Density controllable growth of ZnO quantum dots by MOCVD

High quality self-assemble ZnO quantum dots (QDs) have been successfully grown on the Si(111) substrates by metalorganic chemical vapor deposition (MOCVD). The diameter of ZnO QDs is about 10 nm in average, and the densities and the sizes of ZnO QDs can be well controlled by adjusting the growth temperature, which were evident in the SEM images. The properties and stress involved in ZnO QDs are studied by X-ray diffraction. In addition, room temperature photoluminescence spectra reveal that the ZnO QDs exhibit a band gap blue shift because of the quantum confinement effects.     

A simple growth route towards ZnO thin films and nanorods

Highly orientated ZnO thin films and the self-organized ZnO nanorods can be easily prepared by a simple chemical vapor deposition method using zinc acetate as a source material at the growth temperature of 180 and 320 °C, respectively. The ZnO thin films deposited on Si (100) substrate have good crystallite quality with the thickness of 490 nm after annealing in oxygen at 800 °C. The ZnO nanorods grown along the [0001] direction have average diameter of 40 nm with length up to 700 nm. The growth mechanism for ZnO nanorods can be explained by a vapor-solid (VS) mechanism. Photoluminescence (PL) properties of ZnO thin films and self-organized nanorods were investigated. The luminescence mechanism for green band emission was attributed to oxygen vacancies and the surface states related to oxygen vacancy played a significant role in PL spectra of ZnO nanorods.     

Synchrotron radiation assistant MOCVD deposition of ZnO films on Si substrate

The growth of ZnO film on Si(1 0 0) substrate has been studied with synchrotron radiation (SR) assisted MOCVD method. The diethylzinc (DEZn) and CO₂ are used as source materials, while Nitrogen is employed as a carrier gas for DEZn. With the assistance of SR the ZnO film can be deposited even at room temperature. XRD, SEM and photoluminescence (PL) studies show that the crystal quality of ZnO films grown with the assistance of SR is higher than that of those without SR assistance. The growth mechanism of ZnO film with the SR assistant MOCVD system is primarily discussed.     

Correlation between substrate bias, growth process and structural properties of phosphorus incorporated tetrahedral amorphous carbon films

We investigate the growth process and structural properties of phosphorus incorporated tetrahedral amorphous carbon (ta-C:P) films which are deposited at different substrate biases by filtered cathodic vacuum arc technique with PH₃ as the dopant source. The films are characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, Raman spectroscopy, residual stress measurement, UV/VIS/NIR absorption spectroscopy and temperature-dependent conductivity measurement. The atomic fraction of phosphorus in the films as a function of substrate bias is obtained by XPS analysis. The optimum bias for phosphorus incorporation is about −80 V. Raman spectra show that the amorphous structures of all samples with atomic-scaled smooth surface are not remarkably changed when PH₃ is implanted, but some small graphitic crystallites are formed. Moreover, phosphorus impurities and higher-energetic impinging ions are favorable for the clustering of sp² sites dispersed in sp³ skeleton and increase the level of structural ordering for ta-C:P films, which further releases the compressive stress and enhances the conductivity of the films. Our analysis establishes an interrelationship between microstructure, stress state, electrical properties, and substrate bias, which helps to understand the deposition mechanism of ta-C:P films.     

Influence of annealing atmosphere on ZnO thin films grown by MOCVD

ZnO films were deposited on c-plane sapphire substrates by metal-organic chemical vapor deposition (MOCVD). Annealing treatments for as-deposited samples were performed in different atmosphere under various pressures in the same chamber just after growth. The effect of annealing atmosphere on the electrical, structural, and optical properties of the deposited films has been investigated by means of X-ray diffraction (XRD), atomic force microscope (AFM), Hall effect, and optical absorption measurements. The results indicated that the electrical and structural properties of the films were highly influenced by annealing atmosphere, which was more pronounced for the films annealed in oxygen ambient. The most significant improvements for structural and electrical properties were obtained for the film annealed in oxygen under the pressure of 60 Pa. Under the optimum annealing condition, the lowest resistivity of 0.28 Ω cm and the highest mobility of 19.6 cm² v⁻¹ s⁻¹ were obtained. Meanwhile, the absorbance spectra turned steeper and the optical band gap red shifted back to the single-crystal value.     

