Geometric modeling of homoepitaxial CVD diamond growth: I. The {1 0 0}{1 1 1}{1 1 0}{1 1 3} system

Plasma-assisted CVD homoepitaxial diamond growth is a process that must satisfy many stringent requirements to meet industrial applications, particularly in high-power electronics. Purity control and crystalline quality of the obtained samples are of paramount importance and their optimization is a subject of active research. In the process of such studies, we have obtained high purity CVD diamond monocrystals with unusual morphologies, namely with apparent {1 1 3} stable faces. This phenomenon has led us to examine the process of CVD diamond growth and build up a 3D geometrical model, presented here, describing the film growth as a function of time. The model has been able to successfully describe the morphology of our obtained crystals and can be used as a predictive tool to predetermine the shape and size of a diamond crystal grown in a given process configuration. This renders accessible control of desirable properties such as largest usable diamond surface area and/or film thickness, before the cutting and polishing manufacture steps take place. The two latter steps are more sensitive to the geometry of the growth sectors, which will be addressed in a companion paper.Our model, applicable to the growth of any cubic lattice material, establishes a complete mapping of the final morphology state of growing diamond, as a function of the growth rates of the crystalline planes considered, namely {1 0 0}, {1 1 1}, {1 1 0}, and {1 1 3} planes, all of which have been observed experimentally in diamond films. The model makes no claim as to the stability of the obtained faces, such as the occurrence of non-epitaxial crystallites or twinning. It is also possible to deduce transient behavior of the crystal morphology as growth time is increased. The model conclusions are presented in the form of a series of diagrams, which trace the existence (and dominance) boundaries of each face type, in presence of the others, and where each boundary crossing represent a topology change in terms of number of faces, edges and vertices. We validate the model by matching it against crystals published in the literature and illustrate its predictive value by suggesting ways to increase usable surface area of the diamond film.     

High-quality diamond films grown at high deposition rates using high-power-density MWPCVD method with conventional quartz-type chamber

Undoped and boron-doped homoepitaxial diamond films with high quality have been successfully grown on high-pressure/high-temperature-synthesized type-Ib single-crystalline diamond (1 0 0) substrates. In the growth process, a conventional microwave-plasma (MWP) chemical-vapor-deposition (CVD) system with an easily-exchangeable 36-mm-inner-diameter quartz-tube growth chamber was employed under a condition of high MW power densities while a rather high methane concentration (4%) and high substrate temperatures (>1000 °C) were used. The growth conditions applied to the undoped and B-doped diamond thin films were separately optimized by controlling the MW plasma density and substrate temperatures. The homoepitaxial films thus grown yielded strong exciton-related luminescence even at room temperature, meaning that their crystalline quality was good and roughly comparable with that of homoepitaxial films deposited using a high-power MWPCVD system with a stainless steel chamber having a rather large diameter. This indicates that by using such a conventional deposition system with inexpensive and easily-exchangeable exclusive-use quartz-tube chambers, various growth experiments can be performed under different process conditions without any severe interference among the different experiments.     

Growth and characterization of GaN and AlN films on (1 1 1) and (0 0 1) Si substrates

GaN and AlN films were grown on (1 1 1) and (0 0 1) Si substrates by separate admittances of trimethylgallium (or trimethylaluminum) and ammonia (NH₃) at 1000°C. A high temperature (HT) or low temperature (LT) grown AlN thin layer was employed as the buffer layer between HT GaN (or HT AlN) film and Si substrate. Experimental results show that HT AlN and HT GaN films grown on the HT AlN-coated Si substrates exhibit better crystalline quality than those deposited on the LT AlN-coated Si substrates. Transmission electron microscopy (TEM) of the HT GaN/HT AlN buffer layer/(1 1 1)Si samples shows a particular orientation relationship between the (0 0 0 1) planes of GaN film and the (1 1 1) planes of Si substrate. High quality HT GaN films were achieved on (1 1 1) Si substrates using a 200 Å thick HT AlN buffer layer. Room temperature photoluminescence spectra of the high quality HT GaN films show strong near band edge luminescence at 3.41 eV with an emission linewidth of ∼110 meV and weak yellow luminescence.     

