Thermal stability of SiGe films on an ultra thin Ge buffer layer on Si grown at low temperature

The thermal stability of SiGe films on an ultra thin Ge buffer layer on Si fabricated at low temperature has been studied. The microstructure and morphology of the samples were investigated by high-resolution X-ray diffraction, Raman spectra and atomic force microscopy, and using a diluted Secco etchant to reveal dislocation content. After thermal annealing processing, it is observed that undulated surface, threading dislocations (TDs) and stacking faults (SFs) appeared at the strained SiGe layer, which developed from the propagation of a misfit dislocation (MD) during thermal annealing, and no SFs but only TDs formed in strain-relaxed sample. And it is found that the SiGe films on the Ge layer grown at 300 °C has crosshatch-free surface and is more stable than others, with a root mean square surface roughness of less than 2 nm and the threading dislocation densities as low as ∼10⁵ cm⁻². The results show that the thermal stability of the SiGe films is associated with the Ge buffer layer, the relaxation extent and morphology of the SiGe layer.     

Study of the surface cleaning of GOI and SGOI substrates for Ge epitaxial growth

An effective wet cleaning process, optimized for low temperature Ge epitaxial growth on thin Ge or SiGe structures with reduced surface roughening, is proposed. It is found that HF + HCl cleaning is the most effective wet cleaning method that is applicable to the low temperature thermal cleaning. It is also found that temperature of the thermal cleaning appropriate to 25-30 nm thick germanium on insulator (GOI) or silicon-germanium on insulator (SGOI) substrates is approximately 450 °C. Moreover, it is also found that the temperatures of Ge epitaxial growth even in lattice-matched systems must be reduced to around 400 °C to prevent surface roughening and those in lattice-mismatched systems also must be reduced sufficiently (300 °C for strained Ge growth on SGOI (X_eff = 0.6)) to prevent lattice relaxation as well as surface roughening. Finally, the successful formation of the compressively strained GOI structures is demonstrated by applying these wet cleaning and low temperature thermal cleaning processes and low temperature Ge epitaxy to thin SGOI substrates.     

Strain relaxation in nano-patterned strained-Si/SiGe heterostructure on insulator

In order to evaluate the strain stability, arrays of strained Si/SiGe nano-stripes and nano-pillars were fabricated by Electron-Beam Lithography (EBL) and Reactive-Ion Etching (RIE). The strain relaxation in the patterned strained Si on SiGe-on-insulator (SGOI) was investigated by high-resolution UV micro-Raman spectroscopy. The Raman measurements before and after patterning indicate that most of the strain in the top strained Si is maintained until scaling down to 300 nm, and relaxation of <15% is observed in pillars with a dimension of 150 nm × 150 nm. In the nano-patterned heterostructure strained Si/SiGe, the observed relaxation is small, which is mainly attributed to the fully relaxed and dislocation-free SiGe virtual substrate fabricated by modified Ge condensation.     

Relaxed SiGe-on-insulator with high Ge fraction obtained by oxidation of SiGe/Si-on-insulator with hydrogen ions implantation

The SiGe-on-insulator (SGOI) materials were obtained by thermal oxidation of SiGe layers on SOI wafers. As a comparison, H ions were implanted into SiGe layer of some samples before oxidation. The high degree relaxed SGOI materials with high Ge fraction were fabricated by two kinds of samples, including the samples without and with H ions implantation, and relaxation degree of SiGe layers is above 93%. The different result is that implantation of H ions decreased the oxidation rate of SiGe layer and decreased the loss of Ge in SiGe layer during oxidation. The effect of implantation of H ions is discussed in the paper.     

