Deformation behavior during nanoindentation of epitaxial ZnO thin films on sapphire substrate

Nanoindentation studies were carried out on epitaxial ZnO thin films on (0001) sapphire substrates grown by radio frequency magnetron sputtering. A single discontinuity (‘pop-in’) in the load–displacement curve was observed at a specific depth (13−16 nm) irrespective of the film thickness. The physical mechanism responsible for the ‘pop-in’ event in these epitaxial films may be due to the nucleation, propagation and interaction behavior of the glissile threading dislocations during mechanical deformation. Indentation well below the critical depth was found to be plastic deformation behavior (residual impression of 4 nm).     

The influence of previous substrate heat treatment on the epitaxial growth of silver on mica

The growth of silver films prepared by evaporation in ultrahigh vacuum onto mica cleaved in air and previously heat treated at various temperatures T_H for 24 h was studied by reflection high energy electron diffraction. It was found that for T_H < 250 °C the silver films are well oriented from the initial stages of growth. At higher T_H the initial stages are characterized by crystallites with random orientation and with two main orientations (each with double positioning). With increasing thickness, first the randomly oriented crystallites disappear and then those with one of the main orientations; finally a single-crystal film is obtained (T_H < 320 °C. For films with a certain thickness it is found that, the higher T_H is, the higher is the fraction of randomly oriented crystallites. The results are explained by the decrease in water vapour concentration on the mica surface as T_H is increased, which in turn causes the reduction in the orientation of the initial nuclei as well as in their density.     

Some aspects of substrate pretreatment for epitaxial Si nanowire growth

We report on the influence of the surface pretreatment for vapor-liquid-solid growth of epitaxial silicon nanowires with gold catalyst and silane precursor on Si(111) substrates. In this paper we make it obvious that a thin native oxide layer on the Si substrate-as is present under most technological conditions-or a thin layer of oxide formed on top of the catalytic gold particle restrain nucleation and nanowire growth. High resolution transmission electron microscopy, and electron energy loss spectroscopy were utilized to demonstrate Si diffusion from the substrate through the catalytic Au layer and further the formation of a thin oxide layer atop. Based on this observation we present a sample pretreatment practice, making the catalyst insensitive for further oxide formation, thereby preserving epitaxy for nanowire synthesis.     

Rapid thermal annealing of rare earth implanted ZnO epitaxial layers

Zinc oxide epilayers grown by metal organic vapour phase epitaxy on (0 0 0 1) sapphire substrates were doped with Praseodymium and Europium by ion implantation. The as-implanted samples were either annealed in air for 20 min in a tube furnace or rapid thermal annealing (RTA) was performed, for 2 min, in a nitrogen atmosphere. The samples were characterized by Rutherford Backscattering Spectrometry/Channelling and photoluminescence. The presented results indicate that in the as-implanted samples the majority of the rare earth (RE) ions are incorporated into substitutional Zn-sites. Furnace annealing at 1000 °C recovers the crystal quality of the samples but leads to an out-diffusion of the RE. RTA suppresses diffusion but lattice damage is not fully recovered at 1000 °C. More importantly, during RTA the RE ions are driven from the substitutional site and are now found mainly on random interstitial sites and no optical activation could be achieved.     

Effect of annealing temperature on the microstructural and electrical properties of epitaxial Ga-doped ZnO film deposited on c-sapphire substrate

4 wt. % Ga-doped ZnO (GZO) film has been prepared on c (0001)—sapphire (Al₂O₃) substrate by Pulse Laser Deposition method. The effect of annealing temperature on the microstructural and electrical properties of the GZO thin film was investigated. X-ray diffraction and High-Resolution Transmission electron microscopy (HR–TEM) studies showed that the electrical and defects properties of GZO thin film were greatly influenced by annealing temperature. The crystallinity and electrical properties of the film can be improved by annealing at 800 °C. However, at a too high annealing temperature of 1,000 °C, the newly processing defects such as extended dislocations and a new nanoscale stacking fault were formed. Consequently, the crystallinity and electrical properties of the film annealed at 1,000 °C were degraded. The study was useful to acquire optimal annealing conditions to improve the properties of film.     

