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.     

Self-assembled growth of nanostructural Ge islands on bromine-passivated Si(111) surfaces at room temperature

We have deposited relatively thick (∼60 nm) Ge layers on Br-passivated Si(111) substrates by thermal evaporation under high vacuum conditions at room temperature. Ge has grown in a layer-plus-island mode although it is different from the Stranski-Krastanov growth mode observed in epitaxial growth. Both the islands and the layer are nanocrystalline. This appears to be a consequence of reduction of surface free energy of the Si(111) substrate by Br-passivation. The size distribution of the Ge nanoislands has been determined. The Br-Si(111) substrates were prepared by a liquid treatment, which may not produce exactly reproducible surfaces. Nevertheless, some basic features of the nanostructural island growth are reasonably reproducible, while there are variations in the details of the island size distribution.     

MBE growth of SiGe with high Ge content for optical applications

The molecular beam epitaxy is a powerful technology for integrating optoelectronic devices in standard Si microelectronics. The MBE growth of high speed germanium detectors is discussed. The necessary lattice accommodation between Si and Ge is realized by an ultra thin virtual substrate. Contact layers with very high doping concentration and very sharp transitions are grown with special doping strategies. As special growth method the differential epitaxy allows the growth of epitaxial layers in oxide windows.     

Growth dynamics studied by RHEED during Si/Ge epitaxy from gaseous hydrides

Si and Ge epitaxial growth from disilane and germane in a gas-source molecular beam epitaxy (GSMBE) system is followed in situ by reflection high-energy electron diffraction (RHEED) intensity oscillations. During Ge homoepitaxy, the growth rate on a Ge(100) substrate is found to be limited by surface hydrogen desorption below 350°C and by hydride adsorption above this temperature. Ge heteroepitaxy on Si results in incomplete layer growth leaving exposed Si at the surface during the initial stages of growth. Therefore, a gradual change in the observed Si surface concentration is seen as growth proceeds. Si heteroepitaxy on Ge follows the Volmer-Weber growth mode and proceeds via island formation. This, combined with Ge surface segregation, results in a slow decrease of the Ge surface population at the growth front. During heteroepitaxial growth, hydride reaction rates differ on Si and Ge surfaces, and therefore a changing concentration of the surface species is manifest as a gradual change in the observed oscillation frequency. This effect, observed during the early stages of growth, shows strong temperature dependence, consistent with previous observations on SiGe alloys. Following several layers of growth, however, the surfaces become rough. The influence of this roughness on the oscillation frequency is also discussed.     

STM observation of initial growth of Sn atoms on Ge(0 0 1) surface

We have studied initial growth of Sn atoms on Ge(0 0 1) surfaces at room temperature and 80 K by scanning tunneling microscopy. For Sn deposition onto the Ge(0 0 1) substrate at room temperature, the Sn atoms form two kinds of one-dimensional structures composed of ad-dimers with different alignment, in the 〈3 1 0〉 and the 〈1 1 0〉 directions, and epitaxial structures. For Sn deposition onto the substrate at 80 K, the population of the dimer chains aligning in the 〈3 1 0〉 direction increases. The diffusion barrier of the Sn adatom on the substrate kinetically determines the population of the dimer chain. We propose that the diffusion barrier height depends on surface strain induced by the adatom. The two kinds of dimer chains appearing on the Ge(0 0 1) and Si(0 0 1) surfaces with adatoms of the group-IV elements are systematically interpreted in terms of the surface strain.     

Photoconductivity of erbium-doped germanium

We have applied the technique of Photo Thermal Ionization Spectroscopy (PTIS) to the study of an erbium-doped p-Ge epitaxial layer, grown by MBE on an undoped n-type germanium substrate. The Er-doped Ge layer shows continuum photoconductivity response in the far-infrared region extending from 70 cm^–1 to 900 cm^–1. This type of epitaxial Er-doped Ge layers is a potentially attractive system for photoconductivity detectors of far-infrared radiation. Below 900 cm^–1 three acceptor-like charged states can be distinguished with ionization energies of 9, 26.6 and 50 meV. Additionally, a study of the photoconductive response of the same sample for radiation from 1000 cm^–1 to 10000 cm^–1, i.e., for radiation energies well inside the forbidden gap to energies above it, shows a wealth of levels, some of which have previously been associated with erbium.On leave from: Instituto de Física, Universidad Autónoma de Puebla, Puebla, México     

Fundamental processes in Si/Si and Ge/Si epitaxy studied by scanning tunneling microscopy during growth

Experimental results on the epitaxy of Si and Ge on Si(0 0 1) and Si(1 1 1) surfaces, which are obtained by scanning tunneling microscopy (STM) imaging during growth, are reviewed. Techniques for simultaneous epitaxial growth and STM measurements at high temperature are described. The ability to access the evolution of the growth morphology during growth down to the atomic level enables the study of the influence of surface reconstruction on the growth. The relatively complete characterization of the growth process facilitates comparison to theoretical models and allows the identification of fundamental growth processes. For instance, the observed transition between different growth modes can be explained by specific growth processes included in a model. The influence of strain on the growth morphology is reviewed for the case of heteroepitaxial growth of Ge on Si. With the method of combining STM imaging and epitaxial growth, the transition from two-dimensional to three-dimensional growth as well as the evolution of size and shape of three-dimensional islands can be studied.     

