Ge island assembly on metal-patterned Si: truncated pyramids, nanorods, and beyond

The organization of semiconductor nanostructures into functional macroassemblies remains a fundamental challenge in nanoscience and nanotechnology. In the context of semiconductor epitaxial growth, efforts have focused on the application of advanced substrate patterning strategies for the directed assembly quantum-dot islands. We present a comprehensive investigation on the use of simple metal patterns to control the nucleation and growth of heteroepitaxial islands. In the Ge on Si model system, a square array of metal dots induces the assembly of Ge islands into an extensive two-dimensional lattice. The islands grow at sites between the metal dots and are characterized by unique shapes including truncated pyramids and nanorods, which are programmed prior to growth by the choices of metal species and substrate orientation. Our results indicate that ordering arises from the metal-induced oxidation of the Si surface; the oxide around each metal dot forms an array of periodic diffusion barriers that induce island ordering. The metals decorate the island surfaces and enhanced the growth of particular facets that are able to grow as a result of significant intermixing between deposited Ge and Si substrate atoms.     

Repetitive growth stages in the solid phase epitaxy of silicon

We have studied the solid phase epitaxial growth of Si in the thin film system with a layer structure of Si(〈100〉 substrate)/Pd silicide/Si(amorphous). At approximately 500°C the 〈100〉Si single-crystal substrate grows with a corresponding consumption of the Si(amorphous) layer. Growth starts with nucleation of islands on the substrate. These islands then grow laterally to form a uniform layer. A second stage of island growth then develops and the process goes on repetitively. However, differences between the first and subsequent stages are observed.     

Growth of oriented Ag nanocrystals on air-oxidized Si surfaces: An in-situ reflection high energy electron diffraction study

Growth of Ag nanoislands on air-oxidized Si(001), (111) and (110) surfaces has been investigated by reflection high energy electron diffraction (RHEED), scanning tunneling microscopy (STM) and cross-sectional transmission electron microscopy. We have shown that the oriented nanocrystalline Ag, similar to the epitaxial growth of Ag on clean Si surfaces, can be grown on oxide-covered Si surfaces. A thin oxide layer (~ 2-3 nm thick) is formed on ultra-high vacuum (UHV)-cleaned Si surfaces via exposure of the clean reconstructed surface to air. Deposition of Ag was carried out under UHV at different substrate temperatures and monitored by RHEED. RHEED results reveal that Ag deposition at room temperature leads to the growth of randomly oriented Ag islands while, in spite of the presence of the oxide layer between Ag islands and Si, preferred orientations with an epitaxial relationship with the substrate evolve when Ag is deposited at higher substrate temperatures. STM images of the oxidized surfaces, prior to Ag deposition, apparently do not show any order. However, Fourier transforms of STM images show the presence of a short range order on the oxidized surface following the unit cells of the underlying reconstructed Si surface. It is intriguing that Ag nanoislands follow an epitaxial orientational relationship with the substrate in spite of the presence of a 2-3 nm thick oxide layer between Ag and Si. Apparently, the short range order existing on the oxide surface influences the orientation of the Ag nanoislands.     

Sb mediated formation of Ge/Si quantum dots: Growth and properties

The phenomenon of surfactant (Sb) mediated formation of Ge/Si(100) islands (quantum dots) by means of molecular beam epitaxy is discussed. The limited diffusivity of Si and Ge adatoms caused by the Sb layer leads to a reduction of the size of Ge islands, the increase in the island density, and the sharpening of the interfaces of Ge islands. Thereby, a thin Sb layer is considered to be a powerful tool that provides more freedom in designing Ge quantum dot features. Ge quantum dots, grown via a thin Sb layer and embedded coherently in a Si p-n junction, are revealed to be the origin of the intense photo- and electroluminescence in the spectral range of about 1.5 μm at room temperature.     

Fabrication of discrete gallium nanoislands on the surface of a Si(001) substrate using a focused ion beam

A gallium focused ion beam (FIB) has been used to implant Ga at specific sites on the surface of undoped Si(001) substrates. Upon annealing at 600?°C, discrete nanoscale surface islands form within the FIB patterned regions when the total Ga ion dose, or fluence, is greater than 1.0 × 10(16) ions cm( - 2). The number of islands depends on the size of the irradiated region and a single island can be achieved for a FIB milled region that is 100 nm × 100 nm. The average sizes of the islands were found to range from 24.5 nm when exposed to a total ion dose of 1.2 × 10(16) ions cm( - 2) to 45 nm for a dose of 3.0 × 10(16) ions cm( - 2). We have confirmed that these surface islands are metallic Ga by performing a selective chemical etch that removes the islands and by transmission electron microscopy characterization. These patterned Ga surface templates could serve as nucleation sites for the lateral arrangement of discrete quantum dot structures.     

