Three-dimensional (3D) self-ordered Ge nanodots in cyclic epitaxial growth of Ge/SiGe superlattice on Si0.4Ge0.6 virtual substrate (VS) were fabricated by reduced pressure chemical vapor deposition. By the Ge/SiGe superlattice deposition, dot-on-dot alignment and <100> alignment were obtained toward the vertical and lateral direction, respectively. Facets and growth mechanism of Ge nanodots and key factors of alignment were studied. Two types of Ge nanodots were observed, diamond-like nanodots composed of {105} and dome-like nanodots composed of {113} and {159} facets. The Ge nanodots tend to grow directly above the nanodots of the previous period as these regions show a relative higher tensile strain induced by the buried nanodots. Thus, this dot-on-dot alignment is sensitive to the SiGe spacer thickness, and it degrades when the SiGe spacer is over 82 nm. The Ge content of the SiGe spacer ranging 45-52% affects the lateral alignment and the size uniformity of Ge nanodots because of the strain balance between the superlattice and the VS. When the strain is balanced, 3D aligned Ge nanodots can be achieved.

A method for high-quality epitaxial growth of Ge on Si (111) and Si (110) was investigated by reduced pressure chemical vapor deposition. Two-step Ge epitaxy (low-temperature Ge seed and high-temperature main Ge growth) with several cycles of annealing by interrupting the Ge growth (cyclic annealing) was performed. In the case of Ge seed layer growth below 350°C for (111) orientation and 400°C for (110) orientation, huge surface roughening due to too high dislocation density is observed after the following annealing step. For both crystal orientations, a high crystallinity Ge seed layer is realized by combination of 450°C growth with 800°C annealing. Once the high-quality Ge seed layer is deposited, high crystal quality Ge can be grown at 600°C on the seed layer for both crystal orientations. For the 5 µm thick Ge layer deposited with the cyclic annealing process at 800°C, a Si diffusion length of ~400 nm from the interface, RMS roughness below 0.5 nm and threading dislocation density of 5×106 cm-2 are achieved for both (111) and (110) substrates.

Heteroepitaxial growth of Ge on Si has great interest for various optoelectronic applications such as Ge photodiodes(1). However 4.2% of lattice mismatch causes dislocation formation and island growth. High quality Ge(001) growth techniques are reported in ref.(2-4). Moreover, Ge(111) surface is also interesting because of higher carrier mobility(5). Furthermore, Ge(110) is preferred orientation of virtual substrates for epitaxial graphene growth(6). In the case of the Ge deposition on Si(111) and Si(110) substrates, it seems that the process conditions used for Ge growth on Si(001) are not suitable to realize high crystallinity and smooth surface (7). In this paper, we present a method of high quality and smooth Ge layer growth on Si(111) and Si(110), which is the same level as the Ge growth on Si(001). Epitaxial growth of Ge on Si(111) and Si(110) is carried out using a reduced pressure chemical vapor deposition system. After HF last clean, a wafer is baked at 1000°C and cooled down to 600°C in H2 and further to 300-550°C in N2 to form a hydrogen-free Si surface. Then a 100 nm thick Ge layer is deposited as a seed layer using GeH4 with N2 carrier gas. Afterward the wafer is heated up to 450-650°C in H2 and the main part of Ge is deposited using a H2-GeH4 gas mixture. For threading dislocation density (TDD) reduction, annealing at 800°C in H2 is performed for several times (cyclic annealing) by interrupting the Ge growth. Atomic-force microscopy (AFM) is used for surface roughness analysis. Scanning transmission electron microscopy (STEM) and X-ray diffraction (XRD) are used for structural characterization of the Ge layer. Secco defect etching combined with angle view scanning electron microscopy (SEM) or optical microscope is used for TDD evaluation. Figure 1(a,b) summarize the root mean square (RMS) roughness of Ge(111) and Ge(110) seed layers grown at 300-550°C before and after postannealing at 600-800°C. If the growth