Fabrication of ZnO tetrapods on silicon substrate by thermal evaporation

Large-scale ZnO tetrapods have been fabricated on silicon substrate by a simple thermal evaporation method at 700 °C without vapor transportation and characterized by FESEM, XRD, Micro-Raman, and PL, respectively. FESEM images indicate that the length of tetrapod arm is about 3–4 μm, and the diameter of the tip is about 50 nm. XRD and Raman spectrum reveal that ZnO tetrapods are highly pure hexagonal wurtzite structure. The PL spectrum indicates that the ZnO tetrapods have strong green emission at 510 nm.     

Liquid phase epitaxial growth of gallium arsenide on an etched substrate

A method is described for etching the surface of GaAs substrates with a Ga solution $\text{in}$$\text{situ}$ immediately prior to epitaxial layer growth from the liquid phase. Layers grown by this procedure show excellent surface morphologies and electrical properties ($\text{μ～5100}\text{cm}{}^2\text{v-sec}$ at 300°K for $\text{n～ 7.8×10}{}^{16}\text{cm}{}^3$). Advantages of the method and its applicability to epitaxial growth of other III-V compounds are discussed.     

An one-pot epitaxial growth method to synthesize cactus-like ZnO

In this work, we have developed a one-pot, morphology controlled epitaxial growth method to synthesize novel cactus-like ZnO in solution. Utilizing zinc acetate and hexamethylenetetramine as the precursors, ZnO nanorods synthesized in the first step remained in the solution, without any separation, served directly as the matrix for the epitaxial growth in the second step. Control experiments revealed that a proper mass of precursors added in the second step was crucial to form cactus-like ZnO. The as-synthesized ZnO was single crystalline and possessed three photoluminescence emissions centered at 390, 425 and 490 nm. Finally, a possible mechanism for the epitaxial growth ZnO was proposed and discussed.     

化学溶液法外延组装ZnO分级纳米结构

采用气相法、液相法相结合的方法外延组装了一种形貌新颖的复杂ZnO分级纳米结构--"纳米毛刷".首先用热蒸发的方法制备了宽面为极性面的ZnO纳米带,然后采用化学溶液法,在强碱溶液中在ZnO纳米带的极性面上外延生长Zno纳米棒阵列,实现了ZnO分级纳米结构"由下而上"地外延组装.采用负离子配位多面体生长基元模型讨论了ZnO分级纳米结构的外延组装机理.这种ZnO分级结构的实现,可望作为ZnO纳米器件的原型材料构建新型光电器件.     

Low temperature epitaxial growth of ZnO layer by plasma-assisted epitaxy

Plasma-assisted epitaxial growth of ZnO layers were achieved on C- and R-plane sapphire substrates in oxygen plasma excited by radio frequency power at 13.56 MHz with evaporation of pure elemental Zn. The ZnO layers were grown at 300–400°C with high growth rate around 1.7 μm/h. Surface cleaning of sapphire substrates using Ar-plasma was crucial for good quality ZnO growth. Photoluminescence spectra at 10 K were dominated by band-edge emission due to bound excitons without deep level emission in green-light region. The intensity of band-edge emission was strongly dependent on applied radio frequency power to excite Ar- and O₂-plasma for sapphire surface cleaning and ZnO growth, respectively, and was about 50 times larger on the layer grown in oxygen plasma than that grown in non-excited oxygen gas. The ZnO layer grown on R-plane sapphire was epitaxially grown above 300°C in oxygen plasma, however, on C-plane sapphire the ZnO layer was easily polycrystallized for thick films even at 400°C. Growth mode and surface morphology of ZnO layers were drastically changed with the substrate orientation.     

Hydrothermal synthesis of improved ZnO crystals for epitaxial growth of GaN thin films

ZnO single crystals with thickness up to 12 mm, 2 inches in “diameter” and weight of about 150 g have been grown from KOH, NaOH, and K₂CO₃ based hydrothermal solutions on the seeds of (0001) orientation. The addition of LiOH up to 3.0–4.5 mol/L allowed to decrease the growth rate of ZnO crystals along the 〈0001〉 crystallographic direction. For positive and negative monohedra, it was achieved 0.12 and 0.01 mm/day, respectively, at temperature 340 °С and ΔТ = 10 °С. The best ZnO etching agent was found to be the solutions 25 mol% HCl + 3 mol% NH₄F at room temperature, and etching time 5 min. The dislocation density of ZnO crystals varied from 240 cm⁻² to 3,200 cm⁻² in the case of growth rates 0.04 mm/day to 0.11 mm/day, respectively. It was also found that ZnO crystals grown are stable in air, oxygen, nitrogen, and argon atmosphere as well as in vacuum at the temperatures up to 1,000 °C under thermal treatment during 4 h.     

