Influence of the surface-termination of hexagonal SiC(0 0 0 1) on the temperature dependences of Ge growth modes and desorption

With the aim of comparing initial Ge adsorption and desorption modes on different surface terminations of 4H-SiC(0 0 0 1) faces, 3 × 3, √3×√3R30° (R3) and 6√3×6√3R30° (6R3) reconstructions, of decreasing Si surface richness, have been prepared by standard surface preparation procedures. They are controlled by reflection high energy electron diffraction (RHEED), low energy electron diffraction and photoemission. One monolayer of Ge has been deposited similarly at room temperature on each of these three surfaces, followed by the same set of isochronal heatings at increasing temperatures up to complete Ge desorption. At each step of heating, the structural and chemical status of the Ge ad-layer has been probed. Marked differences between the Si- (3 × 3 and R3) and C-rich (6R3) terminations have been obtained. Ge wetting layers are only obtained up to 400 °C on 3 × 3 and R3 surfaces in the form of a 4 × 4 reconstruction. The wetting is more complete on the R3 surface, whose atomic structure is the closest to an ideally Si-terminated 1 × 1 SiC surface. At higher temperatures, the wetting layer stage transiets in Ge polycrystallites followed by the unexpected appearance on the 3 × 3 surface of a more ordered Si island structure. It denotes a Si clustering of the initial Si 3 × 3 excess, induced by the presence of Ge. A phase separation mechanism between Si and Ge prevails therefore over alloying by Ge supply onto a such Si-terminated 3 × 3 surface. Conversely, no wetting is obtained on the 6R3 surface and island formation of exclusively pure Ge takes place already at low temperature. These islands exhibit a better epitaxial relationship characterized by Ge(1 1 1)//SiC(0 0 0 1) and Ge〈1 1 −2〉//SiC〈1 −1 0 0〉, ascertained by a clear RHEED spot pattern. The absence of any Ge-C bond signature in the X-ray photoelectron spectroscopy Ge core lines indicates a dominant island nucleation on heterogeneous regions of the surface denuded by the 6R3 graphite pavings. Owing to the used annealing cycles, the deposited Ge amount desorbs on the three surfaces at differentiated temperatures ranging from 950 to 1200 °C. These differences probably reflect the varying morphologies formed at lower temperature on the different surfaces. Considering all these results, the use of imperfect 6R3 surfaces appears to be suited to promote the formation of pure and coherent Ge islands on SiC.     

A structural parallel between Ge- and Si-induced 4 × 4 and 3 × 3 reconstructions on SiC(0 0 0 1) drawn from comparative RHEED oscillations

The initial Ge growth stages on a (√3 × √3)R30°-reconstructed SiC(0 0 0 1) surface (√3) have been studied using a complete set of surface techniques such as reflection high energy electron diffraction (RHEED), low energy electron diffraction (LEED), atomic force microscopy (AFM) and photoemission and compared with similar Si surface enrichments in place of Ge. The investigations essentially focus on the wetting growth-regimes that are favoured by the use of the √3 surface as a starting substrate, this surface being the closest to a smooth and ideally truncated Si-terminated face of hexagonal SiC(0 0 0 1). Depending on temperature and Ge or Si coverages, varying surface organizations are obtained. They range from unorganized layer by layer growths to relaxed Ge(1 1 1) or Si(1 1 1) island growths, through intermediate attempts of coherent and strained Ge or Si surface layers, characterized by 4 × 4 and 3 × 3 surface reconstructions, respectively. RHEED intensity oscillation recordings, as a function of Ge or Si deposited amounts, have been particularly helpful to pinpoint the limited (by the high lattice mismatch) existence domains of these interesting coherent phases, either in terms of formation temperature or surface coverages. Prominently comparable data for these two Ge- and Si-related reconstructions allow us to propose an atomic model for the still unexplained Ge-4 × 4 one. It is based on a same local organization in trimer and ad-atom units for the Ge excess as admitted for the Si-excess of the 3 × 3 surface, the higher strain nevertheless favouring arrangements, for the Ge-units, in 4 × 4 arrays instead of 3 × 3 Si ones. Admitting such models, 1.25 and 1.44 monolayers of Ge and Si, should, respectively, be able to lie coherently on SiC, with respective lattice mismatches near 30% and 25%. The experimental RHEED-oscillations values are compatible with such theoretical ones. Moreover, these RHEED coverage determinations (for layer completion, for instance) inform us in turn about the initial Si richness of the starting √3 reconstruction and help us to discriminate between earlier contradictory atomic models proposed in the literature.     

