Wafer bonding can be substituted for heteroepitaxy when manufacturing specific heterojunction-based devices. Devices manufactured using wafer bonding include multijunction solar cells, integrated sensors, heterogeneously integrated photonic devices on Si (such as high-performance laser diodes), Mach-Zehnder modulators, photodetectors, optical filters, and surface acoustic wave devices. In these devices, creating heterointerfaces between different semiconductors with heavily mismatched lattice constants and/or significant thermal expansion mismatch presents significant challenges for heteroepitaxial growth. High costs and poor yields in heavily mismatched heteroepitaxy can be addressed by wafer bonding in these optoelectronic devices and sensors, including the LiTaO3/Si and LiTaO3/SiO2 heterostructures. In the present work, heterostructure formation between piezoelectric LiTaO3 (100) and Si (100) and α-quartz SiO2 (100) is investigated via wafer bonding. Direct bonding is selected instead of heteroepitaxy due to a significant thermal expansion mismatch between LiTaO3 and Si-based materials. The coefficient of thermal expansion (CTE) of LiTaO3 is 18.3 × 10−6/K. This is 1 order of magnitude larger than the CTE for Si, 2.6–2.77 × 10−6/K and 25–30 times larger than the CTE for fused SiO2 and quartz (which ranges 0.54–0.76 × 10−6/K). Thus, even at 200 °C, a 4 in. LiTaO3/Si bonded pair would delaminate with LiTaO3 expanding 300 μm in length while Si would expand only by 40 μm. Therefore, direct wafer bonding of LiTaO3/Si and LiTaO3/SiO2 is investigated with low temperature (T < 500 K) Nano-Bonding™, which uses surface energy engineering (SEE). SEE is guided by fast, high statistics surface energy measurements using three liquid contact angle analysis, the van Oss/van Oss–Chaudhury–Good theory, and a new, fast Drop Reflection Operative Program analysis algorithm. Bonding hydrophobic LiTaO3 to hydrophilic Si or SiO2 is found to be more effective than hydrophilic LiTaO3 to hydrophobic Si or SiO2 temperatures for processing LiTaO3 are limited by thermal decomposition LiTaO3 into Ta2O5 at T ≥ 180 °C due to Li out-diffusion as much as by LiTaO3 fractures due to thermal mismatch.
The goal of this study is to investigate the effect of carbon incorporation upon thermal oxidation of Si1−xGex alloys and its role on strain compensation in Si1−xGex alloys. Si1−xGex and Si1−x−yGexCy alloys on Si(100) are grown by combined ion and molecular beam deposition and are then oxidized at 1000 °C in a dry oxygen ambient for two h. The thickness and the composition of all samples before and after oxidation are measured by Rutherford backscattering spectrometry (RBS) combined with ion channeling at 2.0 MeV and carbon nuclear resonance analysis at 4.3 MeV using 4He++ ions. In agreement with previously reported results of dry oxidation on Si1−xGex thin films, 2.0 MeV RBS analysis shows that a layer of SiO2 is formed on the top surface of both Si1−xGex and Si1−x−yGexCy thin films, while Ge segregates towards the top surface and at the SiO2/Si1−xGex and SiO2/Si1−x−yGexCy interfaces. However, it is observed for the first time that dry oxidation rates of Si1−xGex thin films decrease with increasing Ge fraction x for x≳0.20 and with increasing minimum yield. Ion channeling analysis and strain measurements indicate that the incorporation of C rather than the amount of C itself affects the dry oxidation mechanism because of its strong influence on film strain and crystalline quality. These results are discussed in conjunction with observations by secondary ion mass spectrometry, high resolution transmission electron microscopy, Fourier transform infrared spectrometry, and tapping mode atomic force microscopy.
The heteroepitaxial growth of the new ternary, group-IV, semiconductor material, Si1−x−yGexCy on Si(100), has been investigated. The epitaxial quality of Si1−x−yGexCy is found to be inferior to that of Si1−xGex with similar Si/Ge concentration ratio, grown under identical conditions, and the quality deteriorates with increasing C fraction. Also, the surface roughness, as studied by tapping mode atomic force microscopy, increases with increasing C fraction as well as with increasing Ge fraction, suggesting a transition from Frank–van der Merwe to Stranski–Krastanov type growth. We suggest that the very large mismatch between the average bond length in the Si1−x−yGexCy material, as determined by Vegard’s law, and the equilibrium Si–C bond length, weakens the Si–C bonds and reduces the elastic range of the material, thus lowering the barrier for dislocation and stacking fault formation. The change in elasticity may also be responsible for the change in growth morphology, either directly by a lowered barrier for island formation or indirectly through the formation of defects. A decrease in Ge incorporation in the Si1−x−yGexCy films with increasing C incorporation suggests a repulsive Ge–C interaction. Moreover, we observe a C-rich, Ge-deficient precursor phase to SiC precipitates at a growth temperature of 560 °C, whereas at 450 °C no such phase can be observed. The temperature dependence of the precursor formation is consistent with C bulk diffusion. Infrared absorption measurements cannot be used to detect the precursor phase. Finally, the onset of epitaxial breakdown is discussed and an accurate and independent determination of the C fraction and its substitutionality is emphasized.
Chemical bonding in native oxides of GaAs, before and after etching, is detected by X-Ray Photoelectron Spectroscopy (XPS). It is correlated with surface energy engineering (SEE), measured via Three Liquid Contact Angle Analysis (3LCAA), and oxygen coverage, measured by High Resolution Ion Beam Analysis (HR-IBA).Before etching, GaAs native oxides are found to be hydrophobic with an average surface energy, γT, of 33 ± 1 mJ/m2, as measured by 3LCAA. After dilute NH4OH etching, GaAs becomes highly hydrophilic and its surface energy, γT, increases by a factor 2 to a reproducible value of 66 ± 1 mJ/m2. Using HR-IBA, oxygen coverage on GaAs is found to decrease from 7.2 ± 0.5 monolayers (ML) to 3.6 ± 0.5 ML. The 1.17 ratio of Ga to As, measured by HR-IBA, remains constant after etching.XPS is used to measure oxidation of Ga and As, as well as surface stoichiometry on two locations of several GaAs(100) wafers before and after etching. The relative proportions of Ga and As are unaffected by adventitious carbon contamination. The 1.16 Ga:As ratio, measured by XPS, matches HR-IBA analysis. The proportions of oxidized Ga and As do not change significantly after etching. However, the initial ratio of As2O5 to As2O3, within the oxidized As, significantly decreases after etching from approximately 3:1 to 3:2.Absolute oxygen coverage, as a function of surface processing, is determined within 0.5 ML by HR-IBA. XPS offers insight into these modifications by detecting electronic states and phase composition changes of GaAs oxides. The changes in surface chemistry are correlated to changes in hydro-affinity and surface energies measured by 3LCAA.
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