GeSn Thin Films Research Articles

Theoretical Analysis of GeSn Quantum Dots for Photodetection Applications.

GeSn alloys have recently emerged as complementary metal-oxide-semiconductor (CMOS)-compatible materials for optoelectronic applications. Although various photonic devices based on GeSn thin films have been developed, low-dimensional GeSn quantum structures with improved efficiencies hold great promise for optoelectronic applications. This study theoretically analyses Ge-capped GeSn pyramid quantum dots (QDs) on Ge substrates to explore their potential for such applications. Theoretical models are presented to calculate the effects of the Sn content and the sizes of the GeSn QDs on the strain distributions caused by lattice mismatch, the band structures, transition energies, wavefunctions of confined electrons and holes, and transition probabilities. The bandgap energies of the GeSn QDs decrease with the increasing Sn content, leading to higher band offsets and improved carrier confinement, in addition to electron-hole wavefunction overlap. The GeSn QDs on the Ge substrate provide crucial type-I alignment, but with a limited band offset, thereby decreasing carrier confinement. However, the GeSn QDs on the Ge substrate show a direct bandgap at higher Sn compositions and exhibit a ground-state transition energy of ~0.8 eV, rendering this system suitable for applications in the telecommunication window (1550 nm). These results provide important insights into the practical feasibility of GeSn QD systems for optoelectronic applications.

Photoconductivity of GeSn thin films with up to 15% Sn content

Photoconductivity of GeSn thin films with up to 15% Sn content

Strain-driven anomalous elastic properties of GeSn thin films

Elastic strain engineering in the GeSn bandgap structure is an attractive area for designing novel material properties. The linear interpolation of the elastic constants of Ge and Sn is commonly used to estimate their respective values for Ge1−xSnx alloys. This work reveals that Young's modulus of Ge1−xSnx epitaxial layers has a non-monotonic dependence on Sn composition. It is shown that the decrease in the elastic modulus correlates with the increase in Sn content in pseudomorphically grown Ge1−xSnx-epilayers with Sn concentration in the range of 1–5 at. % and subcritical thicknesses. An anomalous increase in the elastic modulus is observed with the further increase in Sn content (12 at. %), which is also accompanied by an increase in in-plane tensile strain. Phase separation and a decrease in the elastic modulus are observed for Ge1−xSnx-epilayers grown above the critical thickness with Sn concentration ≥ 12 at. %. A correlation between the experimental elastic moduli and calculated elastic energies explains the complexity of strain-driven anomalous elastic properties of Ge1−xSnx-epilayers. The observed anomalous behavior of the Young's modulus for these GeSn epitaxial layers appears to be related to their recently predicted and observed short-range atomic order.

High-quality GeSn thin-film resonant cavities for short-wave infrared applications

High-quality infrared (IR) devices made of group IV materials are highly promising to replace traditional III–V semiconductor-based IR optoelectronics due primarily to their compatibility with mature silicon-based technologies and much lower costs. In this regard, germanium tin (GeSn) has emerged as the only direct bandgap material in the group IV family exhibiting superior electrical and optical characteristics. In the past years, GeSn IR optoelectronics including lasers and photodetectors have been realized, although novel device architectures are still needed to enhance their device performance. Here, we experimentally demonstrate high-performance, large-area (mm2) GeSn thin-film resonant cavities (film thickness resonance operating at short-wave IR wavelengths by employing membrane transfer techniques). The fabricated asymmetric air/GeSn/metal structures exhibit high absorptance (>90%) at designed resonance wavelengths, which are easily tuned by tailoring the GeSn layer thickness. The measured resonance absorption reveals excellent agreement with numerical simulations, which further elucidates the mode characteristics of the observed cavity resonances. The demonstrated thin-film device architectures could greatly facilitate the development of novel GeSn photonic devices with tunable wavelengths and enhanced performance enabled by strain engineering, and could allow for the integration of GeSn into many existing group IV-based devices for next-generation IR optoelectronics where high performance, small footprint, and low cost are all required.