Properties of ZnO thin films grown on Si substrates by photo-assisted MOCVD

ZnO thin films were grown on (1 0 0) p-Si substrates by Photo-assisted Metal Organic Chemical Vapor Deposition (PA-MOCVD) using diethylzinc (DEZn) and O₂ as source materials and tungsten-halogen lamp as a light source. The effects of tungsten-halogen lamp irradiation on the surface morphology, structural and optical properties of the deposited ZnO films have been investigated by means of atomic force microscope (AFM), X-ray diffraction and photoluminescence (PL) spectra measurements. Compared with the samples without irradiation, the several characteristics of ZnO films with irradiation are improved, including an improvement in the crystallinity of c-axis orientation, an increase in the grain size and an improvement in optical quality of ZnO films. These results indicated that light irradiation played an important role in the growth of ZnO films by PA-MOCVD.     

Photoluminescence and X-Ray Photoelectron Spectroscopy of p-Type Phosphorus-Doped ZnO Films Prepared by MOCVD

Reproducible p-type phosphorus-doped ZnO （p-ZnO：P） films are prepared on semi-insulating InP substrates by metal-organic chemical vapour deposition technology. The electrical properties of these films show a hole concentration of 9.02 × 10^17 cm ^-3, a mobifity of 1.05 cm^2 /Vs, and a resistivity of 6.6 Ω.cm. Obvious acceptorbound-exciton-related emission and P-induced zinc vacancy （Vzn） emission are observed by low-temperature photoluminescence spectra of the films, and the acceptor binding energy is estimated to be about 125meV. The local chemical bonding environments of the phosphorus atoms in the ZnO are also identified by x-ray photoelectron spectra. Our results show direct experimental evidence that Pzn-2Vzn shallow acceptor complex most likely contributes to the p-type conductivity of ZnO：P films.     

Effect of Different Substrate Temperature on Phosphorus-Doped ZnO Thin Films Prepared by PLD on Sapphire Substrates

Phosphorus-doped ZnO （ZnO：P） thin films are deposited on a c-plane sapphire in oxygen at 350℃, 450℃, 550℃ and 650℃, respectively, by pulsed laser deposition （PLD）, then all the ZnO：P samples are annealed at 650℃ in oxygen with a pressure of 1 × 10^5 Pa. X-ray diffraction measurements indicate that the crystalline quality of the ZnO：P thin films is improved with the increasing substrate temperature from 350℃ to 550℃. With a further increase of the deposition temperature, the crystalline quality of the ZnO：P sample is degraded. The measurements of low-temperature photoluminescence spectra demonstrate that the samples deposited at the substrate temperatures of 350℃ and 450℃ show a strong acceptor-bound exciton （A^0X） emission. The electrical properties of ZnO：P films strongly depend on the deposition temperature. The ZnO：P samples deposited at 350℃ and 450℃ exhibit p-type conductivity. The p-type ZnO：P film deposited at 450℃ shows a resistivity of 1.846Ω·cm and a relatively high hole concentration of 5.100 × 10^17 cm^-3 at room temperature.     

Comparative studies on structural and optical properties of ZnO films grown on c-plane sapphire and GaAs (001) by MOCVD

ZnO thin films were grown on c-plane sapphire and GaAs (001) substrates by metalorganic chemical vapor deposition. Atomic force microscopy and double-crystal X-ray diffractometry were utilized to investigate the structural properties of the ZnO films. The optical properties of ZnO films were also investigated in terms of time integrated and resolved photoluminescence (TIPL and TRPL). Large hexagonal crystallites and better crystalline quality were observed from the ZnO film on sapphire. Also, both the TIPL and TRPL showed a significant difference as the substrate changed. In particular, a detected sharp contrast in the result of TRPL measurement is due to the different defect structure and the lattice strain and stress of ZnO films on different substrates.     

Growth and field emission of tungsten oxide nanotip arrays on ITO glass substrate

High-density and uniformly aligned tungsten oxide nanotip arrays have been deposited by a conventional thermal evaporation on ITO glass substrates without any catalysts or additives. The temperature of substrate was 450-500 °C. It was shown that the tungsten oxide nanotips are single-crystal grown along [0 1 0] direction. For commercial applications, field emission of the tungsten oxide nanotip arrays was characterized in a poor vacuum at room temperature. The field emission behaviors are in agreement with Fowler-Nordheim theory. The turn-on field is 2.8 V μm⁻¹ as d is 0.3 mm. The excellent field emission performances indicated that the tungsten oxide nanotip arrays grown by the present approach are a good candidate for application in vacuum microelectronic devices.     