Ordering of Ge nanocrystals using FIB nanolithography

Formation and ordering of Ge nanocrystals (NC) are studied on Si(0 0 1) and SiO₂/Si(0 0 1) substrates patterned by focused ion beam (FIB). In both cases we use a three step process consisting of FIB milling of hole patterns with various periodicities, ex-situ substrate cleaning to remove Ga contamination and Ge NC growth by molecular beam epitaxy (MBE). We show that Ge NC can be ordered between or inside the holes on patterned Si(0 0 1) substrates and inside the holes on patterned SiO₂/Si(0 0 1) substrates.     

Surface kinetics driven annealing and phase segregation in non-equilibrium crystal growth

We simulate the epitaxial growth and annealing of Ge_xSi_1−x alloys on a Si(001) substrate using a stochastic Monte Carlo technique. Initiation of phase segregation into Si(001) and Ge(001) layers is obtained in our simulation. This results from the kinetically more active nature of Ge atoms as compared to Si atoms, together with an effect arising from the compressive strain in the alloy layers. We discuss our results in the light of the existing experimental data.     

半导体量子点形成临界尺寸的定量预测

半导体量子点是一类具有显著量子效应的零维量子结构,自组的模型系统,表现为Stranski-Krastanov型生长.其特征为,当超过3—4个Ge单原子层（浸润层）时,则由二维层状生长转变为三维岛状生长.Ge/Si量子点是初期形成的与衬底共格无位错的三维岛,岛表面由{105}晶面组成.文章作者利用第一性原理计算和介观理论模拟相结合的连续式多尺度（sequential multi-scale）方法,第一次对纯Ge和GeSi合金量子点在Si(001)表面的成核临界尺寸进行了定量的理论预测,同时研究了岛边缘的应力不连续对量子点稳定性的影响,实现了对Ge/Si量子点的形成和稳定性定量的理论研究.     

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.     

Intermixing-controlled epitaxy for Si–Ge heterostructure devices

To fabricate high quality SiGe/Si heterostructures, control of intermixing between Si and Ge is essential during crystal growth. This paper describes the recent progress of ‘intermixing-controlled epitaxy’. A combined method of MBE (molecular beam epitaxy) and SPE (solid-phase epitaxy) was developed and used to fabricate a new heterostructure (n-Si_0.8Ge_0.2/Si channel/Si_1 − xGe_xbuffer layer/Si substrate). Observation by TEM demonstrated that the hetero-interface obtained by SPE was atomically flat. This interface provides the ultrahigh mobility of a two-dimensional electron gas (2DEG). In addition, the influence of atomic-hydrogen irradiation during MBE on Ge dispersion in the SiGe mixed crystal is examined. Results indicate that the number of Ge–Ge pairings was decreased by hydrogen irradiation. Such a decrease deformed the local symmetry of the Si–Ge bond from tetrahedral symmetry. As a result, photoluminescence intensity was sucessfully increased.     

Surface reconstructions of the Si(100)–Ge system

The surface reconstruction of epitaxial Ge layer on Si(100) was studied with ultrahigh vacuum scanning tunneling microscopy. The surface with 0.8 ML Ge grown in the presence of a hydrogen surfactant reveals the same structures as found in chemical-vapor-deposited Ge on Si(100): (i) defective (2×1) structure at 290°C, (ii) irregular (2×N) in Ge layer and defective (2×1) in bare Si regions at 420°C, and (iii) (2×N) in Ge-covered regions and c(4×4) in bare Si regions at 570°C. The morphology of step edges does not change with temperature, implying that the c(4×4) reconstruction is anisotropic in nature.     

Nitrogen plasma cleaning of Ge(1 0 0) surfaces

We propose a dry method of cleaning Ge(1 0 0) surfaces based on nitrogen plasma treatment. Our in situ Auger electron spectroscopy (AES) and low-energy electron diffraction (LEED) analyses demonstrate that surface contamination remaining after wet treatment was effectively removed by nitrogen radical irradiation at low substrate temperatures. The nitrogen plasma cleaned Ge(1 0 0) surface shows a well-ordered 2 × 1 reconstruction, which indicates the formation of a contamination-free Ge(1 0 0) surface with good crystallinity. We discuss the possible reaction mechanism considering how chemisorbed carbon impurities are removed by selective C-N bond formation and subsequent thermal desorption. These findings imply the advantage of plasma nitridation of Ge surfaces for fabricating nitride gate dielectrics, in which we can expect surface pre-cleaning at the initial stage of the plasma treatment.     