Ultrafast carrier dynamics in GeSn thin film based on time-resolved terahertz spectroscopy

We measure the time-resolved terahertz spectroscopy of GeSn thin film and studied the ultrafast dynamics of its photo-generated carriers. The experimental results show that there are photo-generated carriers in GeSn under femtosecond laser excitation at 2500 nm, and its pump-induced photoconductivity can be explained by the Drude–Smith model. The carrier recombination process is mainly dominated by defect-assisted Auger processes and defect capture. The first- and second-order recombination rates are obtained by the rate equation fitting, which are (2.6 ± 1.1) × 10−2 ps−1 and (6.6 ± 1.8) × 10−19 cm3⋅ps−1, respectively. Meanwhile, we also obtain the diffusion length of photo-generated carriers in GeSn, which is about 0.4 μm, and it changes with the pump delay time. These results are important for the GeSn-based infrared optoelectronic devices, and demonstrate that GeSn materials can be applied to high-speed optoelectronic detectors and other applications.

Local ordering in Ge/Ge–Sn semiconductor alloy core/shell nanowires revealed by extended x-ray absorption fine structure (EXAFS)

Short-range atomic order in semiconductor alloys is a relatively unexplored topic that may promote design of new materials with unexpected properties. Here, local atomic ordering is investigated in Ge–Sn alloys, a group-IV system that is attractive for its enhanced optoelectronic properties achievable via a direct gap for Sn concentrations exceeding ≈10 at. %. The substantial misfit strain imposed on Ge–Sn thin films during growth on bulk Si or Ge substrates can induce defect formation; however, misfit strain can be accommodated by growing Ge–Sn alloy films on Ge nanowires, which effectively act as elastically compliant substrates. In this work, Ge core/Ge1−xSnx (x ≈ 0.1) shell nanowires were characterized with extended x-ray absorption fine structure (EXAFS) to elucidate their local atomic environment. Simultaneous fitting of high-quality EXAFS data collected at both the Ge K-edge and the Sn K-edge reveals a large (≈ 40%) deficiency of Sn in the first coordination shell around a Sn atom relative to a random alloy, thereby providing the first direct experimental evidence of significant short-range order in this semiconductor alloy system. Comparison of path length data from the EXAFS measurements with density functional theory simulations provides alloy atomic structures consistent with this conclusion.

Polycrystalline GeSn thin films fabricated by simultaneous laser sintering and recrystallization

Polycrystalline GeSn thin films fabricated by simultaneous laser sintering and recrystallization

Secondary epitaxy of high Sn fraction GeSn layer on strain-relaxed GeSn virtue substrate by molecular beam epitaxy

Strain relaxation is critical for GeSn alloys transforming from indirect to direct bandgap nature with Sn fraction above 6.5%, but difficult for them grown by molecular beam epitaxy (MBE), in which low temperature has to be set up to avoid Sn segregation. In this work, compressively strained Ge0.935Sn0.065 thin films grown on Si with a Ge buffer layer by MBE are firstly treated by ex-situ rapid thermal annealing, rendering partially strain relaxation in the Ge0.935Sn0.065 by generation of misfit dislocation networks without Sn segregation. Then, secondary epitaxy of Ge0.905Sn0.095 layer is carried out on the thermally annealed Ge0.935Sn0.065 virtual substrate. The secondary epitaxial GeSn layers exhibit partial strain relaxation and strong photoluminescence with red-shift of peak position, compared to that of fully compressive strained GeSn thin films with the same structure grown primary epitaxially. Those results manifest that secondary epitaxy, combining with ex-situ rapid thermal annealing for strain relaxed GeSn virtual substrate, is a practical way to achieve strain relaxed GeSn thin films with direct bandgap nature by MBE.

