Growth and process modeling studies of nickel-catalyzed metalorganic chemical vapor deposition of GaN nanowires

A combination of experimental and computational fluid dynamics-based reactor modeling studies were utilized to study the effects of process conditions on GaN nanowire growth by metalorganic chemical vapor deposition (MOCVD) in an isothermal tube reactor. The GaN nanowires were synthesized on (0 0 0 1) sapphire substrates using nickel thin films as a catalyst. GaN nanowire growth was observed over a furnace temperature range of 800–900 °C at V/III ratios ranging from 33 to 67 and was found to be strongly dependent on the position of the substrate relative to the group III inlet tube. The modeling studies revealed that nanowire growth consistently occurred in a region in the reactor where the GaN thin-film deposition rate was reduced and the gas phase consisted primarily of intermediate species produced by the reaction and decomposition of trimethylgallium–ammonia adduct compounds. The GaN nanowires exhibited a predominant [1 1 2¯ 0] growth direction. Photoluminescence measurements revealed an increase in the GaN near-band edge emission intensity and a reduction in the deep-level yellow luminescence with increasing growth temperature and V/III ratio.     

Growth of hexagonal and cubic InN nanowires using MOCVD with different growth temperatures

We have performed a detailed investigation of the metal-organic chemical vapor deposition (MOCVD) growth and characterization of InN nanowires formed on Si(1 1 1) substrates under nitrogen rich conditions. The growth of InN nanowires has been demonstrated by using an ion beam sputtered (∼10 nm) Au seeding layer prior to the initiation of growth. We tried to vary the growth temperature and pressure in order to obtain an optimum growth condition for InN nanowires. The InN nanowires were grown on the Au+In solid solution droplets caused by annealing in a nitrogen ambient at 700 °C. By applying this technique, we have achieved the formation of InN nanowires that are relatively free of dislocations and stacking faults. Scanning electron microscopy (SEM) showed wires with diameters of 90–200 nm and lengths varying between 3 and 5 μm. Hexagonal and cubic structure is verified by high resolution X-ray diffraction (HR-XRD) spectrum. Raman measurements show that these wurtzite InN nanowires have sharp peaks E₂ (high) at 491 cm⁻¹ and A₁ (LO) at 591 cm⁻¹.     

Structural control and magnetic properties of electrodeposited Co nanowires

Co nanowires with a preferred orientation were fabricated by direct current electrodeposition into the pores of porous anodic alumina membrane, and the structure of Co nanowires was studied by X-ray diffraction and high-resolution transmission electron microscopy with selected-area electron diffraction. It is found that the crystal structure of Co nanowires lies on the deposition potential. When electrodeposition is performed far from equilibrium conditions, i.e., at a high potential, face-centered cubic Co nanowires are deposited, while hexagonal close packing Co nanowires are formed at the low potential. The experimental results indicate that the orientation of the nanowires has effects on the coercivity for both hexagonal close packing (hcp) and face-centered cubic (fcc) Co.     

Growth of undoped and Zn-doped GaN nanowires

Undoped and Zn-doped GaN nanowires were synthesized by chemical vapor deposition (CVD), and the effects of substrates, catalysts and precursors were studied. A high density of GaN nanowires was obtained. The diameter of GaN nanowires ranged from 20 nm to several hundreds of nm, and their length was about several tens of μm. The growth mechanism of GaN nanowires was discussed using a vapor–liquid–solid (VLS) model. Furthermore, room-temperature cathodoluminescence spectra of undoped and Zn-doped GaN nanowires showed emission peaks at 364 and 420 nm, respectively.     

Formation of Ge nanoislands before the completion of a wetting layer in the Ge/Si(1 1 1) system

The formation of Ge nanoislands directly on Si(1 1 1) surface before the completion of a wetting layer was studied by scanning tunneling microscopy and Raman scattering spectroscopy. The mechanism of the wetting layer formation in the Ge/Si(1 1 1) system depends on the rate of Ge deposition. Within the temperature range 350–500 °C, with Ge deposition rates of the order of 10⁻³ bilayers/min, the Ge wetting layer is formed by the multilayer growth mechanism. Therefore, the arrays of Ge islands with the densities of 10⁹–10¹² cm⁻², depending on the rate of Ge deposition, appear directly on the Si surface during the evolution of the wetting layer. The height of Ge islands is limited by 3 bilayers. The lateral dimensions depend on the coverage of Ge and on the growth temperature. A series of lines related to the quantization of the phonon spectrum along the growth direction [1 1 1] was observed in the spectra of Raman scattering by optical phonons of Ge nanoislands.     

