Single-crystal heteroepitaxial growth of PbxSn1−xTe films on germanium substrates by r.f. sputtering

Single-crystal heteroepitaxial growth of Pb_xSn_1?xTe films was achieved by r.f. sputtering deposition onto single crystals of germanium (both 〈100〉 and 〈111〉 orientations), although there is a large mismatch (～12%) in the lattice parameters between the grown film and the substrate.The structures of the r.f. sputtered films were investigated by high energy electron diffraction microscopy, electron surface replicas and scanning electron microscopy.Differences in the substrate temperature needed for the epitaxial growth on 〈100〉 or 〈111〉 orientations are attributed to the tendency of Pb_xSn_1?xTe films to grow parallel to the (100) plane, which is the cleavage plane of the NaCl structure. This causes a mixed (100)-oriented phase in addition to the (111) orientation expected from the symmetry of the substrate surface in the case of (111) germanium substrates.Examples of the effects on the heterogeneous nucleation of the substrate temperature and deposition rate are shown for both orientations.The first stages of growth (initial reactions with the substrates) and the thickness and concentration profiles were investigated by ion beam backscattering analysis.Channelling techniques confirmed the high degree of order in the single- crystal structure of films deposited on large areas (～1 cm²).     

Epitaxial growth of the nickel disilicide phase

The nickel disilicide (NiSi₂) phase which forms epitaxially on silicon single-crystal substrates in many ways exhibits an interesting behavior. A regular network of the silicon-rich phase was observed to originate at or near the Si-silicide interface using the Berg-Barrett X-ray topographic technique. The regularity, the thickness and the density of the network increase as the epitaxial layer increases in thickness. For (100)-oriented silicon substrates the network runs along two perpendicular 〈110〉 directions; for (111)-oriented silicon substrates the network runs along 〈112〉 directions. Large voids on the surface of the epitaxial layer and fracturing of the layer along the edges of the network for thick epitaxial layers were also observed. The results are explained in terms of the corrugated morphology of the NiSi₂-Si structure.     

Cu films formed simultaneously on (111) and (100) NaCl

Copper films were deposited simultaneously in high vacuum on three different monocrystalline NaCl substrates: evaporated (111) NaCl on mica, evaporated (100) NaCl and air-cleaved (100) NaCl. The occurence and microstructure of monocrystalline or polycrystalline copper films were determined by transmission electron microscopy and diffraction as a function of deposition rate R and substrate temperature T. When log R was plotted against 1/T, straight lines could be drawn separating the monocrystalline and the polycrystalline regions. Activation energies for the polycrystalline to monocrystalline transition of Cu films were calculated to be 1.48, 1.22 and 1.27 eV for the (111), evaporated (100) and air-cleaved (100) NaCl substrates respectively. It is shown that these results can be related to the atomistic theory of nucleation by Walton. Moreover, the results indicate that both the binding energy U between a single adatom and a growing oriented cluster and the atomic adsorption energy Q_ad on the substrate surface are proportional to the planar atom densities in the growing cluster and in the substrate surface respectively. It is further shown that while the activation energies for Cu films formed on the two (100) substrate surfaces are about the same, the actual epitaxial temperatures for the same R are significantly different.     

Structural and dielectric properties of (001) and (111)-oriented BaZr0.2Ti0.8O3 epitaxial thin films

We have grown and characterized BaZr_0.2Ti_0.8O₃ (BZT) epitaxial thin films deposited on (001) and (111)-oriented SrRuO₃-buffered SrTiO₃ substrates by pulsed laser deposition. Structural and morphological characterizations were performed using X-ray diffractometry and atomic force microscopy, respectively. A cube-on-cube epitaxial relationship was ascertained from the θ-2θ and φ diffractograms in both (001) and (111)-oriented films. The (001)-oriented films showed a smooth granular morphology, whereas the faceted pyramid-like crystallites of the (111)-oriented films led to a rough surface. The dielectric response of BZT at room temperature was measured along the growth direction. The films were found to be ferroelectric, although a well-saturated hysteresis loop was obtained only for the (001)-oriented films. High leakage currents were observed for the (111) orientation, likely associated to charge transport along the boundaries of its crystallites. The remanent polarization, coercive field, dielectric constant, and relative change of dielectric permittivity (tunability) of (111)-oriented BZT were higher than those of (001)-oriented BZT.     