Interpretation of initial stage of 3C-SiC growth on Si(1 0 0) using dimethylsilane

The initial stage of cubic silicon carbide (3C-SiC) growth on a Si(0 0 1) surface using dimethylsilane (DMS) as a source gas was observed using scanning tunneling microscopy (STM) and reflection high-energy electron diffraction (RHEED). It was found that the dimer vacancies initially existing on the Si(0 0 1)-(2 × 1) surface were repaired by the Si atoms in DMS molecules, during the formation of the c(4 × 4) surface. From the STM measurement, nucleation of SiC was found to start when the Si surface was covered with the c(4 × 4) structure but before the appearance of SiC spots in the RHEED pattern. The growth mechanism of SiC islands was also discussed based on the results of RHEED, STM and temperature-programmed desorption (TPD).     

Effect of different Ge predeposition amounts on SiC grown on Si (1 1 1)

The SiC films were grown by solid source molecular beam epitaxy (SSMBE) on Si (1 1 1) with different amounts of Ge predeposited on Si prior to the epitaxial growth of SiC. The samples were investigated with reflection high energy electron diffraction (RHEED), atomic force microscopy (AFM), and X-ray diffraction (XRD). The results indicate that there is an optimized Ge predeposition amount of 0.2 nm. The optimized Ge predeposition suppress the Si outdiffusion and reduce the formation of voids. For the sample without Ge predeposition, the Si outdiffusion can be observed in RHEED and the results of XRD show the worse quality of SiC film. For the sample with excess amount of Ge predeposition, the excess Ge can increase the roughness of the surface which induces the poor quality of the SiC film.     

Growth dynamics of C-induced Ge dots on Si1−xGex strained layers

We address the growth mechanism of Ge quantum dots (QDs) on C-alloyed strained Si_1−xGe_x layers by in situ reflection high-energy electron-diffraction (RHEED). We show that C-induced growth on a Si-rich surface leads to a high density (about 10¹¹ cm⁻²) of small dome-shaped islands. On surfaces up to ≈65% richer in Ge we observe a decrease of the dot density by two orders of magnitude, which is associated to the increase of the adatom diffusion. Based on quantitative RHEED analysis, the islands are believed to grow in a Volmer-Weber mode even though their spotty electron transmission pattern is not detectable in the initial stages of growth due to the reduced size of the three-dimensional nucleation islands.     

Temperature dependent low energy electron microscopy study of Ge growth on Si(1 1 3)

We investigated the initial Ge nucleation and Ge island growth on a Si(1 1 3) surface using low energy electron microscopy and low energy electron diffraction. The sample temperature was varied systematically between 380 °C and 590 °C. In this range, a strong temperature dependence of the island shape is observed. With increasing temperature the Ge islands are elongated in the direction. Simultaneously, the average island size increases while their density decreases. From the Arrhenius-like behaviour of the island density, a Ge adatom diffusion barrier height of about 0.53 eV is deduced.     

Growth of Ge islands on prepatterned Si (0 0 1) substrates

We report on the growth and properties of Ge islands grown on (0 0 1) Si substrates with lithographically defined two-dimensionally periodic pits. After thermal desorption and a subsequent Si buffer layer growth these pits have an inverted truncated pyramid shape. We observe that on such prepatterned substrates lens-like Ge-rich islands grow at the pit bottoms with less Ge deposition than necessary for island formation on flat substrates. This is attributed to the aggregation of Ge at the bottom of the pits, due to Ge migration from the pit sidewalls. At the later stages of growth, dome-like islands with dominant {1,1,3} or {15,3,23}, or other high-index facets [i.e. {15,3,20} facets] are formed on the patterned substrates as shown by surface orientation maps using atomic force microscopy. Furthermore, larger coherent islands can be grown on patterned substrates as compared to Ge deposition on flat ones.     

