Study of the ZnO crystal growth by vapour transport methods

The crystal growth of ZnO by vapour transport is classically made with the assistance of additional species that produce a gaseous mixture, the role of which remains often uncertain in the transport and growth process. Initially, in order to study the mass transport process, a numerical simulation is made to analyse which are the requirements to have an effective transport. As the pressure of each gaseous species is generally unknown, the numerical study has been performed for different total pressures. It is found that, if congruent and equilibrium conditions are assumed at the sublimation and crystallisation interfaces, effective growth conditions can only be attained for a narrow range of total pressures. Nevertheless, it is well known that ZnO growth by vapour transport is possible for a wide range of pressures of gaseous species. As a consequence, partial pressures higher than the equilibrium ones must be present in order to justify the experimental results. We suggest that the thermal decomposition of ZnO is given by an activated process. The analysis of different mechanisms that could justify the activated decomposition, in accord with a systematic set of growth experiments, suggests that some additional species in the growth of ZnO by vapour transport promote the generation of an additional Zn pressure. This zinc pressure would act autocatalytically inducing O₂ and Zn partial pressures higher than the equilibrium ones and promoting thermal decomposition. The above-cited set of experimental growth experiences, that include the presence of C, Zn, Fe, Cu and H₂, will be analysed and interpreted according to this approach.     

Silicon nanowire growth by electron beam evaporation: Kinetic and energetic contributions to the growth morphology

The vertical and epitaxial growth of long (up to a few microns) silicon nanowires on Si(1 1 1) substrates by electron beam evaporation (EBE) (10⁻⁶–10⁻⁷ mbar) is demonstrated at temperatures between 600 and 700 °C following the vapour–liquid–solid (VLS) growth mechanism from gold nanoparticles. The silicon atoms are provided by evaporating silicon at varying evaporation currents (I_E) between 35 and 80 mA, which results in growth rates between 1 and 100 nm/min. The growth peculiarities in the interaction triangle, evaporation current (I_E), growth temperature (T_S) and gold layer thickness (d_Au) will be reported. Kinetic and energetic contributions to the morphology of silicon nanowires will be discussed.     

Physical properties of Ag-doped cadmium telluride thin films fabricated by closed-space sublimation technique

Cadmium telluride (CdTe) thin films were prepared by the closed-space sublimation (CSS) technique, using CdTe powder as evaporant onto substrates of water-white glass. In the next step, the annealed films at 450 °C for 30 min were dipped in AgNO₃–H₂O solution at room temperature. These films were again annealed at 450 °C for 1 h to obtain silver-doped samples. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), electrically i.e. DC electrical resistivity as well as photo resistivity by van der Pauw method at room temperature, dark conductivity, activation energy analysis as a function of temperature by two-probe method under vacuum, and spectrophotometry. The electron microprobe analyzer (EMPA) results showed an increase of Ag content composition in the samples by increasing the immersion time of films in solution. The Hall measurements indicated the increase in mobility and carrier concentrations of CdTe films by doping of Ag. A significant change in the shape and size of the CdTe grains were observed.     

Metalorganic vapor-phase epitaxy of III/V phosphides with tertiarybutylphosphine and tertiarybutylarsine

Indium phosphide, gallium arsenide phosphide, and aluminum indium phosphide have been deposited by metalorganic vapor-phase epitaxy using tertiarybutylphosphine and tertiarybutylarsine. The effects of growth temperature and V/III ratio on the amount of silicon, sulfur, carbon, and oxygen in InP have been determined. Minimum incorporation was observed at 565 °C and a V/III ratio of 32. In this case, the material contained a background carrier concentration of 2.7×10¹⁴ cm⁻³, and the Hall mobilities were 4970 and 135,000 cm²/V s at 300 and 77 K. The oxygen contamination in AlInP was found to be only 9.0×10¹⁵ cm⁻³ for deposition at 650 °C and a V/III ratio of 35. The relative distribution of arsenic to phosphorus in GaAs_yP_1−y was determined at temperatures between 525 and 575 °C. The distribution coefficient [(N_As/N_P)_film/(P_TBAs/P_TBP)_gas] ranged from 25.4 to 8.4, and exhibited an Arrhenius relationship with an apparent activation energy of 1.2 eV.     