Fabrication of UV detectors based on ZnO nanowires using silicon microchannel

Aligned ZnO nanowires were grown by metal organic chemical vapor deposition on patterned silicon substrate. The shape of nanostructures was greatly influenced by the micropatterned surface. The aspect ratio, packing fraction and the number density of nanowires on top surface are around 10, 0.8 and 10⁷ per mm², respectively, whereas the values are 20, 0.3 and 5×10⁷ per mm², respectively, towards the bottom of the cavity. XRD patterns suggest that the nanostructures have good crystallinity. High-resolution transmission electron microscopy confirmed the single-crystalline growth of the ZnO nanowires along the [0 0 0 1] direction. Photosensitivity of the nanowires, grown on both top and bottom surface of the microchannel, was observed. However, the nanowires grown on bottom surface have shown better UV response with base line recovery at dark condition.     

A simple method to synthesize α-Si3N4, β-SiC and SiO2 nanowires by carbothermal route

α-Si₃N₄ nanowires, β-SiC nanowires and SiO₂ amorphous nanowires are synthesized via the direct current arc discharge method with a mixture of silicon, activated carbon and silicon dioxide as the precursor. The α-Si₃N₄ nanowires, β-SiC nanowires and SiO₂ amorphous nanowires are about 50–200 nm in stem diameter and 10–100 μm in length. α-Si₃N₄ nanowires and β-SiC nanowires consist of a solid single-crystalline core along the [0 0 1] and [1 1 1] directions, respectively, wrapped within an amorphous SiO_x layer. The direct current arc plasma-assisted self-catalytic vapor–solid and/or vapor–liquid–solid (VLS) growth processes are proposed as the growth mechanism of the nanowires.     

Thick homoepitaxial GaN with low carrier concentration for high blocking voltage

High voltage GaN Schottky diodes require a thick blocking layer with an exceptionally low carrier concentration. To this aim, a metal organic chemical vapor deposition process was developed to create a (14 μm) thick stress-free homoepitaxial GaN film. Low temperature photoluminescence measurements are consistent with low donor background and low concentration of deep compensating centers. Capacitance–voltage measurements performed at 30 °C verified a low level of about 2×10¹⁵ cm⁻³ of n-type free carriers (unintentional doping), which enabled a breakdown voltage of about 500 V. A secondary ion mass spectrometry depth profile confirms the low concentration of background impurities and X-ray diffraction extracted a low dislocation density in the film. These results indicate that thick GaN films can be deposited with free carrier concentrations sufficiently low to enable high voltage rectifiers for power switching applications.     

HRTEM investigation of high-reflectance AlN/GaN distributed Bragg-reflectors by inserting AlN/GaN superlattice

A high-quality AlN/GaN distributed Bragg-reflectors (DBR) was successfully grown on sapphire substrate by low-pressure metal-organic chemical vapor deposition using ultra-thin AlN/GaN superlattice insertion layers (SLILs). The reflectivity of AlN/GaN DBR with ultra-thin AlN/GaN SLIL was measured and achieved blue peak reflectivity of 99.4% at 462 nm. The effect of ultra-thin AlN/GaN superlattice insertion layer was examined in detail by transmission electron microscopy, and indicated that the crack of AlN/GaN DBR can be suppress by inserting AlN/GaN SLIL. For electronic properties, the turn on voltage is about 4.1 V and CW laser action of vertical-cavity surface-emitting laser (VCSEL) was achieved at a threshold injection current of 1.4 mA at 77 K, with an emission wavelength of 462 nm.     

ZnSe/ZnCdSe heterostructure nanowires

The authors report the growth of high density ZnSe/ZnCdSe heterostructure nanowires on oxidized Si substrate. It was found that the as-grown nanowires were tapered with mixture of cubic zinc-blende and hexagonal wurtzite structures. It was also found that photoluminescence intensities observed from these ZnSe/ZnCdSe heterostructure nanowires were much larger than observed from the homogeneous ZnSe nanowires. Furthermore, it was found that activation energies for the nanowires with well widths of 6, 12, 18 and 24 nm were 22, 41, 67 and 129 meV, respectively.     

HVPE growth of semi-polar (1 1 2¯ 2)GaN on GaN template (1 1 3)Si substrate

The hydride-vapour-phase-epitaxial (HVPE) growth of semi-polar (1 1 2¯ 2)GaN is attempted on a GaN template layer grown on a patterned (1 1 3) Si substrate. It is found that the chemical reaction between the GaN grown layer and the Si substrate during the growth is suppressed substantially by lowering the growth temperatures no higher than 900 °C. And the surface morphology is improved by decreasing the V/III ratio. It is shown that a 230-μm-thick (1 1 2¯ 2)GaN with smooth surface is obtained at a growth temperature of 870 °C with V/III of 14.     