Ag films formed simultaneously on (111) and (100) NaCl

The ranges of epitaxial deposition have been explored for Ag evaporated simultaneously under high vacuum onto three NaCl substrate surfaces designated (111), (100)_E and (100)_c. The first substrate consisted of a thin (111)-oriented monocrystalline NaCl film deposited onto air-cleaved mica. The substrate designated (100)_E consisted of a thin (100)-oriented monocrystalline NaCl film evaporated onto air-cleaved NaCl, and that designated (100)_c consisted of air- cleaved NaCl. The occurrence of monocrystalline and polycrystalline films and their microstructure were determined by transmission electron microscopy and diffraction as a function of deposition rare R and substrate temperature T. The results are presented on 1n R versus$\text{1}\text{T}$ plots. Activation energies for the transition from a low temperature polycrystalline region to a higher temperature monocrystalline region were determined as approximately 0.8 and 1.0 eV respectively for (111) and (100)_E NaCl substrates. No such transition was found in the case of (100)_c substrates. In the case of (100)_E substrates a steep high temperature demarcation line (activation energy 3.9 eV) was found to separate the monocrystalline region from a high temperature polycrystalline region. The latter region was identified with the coalescence stage of film growth. These results agree with earlier reports suggesting that the coalescence stage rather than the nucleation stage is pre-eminent in determining the occurrence of epitaxy.     

Low-pressure growth of single-crystal silicon carbide

We report on a low-pressure, reproducible process for producing large-area device-quality single-crystal silicon carbide (SiC) on 〈100〉 and 〈111〉 p-type silicon substrates. The process has been used to produce epitaxial layers up to 20 μm thick, and 2″ in diameter. The unintentional doping (n-type) was in the 10¹⁷ cm⁻³ range with mobilities of several hundred cm²/V s.     

Growth and hydrogenation of epitaxial yttrium switchable mirrors on CaF2

Rutherford backscattering (RBS) ion channeling measurements and X-ray diffraction experiments are performed to study the epitaxial nature of as-deposited yttrium on CaF₂〈111〉 substrates and the effect of hydrogenation on the crystalline quality. The RBS and X-ray results clearly demonstrate the unique epitaxial relation between as-deposited films and the substrate, which is preserved upon loading with hydrogen. X-Ray diffraction reveals: (i) a remarkably large lattice expansion in the direction normal to the substrate, which decreases with increasing film thickness; and (ii) an in-plane compression of the lattice. This peculiar result is related to the difference in thermal expansion coefficients of film and substrate. RBS ion channeling measurements reveal a thickness dependence of the mismatch-induced stresses. As expected, the stresses relax with increasing distance from the film/substrate interface, but surprisingly, even with films as thick as 400 nm considerable dechanneling is still observed at the film surface. Film quality, i.e. the film/substrate mismatch as well as the induced stresses and their relaxation, are discussed in relation to atomic force microscopy (AFM) results on these epitaxial films.     

On the in situ relaxation of interphase interfaces

A previously used method for the study of twist boundaries in Au bicrystals is extended to interfaces in Au/AuPd and Au/Pd bicrystals. Transmission electron microscopy and electron diffraction results of the relaxation of small-angle boundaries, boundaries close to the coherent twin orientation and epitaxial layers are reported and interpreted in terms of dislocation networks with Burgers vectors of the typea/2 〈ˉ1 1 0〉 ofa/6 〈1 1 ˉ2〉.     

Au/Ni bilayers on n-type silicon: Metallurgical and electrical behaviour

Diffusion effects during the formation of silicides in the Ni-Au-Si system were investigated by means of ⁴He⁺ MeV Rutherford backscattering spectrometry, Auger electron spectroscopy coupled with Ar⁺ ion sputtering and X-ray diffraction as a function of the heat treatment temperature (280–350°C) and time (10–1000 min). Schottky barrier heights were used to identify the type of metal present at the silicon surface. Au/Ni/Si and Ni/Au/Si structures were prepared by electron gun deposition of thin gold and nickel films onto n-type Si〈111〉 single crystals. After thermal treatment only Ni₂Si and NiSi compounds were observed and their formation follows the phase order confirmed by previous investigations on the Ni/Si system, with a growth controlled by a lattice diffusion process. In the Ni/Au/Si〈111〉 structure the diffusion of the silicon through the gold film was detected during the formation of nickel silicide and the kinetics of growth of Ni₂Si and NiSi were similar to those studied in the Ni/Si〈100〉 system. A diffusion of gold towards the Si-NiSi interface was observed during the growth of NiSi in the Au/Ni/Si〈111〉 structure. The Schottky barrier height measurements confirm these findings.     