Self-limiting nature in atomic-layer epitaxy of rutile thin films from TiCl4 and H2O on sapphire (0 0 1) substrates

The atomic-layer epitaxy of rutile thin films on sapphire (0 0 1) substrates was studied in the controlled growth of titanium oxide films by sequential surface chemical reactions using sequentially fast pressurized titanium tetrachloride (TiCl₄) and water (H₂O) vapor pulses. Optical constants and thicknesses of these rutile films were investigated in terms of vapor pressure using a variable-angle spectroscopic ellipsometer. As a result, the self-limiting nature in the atomic-layer epitaxy of rutile thin films was demonstrated clearly under various conditions of dosing reactant vapors, where growth rates were almost constant at approximately 0.077 nm/cycle (0.77 nm/min) and refractive indices were also constant at 2.59.     

Growth and characterization of GaSb/AlGaSb multi-quantum well structures on Si (0 0 1) substrates

GaSb/AlGaSb multi-quantum well (MQW) structures with an AlSb initiation layer and a relatively thick GaSb buffer layer grown on Si (0 0 1) substrates were prepared by molecular beam epitaxy (MBE). Transmission electron microscopy (TEM) images and high-resolution X-ray diffraction (XRD) patterns indicated definite MQW structures. The photoluminescence (PL) emission around 1.55 μm wavelength was observed for 10.34 nm GaSb/30 nm Al_0.6Ga_0.4Sb MQW structure at room temperature. Dependence of PL emission energy on GaSb well width was well explained by finite square well potential model.     

Characterization of homoepitaxial diamond for ionizing radiation detectors

Synthetic diamond has been proven as an important material for advanced electronic applications, such as those encountered in high energy physics and astrophysics. In fact, diamond transparency to visible light, its high carrier mobility, high breakdown field and strong resistance to chemical attack and radiation damage have suggested the potential application of this material for ‘solar-blind’ UV detectors which have to operate in extreme environments. To avoid the possible problems connected with the presence of grain boundaries in polycrystalline diamond films, a great effort has been devoted to the optimization of the growth process leading to high-quality single-crystal diamond on diamond substrates (homoepitaxy). In this view, characterization studies play a crucial role, because they provide the feedback for the optimization of the deposition process, in order to obtain the best quality material. In this work, a characterization study of homoepitaxial diamond grown by chemical vapor deposition (CVD) on synthetic diamond substrates is presented. The samples have been deposited in a CVD tubular reactor using a CH₄–H₂ gas mixture (1–7%) at approximately 560 °C substrate temperature. The growth rate ranged between 0.9 μm/h and 2.2 μm/h, microwave powers between 520 W and 720 W. The crystalline quality of the diamond layer has been studied by means of Raman spectroscopy. Photoluminescence has been used to study the nature and the distribution of impurities, having energy levels in the diamond band gap, which influence negatively the electronic quality of the material. The results have been compared with electro-optical characterization of UV detectors for astrophysics based on the analyzed diamond samples. The growth parameters which guarantees both high material quality and optimal device response have been determined.     

The preferential orientation of the directionally solidified Si–TaSi2 eutectic in situ composite

The Si–TaSi₂ eutectic in situ composite is a favorable field emission material due to relatively low work function, good electron conductivity, and three-dimensional array of Schottky junctions grown in the composite spontaneously. The preferential orientation during directional solidification is determined by the growth anisotropy. In order to obtain the preferential direction of the steady-state crystal growth, the transmission electron microscopy (TEM) is used for analysis. It is found that the preferential orientation of the Si-TaSi₂ eutectic in situ composite prepared by Czochralski (CZ) technique is [3 3¯ 2¯] Si∥[0 0 0 1] TaSi₂, (2 2 0)Si∥(2 2¯ 0 0) TaSi₂. Whereas the preferential orientation of the Si–TaSi₂ eutectic in situ composite prepared by electron beam floating zone melting (EBFZM) technique is [0 1¯ 1¯ ]] Si∥[0 0 0 1] TaSi₂,(0 1¯ 1) Si∥(0 1¯ 1 1)TaSi₂. The preferential directions of the Si-TaSi₂ eutectic in situ composites prepared by two kinds of crystal growth techniques are distinctly different from each other, which results from different solid–liquid interface temperatures on account of the different crystal growth conditions, e.g. different solidification rate, different temperature gradient, different solid–liquid interface curvature and different kinetic undercooling.     

