Effect of growth parameters on crystallinity and properties of ZnO films grown by plasma assisted MOCVD

Thin films of ZnO have been grown by plasma assisted metal–organic chemical vapour deposition (PA-MOCVD) using a 13.56 MHz O₂ plasma and the (HTTA=2-thenoyltrifluoroacetone, TMED=N,N,N′,N′-tetramethylethylendiamine) precursor. The effects of growth parameters such as the plasma activation, the substrate, the surface temperature, and the ratio of fluxes of precursors on the structure, morphology, and optical and electrical properties of ZnO thin films have been studied. Under a very low plasma power of 20 W, c-axis oriented hexagonal ZnO thin films are grown on hexagonal sapphire (0001), cubic Si(001) and amorphous quartz substrates. The substrate temperature mainly controls grain size.     

The role of a ZnO buffer layer in the growth of ZnO thin film on Al2O3 substrate

A ZnO buffer layer and ZnO thin film have been deposited by the pulsed laser deposition technique at the temperatures of 200 C and 400 C, respectively. Structural, electrical and optical properties of ZnO thin films grown on sapphire (Al₂O₃) substrate with 1, 5, and 9 nm thick ZnO buffer layers were investigated. A minute shift of the (101) peak was observed which indicates that the lattice parameter was changed by varying the thickness of the buffer layer. High resolution transmission electron microscopy (TEM) was used to investigate the thickness of the ZnO buffer layer and the interface involving a thin ZnO buffer between the film and substrate. Selected area electron diffraction (SAED) patterns show high quality hexagonal ZnO thin film with 30 in-plane rotation with respect to the sapphire substrate. The use of the buffer can reduce the lattice mismatch between the ZnO thin film and sapphire substrate; therefore, the lattice constant of ZnO thin film grown on sapphire substrate became similar to that of bulk ZnO with increasing thickness of the buffer layer.     

ZnO films grown by laser ablation with and without oxygen CVD

In the present work we have studied the properties of zinc oxide (ZnO) thin films grown by laser ablation of ZnO targets under different substrate temperature and background oxygen conditions. The ZnO layers were deposited with a Pulsed Laser Deposition (PLD) system on pre-nitrided (0001) sapphire (Al₂O₃), using the base line of a Nd:YAG laser at 1064 nm. The films were characterized by different structural and optical methods, including X-ray diffraction (XRD), scanning electron microscopy (SEM), optical transmission spectroscopy, and steady-state photoluminescence (PL). XRD analysis with rocking curves and θ–2θ scans indicates preferential growth along the c-axis direction with a full width at half maximum (FWHM) smaller than 1.5. Low-temperature photoluminescence (PL) showed strong excitonic emission near 3.36 eV between 9 and 65 K.     

Fabrication of a solution-processed thin-film transistor using zinc oxide nanoparticles and zinc acetate

We have fabricated a solution-processed ZnO thin-film transistor without vacuum deposition. ZnO nanoparticles were prepared by the polyol method from zinc acetate, polyvinyl pyrrolidone, and diethyleneglycol. The solution-processable semiconductor ink was prepared by dispersing the synthesized ZnO in a solvent. Inverted stagger type thin-film transistors were fabricated by spin casting the ZnO ink on the heavily doped Si wafer with 200 nm thick SiO₂, followed by evaporation of Cr/Au source and drain electrodes. After the drying and heat treatment at 600 C, a relatively dense ZnO film was obtained. The film characteristics were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). In order to obtain the electrical properties of the solution-derived transistor, the on–off ratio, threshold voltage, and mobility were measured.     

Morphological properties of AlN and GaN grown by MOVPE on porous Si(111) and Si(111) substrates

Metal Organic Vapour Phase Epitaxy (MOVPE) of AlN and GaN layers at a temperature of 1080 C were performed on porous Si(111) and Si(111) substrates. The thermal stability of porous silicon (PS) is studied versus growth time under AlN and GaN growth conditions. The surface morphology evolution of the annealed PS is revealed by scanning electron microscopy (SEM). Porous Si(111) with low porosity (40%) is more thermally stable than porous Si(100) with relatively high porosity (60%).AlN layers with various thicknesses were grown under the same conditions on the two substrates. Morphological properties of AlN were studied by atomic force microscopy (AFM) and compared taking into account the two different surfaces of the substrates. The two growth kinetics of AlN were found to be different due to the initial surface roughness of the PS substrate. The effect of AlN buffer morphology on the qualities of subsequent GaN layers is discussed. Morphological qualities of GaN layers grown on PS are improved compared to those obtained on porous Si(100) but are still less than those grown on Si substrate.     