In-situ X-ray diffraction study of the initial dealloying of Cu3Au(001) and Cu0.83Pd0.17(001)

Dealloying and selective dissolution are serious corrosion processes, but also employed in technology. We studied the surface structure of Cu_0.83Pd_0.17(001) and Cu₃Au(001) during electrochemical selective Cu dissolution below the critical potential in-situ in 0.1 M H₂SO₄ (pH = 1) electrolyte. In both cases we observe the formation of an epitaxial layer of nano-scale islands of the noble component of the original alloy (Au or Pd). These islands form a metallic passivation layer suppressing massive dissolution of Cu. The Au islands developed {111} facets. By re-deposition of Cu ions from the electrolyte solution onto Pd islands, an epitaxial Cu layer is formed.     

Epitaxial growth of CoSi2 on Si(001) by reactive deposition epitaxy: Island growth and coalescence

Epitaxial CoSi₂ layers, which are phase pure but contain {111} twins, are grown on Si(001) at 700 °C by reactive deposition epitaxy. Transmission electron microscopy analyses show that the initial formation of CoSi₂(001) follows the Volmer-Weber mode characterized by the independent nucleation and growth of three-dimensional islands whose evolution we follow as a function of deposited Co thickness t_Co in order to understand the origin of the observed twin density. We find that there are two families of island shapes: inverse pyramids and platelets. The rectangular-based pyramidal islands extend along orthogonal 〈110〉 directions, bounded by four {111} CoSi₂/Si interfaces, and grow with a cube-on-cube orientation with respect to the substrate: (001)_CoSi2||(001)_Si and [100]_CoSi2||[100]_Si. Platelet-shaped CoSi₂ islands are bounded across their long 〈110〉 directions by {111} twin planes (i.e. {111}(001)_CoSi2||{111}_Si) and their narrow 〈110〉 directions by {511}_CoSi2||{111}_Si interfaces. The top and bottom surfaces are {22¯1}, with {22¯1}_CoSi2||(001)_Si, and {1¯1¯1}, with {1¯1¯1}_CoSi2||{11¯1}_Si, respectively. The early stages of film growth (t_Co ≤ 13 Å) are dominated by the twinned platelets due to a combination of higher nucleation rates resulting from a larger number of favorable adsorption sites in the Si(001)2 × 1 surface unit cell and rapid elongation of the platelets along preferred 〈110〉 directions. However, at t_Co ≥ 13 Å island coalescence becomes significant as orthogonal platelets intersect and block elongation along fast growth directions. In this regime, where both twinned and untwinned island number densities have saturated, further island growth becomes dominated by the untwinned islands. A continuous epitaxial CoSi₂(001) layer, with a twin density of 2.8 × 10¹⁰ cm^− 2, is obtained at t_Co = 50 Å.     

The growth and transformation of Pd2Si on (111), (110) and (100) Si

Thin Pd films on (111), (110), (100) and amorphous Si substrates form [001] fiber textured Pd₂Si in the temperature range 100°–700°C. The degree of texture is a function of substrate orientation, increasing in the order amorphous Si, (100) Si, (110) Si and (111) Si. Only on the (111) Si substrate is the Pd₂Si film epitaxially oriented. Temperature-dependent growth on this orientation can be characterized by [001] textured growth, epitaxial azimuth orientation at the Si interface and progressive layer by layer formation of the mosaic crystal to the thin film surface.During Pd deposition, rapid non-diffusion-controlled growth of epitaxial Pd₂Si on (111) Si occurs at substrate temperatures of 100° and 200°C. An unidentified palladium silicide of low crystallographic symmetry forms during Pd deposition onto a 50°C substrate. The diffusion-controlled growth of Pd₂Si on (111) Si follows a t^0.5 dependence. The velocity constant is