Metal-induced assembly of a semiconductor island lattice: Ge truncated pyramids on Au-patterned Si

We report the two-dimensional alignment of semiconductor islands using rudimentary metal patterning to control nucleation and growth. In the Ge on Si system, a square array of submicron Au dots on the Si (001) surface induces the assembly of deposited Ge adatoms into an extensive island lattice. Remarkably, these highly ordered Ge islands form between the patterned Au dots and are characterized by a unique truncated pyramidal shape. A model based on patterned diffusion barriers explains the observed ordering and establishes general criteria for the broader applicability of such a directed assembly process to quantum dot ordering.     

From oxygen adsorption to the growth of thin oxides on silicon surfaces

Oxidation of silicon surfaces at relatively low temperatures is shown to go through several activated steps, in the form of configurations inert to further uptake of oxygen. Starting from room temperature adsorption, different configurations of oxygen atoms adsorbed on and in the Si(1 1 1) and Si(0 0 1) surfaces are found, with history and/or coverage dependent energy barriers connecting them. From well below to slightly above an effective oxide coverage of a monolayer, clustering of up to three oxygen atoms around one single silicon atom has been predicted for the Si(0 0 1) surface to represent one such energy minimum; this model is confirmed here experimentally. These and other clusters are shown to agglomerate into silicon dioxide islands before coalescing into a contiguous, inert layer upon higher oxygen supplies. Another problem addressed here is the presence of molecular adsorbates in the oxidation reaction path, an issue which is still debated in the literature. For the Si(1 1 1) surface a molecular, charged oxygen species has earlier been found at temperatures up to room temperature, but not for the Si(0 0 1) surface. This is confirmed in the present experiments, and new data for this state shows that it is highly mobile until quenched at a critical oxygen coverage. It is not the initial state of oxygen on silicon, and therefore not the precursor for atomic insertion of oxygen; rather, it is found to co-exists with atomic oxygen inserted in back-bonds, at a certain, low coverage regime in which parts of the Si(1 1 1) surface are still ordered.     

Ordering of Ge islands on Si(001) substrates patterned by nanoindentation

Spatial organization of Ge islands, grown by physical vapor deposition, on prepatterned Si(001) substrates has been investigated. The substrates were patterned prior to Ge deposition by nanoindentation. Characterization of Ge dots is performed by atomic force microscopy and scanning electron microscopy. The nanoindents act as trapping sites, allowing ripening of Ge islands at those locations during subsequent deposition and diffusion of Ge on the surface. The results show that island ordering is intrinsically linked to the nucleation and growth at indented sites and it strongly depends on pattern parameters.     

锰及其硅化物在Si(100)表面的反应外延生长

采用超高真空分子束外延-扫描隧道显微镜(UHVMBE-STM)系统研究了不同温度下锰及其硅化物在Si(100)-2 ×1重构表面上的外延生长情况.实验结果表明当生长过程中衬底温度控制在室温到135℃时,生成大小基本一致的锰纳米团簇;当衬底温度达到210℃时锰与硅开始发生反应,形成硅化物,并有纳米线结构出现;当衬底温度达到330℃时,纳米线完全被棒状物或不规则的三维岛状硅化物取代.随着沉积时衬底温度升高,生成物的成核密度与生长温度的关系与经典的二维岛成核理论相符合.     

Exclusion zone model of islands spatial distribution in molecular beam epitaxy

A simple model of islands spatial distribution based on the statistical nucleation model combined with a forbidden for nucleation zone is proposed. Islands nucleate at random points of uncovered substrate with a constant rate and then grow in a hemisphere at a constant velocity. Around each growing island there exists an exclusion zone of some width L within which nucleation is forbidden, while outside this zone islands continue to germinate in a usual spatially random fashion. By this model formulas for the probability that an arbitrarily chosen surface region at any given time moment t will be either empty or contain just one island, W₀(t) and W₁(t), respectively, are derived. Calculations with this formula shows that a simple introduction of the forbidden zone leads to some ordering degree in a spatial distribution of islands, similar to that observed in experiments, and provides a good quantitative coincidence with experiment at reasonable values of the model parameter L.     