Strain relaxation of epitaxial SiGe layer and Ge diffusion during Ni silicidation on cap-Si/SiGe/Si(0 0 1)

Strain relaxation of the epitaxial SiGe layer and Ge diffusion during nickel silicidation by rapid thermal annealing the structure of Ni(≅14 nm)/cap-Si(≅26 nm)/Si_0.83Ge_0.17/Si(0 0 1) at the elevated annealing temperatures, T_A, were investigated by X-ray diffraction analyses of high-resolution ω-2θ scan and reciprocal space mapping. The analyses showed a much larger strain relaxation at a lower T_A and a reduction in Ge content in the SiGe layer of Ni/SiGe/Si(0 0 1) after thermal annealing compared to the case of cap-Si/SiGe/Si(0 0 1). The results indicate that the strain relaxation of the SiGe layers in NiSi/SiGe/Si(0 0 1) is related to the phenomena of NiSi agglomeration and penetration into the SiGe layer during silicidation at elevated anneal temperatures ≥750 °C. At elevated T_A ≥ 750 °C, Ge diffused into the intact cap-Si area during silicidation.     

Non-homogeneous SiGe-on-insulator formed by germanium condensation process

Ge condensation process of a sandwiched structure of Si/SiGe/Si on silicon-on-insulator （SOI） to form SiGe-on- insulator （SGOI） substrate is investigated. The non-homogeneity of SiGe on insulator is observed after a long time oxidation and annealing due to an increased consumption of silicon at the inflection points of the corrugated SiGe film morphology, which happens in the case of the rough surface morphology, with lateral Si atoms diffusing to the inflection points of the corrugated SiGe film. The transmission electron microscopy measurements show that the non-homogeneous SiGe layer exhibits a single crystalline nature with perfect atom lattice. Possible formation mechanism of the non-homogeneity SiGe layer is presented by discussing the highly nonuniform oxidation rate that is spatially dependent in the Ge condensation process. The results are of guiding significance for fabricating the SGOI by Ge condensation process.     

Effect of Ge surface termination on oxidation behavior

Sulfur-termination was formed on the Ge(1 0 0) surface using (NH₄)₂S solution. Formation of Ge-S and the oxidation of the S-terminated Ge surface were monitored with multiple internal reflection Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. In the 0.5, 5, or 20% (NH₄)₂S solution, H-termination on the Ge(1 0 0) surface was substituted with S-termination in 1 min. When the S-terminated Ge(1 0 0) surface was exposed in air ambient, the oxidation was retarded for about 3600 min. The preservation time of the oxide layer up to one monolayer of S-terminated Ge(1 0 0) surface was about 120 times longer than for the H-terminated Ge(1 0 0) surface. However, the oxidation of S-terminated Ge(1 0 0) surface drastically increased after the threshold time. There was no significant difference in threshold time between S-terminations formed in 0.5, 5, and 20% (NH₄)₂S solutions. With the surface oxidation, desorption of S on the Ge surface was observed. The desorption behavior of sulfur on the S-terminated Ge(1 0 0) surface was independent of the concentration of the (NH₄)₂S solution that forms S-termination. Non-ideal S-termination on Ge surfaces may be related to drastic oxidation of the Ge surface. Finally, with the desulfurization on the S-terminated Ge(1 0 0) surface, oxide growth is accelerated.     

Violet luminescence in Ge nanocrystals/Ge oxide structures formed by dry oxidation of polycrystalline SiGe

Nanocrystals of Ge surrounded by a germanium oxide matrix have been formed by dry thermal oxidation of polycrystalline SiGe layers. Violet (3.16 eV) luminescence emission is observed when Ge nanocrystals, formed by the oxidation of the Ge segregated during the oxidation of the SiGe layer, are present, and vanishes when all the Ge has been oxidized forming GeO₂. Based on the evolution of the luminescence intensity and the structure of the oxidized layer with the oxidation time, the recombination of excitons inside the nanocrystals and the presence of defects in the bulk oxide matrix are ruled out as sources of the luminescence. The luminescence is attributed to recombination in defects at the Ge sub-oxide interface between the Ge nanocrystals and the surrounding oxide matrix, which is GeO₂.     