$\text{k = 7 × 10}{}^{\mathrm{?2}}\text{exp}\text{?}\text{29200±800}\text{RT}\text{cm}{}^2\text{/}\text{sec}$

Palladium deposited on 100°C (111) Ge substrates reacts during deposition to form epitaxially oriented Pd₂Ge. However, growth of this phase at higher temperatures results in a randomly oriented film. The transformation of Pd₂Ge to PdGe is kinetically controlled. After a 15 min anneal at 560°±10°C in N₂ only PdGe is detectable on (111) Ge.The high temperature stability of thin film Pd₂Si is controlled by time- temperature kinetics. For a given annealing cycle, the nucleation and growth rates of the PdSi phase are inversely related to the crystalline perfection of Pd₂Si. Decreasing transformation rates follow the order (100), (110), (111) Si. formation of thin film Pd₂Si occurs by the formation of PdSi and subsequent growth of Si within the PdSi phase. After a 30 min N₂ anneal, initial transformation occurs at 735°C on (100) Si, 760°C on (110) Si and 840°C on (111) Si. Extended high temperature annealing produces a two-phase structure of highly twinned and misoriented Si and small PdSi grains that penetrate as much as 3 μm into the Si.     

Effects of ferroelectric-poling-induced strain on the electronic transport and magnetic properties of (001)- and (111)-oriented La0.5Ba0.5MnO3 thin films

We epitaxially grew La_0.5Ba_0.5MnO₃ (LBMO) films on (001)- and (111)-oriented ferroelectric single-crystal substrates and reduced the in-plane tensile strain of LBMO films by poling the ferroelectric substrates along the 〈001〉$〈001〉$ or 〈111〉$〈111〉$ direction. Upon poling, a large decrease in the resistance and a considerable increase in the magnetization, Curie temperature, and magnetoresistance were observed for the LBMO film, which are driven by interface strain coupling. Such strain effects can be significantly enhanced by the application of a magnetic field. An overall analysis of the findings reveals that the mutual interaction between the strain and the magnetic field is mediated by the electronic phase separation which is sensitive to both strain and magnetic field. Our findings highlight that the electronic phase separation is crucial in understanding the electric-field-manipulated strain effects in manganite film/ferroelectric crystal heterostructures.     

Formation of three-dimensional lead telluride nanoislands on strained barium fluoride (111) surface

The nucleation and growth of three-dimensional lead telluride (PbTe) nanoislands from vapor phase on BaF₂(111) substrates strained by an external load under conditions close to thermodynamic equilibrium have been studied. Evolution of the shape of nanoislands was traced and their size distribution was statistically analyzed as dependent on the character of straining of the substrate. Homogeneous arrays of faceted PbTe nanoislands with an ultrahigh surface number density (above 10¹¹ cm^?2) and an average height of h ₁ ～ 3.5 nm (at a 8–9% rms deviation) are obtained for the first time on elastoplastically strained BaF₂(111) substrates under the conditions of small vapor supersaturation in the condensation zone. The formation of nanoisland arrays with such parameters is possible due to (i) the heterogeneous nucleation of PbTe nanoislands at the surface monatomic slip steps aligned in the 〈110〉 direction and (ii) the influence of straining on the kinetic processes on the substrate surface.     

Comparisons on the properties of (Zn1-xCox)2-W type barium hexaferrite thin films prepared on the Si (100) and (111) substrates

The (Zn_1-xCo_x)₂-W type barium hexaferrite thin films have been prepared by a radio frequency magnetron sputtering method on the Si (100) and the Si (111) substrates respectively. With increasing the annealing temperatures (800, 850, 900, 950, and 1000 °C), the Ba(CoZn)₂Fe₁₆O₂₇ phases emerge from the amorphous matrix. The hexaferrite thin films on Si (111) substrates have a larger saturation magnetic field (636.6 kA/m) than those on Si (100) substrates (159.1 kA/m). The magnetic hysteresis measurements show that they exhibit an isotropic behavior for thin films deposited on both substrates. Films on the Si (111) substrates are magnetically harder than those on the Si (100) substrates.     