The high quality ZnO growth on c-Al2O3 substrate with Cr2O3 buffer layer using plasma-assisted molecular beam epitaxy

High quality epitaxial ZnO films were grown on c-Al₂O₃ substrates with Cr₂O₃ buffer layer by plasma-assisted molecular beam epitaxy (P-MBE). The hexagonal crystalline Cr₂O₃ layer was formed by oxidation of the Cr-metal layer deposited on the c-Al₂O₃ substrate using oxygen plasma. The epitaxial relationship was determined to be ZnO//Cr₂O₃//Cr//Al₂O₃ and ZnO//Cr₂O₃//[0 0 1]Cr//Al₂O_3. The Cr₂O₃ buffer layer was very effective in improving the surface morphology and crystal quality of the ZnO films. The photoluminescence spectrum showed the strong near band-edge emissions with the weak deep-level emission, which implies high optical quality of the ZnO films grown on the Cr₂O₃ buffer.     

Synthesis and photoluminescence of aligned straight silica nanowires on Si substrate

Aligned straight silica nanowires (NWs) have been synthesized on Si wafer by thermal evaporation of mixed powders of zinc carbonate hydroxide and graphite at 1100 °C and condensation on Si substrate without using any catalyst. The straight silica NWs have diameters ranging from 50 to 100 nm, and lengths of several micrometers, with cone-shaped tips at their ends. High deposition temperature and relatively high SiO_x vapor concentration near the growth substrate would be beneficial to the formation of the aligned straight silica NWs. Different morphologies of silica nanostructures have also been obtained by varying the deposition temperature and the vapor concentration of the SiO_x molecules. Room temperature photoluminescence measurements on the oriented silica NWs show that two green emission bands at 510 and 560 nm, respectively, revealing that the aligned straight silica NWs might have potential applications in the future optoelectronic devices.     

Growth of vertically aligned single crystal ZnO nanotubes by plasma-molecular beam epitaxy

Highly oriented and vertically aligned single crystalline ZnO nanotubes were fabricated on Al₂O₃ (0001) substrates by plasma-molecular beam epitaxy without employing any external metal catalysts or templates. Field emission scanning electron microscope images indicate that the regularly aligned ZnO nanotubes with uniform size distribution were obtained. The chimney-like single crystal ZnO nanotube was confirmed by the transmission electron microscope and selected area electron diffraction pattern of the single nanotube. The formation mechanism of the nanotubes was also described briefly.     

ZnO nanorods with different morphologies and their field emission properties

ZnO nanorods with different morphologies were grown by changing the temperature of the process using the thermal vapor deposition method without a catalyst. The X-ray diffraction pattern of these nanorods showed a single-crystalline wurtzite structure and a c-axis orientation. The turn-on fields of the pencil-like and normal ZnO nanorods were 1.7 V/μm and 2.2 V/μm at a current density of 0.1 μA/cm², and the emission current density from the ZnO nanorods reached 1 mA/cm² at bias fields of 5.1 V/μm and 7.5 V/μm, respectively. The results indicated that ZnO nanorods could give sufficient brightness as a field emitter in a flat panel display.     

Use of chlorinated carbon and silicon precursors for epitaxial growth of 4H‐SiC at very high growth rates

A possibility to apply the advantages of chlorinated carbon precursors, which had been previously used in low‐temperature epitaxial growth of 4H‐SiC, to achieve very high growth rates at higher growth temperatures was investigated. Silicon tetrachloride was used as the silicon precursor to suppress gas‐phase homogeneous nucleation. The temperature increase from 1300 °C (which is the temperature of the previously reported low‐temperature halo‐carbon epitaxial growth) to 1600 °C enabled an increase of the precursor flow rates and consequently of the growth rate from 5 to more than 100 μm/h without morphology degradation. High quality of the epilayers was confirmed by low‐temperature photoluminescence spectroscopy and time‐resolved luminescence. No evidences of homogeneous nucleation were detected, however, liquid Si droplet formation on the epilayer surface seems to remain a bottleneck at very high growth rate. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and Characterization of InN Thin Films on Sapphire by MOCVD

Indium nitride thin films are grown on sapphire substrates by metal-organic chemical vapour deposition （MOCVD） By employing three-step layer buffers, the mirror-like layers on two-inch sapphire wafers have been obtained. The structural, optical and electrical characteristics of InN are investigated by x-ray diffraction, scanning electron microscopy, atomic force microscopy, photoluminescence and infrared optical absorption. The photoluminescence and the absorption studies of the materials reveal a marked energy bandgap structure around 0.70eV at room temperature. The room-temperature Hall mobility and carrier concentration of the film are typically 939 cm^2 /Vs, and 3.9 × 1018cm^-3, respectively.     