Growth mechanisms and defect structures of B12As2 epilayers grown on 4 H-SiC substrates

Epitaxial growth of icosahedral B₁₂As₂ on c-plane 4 H-SiC substrates has been analyzed. On on-axis c-plane 4 H-SiC substrates, Synchrotron white beam x-ray topography (SWBXT) revealed the presence of a homogenous solid solution of twin and matrix B₁₂As₂ epilayer domains. High resolution transmission electron microscopy (HRTEM) and scanning transmission electron microscopy (STEM) both revealed the presence of an ～20 nm thick, disordered transition layer at the interface. (0003) twin boundaries are shown to possess fault vectors such as 1/3[1–100]_B12As2, which originate from the mutual shift between the nucleation sites. On the contrary, B₁₂As₂ epilayers grown on c-plane 4 H-SiC substrates intentionally misoriented from (0001) towards [1–100] is shown to be free of rotational twinning. SWBXT, HRTEM and STEM all confirmed the single crystalline nature and much higher quality of the films. In addition, no intermediate layer between the epilayer and the substrate was observed. It is proposed that the vicinal steps formed by hydrogen etching on the off-axis 4 H-SiC substrate surface before deposition cause the film to adopt a single orientation during nucleation process. This work also demonstrates that c-plane 4 H-SiC with offcut toward [1–100] is potentially a good substrate choice for the growth of high-quality, single crystalline B₁₂As₂ epilayers for future device applications.     

Heteroepitaxy of InSb films grown on a Si(0 0 1) substrate with AlSb buffer layer

The growth of InSb films on a Si(0 0 1) substrate with AlSb buffer layer was performed in an ultra high vacuum chamber (UHV) by a co-evaporation of elemental Indium (In) and antimony (Sb) sources. The samples were characterized by Auger electron spectroscopy (AES), X-ray diffraction (XRD) and atomic force microscopy (AFM). The surface morphology and the crystal quality of the grown films strongly depend on the flux ratio of Sb/In. It is found that the optimized flux ratio for the one-step growth procedure is about 2.9 to obtain the InSb films with smooth surface and good crystal quality, for the growth temperature of 300 °C. The two-step growth procedure was also used to further improve the crystal quality of the films.     

Low temperature II–VI nanowire growth using Au–Sn catalysts

Epitaxial lateral overgrowth is reported for semi-polar (Al,Ga)N(1 1 .2) layers. The mask pattern consisted of periodic stripes of SiO₂ oriented parallel to either the GaN[1 1 .0] or the GaN[1 1 .1] direction. Lateral growth occurred either along GaN[1 1 .1] or along GaN[1 1 .0]. For growth along the [1 1 .0] direction, coalescence was achieved for layer thicknesses >4 μm. However, planarization was not observed yielding extremely corrugated surfaces. For growth in [1 1 .1] direction, coalescence was delayed by a diminishing lateral growth rate. Growth of AlGaN during ELOG resulted in coalescence. Improvement in crystal quality of such buffer layers for the growth of InGaN/GaN quantum wells was confirmed by X-ray diffraction and photoluminescence spectroscopy.     

Beryllium doping and silicon amphotericity in (1 1 0) GaAs-based heterostructures: structural and optical properties

The use of beryllium as an acceptor at high doping levels in (1 1 0)GaAs-based heterostructures is found to be deleterious to the structural and optical properties of these epi-layers. This may limit the use of beryllium as a p-type dopant on the (1 1 0) surface. Because silicon is amphoteric on the (1 1 0), it can be used as an alternative p-type dopant, in addition to its traditional role as an n-type dopant. Transmission electron microscopy, optical absorption, and luminescence data indicate that high quality multiple quantum well structures with p-type GaAs buffer layers doped with silicon, rather than beryllium, can be grown.     