The transition of growth behaviors of moderate Sn fraction Ge1-xSnx (8 % < x < 15 %) epilayers with low temperature molecular beam epitaxy

Epitaxial breakdown phenomenon for Ge1-xSnx thin film with Sn fraction of less than 6 % during low-temperature molecular beam epitaxy has been reported [J. Appl. Phys. 97, 044904, 2005]. However more Sn incorporation is required for direct bandgap transition of GeSn alloy, which has much attractive for GeSn optoelectronic devices. In this work, moderate Sn fraction Ge1-xSnx (8 %∼15.3 %), as well as composition-stepped multiple GeSn layers, grown on Ge (001) substrate by molecular beam epitaxy at 120–150 ℃ are investigated. Epitaxy breakdown occurs for the Ge1-xSnx epilayer with Sn fraction of about 8 % and 10 %, even with low Sn fraction buffer layers, in which the film delaminates into a fully compressively strained bottom layer with dislocation free and a fully relaxed top layer spontaneously. Once the epitaxy breakdown occurs, the amorphous columnar structures extend into the following deposited GeSn epilayer, regardless of Sn fraction. While, the strain in the whole Ge1-xSnx epilayer with Sn fraction of 15.3 % is directly released during growth by generation of misfit and threading dislocations or agglomeration of islands. Those results indicate that there are three growth modes including fully compressive strained thin GeSn epilayer, epitaxial breakdown induced self-delamination of GeSn layer with moderate Sn fraction, and strain relaxed Ge1-xSnx epilayer with high Sn fraction of above 15 %. The complex behavior can be attributed to the competition between kinetic roughening and strain- driven GeSn agglomeration or generation of dislocations. The understanding of the growth behavior is helpful for controlling crystal quality of GeSn thin films for their application in optoelectronic devices.

Solid‐Phase Crystallization of GeSn Thin Films on GeO2‐Coated Glass

In article number 2100509, Kaoru Toko and co-workers illustrate how oxygen diffusion from the GeO2 layer during crystallization enables the synthesis of GeSn layers with large grains, which considerably reduces acceptor defects while maintaining a high hole mobility. These achievements will pave the way for advanced Ge-based thin-film transistors.

Sn Concentration Effects on Polycrystalline GeSn Thin Film Transistors

Thin-film transistor (TFT) applications of GeSn have attracted attention as a means of improving the performance of electronic devices. Based on our advanced solid-phase crystallization and TFT process technologies, we comprehensively studied the relationship between the film properties and TFT characteristics of polycrystalline GeSn. The initial Sn concentration <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">${x}_{\mathrm {i}}$ </tex-math></inline-formula> significantly changed the crystal and electrical properties of the GeSn layer. Excess Sn ( <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">${x}_{\mathrm {i}} \ge 4.5$ </tex-math></inline-formula> %) precipitated in GeSn and degraded its properties, whereas the appropriate amount of Sn effectively passivated defects in Ge and reduced the density of defect-induced acceptors and grain boundary traps while maintaining a high Hall hole mobility (>200 cm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sup> V <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">−1</sup> s <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">−1</sup> ). The performance of the accumulation-mode TFTs fabricated under 400 °C also strongly depended on <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\boldsymbol {x}_{\mathrm {i}}$ </tex-math></inline-formula> , achieving both a high field-effect mobility (170 cm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sup> V <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">−1</sup> s <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">−1</sup> ) and on/off ratio (10 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sup> ) at <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">${x}_{\mathrm {i}} = 1.6$ </tex-math></inline-formula> %. This performance was shown to be the highest among Ge-based TFTs with grain boundaries in the channel.