Preparation of single-crystal TiC (111) by radio frequency magnetron sputtering at low temperature

Single-crystal films of TiC (111) have been synthesized at room temperature on Al₂O₃ (0001) substrates by radio frequency magnetron sputtering using a compound Ti-C target. The substrate temperature and bias were varied to explore the influence of deposition parameters on the crystal structure. Both Al₂O₃ (0001) and Si (100) substrates were used for epitaxial growth of TiC films. A series of characterizations of TiC films were carried out, including Rutherford backscattering spectroscopy, X-ray diffraction, Raman and X-ray photoelectron spectroscopy. Single-crystal films of TiC (111) on the Al₂O₃ (0001) were demonstrated.     

Compositionally graded Pb(Zr,Ti)O3 thin films with different crystallographic orientations

Compositionally graded ferroelectric PbZr_xTi_1−xO₃ (PZT) films were deposited using a sputtering method and crystallized in situ at 500 °C. The films showed purely (100) or (111) crystallographic orientation when grown on Si/SiO₂/TiO₂/Pt substrates, while they exhibited c-axis epitaxial microstructure when prepared on MgO/Pt substrates. Their crystallographic orientation was controlled owing to a thin TiO_x layer sputtered on substrates prior to PZT deposition. Analysis performed by Auger depth profile clearly confirmed the variation of composition in the films. Coercive fields from 80 kV/cm to 200 kV/cm and remnant polarization as large as 45 μC/cm² were obtained. However, no typical offset was observed on hysteresis loops, unlike previous works related to graded PZT films.     

Growth of epitaxial Cu on MgO(001) by magnetron sputter deposition

100-nm-thick Cu layers were grown on MgO(001) substrates by ultra-high vacuum magnetron sputter deposition at substrate temperatures T_s ranging from 40 to 300 °C. X-ray diffraction ω−2θ scans, ω-rocking curves, and pole figures show that layers grown at T_s = 40 and 100 °C are complete single crystals with a cube-on-cube epitaxial relationship with the substrate: (001)_Cu||(001)_MgO with [100]_Cu||[100]_MgO. In contrast, T_s ≥ 200 °C leads to polycrystalline Cu layers with 001, 203, and 1¯75-oriented grains. The transition from a single- to a polycrystalline microstructure with increasing T_s is attributed to temperature-induced mass transport that allows Cu nuclei to sample a larger orientational space and find lower energy (and/or lower lattice mismatch) configurations. The large Cu- to-MgO lattice mismatch of 14% is relieved by 7 × 7 Cu unit cells occupying 6 × 6 MgO cells. In addition, for T_s ≥ 200 °C, the 001-oriented grains relax by tilting by 4° or 15° about 〈110〉 or 〈100〉 axes, respectively, while the 203 and 1¯75-oriented grains exhibit complex epitaxial relationships with the substrate: (203)_Cu||(001)_MgO with [010]_Cu||[110]_MgO and [302¯]_Cu||[11¯0]_MgO; and (1¯75)_Cu||(001)_MgO with [211¯]_Cu||[100]_MgO and [43¯5]_Cu||[010]_MgO. The surface roughness, as determined by X-ray reflectivity, increases with growth temperature. The smoothest layers are grown at 40 °C and exhibit an rms surface and buried interface roughness of 0.7 and 1.4 nm, respectively.     

Anisotropic crystallite size analysis of textured nanocrystalline silicon thin films probed by X-ray diffraction

A newly developed X-ray technique is used, which is able to quantitatively combine texture, structure, anisotropic crystallite shape and film thickness analyses of nanocrystalline silicon films. The films are grown by reactive magnetron sputtering in a plasma mixture of H₂ and Ar onto amorphous SiO₂ and single-crystal (100)-Si substrates. Whatever the used substrate, preferred orientations are observed with texture strengths around 2-3 times a random distribution, with a tendency to achieve lower strengths for films grown on SiO₂ substrates. As a global trend, anisotropic shapes and textures are correlated with longest crystallite sizes along the 〈111〉 direction but absence of 〈111〉 oriented crystallites. Cell parameters are systematically observed larger than the value for bulk silicon, by approximately 0.005-0.015 Å.     

Ab initio studies of pristine and oxidized Cu3Au(100) and (111) surfaces

We review the previous literature and our recent work on first-principles studies of Cu₃Au(100) and (111) surfaces, with focus on the segregation of atomic species to the surface at pristine conditions and in the presence of oxygen. In particular, the combined use of experimental and theoretical tools to achieve chemical identification at an atomic level of the surface species is emphasized and discussed.