Luminescence properties of Ge implanted SiO2:Ge and GeO2:Ge films

We have investigated cathodeluminescence (CL) of Ge implanted SiO₂:Ge and GeO₂:Ge films. The GeO₂ films were grown by oxidation of Ge substrate at 550 °C for 3 h in O₂ gas flow. The GeO₂ films on Ge substrate and SiO₂ films on Si substrate were implanted with Ge-negative ions. The implanted Ge atom concentrations in the films were ranging from 0.1 to 6.0 at%. To produce Ge nanoparticles the SiO₂:Ge films were thermally annealed at various temperatures of 600-900 °C for 1 h in N₂ gas flow. An XPS analysis has shown that the implanted Ge atoms were partly oxidized. CL was observed at wavelengths around 400 nm from the GeO₂ films before and after Ge⁻-implantation as well as from SiO₂:Ge films. After Ge⁻-implantation of about 0.5 at% the CL intensity has increased by about four times. However, the CL intensity from the GeO₂:Ge films was several orders of magnitude smaller than the intensity from the 800 °C-annealed SiO₂:Ge films with 0.5 at% of Ge atomic concentration. These results suggested that the luminescence was generated due to oxidation of Ge nanoparticles in the SiO₂:Ge films.     

Evidence for fast decay dynamics of the photoluminescence from Ge nanocrystals embedded in SiO2

We have investigated the origin of room temperature photoluminescence from ion-beam synthesized Ge nanocrystals (NCs) embedded in SiO₂ using steady state and time-resolved photoluminescence (PL) measurements. Ge NCs of diameter 4-13 nm were grown embedded in a thermally grown SiO₂ layer by Ge⁺ ion implantation and subsequent annealing. Steady state PL spectra show a peak at ∼2.1 eV originating from Ge NCs and another peak at ∼2.3 eV arising from ion-beam induced defects in the SiO₂ matrix. Time-resolved PL studies reveal double exponential decay dynamics on the nanoseconds time scale. The faster component of the decay with a time constant τ₁∼3.1 ns is attributed to the nonradiative lifetime, since the time constant reduces with increasing defect density. The slower component with time constant τ₂∼10 ns is attributed to radiative recombination at the Ge NCs. Our results are in close agreement with the theoretically predicted radiative lifetime for small Ge NCs.     

Fabrication of multilayered Ge nanocrystals embedded in SiOxGeNy films

Multilayered Ge nanocrystals embedded in SiO_xGeN_y films have been fabricated on Si substrate by a (Ge + SiO₂)/SiO_xGeN_y superlattice approach, using a rf magnetron sputtering technique with a Ge + SiO₂ composite target and subsequent thermal annealing in N₂ ambient at 750 °C for 30 min. X-ray diffraction (XRD) measurement indicated the formation of Ge nanocrystals with an average size estimated to be 5.4 nm. Raman scattering spectra showed a peak of the Ge-Ge vibrational mode downward shifted to 299.4 cm⁻¹, which was caused by quantum confinement of phonons in the Ge nanocrystals. Transmission electron microscopy (TEM) revealed that Ge nanocrystals were confined in (Ge + SiO₂) layers. This superlattice approach significantly improved both the size uniformity of Ge nanocrystals and their uniformity of spacing on the ‘Z’ growth direction.     

Formation of relaxed SiGe on the buffer consists of modified SiGe stacked layers by Si pre-intermixing

High-quality relaxed SiGe films on Si (0 0 1) have been demonstrated with a buffer layer containing modified SiGe (m-SiGe) islands in ultra-high vacuum chemical vapor deposition (UHV/CVD) system. The m-SiGe islands are smoothened by capping an appropriate amount of Si and the subsequent annealing for 10 min. This process leads to the formation of a smooth buffer layer with non-uniform Ge content. With the m-SiGe-dot multilayer as a buffer layer, the 500-nm-thick uniform Si_0.8Ge_0.2 layers were then grown. These m-SiGe islands can serve as effective nucleation centers for misfit dislocations to relax the SiGe overlayer. Surface roughness, strain relaxation, and crystalline quality of the relaxed SiGe overlayer were found to be a function of period's number of the m-SiGe-dot multilayer. By optimizing period number in the buffer, the relaxed Si_0.8Ge_0.2 film on the 10-period m-SiGe-dot multilayer was demonstrated to have a threading dislocation density of 2.0 × 10⁵ cm⁻² and a strain relaxation of 89%.     