Al Schottky contact on p-GaSe

A new Schottky diode, Al/p-GaSe, was presented in this study. It shows an effective barrier height of 0.96 eV with an ideality factor of 1.24 over five decades and a reverse leakage current density of 4.12×10⁻⁷ A/cm² at −2 V after rapid thermal annealing at 400 C for 30 s. The generation–recombination effect of the Schottky diode was decreased as the annealing temperature was increased. The formation of Al_1.33Se₂ was observed by X-ray diffraction analysis after the diode was annealed at 400 C for 30 s. Owing to the grains’ growth, the surface morphology of the 400 C-annealed diode was rougher than that of the unannealed diode, which was observed both by the AFM and the SEM analysis.     

Dielectric/piezoelectric properties and temperature dependence of domain structure evolution in lead free single crystal

(K_0.5Na_0.5)NbO₃ (KNN) single crystals were grown using a high temperature flux method. The dielectric permittivity was measured as a function of temperature for [001]-oriented KNN single crystals. The ferroelectric phase transition temperatures, including the rhombohedral–orthorhombic T_R−O, orthorhombic–tetragonal T_O−T and tetragonal–cubic T_C were found to be located at −149  C, 205 C and 393 C, respectively. The domain structure evolution with an increasing temperature in [001]-oriented KNN single crystal was observed using polarized light microscopy (PLM), where three distinguished changes of the domain structures were found to occur at −150  C, 213 C and 400 C, corresponding to the three phase transition temperatures.     

Study of structural, optical and electrical properties of ZnO and SnO2 thin films

The investigation of structure, optical and electrical properties of tin and zinc oxide films on glass substrates by using magnetron sputtering are carried out. X-ray data show the formation of textured tin oxides film during deposition and its transformation to SnO₂ polycrystalline film at low temperature (200 C) if the concentration of oxygen in the chamber is high (O₂ — 100%, Ar — 0%). Optimal conditions of SnO₂ polycrystalline film deposition (pressure of Ar–O₂ mixture in chamber — 2.7 Pa, concentration of O₂ — 10%) are determined. Low resistivity of as-deposited ZnO film and increasing ZnO crystallite sizes and phase volume at temperatures higher than the melting point of Zn (419.5 C) are explained by formation of conductive Zn and ZnO particle chains and their destruction, respectively.     

DLTS study of n-type GaN grown by MOCVD on GaN substrates

Electron traps in n-type GaN layers grown homoepitaxially by MOCVD on free-standing GaN substrates have been characterized using DLTS for vertical Schottky diodes. Two free-standing HVPE GaN substrates (A and B), obtained from two different sources, are used. The Si-doped GaN layers with the thickness of 5 μm are grown on an area of 0.9×0.9 cm² of substrate A and on an area of 1×1 cm² of substrate B. Two traps labeled B1 and B2 are observed with trap B2 dominant in GaN on both substrates. There exist no dislocation-related traps which have been previously observed in MOCVD GaN on sapphire. This might be correlated to the reduction in dislocation density due to the homoepitaxial growth. However, it is found that there is a large variation, more than an order of magnitude, in trap B2 concentration and that the B2 spatial distributions are different between the two substrates used.     

Control of diameter of ZnO nanorods grown by chemical vapor deposition with laser ablation of ZnO

We made a study of controlling diameters of well-aligned ZnO nanorods grown by low-pressure thermal chemical vapor deposition combined with laser ablation of a sintered ZnO target, which was developed by us. Until now, it has been impossible to control diameters of ZnO nanorods, while the growth orientation was maintained well-aligned. In this study we developed a multi-step growth method to fabricate well-aligned nanorods whose diameters could be controlled. Metal Zn vapor and O₂ are used as precursors to grow ZnO nanorods. N₂ is used as a carrier gas for the precursors. A substrate is an n-Si (111) wafer. A sintered ZnO target is placed near the substrate and ablated by a Nd–YAG pulsed laser during ZnO nanorod growth. The growth temperature is 530 C and the pressure is 66.5 Pa. A vertical growth orientation of ZnO nanorods to the substrate is realized in the first-step growth although the diameter cannot be controlled in this step. When an O₂ flow rate is 1.5 sccm, well-aligned nanorods with 100 nm diameter are grown. Next, the second-step nanorods are grown on only the flat tip of the first-step nanorods. The diameters of the second-step nanorods can be controlled by adjusting the O₂ flow rate, and the growth direction is kept the same as that of the first-step nanorods. When the O₂ flow rate in second-step growth is smaller than 0.6 sccm, the diameter of the second-step nanorods is 30–50 nm. When the O₂ flow rate is between 0.75 and 3.0 sccm, the diameter is almost same as that of the first-step nanorods. When the O₂ flow rate is larger than 4.5 sccm, the diameter is increased with increasing O₂ flow rate. Further, the third-step ZnO nanorods with gradually increased diameters can be grown on the second-step nanorods with 1.5 sccm O₂ flow rate and without laser ablation.     