Growth of High Sn Concentration Germanium-Tin Films on Insulators by Microsecond Laser Annealing

1. IntroductionThanks to their high carrier mobility, germanium based group IV semiconductors are promising materials to realize next generation electronics [1]. Especially, germanium tin alloys (GeSn) having high Sn concentration (> 6 at. %) are attracting much attention due to their direct band structure [2]. To apply such significant advantage to thin-film devices such as thin-film transistors (TFTs) or three dimensional large-scale integrated circuits (3D-LSIs), various groups are working on to crystallize these materials on insulating substrates by various approaches such as germanium condensation [3], solid phase crystallization [4], and so on.Recently, we have established a technique to grow highly strained germanium based materials on insulating substrates by microsecond annealing using novel high speed continuous wave laser annealing (CWLA) system [5]. Here, in this presentation, we will introduce our recent achievements in GeSn crystal growth by the microsecond annealing technique.2. Experimental ProcedureIn the experiment, amorphous GeSn films with Sn concentration of 15% (thickness: 100 nm) were firstly deposited on quartz substrates by molecular beam deposition. Then the samples were annealed by the high speed CWLA system, which can scan laser light (focused to 20 μm diameter) on samples with very high speed up to 15 m/s. The laser irradiation time (tirr) can be varied from 1.5 to 6.0 μs by controlling the scanning speed. Here, Nd:YVO4 solid state laser with wavelength of 532 nm was used as a light source, and laser power was controlled from 350 to 1000 mW. After the laser annealing, the samples were characterized by microscopic Raman spectroscopy and electron back scattered diffraction (EBSD) method.3. Results and DiscussionsFig. 1(a) shows Nomarski microscopic image after laser annealing (500 mW, tirr: 1.5 μs), which shows bright contrast at annealed region. Raman signals measured at surface of GeSn thin film before and after LA (tirr: 1.5 μs) are shown in Fig. 1(b). We can see clear peak around 300 cm-1 due to Ge-Ge atomic bond at the annealed region, which supports that GeSn film has been successfully crystallized by the annealing.To discuss about the growth feature of GeSn films, EBSD measurements were carried out. Mapping images of Ge and Sn phase signals at surfaces of samples are summarized in Fig. 2 as a function of tirr. Here, we can clearly see that the area of Sn phase signal is expanding by increasing tirr. These results (Raman and EBSD) suggest that by increasing tirr, Sn precipitation toward surface of GeSn occurs after crystallization of GeSn films, due to excess annealing. As a result, by increasing tirr, substitutional Sn concentration in the films decreases after LA [Fig. 3], showing that short time annealing is essential to prevent the precipitations. Fig. 4 summarizes substitutional Sn concentration in GeSn films grown with shortest irradiation time (1.5 μs) as a function of laser power. By minimizing the irradiation time and tuning laser power to minimum value for crystallization, we could realize GeSn thin films with a high substitutional Sn concentration (13 %) on insulating substrates. These are very attracting results to realize next generation electronics.Detailed physics and further tin concentration improvement methods will be discussed in the presentation.[References][1] J.R. Haynes, W. Shockley, Phys. Rev. 81 835–843 (1951).[2] S. Gupta, K. C. Saraswat, et.al., J. Appl. Phys. 113 073707 (2013).[3] S. Nakaharai, S. Takagi, et. al., J. Appl. Phys. 105 024515 (2009).[4] K. Toko, et. al., Sci. Rep., 7, 16981 (2017)[5] R. Matsumura, N. Fukata, ECS J. Solid State Sci. Technol, 9 063002 (2020). Figure 1

Evaluation of Thermal Expansion Coefficient in Ge1-x Sn x Nanowire Using Reciprocal Space Mapping