Effect of substrate cooling on the epitaxial growth of Ni-based single-crystal superalloy fabricated by direct energy deposition

The columnar-to-equiaxed transition(CET)or the formation of stray grains in the laser melting deposition is the least desirable for the repair of single-crystal blades.In this work,the forced water-cooling was conducted on a single-crystal Rene N5 substrate during the direct energy deposition(DED).The single track remelting,one-layer,two-layer,and eight-layer depositions were investigated to explore the grain growth mechanism.The solidification conditions of the DED process,including temperature field,temperature gradient,and solidification speed,were numerically analyzed by a finite element model.The single-track remelting results showed that the fraction of columnar crystal regions increases from55.81%in the air-cooled sample to 77.14%in the water-cooled one.The single-track deposits of one-and two-layer have the same trend,where the proportion of columnar crystal height was higher under the forced water-cooled condition.The electron backscattered diffraction(EBSD)grain-structure maps of an eight-layer deposit show that the epitaxial growth height increases from 1 mm in the air-cooling sample to 1.5 mm in the water-cooling one.The numerical results showed that the tempe rature gradient in[0011 direction was significantly increased by using forced water-cooling.In conclusion,the in-situ substrate cooling can become a potential method to promote epitaxial growth during DED via the influence on CET occurrence.     

Simulation of epitaxial growth on convex substrate using phase field crystal method

Phase field crystal （PFC） model is employed to simulate the process of growth of epitaxial layer on plane-convex substrate with a lattice mismatch and a small inclination angle. The variation of the systematic free energy, the total atomic number of the epitaxial layer, and the effect of the curvature and the angle of the substrate are analyzed. The results show that when the surface of the substrate is plane, the free energy increases with the increase of the substrate inclination angle, and also the total atomic number of the epitaxial layer increases; while the surface of the substrate is convex, the free energy decreases with the increase of substrate angle and so also the total atomic number of the epitaxial layer decrease. This is the reason that the frontier of surface of epitaxial layer changes from the step bunching to the hill-and-valley facet structure with the increasing of the inclination angle of convex substrate. These results are in good agreement with the other method results.     

ZnO nanostructures grown on epitaxial GaN

Presented is the growth of zinc oxide nanorod/nanowire arrays on gallium nitride epitaxial layers. A hierarchical zinc oxide morphology comprising of different scale zinc oxide nanostructures was observed. The first tier of the surface comprised of typical zinc oxide nanorods, with most bridging to adjacent nanorods. While the second tier comprised of smaller zinc oxide nanowires approximately 30 nm in width often growing atop the aforementioned bridges. Samples were analysed via scanning electron microscopy, as well as, cross-sectional and high resolution transmission electron microscopy to elucidate the detailed growth and structural elements of the heterostructure.     

Developing an epitaxial growth process for ZnO by MOCVD using real-time spectroscopic ellipsometry

Real-time diagnostics are an essential tool in the development and improvement of growth processes for new materials. Here we use real-time spectroscopic polarimetric observations of zinc oxide deposition, and a chemical model derived therefrom, to develop a method of growing dense, two-dimensional zinc oxide epitaxially on sapphire by metalorganic chemical vapor deposition. With the transition between deposition and etching being 13% in the diethylzinc flow rate, it is unlikely that we would have discovered this process without the use of real-time spectroscopic ellipsometry. New photoluminescence data support our conclusion that using this cyclical growth process yields improved material.     

Direct growth of ZnO nanosheets on FTO substrate for dye-sensitized solar cells applications

ZnO nanosheets were directly grown on fluorine-doped tin oxide (FTO) substrate via simple solution process at low temperature by using zinc chloride and hexamethylenetetramine (HMTA). The morphological characterizations by SEM and TEM confirmed that the deposited structures are nanosheets in which some are assembled in flower-shaped morphologies. The detailed structural investigations revealed that the deposited nanosheets are pure and crystalline ZnO and composed of Zn and O only. The obtained ZnO nanosheets on FTO substrate were used as a photoanode to fabricate the dye sensitized solar cells (DSSCs). The fabricated DSSCs exhibited an overall light-to-electricity conversion efficiency of 1.45%. A short-circuit current of 4.51 mA/cm2, open-circuit voltage of 0.610 V, and a fill factor of 0.53 were achieved from the fabricated ZnO nanosheets-based DSSCs.     