Shape, facet evolution and photoluminescence of Ge islands capped with Si at different temperatures

We investigate the embedding of Ge islands in a Si matrix by means of atomic force microscopy and photoluminescence (PL) spectroscopy. The Ge islands were grown between 360°C and 840°C and subsequently capped with Si at different temperatures. For the highest Ge growth temperature (840°C), we show that the surface flattens at high Si capping temperatures while new facets can be identified at the island base for intermediate capping temperatures (650–450°C). At low capping temperatures (300–350°C), the island morphology is preserved. In contrast to the observed island shape changes, the decreasing Si capping temperature causes only a small redshift of the island related PL signal for islands grown on high temperatures. This redshift increases for Ge islands grown at lower temperatures due to an increased Ge content in the islands. By applying low-temperature capping (300°C) on the different island types, we show that the emission wavelength can be extended up to 2.06 μm for hut clusters grown at 400°C. Further decreasing of the island growth temperature to 360°C leads to a PL blueshift, which is explained by charge carrier confinement in Ge quantum dots.     

STM study of successive Ge growth on “V”-stripe patterned Si (0 0 1) surfaces at different growth temperatures

The self-assembly process of Ge islands on patterned Si (0 0 1) substrates is investigated using scanning tunneling microscopy. The substrate patterns consist of one-dimensional stripes with “V”-shaped geometry and sidewalls inclined by an angle of 9° to the (0 0 1) surface. Onto these stripes, Ge is deposited in a step-wise manner at different temperatures from 520 °C to 650 °C. At low temperature, the Ge first grows nearly conformally over the patterned surface but at about 3 monolayers a strong surface roughening due to reconstruction of the surface ridges as well as side wall ripple formation occurs. At 600 °C, a similar roughening takes place, but Ge accumulates within the grooves such that at a critical thickness of 4.5 monolayers, 3D islands are formed at the bottom of the grooves. This accumulation process is enhanced at 650 °C growth, so that the island formation starts about 1 monolayers earlier. At 600 and 650 °C, all islands are all aligned at the bottom of the stripes, whereas at 550 °C Ge island form preferentially on top of ridges. The experimental observations are explained by the strong temperature dependence of Ge diffusion over the patterned surface.     

Nanowedge island formation on Mo(1 1 0)

The deposition of ultrathin Fe films on the Mo(1 1 0) surface at elevated temperatures results in the formation of distinctive nanowedge islands. The model of island formation presented in this work is based on both experiment and DFT calculations of Fe adatom hopping barriers. Also, a number of classical molecular dynamics simulations were carried out to illustrate fragments of the model. The islands are formed during a transition from a nanostripe morphology at around 2 ML coverage through a Bales-Zangwill type instability. Islands nucleate when the meandering step fronts are sufficiently roughened to produce a substantial overlap between adjacent steps. The islands propagate along the substrate [0 0 1] direction due to anisotropic diffusion/capture processes along the island edges. It was found that the substrate steps limit adatom diffusion and provide heterogeneous nucleation sites, resulting in a higher density of islands on a vicinal surface. As the islands can be several layers thick at their thinnest end, we propose that adatoms entering the islands undertake a so-called “vertical climb” along the sides of the island. This is facilitated by the presence of mismatch-induced dislocations that thread to the sides of the islands and produce local maxima of compressive strain. Dislocation lines also trigger initial nucleation on the surface with 2-3 ML Fe coverage. The sides of the nanowedge islands typically form along low-index crystallographic directions but can also form along dislocation lines or the substrate miscut direction.     

Impact of O2 exposure on surface crystallinity of clean and Ba terminated Ge(1 0 0) surfaces

In analogy with the case of Sr on Si [Y. Liang, S. Gan, M. Engelhard, Appl. Phys. Lett. 79 (2001) 3591], we studied surface crystallinity and oxidation behaviour of clean and Ba terminated Ge(1 0 0) surfaces as a function of oxygen pressure and temperature. The structural and chemical changes in the Ge surface layer were monitored by LEED, XPS and real-time RHEED. In contrast to the oxidation retarding effect, observed for 1/2 monolayer of Sr on Si, the presence of a Ba termination layer leads to a pronounced increase in Ge oxidation rate with respect to clean Ge. In fact, while the Ge(1 0 0) surface terminated with 1/2 ML Ba amorphizes for a pO₂ of 10⁻² Torr, LEED indicates that clean Ge forms a thin (4.5 Å), 1 × 1 ordered oxide upon aggressive O₂ exposure (150 Torr, 200 °C, 30 min). We briefly discuss the origins for the difference in behaviour between Ba on Ge and Sr on Si.     