Ge1-x Sn x is expected to be a new material for next-generation electronic and thermoelectric device because it has higher carrier mobilities and lower thermal conductivity than pure Si and Ge. Here, strain is an important factor for designing electric and thermoelectric devices. It has been reported that there is a correlation between strain and thermal conductivity for group IV semiconductors [1]. In plane compressive strain is induced in epitaxially grown GeSn thin film on a Ge substrate due to the difference in lattice parameter. Anisotropic strain relaxation has been occurred in the GeSn nanowires. Anisotropic strain may cause anisotropic thermal expansion and thermal conductivity. In this study, we evaluated the thermal expansion of Ge1-x Sn x nanowire fabricated on Ge substrate using reciprocal space mapping (RSM) by synchrotron radiation X-ray diffraction (XRD) measurement.The Ge1-x Sn x thin films were epitaxially grown on Ge (001) substrate for 34 and 45 nm by home-made metal organic chemical vapor deposition [2]. Sn concentrations (x) is 3.2% as confirmed by Rutherford backscattering spectrometry. Then, the nanowires were fabricated by electron beam lithography and dry etching as shown in Fig. 1. The major axis length (L) parallel to [110] were fixed at 10 µm while the minor axis width (W) parallel to [-110] were 200 or 500 nm. For the measurement of RSM, multi-axis diffractometer in BL19B2 of SPring-8 was used. The photon energy was 10 keV, which is just under the K-edge of Ge at 11 keV. We fabricated many nanowires to obtain sufficiently strong X-ray diffraction. The sample temperature was controlled using a heating stage (Anton Paar DHS1100).Figure 2 shows the relationship between temperature and the lattice parameters in Ge0.968Sn0.032 nanowire with W=500 nm. Thermal expansion for the sample with W=200 nm showed an isotropic change. However, it was revealed that the thermal expansion between the in-plane minor axis [-110] and the out-of-plane [001] directions were different for the sample with W=500 nm. In the previous study, we have confirmed the uniaxial strain relaxation (minor axis direction [-110]) has been occurred with decreasing W for Ge1-x Sn x nanowire [3]. Thus, it is considered that the thermal expansion become isotropic as the nanowire width gets shorter. References Xu et al., J. Appl. Phys. 106, 114302 (2009).Suda et al., ECS Trans. 64 (6). 697 (2014).K. Yoshioka et al., Thin Solid Films 697, 137797 (2020). Figure 1

(Invited) Heteroepitaxy and Strain Engineering of Germanium-Silicon-Tin Ternary Alloy Semiconductor Thin Films for Energy Band Design

Ternary alloy semiconductor of germanium-silicon-tin (GeSiSn) has attracted for electronic and optoelectronic applications, because this group-IV alloy material provides energy band engineering independent on the lattice constant like group III-V compound semiconductors [1]. In addition, GeSiSn/Ge(Sn) heterostructure realizes type-I energy band alignment with a sufficiently large band offset at both conduction and valence band edges with no or very small lattice mismatching [2,3], and that is preferable for effective carrier confinement for light emitting devices and high mobility transistors. On the other hand, there are still challenges for crystal growth with strain and band engineering of group-IV ternary alloy semiconductor thin films. GeSn is one of promising candidates for optoelectronic applications since it realizes direct transition group-IV semiconductor. GeSn with an in-plane lattice constant larger than Ge is better to enhance the emission efficiency, as the conduction band edge of the gamma-valley lowers than that of the L-valley with large lattice constant and/or in-plane tensile strain. Thus, a buffer layer such as GeSiSn with a lattice constant sufficiently larger than Ge is required to obtain direct transition GeSn thin films, and lattice-constant engineering technology of buffer and GeSn layers should be developed with well-controlled strain relaxation technique. Recently, we explored effective strain engineering technique of GeSiSn ternary alloy epitaxial layers on Ge and Si substrate to obtain much larger in-plane lattice constant. We investigated the effect of low-temperature growth of Ge buffer layer on the strain relaxation of GeSiSn layer [4,5]. Also, we examined the ion implantation technique into substrate to enhance the strain relaxation of GeSiSn epitaxial layers grown on Ge substrate [6]. We can achieve GeSiSn epitaxial layers with the enhancement of strain relaxation and the lattice constant larger than Ge, although the crystalline quality of these epitaxial layers should be still improved. We previously reported that the strain direction as compressive and tensile ones is significantly influence of GeSiSn epitaxial layers [7]. The control of strain structure and its relaxation process is keys to obtain high crystalline quality of GeSiSn and GeSn heteroepitaxial layers for improving the electronic and optoelectronic properties of group-IV heterostructures.