temperature is lower than 350°C for Ge(111) and 400°C for Ge(110), a significant increase of the surface roughness is observed after postannealing at 700°C and 800°C, respectively. For both crystal orientations, the lowest RMS roughness is observed by depositing at 450°C for as deposited and postannealed samples. The maintained RMS roughness even after postannealing at 800oC may be indicating good crystal quality even at as deposited condition. To confirm the influence of the growth temperature on the crystallinity, cross section TEM images of the Ge(111) and the Ge(110) seed layers deposited at 300°C and 450°C are shown in Fig. 2(a-d). In the case of Ge growth at 300°C (Fig. 2(a,b)), a very high density of stacking faults (SF) and high surface roughness are observed for both crystal orientations. In contrast, by depositing at 450°C (Fig. 2(c,d)), lower SF density in the Ge layer is observed compared to that at 300°C. By postannealing, an improvement of crystallinity is observed for the Ge seed layers deposited at 450°C. However, in the case of 300°C, the crystallinity cannot be improved by the postannealing, because a too high density of dislocations and SF may cause irregular Ge atom migration. As the result, surface roughening occurs. Figure 3(a,b) show AFM surface roughness images after 5 μm-thick Ge(111) and Ge(110) deposited with cyclic annealing at 800°C, respectively. Clear terraces of ~0.3 and ~0.2 nm, whose heights are close to those of Ge(111) bilayer and Ge(110) monolayer, are observed, respectively. RMS roughness of the Ge(111) and the Ge(110) are 0.51 and 0.35 nm, respectively. These RMS roughnesses are comparable to a level reported for Ge (001) in ref.(1). Figure 4 shows TDD of Ge(111) and Ge(110) surfaces as a function of the Ge thickness deposited with cyclic annealing on Si(111) and Si(110) substrates. For both orientations, TDD of ~4×108 cm-2 is obtained for 500 nm-thick samples. With increasing the Ge thickness, the TDD is reduced and levels below TDD of ~5×106 cm-2 are achieved for both Ge (111) and Ge(110) for 5 μm-thick Ge. These methods enable high quality virtual substrate fabrication not only for (001) surfaces but also for (111) and (110) orientation without a chemical mechanical polishing process. References Lischke et al. Nature Photonics15 (2021) 925 Yamamoto et al. Solid-State Electron. 60 (2010) 2 Yamamoto et al. Semicond. Sci. Technol. 33 (2018) 124007 M. Hartmann et al. J. Appl. Phys. 95 (2004) 5905 H. Lee et al. IEDM Tech. Digest (2009) 09-457 J-H. Lee et al. Science 344 6181(2014) 286 M. Hartmann et al. J. Cryst. Growth 310 (2008) 5287 Figure 1

Multilayered Ge nanodots have drawn much attention due to their potential applications in optoelectronics, such as photodetectors and lasers. Many groups studied multilayered Ge nanodots with Si spacers on Si(001) grown by Stranski-Krastanov (SK) growth mode and vertically aligned by local tensile strain induced by buried Ge nanodots (1-2). However, to avoid plastic relaxation caused by a 4.2% lattice mismatch between Si and Ge, thick nanodots and/or large layer numbers are challenging. Additionally, laterally-aligned Ge nanodots without pre-structuring have not been reported. In this study, we demonstrate 3-dimensional (3D) self-ordered Ge nanodots on SiGe virtual substrate (VS) by SiGe/Ge cyclic epitaxial growth and show the effects of fabrication parameters. The 3D self-ordered Ge nanodots were fabricated by reduced-pressure chemical vapor deposition. A Si0.4Ge0.6 VS with step-graded buffer deposited on Si(001) wafer was used. This VS was post-annealed at 1000°C, followed by chemical-mechanical polishing. After HF dip, the substrate was baked at 850°C in H2, then cooled down to 550°C for epitaxial growth. A 52-82 nm thick Si0.48Ge0.52 layer was deposited using a H2-SiH4-GeH4 gas mixture, then a self-assembled Ge nanodots layer via SK growth mechanism was deposited with 7.5-15.0 nm Ge coverage using a H2-GeH4 gas mixture. This Si0.48Ge0.52/Ge deposition cycle was repeated 5 to 20 times to fabricate the 3D self-ordered Ge nanodot stack. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to analyze the morphology and alignment of the Ge nanodots. The facets of the Ge nanodots were studied by analyzing the cross-section cuts of AFM images and confirmed by scanning transmission electron microscopy (STEM). Nano-beam diffraction (NBD) was used to study strain in the superlattice. Fig. 1(a-c) show the AFM images of the 5-cycle superlattices with Ge coverage 7.5 to 15.0 nm. In fig. 1(a), we can see mainly two types of nanodots, diamond (32%) and dome (68%). The height of the diamond-like nanodots is 9 nm with a standard deviation (s) of 2.6 nm while that of the dome-like nanodots is 23 nm with s=1.8 nm. With increasing Ge coverage, dome-like nanodots dominate (fig. 1(b)) and some nanodots merge with the adjacent nanodots (fig. 1(c)). Since the dome-like nanodots show a lower s in height than the diamond-like nanodots do, engineering of self-ordering is more feasible with the dome-like nanodot. Fig. 2(a-b) show the angle view of SEM images of Ge nanodots on 5- and 20-cycle superlattice of 12.5 nm-Ge/52 nm-SiGe. The dome-like nanodots are dominant and laterally aligned. The alignment and the uniformity improve with the increasing cycle number of the superlattice. However, when the thickness of Si0.48Ge0.52 spacer increases, the lateral- and vertical alignment of nanodots become random, and the amount of diamond-like nanodots increases (not shown). To study facets of two types of nanodots, the tilt of each facet was calculated from the cross-section cuts of AFM images. Fig. 3(a) shows an AFM image of the dome-like nanodot. Fig. 3(b) shows the cross-section cuts of fig. 3(a) along <110>. These cross-section cuts are well-overlapped with the high-angle annular dark-field (HAADF) STEM image as shown in the background of fig. 3(b). Therefore, it is possible and reliable to estimate the facets from the cross-section cuts of our AFM images. By this method, we confirmed that the diamond-like nanodot is composed of {105} and the dome-like nanodot is composed of {113} and {159}. This is consistent with a study of Ge dot on Si substrate except for {159} facet (3). Instead of {159} facet, a relatively similar facet {3 15 23} was reported. This difference may result from the less compressive strain in our Ge nanodots because SiGe VS was used. To explain the vertical correlation of Ge nanodots, a HAADF STEM image and in- and out-of-plane strain distributions measured by NBD are shown in fig. 4(a-c). The nanodots are vertically aligned (fig. 4(a)). The SiGe on the nanodot shows a relatively higher lattice parameter along <110> (fig. 4(b)) and lower lattice parameter along <001> (fig. 4(c)) compared to that on Ge wetting layer, indicating tensile strain. This tensile strain area is the preferred position for Ge nanodot formation because of less lateral lattice mismatch. Consequently, the nanodots tend to grow above the buried nanodots. 3D self-ordered multilayered Ge nanodots on SiGe VS were successfully fabricated, and the facets and the vertical correlation of Ge nanodots were studied. References P.S. Chen et al. Materials Science and Engineering B 108 (2004) 213-218 K.L. Wang et al. Proceeding of the IEEE 95 (2007) 1866 J.T. Robinson et al. Nanotechnology 20 (2009) 085708 Figure 1

Self-ordered multilayered Ge nanodots with SiGe spacers on Si0.4Ge0.6 virtual substrate were fabricated by using reduced-pressure chemical vapor deposition, and the mechanism of vertical ordering was investigated. Process conditions of Ge and SiGe layer deposition are H2-GeH4 at 550 °C and H2-SiH4-GeH4 at 500 °C - 550 °C, respectively. By depositing the SiGe at 550 °C or raising Ge content, the SiGe surface becomes smooth, resulting in vertically-aligned Ge nanodots to reduce strain energy. Ge nanodots prefer to grow on the nanodot where the SiGe is relatively tensile strained due to the buried Ge nanodot underneath. By depositing at 500 °C and lowering Ge content, checkerboard-like surface forms, and the following Ge nanodots grow at staggered positions to reduce surface energy. The Ge nanodots are laterally aligned along elastically soft <100> direction without pre-structuring resulting from the strain distribution.