Epitaxial films of metals from the platinum group (Ir,Rh, Pt and Ru) on YSZ-buffered Si(1 1 1)

In the present work we have grown twin-free single crystal metal films of iridium (Ir), rhodium (Rh), platinum (Pt) and ruthenium (Ru) on silicon (1 1 1) substrates via an yttria-stabilized zirconia (YSZ) buffer layer. A prerequisite for the realisation of heteroepitaxial metal films without additional texture components was the twin-free deposition of the YSZ films by pulsed laser deposition (PLD). For the metal films on top, a novel two-step growth process was applied with an extremely low deposition rate for the first 20 nm. For all metals, a drastic texture improvement by up to a factor of 9 could be observed compared to the oxide buffer layer. Minimum values were 0.18° (Ir) and 0.12° (Rh) for tilt and twist, respectively. For all four metals investigated, twin-free epitaxial films could be grown on YSZ/Si(1 1 1) whereas the twinning problem for platinum films was solved by decoupling the Pt-YSZ interface via an additional iridium interlayer. The grown metal/YSZ/Si(1 1 1) multilayer samples offer the possibility to integrate a variety of interesting nanostructures and functional materials on silicon. They are now available in 4 in wafer size.     

Deposition of mechanically hard amorphous carbon nitride films from decomposition of BrCN. Effects of substrate cooling and pulsed rf-bias voltage

Mechanically hard amorphous carbon nitride films were formed by applying a combination of radio frequency (RF) bias voltage to the substrate and the chemical vapor deposition process using the decomposition reaction of BrCN with the microwave discharge flow of Ar. Cooling water was circulated inside the substrate stage. The maximum hardness was (17 ± 1) GPa for the film prepared under the negative RF bias voltage, −V_RF, of 30 V. This hardness was nearly twice that of the film prepared without cooling, suggesting that substrate cooling was effective for suppressing the relaxation of the internal stress of the film due to the temperature rise during the application of the RF bias voltage. Under the continuous operation of the RF bias voltage, films cannot be formed for −V_RF > 40 V because of the sputtering by the bombardment of energetic Ar⁺. Then, the RF bias voltage was applied with a pulsed operation. By using this operation films were prepared in the range of −V_RF = 40-100 V. The hardness, (36 ± 10) GPa, was obtained for the film obtained under the conditions of −V_RF = 100 V, the pulse period of 1000 s, and the pulse-on time of 800 s. The observed hardness scattered largely for the different observation points within this film; a single observation point in that film showed the maximum hardness of 46 GPa. According to the IR spectra of the films, the three-dimensional C-N network structure was developed.     

Growth and microstructural features of laser ablated LiCoO2 thin films

Thin films of LiCoO₂ were prepared by pulsed laser deposition technique and the properties were studied in relation to the deposition parameters. The films deposited from a sintered composite target (LiCoO₂+Li₂O) in an oxygen partial pressure of 100 mTorr and at a substrate temperature of 300 °C exhibited preferred c-axis (0 0 3) orientation perpendicular to the substrate surface. The AFM data demonstrated that the films are composed of uniform distribution of fine grains with an average grain size of 80 nm. The grain size increased with an increase in substrate temperature. The (0 0 3) orientation decreased with increase in (1 0 4) orientation for the films deposited at higher substrate temperatures (>500 °C) indicating that the films’ growth is parallel to the substrate surface. The composition of the experimental films was analyzed using X-ray photoelectron spectroscopy (XPS). The binding energy peaks of Co(2p_3/2) and Co(2p_1/2) are, respectively, observed at 779.3 and 794.4 eV, which can be attributed to the Co³⁺ bonding state of LiCoO₂. The electrochemical measurements were carried out on Li//LiCoO₂ cells with a lithium metal foil as anode and LiCoO₂ film as cathode of 1.5 cm² active area using a Teflon home-made cell hardware. The Li//LiCoO₂ cells were tested in the potential range 2.6-4.2 V. Specific capacity as high as 205 mC/cm² μm was measured for the film grown at 700 °C. The growth of LiCoO₂ films were studied in relation to the deposition parameters for their effective utilization as cathode materials in solid-state microbattery application.     

In-situ visualization of a super-accelerated synthesis of zinc oxide nanostructures through CO2 laser heating

A simple growth technique capable of growing a variety of zinc oxide (ZnO) nanostructures with record growth rates of 25 μm/s is demonstrated. Visible lengths of ZnO nanowires, nanotubes, comb-like and pencil-like nanostructures could be grown by employing a focused CO₂ laser-assisted heating of a sintered ZnO rod in ambient air, in few seconds. For the first time, the growth process of nanowires was videographed, in-situ, on an optical microscope. It showed that ZnO was evaporated and presumably decomposed into Zn and oxygen by laser heating, reforming ZnO nanostructures at places with suitable growth temperatures. Analysis on the representative nanowires shows a rectangular cross-section, with a [0 0 0 1] growth direction. With CO₂ laser heating replacing furnace heating used conventionally, and using different reactants and forming gases, this method could be easily adopted for other semiconducting inorganic nanostructures in addition to ZnO.     