Structural Property Study for GeSn Thin Films.

The structural properties of GeSn thin films with different Sn concentrations and thicknesses grown on Ge (001) by molecular beam epitaxy (MBE) and on Ge-buffered Si (001) wafers by chemical vapor deposition (CVD) were analyzed through high resolution X-ray diffraction and cross-sectional transmission electron microscopy. Two-dimensional reciprocal space maps around the asymmetric (224) reflection were collected by X-ray diffraction for both the whole structures and the GeSn epilayers. The broadenings of the features of the GeSn epilayers with different relaxations in the ω direction, along the ω-2θ direction and parallel to the surface were investigated. The dislocations were identified by transmission electron microscopy. Threading dislocations were found in MBE grown GeSn layers, but not in the CVD grown ones. The point defects and dislocations were two possible reasons for the poor optical properties in the GeSn alloys grown by MBE.

Liquid-mediated crystallization of amorphous GeSn under electron beam irradiation

Crystallization processes of amorphous germanium–tin (GeSn) under low-energy electron-beam irradiation were examined using transmission electron microscopy (TEM). Freestanding amorphous GeSn thin films were irradiated with a 100 keV electron beam at room temperature. The amorphous GeSn was athermally crystallized by electron-beam irradiation, when the electron flux exceeded the critical value. Heterogeneous structures consisting of nano- and micro-crystallites were formed after crystallization of amorphous GeSn with ∼24 at. % Sn in the as-sputtered amorphous state. In situ TEM observations of structural changes under electron-beam irradiation revealed that random nucleation and growth of nanocrystallites occur at the early stage of crystallization, followed by rapid formation of micro-grains surrounding the nanocrystals. It has been suggested that the growth of micro-grains progresses via supercooled liquid Sn at the amorphous/crystalline interface. The resultant GeSn grains with a size of a few micrometers contained ∼15 at. % Sn, much larger than the solubility limit of Sn in Ge (∼1 at. % Sn).

Impact of defects on photoexcited carrier relaxation dynamics in GeSn thin films

We report the results of a study that was conducted to investigate the recombination paths of photoexcited charge carriers in GeSn thin films. The charge carrier lifetime was predicted as a function of temperature from a description of photoconductivity transients, assuming co-influence of Shockley–Read–Hall and radiative carrier recombination paths. We identify that dislocations are the source of a band of electronic states with the highest occupied state at E V + (85÷90) meV that acts as Shockley–Read–Hall centers determining the charge carrier lifetime. The photoluminescence (PL) and photoconductivity spectroscopy have been applied to distinguish between the contribution of both band-to-band and dislocation-related electron transitions. The PL band was found to demonstrate a low-energy shift of about 80 ± 20 meV relative to the edge of the photoconductivity spectra in the indirect bandgap GeSn films with dislocations. The role of a different nature deeper acceptor level at E V + (140 ÷ 160) meV in the recombination processes of the GeSn layers with better structural quality and the Sn content higher than 4% was discussed. This detailed understanding of the recombination processes is of critical importance for developing GeSn/Ge-based optoelectronic devices.

Formation and characterization of Ni, Pt, and Ti stanogermanide contacts on Ge0.92Sn0.08

In this article we provide a comparative and systematic study on contact formation for germanium-tin (GeSn) thin films containing a high percentage of Sn (8 at.%). 20 nm of Nickel (Ni), Titanium (Ti), or Platinum (Pt) was deposited on Ge0.92Sn0.08 layers grown on Ge substrates, and subsequently annealed between 300 and 500 °C to form stanogermanide alloys. Several experimental techniques were employed to characterize the material and the electrical contact behaviour, with the purpose of identifying the most promising stanogermanide contact candidate, in terms of low sheet resistance, low surface roughness and low formation temperature. Among these three different metals we found that, for nanoelectronic applications, nickel-stanogermanide (NiGeSn) was the most promising candidate based on a low sheet resistance combined with a low formation temperature, below 400 °C. PtGeSn showed better behaviour in terms of thermal stability compared with the other two options, while Ti was found to be relatively unreactive under these annealing conditions, resulting in poor TiGeSn formation. For the lowest resistance stanogermanide contact generated, namely NiGeSn formed at 300 °C, detailed lattice resolution Transmission Electron Microscopy imaging, combined with fast Fourier transformation analysis, identified the formation of the Nix-1(GeSn)y-1 phase.