Ge-rich islands grown on patterned Si substrates by low-energy plasma-enhanced chemical vapour deposition

Si(1-x)Ge(x) islands grown on Si patterned substrates have received considerable attention during the last decade for potential applications in microelectronics and optoelectronics. In this work we propose a new methodology to grow Ge-rich islands using a chemical vapour deposition technique. Electron-beam lithography is used to pre-pattern Si substrates, creating material traps. Epitaxial deposition of thin Ge films by low-energy plasma-enhanced chemical vapour deposition then leads to the formation of Ge-rich Si(1-x)Ge(x) islands (x > 0.8) with a homogeneous size distribution, precisely positioned with respect to the substrate pattern. The island morphology was characterized by atomic force microscopy, and the Ge content and strain in the islands was studied by μRaman spectroscopy. This characterization indicates a uniform distribution of islands with high Ge content and low strain: this suggests that the relatively high growth rate (0.1 nm s(-1)) and low temperature (650?°C) used is able to limit Si intermixing, while maintaining a long enough adatom diffusion length to prevent nucleation of islands outside pits. This offers the novel possibility of using these Ge-rich islands to induce strain in a Si cap.     

Microphotoluminescence and perfect ordering of SiGe islands on pit-patterned Si(001) substrates

We show that both the morphology and the optoelectronic properties of SiGe islands growing in the pits of periodically pre-patterned Si(001) substrates are determined by the amount of Ge deposited per unit cell of the pattern. Pit-periods (p) ranging from 300 to 900 nm were investigated, and Ge growth was performed by molecular beam epitaxy (MBE) at temperatures of 690 and 760?°C. The ordered SiGe islands show photoluminescence (PL) emission, which becomes almost completely quenched, once a critical island volume is exceeded. By atomic force and transmission electron microscope images we identify the transition from pyramid-shaped to dome-shaped islands with increasing p. Eventually, the nucleation of dislocations in the islands leads to PL quenching. Below a critical Ge coverage a narrowing and a blue shift of the PL emission is observed, as compared to islands grown on a planar reference area of the same sample.     

硅、锗材料在Si(100)表面的生长研究

利用扫描隧道显微镜和超高真空实验装置系统进行了Si(10 0 )表面生长Si,Ge的实验研究。分析了所生成表面的形貌、结构等物理性质。研究表明 :Si在Si(10 0 )表面的同质生长可以形成纳米结构薄膜。Ge在Si(10 0 )表面生长形成规则的三维小岛。而在Si/Ge/Si(10 0 )多层膜上生长则形成大小二种三维岛。研究表明大岛具有Ge/Si/Ge的壳层结构     

Effect of the bimodal size distribution on the optical properties of self-assembled Ge/Si(001) quantum dots

In situ reflection high-energy electron diffraction, atomic force microscopy and photoluminescence spectroscopy have been combined to investigate the effects of a bimodal size distribution and of the pyramid/dome transition on the optical properties of related Ge/Si layers. It is shown that the wetting layers are inhomogeneous in thickness due to the lateral diffusion of Ge from 2D layers towards islands, while no change is observed in the island-related photoluminescence. These results obtained indicate that 3D islands are, in their early nucleation stages, formed by consuming Ge from 2D layers, and that island luminescence energy is not sensitive to the vertical confinement inside islands.     

Raman study of the strain and H<Subscript>2</Subscript> preconditioning effect on self-assembled Ge island on Si (001)

An investigation of the microscopic mechanisms of Ge self-assembling island growth is of great importance for future optoelectronic applications of quantum dot nanostructures. In this study, two sets of self-assembled germanium islands on Si (001) substrate, with and without preconditioning using a high-temperature hydrogenation step on their nucleation and subsequent temporal evolution, were grown by low-pressure chemical vapor deposition (LPCVD). The average germanium concentration, mean diameter of Ge crystalline regions and the strain inside the germanium quantum dots are characterized with high resolution micro-Raman spectroscopy (μRS). Both the intensity and peak position of the Si–Si vibration mode at about 520.07 cm⁻¹ in the Raman spectra have been used as a reference to separate the germanium Raman signal from the overlapping localized Si–Si optical phonon at ∼300 cm⁻¹.In the absence of preconditioning, both the island size and germanium composition increase steadily as a function of deposition time. However, on the H₂ preconditioned surface, the nucleation and growth rates are greatly increased during the first stages and slow down significantly after deposition for 10 s.Our results indicate that the compressive strain inside the islands acts as a barrier for Ge adatoms to diffuse from the wetting layer into the islands. For the growth times used in this study, for both sets of samples with and without H₂ preconditioning, the normalized rate of increase of the Ge concentration (%Δ [Ge]/Δ t) decreases by ∼0.13/s for a 1% compressive strain increase. The H₂ preconditioning can initially increase the density of island nucleation sites, but cannot accelerate the Ge island growth. It tends to lower %Δ [Ge]/Δ t by 0.015/s instead. The decreased strain due to surface roughing is the principal reason why the Ge islands grow so rapidly at the beginning on the H₂ preconditioned samples.     