Nanostructural and optical features of amorphous AlxSi0.45−xO0.55 (0 ⩽ x ⩽ 0.05) thin films prepared by RF-magnetron sputter techniques

The nanostructural, chemical, and optical features of Al_xSi_0.45−xO_0.55 (0 ⩽ x ⩽ 0.05) thin films were investigated in terms of Al concentration and post-deposition annealing conditions; the films were prepared by co-sputtering a Si main target and Al-chips, and the annealing was carried out at temperatures of 400–1100 °C. The a-Si_0.45O_0.55 films prepared without Al-chips and annealed at 800 °C contain ∼3.5 nm-sized Si nanocrystallites. The photoluminescence (PL) intensity as well as the volume fraction of Si nanocrystallites increased with increasing the concentration of Al to a certain level. In particular, the intensity of the PL spectra of the Al_0.025Si_0.425O_0.550 films which were annealed at 800 °C increased significantly at wavelengths of ∼580 nm. It is highly likely that the observed increase in the PL intensity is caused by the raise in the total volume of the ∼3.5 nm-sized nanocrystallites in the films. The addition of Al as well as the post-deposition annealing allow adjustment and control of the nanostructural and light-emission features of the a-SiO_x films.     

Properties and structure of (1 − x)Li2O–xNa2O–Al2O3–4SiO2 glass systems

(1 − x)Li₂O–xNa₂O–Al₂O₃–4SiO₂ glasses were studied for the progressive percentage substitution of Na₂O for Li₂O at the constant mole of Al₂O₃ and SiO₂. The crystallization temperature at the exothermic peak increased from 898 to 939 °C when the Na₂O content increases from 0 to 0.6 mol. The coefficient of thermal expansion and density of these as-quenched glasses increase from 6.54 × 10⁻⁶ °C⁻¹ to 10.1 × 10⁻⁶ °C⁻¹ and 2.378 g cm⁻³ to 2.533 g cm⁻³ when the Na₂O content increases from 0 to 0.4 mol, respectively. The electrical resistivity has a maximum value at Na₂O · (Li₂O + Na₂O)⁻¹ = 0.4. The activation energy of crystallization decreases from 444 to 284 kJ mol⁻¹ when the Na₂O content increased from 0 to 0.4 mol. Moreover, the activation energy increases from 284 kJ mol⁻¹ to 446 kJ mol⁻¹ when the Na₂O content increased from 0.4 to 0.6 mol. The FT-IR spectra show that the symmetric stretching mode of the SiO₄ tetrahedra (1035–1054 cm⁻¹) and AlO₄ octahedra (713–763 cm⁻¹) exhibiting that the network structure is built by SiO₄ tetrahedra and AlO₄.     

Epitaxial growth of CoO films on semiconductor and metal substrates by constructing a complex heterostructure

Epitaxial growth of CoO films was studied using reflection high-energy electron diffraction (RHEED), electron energy loss spectroscopy (EELS), ultraviolet photoelectron spectroscopy (UPS) and Auger electron spectroscopy (AES). The RHEED results indicated that an epitaxial CoO film grew on semiconductor and metal substrates (CoO (0 0 1)∥GaAs (0 0 1), Cu (0 0 1), Ag (0 0 1) and [1 0 0]CoO∥[1 0 0] substrates) by constructing a complex heterostructure with two alkali halide buffer layers. The AES, EELS and UPS results showed that the grown CoO film had almost the same electronic structure as bulk CoO. We could show that use of alkali halide buffer layers was a good way to grow metal oxide films on semiconductor and metal substrates in an O₂ atmosphere. The alkali halide layers not only works as glue to connect very dissimilar materials but also prevents oxidation of metal and semiconductor substrates.     