Ultrasmall Ge islands with low diameter-to-height aspect ratio on Si(1 0 0)-(2 × 1) surfaces

Scanning tunneling microscopy (STM) and high resolution cross-sectional transmission electron microscopy (XTEM) studies have been used to investigate the formation of Ge nanocrystals grown on Si(1 0 0)-(2 × 1) surfaces by molecular beam epitaxy (MBE). We observe relatively high density of Ge islands where small ‘pyramids’, small ‘domes’ and facetted ‘domes’ of various sizes co-exist in the film. As revealed from XTEM images, a large fraction of islands, especially dome-shaped Ge islands have been found to have an aspect ratio of ∼1 (diameter):1 (height). Observation of truncated-sphere-shaped Ge islands with a narrow neck contact with the wetting layer is reported.     

A core level and valence band photoemission study of the (1 1 1) and ( ) surfaces of 3C–SiC

A core level and valence band photoemission study of thick 3C–SiC(1 1 1) and 3C–SiC( ) epilayers grown by sublimation epitaxy is reported. The as introduced samples show threefold 1×1 low-energy electron diffraction patterns. For the Si face and reconstructed surfaces develop after in situ heating to 1100°C and 1300°C, respectively. For the C face a 3×3 reconstruction form after heating to 980°C. A semiconducting behavior is observed for the and 3×3 reconstructed surfaces while the reconstruction show a Fermi edge and thus a metallic-like behavior. The surface state on the surface is investigated and found to have Λ₁ symmetry and a total band width of 0.10 eV within the first surface Brillouin zone. For the Si 2p and C 1s core levels binding energies and surface shifted components are extracted and compared to earlier reported results for 6H– and 4H–SiC.     

Energetics of Ge nucleation on SiO2 and implications for selective epitaxial growth

We have measured the time evolution of Ge nucleation density on SiO₂ over a temperature range of 673–973 K and deposition rates from 5.1 × 10¹³ atoms/cm² s (5 ML/min) to 6.9 × 10¹⁴ atoms/cm² s (65 ML/min) during molecular beam epitaxy. The governing equations from mean-field theory that describe surface energetics and saturation nucleation density are used to determine the size and binding energy of the critical Ge nucleus and the activation energy for Ge surface diffusion on SiO₂. The critical nucleus size is found to be a single Ge atom over substrate temperatures from 673 to 773 K, whereas a three-atom nucleus is found to be the critical size over substrate temperatures from 773 to 973 K. We have previously reported 0.44 ± 0.03 eV for the Ge desorption activation energy from SiO₂. This value, in conjunction with the saturation nucleation density as a function of substrate temperature, is used to determine that the activation energy for surface diffusion is 0.24 ± 0.05 eV, and the binding energy of the three-atom nucleus is 3.7 ± 0.1 eV. The values of the activation energy for desorption and surface diffusion are in good agreement with previous experiments of metals and semiconductors on insulating substrates. The small desorption and surface diffusion activation barriers predict that selective growth occurring on window-patterned samples is by direct impingement of Ge onto Si and ready desorption of Ge from SiO₂. This prediction is confirmed by the small integral condensation coefficient for Ge on SiO₂ and two key observations of nucleation behavior on the window-patterned samples. The first observation is the lack of nucleation exclusion zones around the windows, and second is the independence of the random Ge nucleation density on patterned versus unpatterned oxide surfaces. We also present the Ge nucleation density as a function of substrate temperature and deposition rate to demarcate selective growth conditions for Ge on Si with a window-patterned SiO₂ mask.     