Kinetics of dopant incorporation in GaAs grown by organometallic vapor-phase epitaxy

A diffusive capture reaction of dopant atoms by relevant host atoms, via the Rideal–Eley mechanism, in GaAs grown by organometallic vapor-phase epitaxy is shown to result in the dopant concentration in the crystal acquiring a dependence on p_Ga (which is proportional to the growth rate) in agreement with data on S_As, Zn_Ga, and Si_Ga where p_Ga is the partial pressure of trimethylgallium in the input gas stream.     

Solvothermal growth of ZnO

The growth of ZnO single crystals and crystalline films by solvothermal techniques is reviewed. Largest ZnO crystals of 3 inch in diameter are grown by a high-pressure medium-temperature hydrothermal process employing alkaline-metal mineralizer for solubility enhancement. Structural, thermal, optical and electrical properties, impurities and annealing effects as well as machining are discussed. Poly- and single-crystalline ZnO films are fabricated from aqueous and non-aqueous solutions on a variety of substrates like glass, (100) silicon, -Al₂O₃, Mg₂AlO₄, ScAlMgO₄, ZnO and even some plastics at temperatures as low as 50 °C and ambient air conditions. Film thickness from a few nanometers up to some tens of micrometers is achieved. Lateral epitaxial overgrowth of thick ZnO films on Mg₂AlO₄ from aqueous solution at 90 °C was recently developed. The best crystallinity with a full-width half-maximum from the (0002) reflection of 26 arcsec has been obtained by liquid phase epitaxy employing alkaline-metal chlorides as solvent. Doping behavior (Cu, Ga, In, Ge) and the formation of solid solutions with MgO and CdO are reported. Photoluminescence and radioluminescence are discussed.     

Epitaxial growth of ZnO thin films on Si substrates by PLD technique

Epitaxial ZnO thin films have been grown on Si(1 1 1) substrates at temperatures between 550 and 700 °C with an oxygen pressure of 60 Pa by pulsed laser deposition (PLD). A ZnO thin film deposited at 500 °C in no-oxygen ambient was used as a buffer layer for the ZnO growth. In situ reflection high-energy electron diffraction (RHEED) observations show that ZnO thin films directly deposited on Si are of a polycrystalline structure, and the crystallinity is deteriorated with an increase of substrate temperature as reflected by the evolution of RHEED patterns from the mixture of spots and rings to single rings. In contrast, the ZnO films grown on a homo-buffer layer exhibit aligned spotty patterns indicating an epitaxial growth. Among the ZnO thin films with a buffer layer, the film grown at 650 °C shows the best structural quality and the strongest ultraviolet (UV) emission with a full-width at half-maximum (FWHM) of 86 meV. It is found that the ZnO film with a buffer layer has better crystallinity than the film without the buffer layer at the same substrate temperature, while the film without the buffer layer shows a more intense UV emission. Possible reasons and preventive methods are suggested to obtain highly optical quality films.     

Chemically assisted vapour transport for bulk ZnO crystal growth

A chemically assisted vapour phase transport (CVT) method is proposed for the growth of bulk ZnO crystals. Thermodynamic computations have confirmed the possibility of using CO as a sublimation activator for enhancing the sublimation rate of the feed material in a large range of pressures (10⁻³ to 1 atm) and temperatures (800–1200 °C). Growth runs in a specific and patented design yielded single ZnO crystals up to 46 mm in diameter and 8 mm in thickness, with growth rates up to 400 μm/h. These values are compatible with an industrial production rate. N type ZnO crystals (μ=182 cm²/(V s) and n=7 10¹⁵ cm⁻³) obtained by this CVT method (Chemical Vapour Transport) present a high level of purity (10–30 times better than hydrothermal ZnO crystals), which may be an advantage for obtaining p-type doped layers ([Li] and [Al] <10⁺¹⁵ cm⁻³). Structural (HR-XRD), defect density (EPD), electrical (Hall measurements) and optical (photoluminescence) properties are presented.     

