters to be optimized for the realization of the attractive optoelectronic properties of these alloys.

Fabrication of amorphous LiPON, LiAlGePO, and GeSn films in low-temperature plasma sputtering process for all-solid-state Li+-ion battery

Plasma-sputtered amorphous films for all-solid-state Li+-ion batteries are investigated. In LiPON electrolyte films, the amount of N incorporated into LiPO films is controlled by the sputtering discharge gas. Ionic conductivity increases with increasing N2 gas proportion in Ar/N2 discharge, reaching a maximum of 2.7 × 10−6 S cm−1 at Li2.39PO3.71N0.13. In amorphous LiAlGePO electrolyte films, the amounts of Al and Ge incorporated into LiPO films are controlled in a combinatorial approach using two-source co-sputtering. The P/Ge ratio varies over a wide range from 23.3 to 1.61 at the radial substrate positions, and the highest ionic conductivity of 4.32 × 10−5 S cm−1 is achieved at Li4.80Al0.80Ge1.16P3O13.1. We evaluate all-solid-state Li+-ion batteries fabricated using the developed amorphous LiPON electrolyte and GeSn anode films, where GeSn films with about 50 nm nanograins are fabricated by high-gas-pressure sputtering at 500 mTorr. A maximum capacity of 2.86 μAh cm−2 is attained for all-solid state Li+-ion battery.

Harvesting strong photoluminescence of physical vapor deposited GeSn with record high deposition temperature

In this work, strong photoluminescence (PL) from physical vapor deposited GeSn on Ge-buffered Si is harvested by pursuing high deposition temperature. High-quality Ge0.938Sn0.062 films are obtained through sputtering epitaxy at a record high temperature of 405 °C. The PL peak intensity of the sputtering-grown GeSn is enhanced by 21 times compared to that of GeSn with similar Sn content grown by molecular beam epitaxy at 150 °C. The PL intensity ratio between the sputtering-grown GeSn and Ge virtual substrate reaches a value of 18. Power-dependent and temperature-dependent PL characterizations demonstrate that band-to-band recombination dominates in the sputtering-grown GeSn film. The results indicate that high-temperature sputtering epitaxy, which has the merit of low cost and high-productivity potential, is promising for preparing high-quality GeSn films for optoelectronic applications.

Effect of bubbles at the bonded interface on the performance of GeSn/Si PIN photodetector

Due to the large lattice mismatch between GeSn and Si materials, high-density threading dislocation (TD) forms when GeSn films are grown by epitaxial growth. This leads to the increase of the dark current density (DCD) of the device. The wafer-bonded technique is a promising method to prepare high-quality thin films. This has been used to produce the Si-based GeSn materials with low TDD. However, there are a lot of bubbles at the bonded interface, resulting in the deterioration of the performance of the device. The study of bubbles on the performance of the GeSn PIN photodetector (PD) has not been reported. In this paper, the effects of the bonding bubbles on the performance of the device are performed. The photocurrent, dark current, charge concentration, electric field, and 3dB-bandwidth (BW) as a function of the bubble radius and thickness are demonstrated. The effects of the bubble radius and thickness on the 3dB-BW (∼18 GHz) are insignificant when the bubble thickness and radius are set as 1 nm and 1 μm, respectively. The 3dB-BW decreases to ∼17 GHz when the bubbles are close to the sizes of the top mesa. However, the 3dB-BW drops drastically with the increase of the bubble thickness when the bubble radius reaches 7 μm. Most importantly, the 3dB-BW sharply decreases to ∼30 MHz regardless of the thickness of the bubble when the bubble radius of 14 μm is set. This may provide guidance for the application of the wafer-bonded GeSn PIN PD.

Explosive crystallization of amorphous germanium-tin films by irradiation with a 3-keV electron beam

Much effort has been expended to obtain thin films of metastable solid solutions of germanium (Ge) that contain as high tin (Sn) content as possible because of their excellent electronic and optoelectronic properties. On the basis of our previous study on amorphous Ge, we demonstrated in this study that irradiation of substrate-free films of amorphous Ge100−xSnx (x = 8, 11, and 19 at. %) with a low-energy electron beam of 3 keV at ambient temperature can induce instantaneous wide-area crystallization (explosive crystallization). Characteristic spiral crystal growth associated with explosive crystallization occurred with areas exceeding 50 μm in diameter around a scanned area of the electron beam of 8 × 8 μm2. As a result, solid solutions of GeSn with Sn concentration up to 19 at. % were obtained with the suppression of precipitation of β-Sn. The region of explosive crystallization reduced in size with increasing Sn content. In addition, thermal analyses revealed that the heat released during crystallization of amorphous GeSn films decreased with increasing Sn content. This relationship indicates that the heat release at the growth front plays a key role in the propagation of explosive crystallization of a-GeSn.

Deposition of GeSn film on Si substrate by plasma-enhanced chemical vapor deposition using GeCl4 and SnCl4 in H2 for developing short-wave infrared Si photonics

The deposition of a GeSn film on Si substrate with GeCl4 and SnCl4 in H2 as precursors was demonstrated by using plasma-enhanced chemical vapor deposition (PECVD). A partially strain-relaxed, impurity-free, monocrystalline GeSn film with a surface roughness of 6 nm and a threading-dislocation density of 1 × 107 cm−2 could be directly grown at a rate of ca. 15 nm/min at a substrate temperature of 180 °C without the need of a buffer layer or post-annealing. A Sn atomic percentage exceeding 9% was achieved, providing a light absorption beyond 2.4μm for the deposited 260-nm-thick film. The same deposition process for Ge and Sn enabled easier control of film deposition conditions and better clarification of the underlying mechanisms. The low deposition temperature renders this method compatible with complementary metal–oxide–semiconductor (CMOS) technology, suitable for developing short-wave infrared Si photonics.