Nanoscale ion-beam mixing in Au–Si and Ag–Si eutectic systems

MeV ion induced mixing in the nanoscale regime for Au and Ag nanoislands on silicon substrates has been studied. Au and Ag nanoislands are grown on silicon substrates at room temperature and irradiated with 1.5-MeV Au²⁺ ions at various fluences. Cross-sectional high-resolution transmission electron microscopy and Rutherford backscattering spectrometry (RBS) are used to study the ion-beam mixing in Au/SiO_x/Si and Ag/SiO_x/Si systems. We observe a metastable mixed phase for the Au–Si system at a fluence of 1×10¹⁴ ionscm^-2, while no mixed phase is formed for the Ag–Si system. For both Au–Si and Ag–Si systems, a part of the islands is pushed into the substrate. The mixed phase of the Au–Si system is found to be crystalline in nature. The higher eutectic temperature and lower heat of mixing of the Ag–Si system compared to the Au–Si system could be responsible for the lack of mixing and silicide formation in the Ag–Si system. PACS 61.80.Jh; 61.82.Rx; 68.37.Lp; 64.75.+g; 61.46.+w     

Electroluminescence from nano-crystalline Si/ SiO2 structures embedded in pn junctions

Phosphorous-doped and boron-doped amorphous Si thin films as well as amorphous SiO₂/Si/ SiO₂ sandwiched structures were prepared in a plasma enhanced chemical vapor deposition system. Then, the p–i–n structures containing nano-crystalline Si/ SiO₂ sandwiched structures as the intrinsic layer were prepared in situ followed by thermal annealing. Electroluminescence spectra were measured at room temperature under forward bias, and it is found that the electroluminescence intensity is strongly influenced by the types of substrate. The turn-on voltages can be reduced to 3 V for samples prepared on heavily doped p-type Si (p⁺-Si) substrates and the corresponding electroluminescence intensity is more than two orders of magnitude stronger than that on lightly doped p-type Si (p-Si) and ITO glass substrates. The improvements of light emission can be ascribed to enhanced hole injection and the consequent recombination of electron–hole pairs in the luminescent nanocrystalline Si/ SiO₂ system.     

Growth of InN layers by MOVPE using different substrates

This study presents the MOVPE growth of InN films onto different substrate materials, including sapphire, nitrided or not, GaN and AlN buffer layers deposited onto sapphire, and Si(111).For InN growth onto nitrided sapphire, different growth parameters were investigated in order to determine the best growth conditions. We found that a low V/III molar ratio has to be used in order to increase the growth rate. A light nitridation treatment gives the best electrical properties: mirror like layers with a mobility of 800 cm²/V  s were obtained. At room temperature, reflectivity experiments show the existence of a transition at 1.2 eV, while photoluminescence appears around 0.8 eV.Using the same growth conditions onto GaN buffers (with thicknesses ranging from 15 to 1000 Å), we found that the best mobilities are obtained above a given buffer thickness.By comparing also with AlN buffer layers and silicon substrates, we found that our previous conclusion still holds; lightly nitrided sapphire substrate leads to the best electrical properties and morphology.     

MBE growth of nitride-based photovoltaic intersubband detectors

In this work, we present the plasma-assisted molecular-beam epitaxial growth of quantum well infrared photodetector (QWIP) structures, including the Si-doped GaN/AlN short-period superlattice of the active region, conductive AlGaN claddings and integration of the final device. The growth of Si-doped GaN/AlN multiple quantum well (QW) structures is optimized by controlling substrate temperature, metal excess and growth interruptions. Structural characterization confirms a reduction of the interface roughness to the monolayer scale. P-polarized intersubband absorption peaks covering the 1.33–1.91 μm wavelength range are measured on samples with QW thickness varying from 1 to 2.5 nm. The absorption exhibits Lorentzian shape with a line width around 100 meV in QWs doped 5×10¹⁹ cm⁻³. To prevent partial depletion of the QWs owing to the internal electric field, we have developed highly-conductive Si-doped AlGaN cladding layers using In as a surfactant during growth. Complete ISB photodetectors with 40 periods of 1 nm-thick Si-doped GaN QWs with 2 nm-thick AlN barriers have been grown on conductive AlGaN claddings, the Al mole fraction of the cladding matching the average Al content of the active region. Temperature-dependent photovoltage measurements reveal a narrow (90 meV) detection peak at 1.39 μm.     