Improving the property of ZnO nanorods using hydrogen peroxide solution

Zinc oxide (ZnO) nanorod arrays made by the hydrothermal method were treated with hydrogen peroxide (H₂O₂) solution through two different approaches. One is to immerse ZnO nanorod sample into H₂O₂ solution. The other is a pre-treatment of spin-coating H₂O₂ solution on the seed layer before the growth of the ZnO nanorods. In the first approach, we found that the ultraviolet (UV) emission peak of the ZnO nanorod photoluminescence (PL) spectra was strongly dependent on the immersion time. In the second approach, the H₂O₂ solution influences not only the quality of the seed layer, but also the amount of the oxygen interstitial defects in the ZnO nanorods grown thereon. As a result, the UV emission intensity from the ZnO nanorods is enhanced almost five times. The ZnO nanorod arrays with few oxygen interstitial defects are prepared by the hydrogen peroxide treatment and expected to enable the fabrication of optoelectronic device with excellent performance.     

Tip-growth mode and base-growth mode of Au-catalyzed zinc oxide nanowires using chemical vapor deposition technique

Tip-growth and base-growth modes of Au-catalyzed zinc oxide nanowires (ZnO NWs) were synthesized on Au-film pre-deposited silicon substrates using Chemical Vapor Deposition (CVD) technique. The diameter of tip-growth Au-catalyzed ZnO NWs was proportional to the Au film thickness, whereas the areal density of these NWs was inversely proportional to the Au film thickness. It would be more appropriate to explain the growth of Au-catalyzed ZnO NWs by a combination of Vapor–Liquid–Solid and Vapor–Solid (VLS–VS) mechanisms instead of the conventional VLS mechanism, regardless of tip-growth or base-growth mode of Au-catalyzed ZnO NWs. The competition between the VLS and VS mechanism in the effectiveness of capturing the adsorbed Zn and O atoms would determine the final morphology of ZnO NWs. In addition, Au catalyst promoted the growth rate of NWs as compared to the self-catalyzed ZnO NWs.     

Growth and optical absorption spectra of ZnO films grown by pulsed laser deposition

ZnO films on Al₂O₃ substrate were grown by using a pulsed laser deposition method. Through photoluminescence (PL) and X-ray diffraction (XRD) measurements, the optimum growth conditions for the ZnO growth were calculated. The results of the XRD measurement indicate that ZnO film was strongly oriented to the c-axis of hexagonal structure and epitaxially crystallized under constraints created by the substrate. The full-width half-maximum for a theta curve of the (0 0 0 2) peak was 0.201°. Also, from the PL measurement, the grown ZnO film was observed to be a free exciton, which indicates a high quality of epilayer. The Hall mobility and carrier density of the ZnO film at 293 K were estimated to be 299 cm²/V sec and , respectively. The absorption spectra revealed that the temperature dependence of the optical band gap on the ZnO films was − .     

Growth characteristics of ultra long double-ended acicular ZnO synthesized by a hydrothermal process

Double-ended acicular ZnO structure can be synthesized via a hydrothermal process with tetramethylammonium hydroxide and zinc acetate as precursors and polyvinyl alcohol (PVA) as a structure-directing agent. The as-prepared ZnO products show the well crystalline wurtzite structure with growth direction along [0 0 0 1]. For the first time, PVA is found to be employed as a reservoir of Zn²⁺ ions in the present study, and can control the concentration of Zn²⁺ in reaction solution, and the acicular morphology can be formed at the two ends of the 1-D ZnO structure, due to the effect of secondary growth that occurs as the sufficient concentration of Zn²⁺ ions chelated by PVA releasing to the reaction solution. Furthermore, the size of the 1-D ZnO structure can be tuned by different amounts of PVA addition.     

Synthesis and magnetic properties of Mn-doped ZnO hollow nanospheres

A facile approach to fabricate Mn-doped ZnO hollow nanospheres is reported. Zn²⁺ and Mn²⁺ cations were adsorbed onto the surface of carbon template to form a core/shell structure in solution. Subsequent calcination of the core/shell structure would lead to the formation of Mn-doped ZnO hollow nanospheres. The magnetic properties of the hollow spheres were dependent on the calcination temperature. The room-temperature ferromagnetism was obtained when the temperature was less than 900 °C. However, the ferromagnetic behavior disappeared when the temperature was elevated to 1200 °C. The possible reason is the short-ranged ferromagnetic spin–spin interaction between neighboring Mn atoms by forming a bridge bond by H_i.     