Enhanced mobility of Sn-doped Ge thin-films (≤50 nm) on insulator for fully depleted transistors by nucleation-controlled solid-phase crystallization

High-speed fully depleted thin-film transistors (TFTs) for low-power consumption are required for next-generation electronics, such as three-dimensional large-scale integrated circuits and advanced system-in-displays. For this purpose, high-carrier-mobility semiconductor thin-films (thickness: ≤∼50 nm) on insulator structures should be fabricated under low-temperature processing conditions (≤500 °C). To achieve this, solid-phase crystallization of amorphous GeSn (a-GeSn) with low Sn concentration (2%) is investigated for a wide range of film thicknesses (30 − 200 nm), where thin a-Si underlayers (thickness: 0 − 20 nm) are introduced between a-GeSn films and substrates. GeSn is polycrystallized by annealing at 450 °C, keeping Si underlayers amorphous. Crystal grains of almost identical sizes are obtained for GeSn thicknesses of 30 − 50 nm, though grain sizes significantly decrease for thicknesses exceeding 50 nm owing to enhanced bulk nucleation. A detailed analysis of GeSn films (thickness: 50 nm) reveals that grain sizes are decreased by introducing a-Si underlayers (thickness: 3 − 20 nm), e.g., from ∼10 μm to 2 − 3 μm. This phenomenon is attributed to the change in dominant nucleation sites from the interface to the bulk, which significantly decreases grain-boundary scattering of carriers through a decrease in the barrier heights at grain boundaries. As a result, a high carrier mobility of 200 − 300 cm2/V s is realized for GeSn thin-films (thickness: 30 − 50 nm) grown with a-Si underlayers. The mobility (200 − 300 cm2/V s) is the largest ever reported data for Ge and GeSn thin-films (thickness: 30 − 50 nm) grown at low temperatures (≤500 °C). This technique will facilitate the realization of high-speed fully depleted TFTs for next-generation electronics.

Direct observations of crystallization processes of amorphous GeSn during thermal annealing: A temperature window for suppressing Sn segregation

The solubility limit of tin (Sn) in germanium (Ge) is very small, and, therefore, it is difficult to synthesize high Sn concentration GeSn crystals by conventional methods. An amorphous phase can contain elements beyond the solubility limit of the crystal state, and, therefore, recrystallization of the amorphous alloy is one of the possible ways to realize materials far from the equilibrium state. To suppress Sn precipitation during thermal annealing, knowledge of crystallization processes is required. In the present study, amorphous GeSn thin films with different Sn concentrations were prepared by sputtering, and their crystallization processes were examined by in situ transmission electron microscopy. It was found that the crystallization temperature decreases with increasing Sn concentration, and it became lower than the eutectic temperature when the Sn concentration exceeded ∼25 at. %. Radial distribution function analyses revealed that phase decomposition occurs in the amorphous state of the specimens which crystallize below the eutectic temperature, and Sn crystallites were simultaneously precipitated with crystallization. On the other hand, no remarkable phase decomposition was detected in amorphous GeSn with &amp;lt;25 at. % Sn. Sn precipitation occurred at a higher temperature than the crystallization in these specimens, and the difference between the crystallization and Sn precipitation temperatures became large with decreasing Sn concentration. Because of the existence of this temperature difference, a temperature window for suppressing Sn segregation existed. We demonstrated that large GeSn grains with high Sn concentration could be realized by annealing the specimens within the temperature window.