反射式高能电子衍射实时监控的分子束外延生长GaAs晶体衬底温度校准及表面相变的研究

以反射式高能电子衍射(RHEED)作为实时监测工具,根据GaAs(100)表面重构相与衬底温度、As₄等效束流压强之间的关系,对分子束外延(MBE)系统中衬底测温系统进行了校准,这种方法也适用于其他的MBE系统.为生长高质量的外延薄膜材料、研究InGaAs表面粗糙化及相变等过程提供了实验依据. 关键词： 分子束外延 反射式高能电子衍射 表面重构 温度校准     

Molecular beam epitaxy of monotype CrSi2 on Si(111)

Low energy electron diffraction (LEED), angle-resolved ultraviolet (ARUPS), and X-ray (XPS) photoemission spectroscopy and work function measurements were used to investigate the growth of epitaxial CrSi₂ on a Si(111) surface. The CrSi₂layers ) (~ 100 Å) are formed by the MBE technique, in which Cr and Si are coevaporated in their stoichiometric ratio on the Si(111) substrate maintained at ~450°C. In comparison with the CrSi₂ epitaxy previously obtained by the SPE technique, where two kinds of CrSi₂ domains with equal formation probability are always observed, the epitaxial CrSi₂ layers obtained by the MBE technique essentially present one definite orientation characterized by CrSi₂(0001)∥Si(111) and CrSi₂[112̄0] ∥[112̄].     

Identification of Ge/Si intermixing processes at the Bi/Ge/Si(111) surface

The chemical contrast between Si and Ge obtained by scanning tunneling microscopy on Bi-covered Si(111) surfaces is used as a tool to identify two vertical Ge/Si intermixing processes. During annealing of an initially pure Ge monolayer on Si, the intermixing is confined to the first two layers approaching a 50% Ge concentration in each layer. During epitaxial growth, a growth front induced intermixing process acting at step edges is observed. Because of the open atomic structure at the step edges, relative to the terraces, a lower activation barrier for intermixing at the step edge, compared to the terrace, is observed.     

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.     

Deviations from exact epitaxial positions in heteroepitaxy

Epitaxy provides thin films in a perfect periodic structure. In heteroepitaxy the misfit may yield perfect pseudomorphic films or relaxed films, which may show the periodicities of the substrate and the film and their combinations. Then non-periodic defects like mosaics may appear, e.g., due to dislocations. Deviations from exact epitaxial positions in strictly periodic structures can be determined from diffraction intensities. For more complex surfaces, e.g., films with defects like mosaics or large superstructures or on substrates with steps such a strict determination is not possible. From the spot profile analysis of low energy electron diffraction (LEED) or X-ray data some structural information is available for these surfaces with defects. This new type of evaluation is demonstrated with spot profile analysis of LEED (SPA-LEED) for ultrathin Pb films on Si(1 1 1)7 × 7 surface, which grow even at 25 K epitaxially in a layer-by-layer growth mode. The analysis provides the first information on deviation from the exact epitaxial positions of the surface Pb atoms. A vertical shift of domains and an inclination between domains provides an explanation of the experimental results.     

Self-patterned Si surfaces as templates for Ge islands ordering

We propose a two-step process, which is based on substrate nano-patterning by means of growth instabilities in a first step and self-assembling of Ge dots on the top of surface instabilities in a second step. We used the instabilities that develop during the growth of Si(Ge) layers on both nominal and vicinal Si (1 1 1) or (0 0 1) surfaces. Depending on the growth conditions (Ge concentration, growth temperature, thickness), various growth instability regimes were observed: pure kinetic regime, kinetically activated strain-induced regime and pure strain-driven regime. In the case of Si/Si growth, kinetic instabilities developed at different growth temperatures depending on the surface orientation. The critical exponents describing evolution with time have been determined: amplitude At^β and wavelength Lt^α. Experimental results show that each instability regime appears for a given growth temperature range that critically depends on the concentration of Ge. Evolution with time also depends on the Ge concentration. But in all cases, we evidence discrepancies between the experimental critical exponents and those predicted by classical modelling. We also give some examples of Ge dots self-organization on substrates nano-patterned (periodically undulated) by means of the different growth instabilities described above. In all cases, we observe Ge dots ordering along the substrate undulations due to step and/or strain effects. On kinetic instabilities (Si/Si(0 0 1) vicinal), Ge islands preferentially nucleate on step bunches. On SiGe(0 0 1) template layers, Ge dots nucleate on top of the SiGe undulations. In that case, strain gradients improved island ordering. The best ordering was achieved using SiGe(0 0 1) 10° off misoriented template layers as a result of almost perfect anisotropic morphology.