Enhancement of near-band edge photoluminescence of ZnO thin films by employing MgF2 buffer layer

ZnO/MgF₂/ZnO sandwich structure films were fabricated. The effects of a buffer layer on structure and optical properties of ZnO films were investigated by X-ray diffraction, photoluminescence, optical transmittance and absorption measurements. Measurement results showed that the buffer layer had the effects of improving the quality of ZnO films and releasing the residual stresses in the films. The near-band edge emissions of ZnO films deposited on the MgF₂ buffer layer were significantly enhanced compared with those deposited on bare substrate due to the smaller lattice mismatch between MgF₂ and ZnO than that between fused silica and ZnO.     

Controllable growth of ZnO nanowires with different aspect ratios and microstructures and their photoluminescence and photosensitive properties

ZnO nanowires with variable aspect ratios and microstructures have been prepared by a hydrothermal reaction of Zn foil and Na₂C₂O₄ solution at 140 °C. The ZnO nanowires are single crystalline with the wurtzite structure and grow in the [0 0 0 1] direction, and their aspect ratios and microstructures can be changed by tuning the reaction time and the Na₂C₂O₄ concentration. UV and blue-green emissions that depended on the Na₂C₂O₄ concentration are observed from the ZnO nanowires with different aspect ratios. The photosensitivity of ZnO ultralong nanowires with honeycomb-like micropatterns is found to be about 10 at 5 V.     

Growth of nitrogen-doped p-type ZnO films by spray pyrolysis and their electrical and optical properties

Nitrogen-doped ZnO films were deposited on silicon (1 0 0) substrate using zinc acetate and ammonium acetate aqueous solution as precursors by ultrasonic spray pyrolysis. Successful p-type doping can be realized at optimized substrate temperature. The p-type ZnO films show excellent electrical properties such as hole concentration of 10¹⁸ cm⁻³, hole mobility of 10² cm² V⁻¹ s⁻¹ and resistivity of 10⁻² Ω cm. In the photoluminescence measurement, a strong near-band-edge emission was observed, while the deep-level emission was almost undetectable in both undoped and N-doped ZnO films. The growth and doping mechanism of N-doped ZnO films were discussed.     

The photoluminescence of ZnO thin films grown on Si (1 0 0) substrate by plasma-enhanced chemical vapor deposition

High-quality ZnO thin films have been grown on a Si(1 0 0) substrate by plasma-enhanced chemical vapor deposition (PECVD) using a zinc organic source (Zn(C₂H₅)₂) and carbon dioxide (CO₂) gas mixtures at a temperature of 180°C. A strong free exciton emission with a weak defect-band emission in the visible region is observed. The characteristics of photoluminescence (PL) of ZnO, as well as the exciton absorption peak in the absorption spectra, are closely related to the gas flow rate ratio of Zn(C₂H₅)₂ to CO₂. Full-widths at half-maximum of the free exciton emission as narrow as 93.4 meV have been achieved. Based on the temperature dependence of the PL spectra from 83 to 383 K, the exciton binding energy and the transition energy of free excitons at 0 K were estimated to be 59.4 meV and 3.36 eV, respectively.     

Effect of substrate temperature on the room-temperature ferromagnetism of Cu-doped ZnO films

Wurtzite structure ZnO films doped with ~2 at% Cu were deposited at substrate temperatures (T_s) from 350 to 600 °C by helicon magnetron sputtering. All the films exhibited room-temperature (RT) ferromagnetism (FM) and the maximum saturation magnetization (M_s) was 1.2 emu/cm³ (~0.15 μ_B/Cu). Cu ions were mainly in a divalent state as identified by X-ray photoelectron spectroscopy. FM tended to increase with decreasing T_s, and vacuum annealing enhanced the M_s. These results suggested that oxygen vacancies and/or zinc interstitials might contribute to the ferromagnetic performance. Thus, the observed FM was explained in terms of the defect related mechanism.     

Low-temperature growth of ZnO with controllable shapes and band gaps

By using polyvinylpyrrolidone (PVP) as the nucleation promoter and directing agent, the shape-selective synthesis of ZnO has been realized at 35 °C. By simply modifying the amount of PVP or/and water, the product shape can be readily changed from one-dimensional structure via monolayer and semi-bilayer to bilayer structure with controlled aspect ratio (defined as monolayer thickness/edge length). As shown by both the photoluminescence and absorption spectra, the ZnO band gap can be modified by adjusting the sample shape. The low-temperature route reported here should open an effective and low-cost approach to the ZnO with tunable shapes and band gaps.