Growth of aligned carbon nanotube arrays on metallic substrate and its application to supercapacitors

Aligned carbon nanotube arrays (ACNTAs) with lengths up to 150 μm were fabricated on metallic alloy (Inconel 600) substrates by pyrolysis of iron (II) phthalocyanine (FePc) in the presence of ethylene (C₂H₄). The as-grown ACNTAs, formed by aligned multi-walled carbon nanotubes with high purity, were characterized by scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), and Raman spectroscopy techniques. The ACNTAs were used directly as electrode materials in supercapacitors with (Et)₄NBF₄ + propylene carbonate (PC) as electrolyte, and their electrochemical properties were investigated. A rectangular-shaped cyclic voltammetry (CV) curve was observed even at a sweep rate of 1000 mV s⁻¹. The specific capacitance measured at 1000 mV s⁻¹ was about 57 % (47 F g⁻¹) of that obtained at 1 mV s⁻¹ (83 F g⁻¹), and an equivalent series resistance (ESR) of 0.55 Ω was measured for the ACNTA and activated carbon pair electrodes embedded in a coin cell. The results indicated that the ACNTAs could be a promising candidate as electrode materials in supercapacitors.     

Effects of growth temperature on Li-N dual-doped p-type ZnO thin films prepared by pulsed laser deposition

Li-N dual-doped p-type ZnO (ZnO:(Li,N)) thin films have been prepared by pulsed laser deposition. The introduction of Li and N was confirmed by secondary ion mass spectrometry measurements. The structural, electrical, and optical properties as a function of growth temperature were investigated in detail. The lowest room-temperature resistivity of 3.99 Ω cm was achieved at the optimal temperature of 450 °C, with a Hall mobility of 0.17 cm²/V s and hole concentration of 9.12 × 10¹⁸ cm⁻³. The ZnO:(Li,N) films exhibited good crystal quality with a complete c-axis orientation, a high transmittance (about 90%) in the visible region, and a predominant UV emission at room temperature. The two-layer-structure p-ZnO:(Li,N)/n-ZnO homojunctions were fabricated on a sapphire substrate. The current-voltage characteristics exhibited the rectifying behavior of a typical p-n junction.     

Shape controllable synthesis of ZnO nanorod arrays via vapor phase growth

ZnO nanorod arrays with peculiar morphologies were synthesized on (111)-oriented Si substrate and glass via a vapor phase growth. The morphology of the individual nanorod can be flat-headed bottle-like, and needle-like, which depends on the deposition positions relative to the source materials in the presence of a controlling element Se. In addition, the arrays of all the three morphologies exhibit good alignment and high coverage. This fabrication technique can be also used to direct the controllable growth of other nanomaterials with similar morphologies.     

Particulate assisted growth of ZnO nanorods and microrods by pulsed laser deposition

Zinc oxide (ZnO) thin films were deposited on the gallium nitride (GaN) and sapphire (Al₂O₃) substrates by pulsed laser deposition (PLD) without using any metal catalyst. The experiment was carried out at three different laser wavelengths of Nd:YAG laser (λ = 1064 nm, λ = 532 nm) and KrF excimer laser (λ = 248 nm). The ZnO films grown at λ = 532 nm revealed the presence of ZnO nanorods and microrods. The diameter of the rods varies from 250 nm to 2 μm and the length varies between 9 and 22 μm. The scanning electron microscopy (SEM) images of the rods revealed the absence of frozen balls at the tip of the ZnO rods. The growth of ZnO rods has been explained by vapor-solid (V-S) mechanism. The origin of growth of ZnO rods has been attributed to the ejection of micrometric and sub-micrometric sized particulates from the ZnO target. The ZnO films grown at λ = 1064 nm and λ = 248 nm do not show the rod like morphology. X-ray photoelectron spectroscopy (XPS) has not shown the presence of any impurity except zinc and oxygen.