Low temperature formation of multi-layered structures of ferromagnetic silicide Fe3Si and Ge

Low-temperature (<300 °C) molecular beam epitaxy of Fe₃Si/Ge was investigated. By optimizing growth conditions, Fe₃Si layers with a flat interface and good crystallinity were epitaxially grown on Ge(1 1 1) substrates. In addition, double heteroepitaxial growth of Fe₃Si/Ge on high quality Fe₃Si/Ge substrates was investigated. Reflective high-energy electron diffraction measurements suggested Fe₃Si and Ge layers were epitaxially grown on Fe₃Si/Ge substrates. However, transmission electron microscopy measurements indicated stacking faults formed in the intermediate Ge and top Fe₃Si layers. Improved crystallinity of the intermediate Ge layer is essential to realize high quality [Fe₃Si/Ge]₂ multi-layered structures.     

循环氧化/退火制备GeOI薄膜材料及其性质研究

采用超高真空化学气相淀积系统在SOI(绝缘体上硅)衬底上生长了Si_0.82Ge_0.18外延层,通过循环氧化/退火工艺,制备出Ge组分从0.24到1的绝缘体上锗硅(SGOI)材料.采用高分辨透射电镜、拉曼散射光谱和光致发光谱表征了其结构及光学性质,对氧化过程中SiGe层中的Ge组分和应变的演变进行了分析.最后制备出11 nm厚的绝缘体上Ge材料(GeOI),具有完整的晶格结构和平整的界面.室温下观测到绝缘体上Ge直接带跃迁光致发光,发光峰值位于1540 nm,发光 关键词： GeOI 氧化 退火 光致发光谱     

Solid phase epitaxy of Ge films on CaF2/Si(1 1 1)

At room temperature deposited Ge films (thickness < 3 nm) homogeneously wet CaF₂/Si(1 1 1). The films are crystalline but exhibit granular structure. The grain size decreases with increasing film thickness. The quality of the homogeneous films is improved by annealing up to 200 °C. Ge films break up into islands if higher annealing temperatures are used as demonstrated combining spot profile analysis low energy electron diffraction (SPA-LEED) with auger electron spectroscopy (AES). Annealing up to 600 °C reduces the lateral size of the Ge islands while the surface fraction covered by Ge islands is constant. The CaF₂ film is decomposed if higher annealing temperatures are used. This effect is probably due to the formation of GeF_x complexes which desorb at these temperatures.     

Thermal annealing effects on a compositionally graded SiGe layer fabricated by oxidizing a strained SiGe layer

Thermal annealing effects on a thin compositionally graded SiGe buffer layer on silicon substrate fabricated by oxidizing a strained SiGe layer are investigated with X-ray diffraction, ultraviolet Raman spectra and atomic force microscopy. Interestingly, we found that the surface roughness and the threading dislocation densities are kept low during the whole annealing processes, while the Ge concentration at the oxidizing interface decreases exponentially with annealing time and the strain in the layer is only relaxed about 66% even at 1000 °C for 180 min. We realized that the strain relaxation of such a compositionally graded SiGe buffer layer is dominated by Si-Ge intermixing, rather than generation and propagation of misfit dislocations or surface undulation.     

Growth of High Quality Strained-Si on Ultra-Thin SiGe-on-Insulator Substrate

Ultra-thin and near-fully relaxed SiCe substrate is fabricated using a modified Ce condensation technique, and then a 25-nm-thiek biaxially tensile strained-Si with a low rms roughness is epitaxially deposited on a SiGe- on-Insulator （SGOI） substrate by ultra high vacuum chemical vapor deposition （UHVCVD）. High-Resolution cross-sectional transmission electron microscope （HR-XTEM） observations reveal that the strained-Si/SiGe layer is dislocation-free and the atoms at the interface are well aligned. Furthermore, secondary ion mass spectrometry （SIMS） results show a sharp interface between layers and a uniform distribution of Ge in the SiCe layer. One percent in-plane tensile strain in the strained-Si layer is confirmed by ultraviolet （UV） Raman spectra, and the stress maintained even after a 30-s rapid thermal annealing （RTA） process at 1000℃. According to those results, devices based on strained-Si are expected to have a better performance than the conventional ones.     