Growth of (√3 × √3)-Ag and (1 1 1) oriented Ag islands on Ge/Si(1 1 1) surfaces

We have studied the growth of Ag on Ge/Si(1 1 1) substrates. The Ge/Si(1 1 1) substrates were prepared by depositing one monolayer (ML) of Ge on Si(1 1 1)-(7 × 7) surfaces. Following Ge deposition the reflection high energy electron diffraction (RHEED) pattern changed to a (1 × 1) pattern. Ge as well as Ag deposition was carried out at 550 °C. Ag deposition on Ge/Si(1 1 1) substrates up to 10 ML has shown a prominent (√3 × √3)-R30° RHEED pattern along with a streak structure from Ag(1 1 1) surface. Scanning electron microscopy (SEM) shows the formation of Ag islands along with a large fraction of open area, which presumably has the Ag-induced (√3 × √3)-R30° structure on the Ge/Si(1 1 1) surface. X-ray diffraction (XRD) experiments show the presence of only (1 1 1) peak of Ag indicating epitaxial growth of Ag on Ge/Si(1 1 1) surfaces. The possibility of growing a strain-tuned (tensile to compressive) Ag(1 1 1) layer on Ge/Si(1 1 1) substrates is discussed.     

Nucleation, coarsening and kinetic scaling of two-dimensional islands on GaSb(0 0 1)

Using a combination of molecular beam epitaxy and in situ surface X-ray diffraction, we investigate the nucleation and coarsening of monolayer high islands on GaSb(0 0 1) during deposition in real time. We find an activation energy for island nucleation of 1.55 ± 0.16 eV, indicating a stable nucleus size larger than two atoms. For intermediate temperatures where GaSb homoepitaxy is stable, the lateral coarsening of the islands after deposition is described by Ostwald ripening. The average island sizes during coarsening are isotropic, although with different size distributions in different directions. The size distributions do not change during coarsening, implying kinetic scaling.     

Large area SiC substrates and epitaxial layers for high power semiconductor devices — An industrial perspective

We review the progress in the industrial production of SiC substrates and epitaxial layers for high power semiconductor devices. Optimization of SiC bulk growth by the sublimation method has resulted in the commercial release of 100 mm n-type 4H-SiC wafers and the demonstration of micropipe densities as low as 0.7 cm⁻² over a full 100 mm diameter. Modelling results link the formation of basal plane dislocations in SiC crystals to thermoelastic stress during growth. A warm-wall planetary SiC-VPE reactor has been optimized up to a 8×100 mm configuration for the growth of uniform 0.01–80-micron thick, specular, device-quality SiC epitaxial layers with low background doping concentrations of <1×10¹⁴ cm⁻³, and intentional p- and n-type doping from 1×10¹⁵ to >1×10¹⁹ cm⁻³. We address the observed degradation of the forward characteristics of bipolar SiC PiN diodes [H. Lendenmann, F. Dahlquist, J.P. Bergmann, H. Bleichner, C. Hallin, Mater. Sci. Forum 389–393 (2002) 1259], and discuss the underlying mechanism due to stacking fault formation in the epitaxial layers. A process for the growth of the epitaxial layers with a basal plane dislocation density <10 cm⁻² is demonstrated to eliminate the formation of these stacking faults during device operation [J.J. Sumakeris, M. Das, H.McD. Hobgood, S.G. Müller, M.J. Paisley, S. Ha, M. Skowronski, J.W. Palmour, C.H. Carter Jr., Mater. Sci. Forum 457–460 (2004) 1113].     

Anisotropic kinetics on growing Ge(0 0 1) surfaces

Reflection high-energy electron diffraction (RHEED), reflectance difference spectroscopy (RDS), and scanning tunneling microscopy (STM) have been used to study the anisotropic kinetics on the growing Ge(0 0 1) surface. While switching of dimer direction in alternate (2 × 1)/(1 × 2) layers causes the bilayer-period oscillations in RD response, RHEED oscillations are governed by variations in surface step densities. We show that the RHEED oscillations are strongly affected by the growth front morphology: when the growth front becomes distributed over several layers, the transition from bilayer- to monolayer-period occurs in RHEED oscillations.     

Ge adsorption on SiC(0 0 0 1): An ab initio study

In this work we have performed an ab initio total energy investigation of the Ge adsorption process on the Si-terminated SiC(0 0 0 1)- and (3 × 3) surfaces. We find that Ge adatoms lying on the topmost sites of the and (3 × 3) surfaces represent the energetically more stable configurations at the initial stage of the Ge adsorption on the SiC(0 0 0 1) surface. The Si → Ge substitutional adsorption processes have been examined as a function of the Si and Ge chemical potentials. Increasing the Ge coverage, we verify that the formation of Ge wetting layer on the surface, and Ge nanocluster on the (3 × 3) surface are the energetically more stable configurations, in accordance with recent experimental findings.     

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.