Crystallization kinetics of 1Na2O · 2CaO · 3SiO2 · glass monitored by electrical conductivity measurements

We investigated the kinetics of crystal nucleation, growth, and overall crystallization of a glass with composition close to the stoichiometric 1Na₂O · 2CaO · 3SiO₂. The nucleation and subsequent growth of sodium-rich crystals in this glass decreases the sodium content in the glassy matrix, drastically hindering further nucleation and growth. Compositional changes of the crystals and glassy matrix at different stages of the crystallization process were determined by EDS. These compositional variations were also monitored by electrical conductivity measurements, carried out by impedance spectroscopy, in glassy, partially, and fully crystallized samples. The electrical conductivity of both crystalline and glassy phases decreases with the increase of the crystallized volume fraction. Starting at a crystallized volume fraction of about 0.5, the crystalline phase dominates the electrical conductivity of the sample. This behavior was corroborated by an analysis of the activation energy for conduction. We show that electrical conductivity is highly sensitive and can indicate compositional shifts, changes in the spatial distribution of mobile ions in the glassy matrix. Conductivity measurements are thus a powerful tool for the investigation of complex heterogeneous systems, such as partially crystallized glasses and glass-ceramics.     

Defects in a mixed-habit Yakutian diamond: Studies by optical and cathodoluminescence microscopy,infrared absorption,Raman scattering and photoluminescence spectroscopy

Widespread occurrences in the crystallisation history of natural diamonds are epochs of mixed-habit growth in which normal {1 1 1}-faceted growth is accompanied by non-faceted growth on curved surfaces of mean orientation ∼{1 0 0}, termed ‘cuboid’. This paper analyses mixed-habit-related phenomena in a near-central, (1 1 0)-polished slice of an octahedron from the Mir pipe, previously studied principally by SIMS probes analysing N impurity content and C and N isotope composition. In the present work, newly studied features include dislocation content, fine structure in cathodoluminescence (CL) patterns, refined IR absorption data, Raman and photoluminescence (PL) microspectroscopy and microscopy of internal non-diamond bodies. Topographic imaging and spectroscopic techniques traced the specimen's morphological evolution from a cubo-octahedral core containing complex relative development of {1 1 1} and cuboid sectors, both populated by graphite crystallites, diameters up to ∼5 μm, lying on all diamond host {1 1 1}. Coherently overgrowing the core was a zone of widely but smoothly varying relative development of {1 1 1} and cuboid sectors, both on birefringence evidence dislocation-free, emitting strongly from cuboid sectors the PL spectra associated with Ni–N-vacancy complexes. An enclosing octahedral shell of solely {1 1 1} lamellae terminated mixed-habit growth. High-resolution FTIR absorption measurements of I(B′), the integrated absorption due to {1 0 0}-platelet defects, showed from its absence or weakness that total or substantial platelet degradation had taken place in the mixed-habit zones, indicating that these had undergone conditions close to the diamond–graphite phase boundary in their history.     

Epitaxial lateral overgrowth of non-polar GaN(1 1̄ 0 0) on Si(1 1 2) patterned substrates by MOCVD

m-Plane GaN was grown selectively by metal–organic chemical vapor deposition (MOCVD) on patterned Si(1 1 2) substrates, where grooves aligned parallel to the Si〈1 1 0〉 direction were formed by anisotropic wet etching to expose the vertical Si{1 1 1} facets for growth initiation. The effect of growth conditions (substrate temperature, chamber pressure, and ammonia and trimethylgallium flow rates) on the growth habits of GaN was studied with the aim of achieving coalesced m-plane GaN films. The epitaxial relationship was found to be GaN(1 1? 0 0) || Si(1 1 2), GaN[0 0 0 1] || Si[1 1 –1], GaN[1? 1? 2 0] || Si[1 1? 0]. Among all growth parameters, the ammonia flow rate was revealed to be the critical factor determining the growth habits of GaN. The distribution of extended defects, such as stacking faults and dislocations, in the selectively grown GaN were studied by transmission electron microscopy in combination with spatially resolved cathodoluminescence and scanning electron microscopy. Basal-plane stacking faults were found in the nitrogen-wing regions of the laterally overgrown GaN, while gallium-wings were almost free of extended defects, except for the regions near the GaN/Si{1 1 1} vertical sidewall interface, where high dislocation density was observed.