DFT study on dissociative adsorption of SiH4 and GeH4 on SiGe(1 0 0)-2 × 1 surface

SiH₄ and GeH₄ dissociative adsorptions on a buckled SiGe(1 0 0)-2 × 1 surface have been analyzed using density functional theory (DFT) at the B3LYP level. The Ge alloying in the Si(1 0 0)-2 × 1 surface affects the dimer buckling and its surface reactivity. Systematic Ge influences on the reaction energetics are found in SiH₄ and GeH₄ reactions with four dimers of Si^∗-Si, Ge^∗-Si, Ge^∗-Ge, and Si^∗-Ge (∗ denotes the protruded atom). On a half H-covered surface, the energy barriers for silane and germane adsorption are higher than those on the pristine surface. The energy barrier for silane adsorption is higher than the corresponding barrier for germane adsorption. Rate constants are also calculated using the transition-state theory. We conclude that the SiGe surface reactivity in adsorption reaction depends on the Ge presence in dimer form. If the surface Ge is present in form of Ge^∗-Ge, the surface reactivity decreases as the Ge^∗-Ge content increases. If the surface Ge prefers to be in form of Ge^∗-Si at low Ge contents, the surface reactivity increases first, then decreases at high Ge surface contents when Ge^∗-Ge prevails. The calculated rate constant ratio of GeH₄ adsorption on Si^∗-Si over Ge^∗-Ge at 650 °C is 2.1, which agrees with the experimental ratio of GeH₄ adsorption probability on Si(1 0 0) over Si(1 0 0) covered by one monolayer Ge. The experimental ratio is 1.7 measured through supersonic molecular beam techniques. This consistency between calculation and experimental results supports that one monolayer of Ge on Si(1 0 0) exists in form of Ge^∗-Ge dimer.     

Oxidation mechanism of hydrogen-terminated Ge(1 0 0) surface

Control of the surface chemistry to prepare a robust termination on the Ge surface is crucial for the development of high-end Ge devices. In this study, oxidation of a H-terminated Ge surface was studied in air ambient and H₂O using a multiple internal reflection Fourier transform infrared spectroscopy (MIR FT-IR) technique. Ge surface treated in less diluted HF exhibited a stronger Ge-H peak intensity, and the surface was easily oxidized in the air ambient. Therefore, it is believed that the treatment of the Ge surface in highly diluted HF solution has an advantage in suppressing the oxidation of Ge in the air ambient. For the oxidation of Ge(1 0 0) surface in air ambient, the Ge surface is attacked by oxidizing agents to break Ge-H and Ge-Ge bonds, and the transition GeO_x layer is first formed, followed by a layer-by-layer GeO₂ formation with the increase in exposure time. When the H-terminated Ge surface was treated in H₂O, GeO_x was mainly formed, the thickness of the oxide layer was not changed with an increase in treatment time, and the Ge surface was maintained in a suboxide state, which exhibits a different oxidation mechanism from that in air ambient.     

Effect of strain relaxation of oxidation-treated SiGe epitaxial thin films and its nanomechanical characteristics

In this study, we examined the effect of high-temperature oxidation treatment on the SiGe epitaxial thin films deposited on Si substrates. The X-ray diffraction (XRD), atomic force microscopy (AFM), and nanoindentation techniques were employed to investigate the crystallographic structure, surface roughness, and hardness (H) of the SiGe thin films, respectively. The high-temperature oxidation treatment led to Ge pileup at the surface of the SiGe thin films. In addition, strain relaxation occurred through the propagation of misfit dislocations and could be observed through the cross-hatch pattern (800-900 °C) and SiGe islands (1000 °C) at the surface of the SiGe thin films. Subsequent hardness (H) measurement on the SiGe thin films by continuous penetration depth method indicated that the phenomenon of Ge pileup caused a slightly reduced H (below 50 nm penetration depth), while relaxation-induced defects caused an enhanced H (above 50 nm penetration depth). This reveals the influence of composition and defects on the structure strength of high-temperature oxidation-treated SiGe thin films.