Dynamics of dysprosium silicide nanostructures on Si(001) and (111) surfaces

The growth and coarsening dynamics of dysprosium silicide nanostructures are observed in real-time using photoelectron emission microscopy. The annealing of a thin Dy film to temperatures in the range of 700–1050 °C results in the formation of epitaxial rectangular silicide islands and nanowires on Si(001) and triangular and hexagonal silicide islands on Si(111). During continuous annealing, individual islands are observed to coarsen via Ostwald ripening at different rates as a consequence of local variations in the size and relative location of the surrounding islands on the surface. A subsequent deposition of Dy onto the Si(001) surface at 1050 °C leads to the growth of the preexisting islands and to the formation of silicide nanowires at temperatures above where nanowire growth typically occurs. Immediately after the deposition is terminated, the nanowires begin to decay from the ends, apparently transferring atoms to the more stable rectangular islands. On Si(111), a low continuous flux of Dy at 1050 °C leads to the growth of kinked and jagged island structures, which ultimately form into nearly equilateral triangular shapes.     

Electrochemical deposition of polypyrrole nanolayers on discontinuous ultrathin gold films

Ultrathin layers of polypyrrole (PPy) were electrochemically grown between microelectrodes on a Si/SiO(2) substrate. Conducting nanolayers of PPy are directly grown onto ultrathin discontinuous gold (Au) film between the microelectrodes, with thicknesses in the range 10-100?nm. The system therefore forms a novel (PPy/Au) nanocomposite conductor. Atomic force microscopy (AFM) imaging and conductivity measurements indicate that at all thicknesses a relatively uniform film is formed but with significant roughness that reflects the roughness of the metallic island layer. In PPy/Au films with thickness ～10?nm, the small barriers around the gold islands dominate the conduction, and as the film thickness increases to 100?nm the intrinsic conductivity of highly doped PPy dominates the charge transport.     

Peculiarities in the morphology of ge island array on Si(100) at a subcritical thickness of the deposited Ge layer

Experiments revealed the formation of Ge islands on a Si(100) surface at an effective thickness of the deposited germanium layer below the critical value for the transition from two-to three-dimensional growth. The number density of Ge islands in the array was 3×10⁸ cm^?2. The results are interpreted within the framework of a kinetic model of the island formation in heteroepitaxial systems with lattice mismatch.     

Gold-catalyzed oxide nanopatterns for the directed assembly of Ge island arrays on Si

The heteroepitaxial growth of Ge on Au-patterned Si(001) is investigated using in situ spectromicroscopy. Patterning of a hydrogen-terminated Si surface with a square array of Au dots followed by brief exposure to air leads to the spontaneous, local oxidation of Si. The resulting oxide nanopattern limits the surface migration of Au during annealing up to 600 degrees C, resulting in complete preservation of the Au pattern. Subsequent deposition of Ge induces a redistribution of Au across the surface even as the oxide nanopattern persists. As a result, the oxide pattern drives the growth of Ge islands into an ordered assembly, while Au decorates the surfaces of the Ge islands and modifies their shape.     

Metalorganic chemical vapour deposition of GaSb quantum dots on germanium

Metalorganic chemical vapour deposition (MOCVD) was used to study the growth of GaSb islands on (100)Ge. For the first time formation GaSb islands on Ge with dimensions of 250 nm wide by 100 nm high were observed using atomic force microscopy. The average density of these islands across the surface was 4×10⁸ cm⁻² for 30 s or 60 monolayers of deposition. For longer growth times, these islands coalesced as three-dimensional growth became dominant. The existence of GaSb islands for 60 monolayers of growth suggests that nucleation of islands in the GaSb/Ge system is slower compared to previously reported island growth in the GaSb/GaAs system. The size of the GaSb islands observed here is compatible with the onset of size quantisation.