Effect of substrate morphology on the nucleation and growth of ZnO nanorods prepared by spray pyrolysis

ZnO nanorods were prepared by a spray pyrolysis technique on both as-received and etched Indium Tin Oxide (ITO)/glass substrates. The morphologies of the ITO substrates, the ZnO nucleation mechanism and the development of ZnO nanorods on both types of ITO substrates were investigated by Atomic Force Microscopy and Scanning Electron Microscopy methods. It was found that the amount of nucleation sites on as-received ITO is significantly higher compared to that on the etched ITO. As a result, well-shaped, elongated, strongly c-axis-oriented ZnO nanorods were obtained on the etched ITO/glass substrates. In contrast, randomly oriented ZnO nanocrystals with different shapes and sizes, as well as low aspect ratios, were obtained on the as-received substrates. It was found that ZnO nucleation follows the grain-boundary nucleation mechanism.     

Control of epitaxial growth orientation in ZnO nanorods on c-plane sapphire substrates

This paper presents a study on low temperature hydrothermal growth of ZnO nanorods (NRs) on pre-seeded (0001) sapphire substrates. Prior to hydrothermal growth of ZnO NRs, epitaxial ZnO seeds were grown by metal-organic chemical vapour deposition under various process conditions. Findings show that the majority of ZnO NRs inclined at a specific angle of about 38° to the direction perpendicular to the substrate surface and exhibited a preferential in-plane alignment, besides other NRs growing vertically from the sapphire surface. X-ray diffraction φ-scan measurements reveal that the ZnO nanorods displayed two distinct epitaxial relationships with sapphire which were (0001)_ZnO//(0001)_sapphire and (0001)_ZnO//(101?4)_sapphire, respectively. Reduced lattice mismatch between ZnO and sapphire is responsible for the inclined ZnO NRs growth. The growth direction of ZnO NRs is remarkably dependent on the growth conditions of ZnO seeds and sapphire substrate pre-treatment. The epitaxial orientations of ZnO seeds grown on the sapphire substrate dominate the subsequent ZnO NRs growth and can be controlled through adjusting growth conditions.     

Preferred growth of epitaxial TiN thin film on silicon substrate by pulsed laser deposition

Epitaxial TiN thin films on silicon substrates were prepared by pulsed excimer laser (KrF, 34 ns) ablation of a hot-pressed TiN target in nitrogen gas atmosphere. X-ray diffraction (XRD) showed that the preferred orientations of TiN thin films did not change with substrate temperatures, nitrogen gas pressure and film thickness; however, they did change with the orientations of substrates. The epitaxial orientation relationships between high-quality epitaxial TiN thin films and silicon substrates [2 4 2] TiN [2 4 2] Si, (1 1 1) TiN(1 1 1) Si and [3 1 1] TiN [3 1 1] Si, (1 0 0) TiN(1 0 0) Si. The full-width at half-maximum (FWHM) of the rocking curve of XRD and the minimum channelling yield of Rutherford backscattered spectroscopy (RBS) of the epitaxial TiN thin film were estimated to be 0.3 ° and 7.3%, respectively, indicating excellent crystalline quality of the grown film. X-ray photoelectron spectroscopy confirmed that the binding energies of Ti 2p 3/2 and N 1s core levels in epitaxial thin film were 455.2 and 397.1 eV, respectively, corresponding to those of TiN bulk. By calibrating the RBS spectra, the chemical composition of TiN thin films was found to be titanium-rich. The typical surface roughness of TiN thin film observed by scanning probe microscopy was about 1.5 nm. © 1998 Chapman & Hall     

Stress variation in epitaxial GaAs films on silicon under thermal treatment

High quality epitaxial GaAs films of 1.8 and 6.3 μm thickness on silicon substrates were examined for lattice distortion, misalignment and curvature by X-ray diffraction (Bond method) at 20–400 °C. These films were deposited by the metal-organic chemical vapour deposition method on the (001) plane of silicon using a buffer layer produced at T_b = 370 or 460 °C. A top layer was then grown at T_t = 560 or 650 °C. The GaAs films contract more strongly on cooling than the substrate, which causes a curvature and a tetragonal distortion below a critical temperature T_c. This temperature varies on thermal treatment at 200–400 °C and approaches T_b, the growth temperature of the buffer layer. The tetragonal distortion can be stabilized, so that T_c approximates T_b, if the GaAs films are annealed for several days at 400 °C.