Growth of cubic InN films with high phase purity by pulsed laser deposition

Cubic InN films have been grown on MgO (1 0 0) substrates with cubic GaN buffer layers by pulsed laser deposition (PLD). It has been found that cubic InN (1 0 0) films grow on the GaN (1 0 0)/MgO (1 0 0) structure with an in-plane epitaxial relationship of [0 0 1]_InN∥[0 0 1]_GaN∥[0 0 1]MgO. The phase purity of a cubic InN film grown at 440 °C was as high as 99% that can probably be attributed to the enhanced surface migration of film precursors in case of PLD. These results indicate that PLD is a suitable technique for the growth of high-quality cubic InN films, and will makes it possible to fabricate optical and electron devices based on cubic InN films.     

Growth and characterization of c-plane AlGaN on γ-LiAlO2

This study demonstrates a pure c-plane AlGaN epilayer grown on a γ-LiAlO₂ (1 0 0) (LAO) substrate with an AlN nucleation layer grown at a relatively low temperature (LT-AlN) by metal-organic chemical vapor deposition (MOCVD). The AlGaN film forms polycrystalline film with m- and c-plane when the nucleation layer grows at a temperature ranging from 660 to 680 °C. However, a pure c-plane AlGaN film with an Al content of approximately 20% can be obtained by increasing the LT-AlN nucleation layer growth temperature to 700 °C. This is because the nuclei density of AlN increases as the growth temperature increases, and a higher nuclei density of AlN deposited on LAO substrate helps prevent the deposition of m-plane AlGaN. Therefore, high-quality and crack-free AlGaN films can be obtained with a (0 0 0 2) ω-rocking curve FWHM of 547 arcsec and surface roughness of 0.79 nm (root-mean-square) using a 700-°C-grown LT-AlN nucleation layer.     

Influence of pulsed laser deposition rate on the microstructure and thermoelectric properties of Ca3Co4O9 thin films

The effects of deposition rate on the microstructure and thermoelectric (TE) properties of Ca₃Co₄O₉ thin films fabricated by pulsed laser deposition (PLD) technique were investigated. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM) revealed that a fast deposition rate resulted in not only low crystallinity but also the existence of the Ca_xCoO₂ secondary phase. Formation of Ca_xCoO₂ was inevitable during the thin film growth, and this was discussed from both structural and compositional point of view. With longer deposition interval or with sufficient oxygen at a lower deposition rate, the Ca_xCoO₂ phase was able to transit into the desired Ca₃Co₄O₉ phase during the coalescence process. The quality of the thin films was further analyzed by electrical properties measurements. The Ca₃Co₄O₉ thin film fabricated at a slower deposition rate was found to exhibit a low electrical resistivity of 9.4 mΩ cm and high Seebeck coefficient of 240 μV/K at about 700 °C, indicating a good quality film.     

Effect of an applied electric current in epitaxial growth of GaAs layer on patterned GaAs substrate

Selective epitaxial growth of a GaAs layer on SiN_x masked Si-doped semi-insulating (1 0 0) GaAs substrate was performed by current-controlled liquid-phase epitaxy (CCLPE) in the conventional liquid-phase epitaxy. Experiments were carried out with and without the application of electric current. Surface morphology of (1 0 0) facet of the grown layer and the vertical and lateral growth rates were significantly improved under applied electric current. A thick layer of about 330 μm was achieved at relatively low growth time of 6 h with a current density of 20 Acm⁻². The epitaxial growth is realized by both electromigration of the solute and supercooling under a constant rate of furnace cooling. The dislocation density of the grown layer was significantly reduced, compared with that of the substrate (4×10⁴ cm²).     

Growth and photoluminescence properties of vertically aligned SnO2 nanowires

Vertically aligned SnO₂ nanowires (NWs) were grown for the first time by a vapor–liquid–solid method on c-sapphire with gold as a catalyst under Ar gas flow. Electron backscatter diffraction analysis indicated the NWs are single crystalline having the rutile structure, grow vertically along the [1 0 0] direction, and exhibit a consistent epitaxial relationship where lattice mismatch is estimated to be 0.3% along the SnO₂ [0 1 0] direction. The growth of these NWs is sensitive to many parameters, including growth duration, substrate type, source vapor concentration, and the thickness of the catalyst layer. Photoluminescence measurements at room temperature showed that the vertically aligned NWs exhibit an intense transition at 3.64 eV, a near band-edge transition which is rarely observed in SnO₂.