Microscopic bonding and macroscopic strain relaxations at Si-SiO<Subscript>2</Subscript> interfaces

Optical second harmonic generation studies of the temperature dependence of the phase angle differences from contributions of terrace and edge bonding at silicon–silicon dioxide interfaces prepared on vicinal Si(111) wafers have revealed an interface relaxation process at an annealing temperature between 850 and 900 °C. Complementary studies by synchrotron soft X-ray photoelectron spectroscopy have established that this relaxation is associated with changes in the concentration and composition of local suboxide bonding environments in an ultrathin, interfacial transition region that is approximately one molecular layer thick. This relaxation occurs at a significantly lower temperature than an approximately 990±10 °C relaxation of macroscopic compressive strain in the bulk of the SiO₂ film. This paper establishes an analogy between i) the Si–SiO₂ interface in which there is a transition from a rigid substrate, Si, to an ideal continuous random covalent network, SiO₂, in which the average number of bonding constraints/atom matches the network dimensionality, and ii) a concentration dependent transition between under- and over-constrained local bonding in non-crystalline glass alloys such as Ge_xSe_1-x. The interfacial suboxide transition region is demonstrated to have properties in common with a regime of alloy compositions in which self-organization reduces bond constraint induced strain, thereby stabilizing these compositions against aging as for example in time-dependent changes in the glass transition temperature. These comparisons provide important new insights into defect formation at Si–SiO₂ interfaces, as well as interfaces between Si and alternative high-k dielectrics being considered for advanced Si devices including Al₂O₃ and transition metal silicate alloys, e.g., (ZrO₂)_x(SiO₂)_1-x. This new perspective is also extended to interfaces between GaN and SiO₂, where the interfacial transition region is a suboxide of Ga, GaO_x, with x<1.5. PACS 85.30.Tv; 42.65.-k; 79.40.+z; 73.20.-r; 77.55.+f     

Growth and characterisation of GaN with reduced dislocation density

Two GaN MOVPE growth methods to reduce the threading dislocation (TD) density have been explored. The combined effects of (1) in situ SiN_x masking of the sapphire substrate and (2) starting the epitaxial growth at low V-to-III ratio on the GaN film quality were studied by atomic force microscopy, transmission electron microscopy and high-resolution X-ray diffraction. It was found that the annealing condition of the low-temperature nucleation layer after in situ SiN_x masking is critical in order to decrease the density of nucleation sites and hence increase the average grain size to about 5 μm. However, the coalescence of large grains with vertical side facets results in the formation of dense bundles of TDs at the grain boundaries combined with large numbers of basal-plane dislocation loops throughout the film. The formation of these dislocations can be prevented by starting the epilayer growth at low V-to-III ratio, resulting in the formation of grains with inclined side facets. The interaction of the TDs with the inclined side facets causes the dislocations to bend 90 as the grains grow in size and coalesce. GaN films with dislocation densities as low as 1×10⁸ cm⁻², giving full-width at half-maximum values of 180 and 220 arcsec for respectively (002) and (302) omega scans, were achieved by the combination of in situ masking and low V–III ratio epilayer growth. Hall carrier mobility values in excess of 900 cm² V ⁻¹ s⁻¹ were deduced for Si-doped layers.     

Surface morphology and composition of c-, a- and m-sapphire surfaces in O2 and H2 environments

This paper reports that monitoring the composition of the c(0 0 0 1), a(11–20) and m(10–10) sapphire surfaces is essential for a proper interpretation of the surface morphologies obtained after annealing at 1253 and 1473 K in ArH₂ or ArO₂ atmospheres. Our experimental investigations, which have used Auger electron spectroscopy (AES) and atomic force microscopy (AFM) on the surfaces of 99.99% pure sapphire wafers, have led to the following original conclusions: (i) Calcium segregates at the c-surface of sapphire both under ArO₂ and ArH₂. (ii) Potassium adsorption enhances the kinetics of step-bunching on the c-surface under ArO₂. (iii) The step edges on the a-surface may develop a comb-like morphology made of parallel strips along the [10–10] direction. (iv) At 1253 K, clean m-surfaces may be stable. (v) Under ArH₂, alumina surface diffusion is much slower than under ArO₂ for all surface orientations, the surface concentration of impurities is low, and the Al–O ratio of the AES signals at the surface is significantly larger.     

AlGaN/GaN HEMTs grown on silicon (001) substrates by molecular beam epitaxy

We report the realization of an AlGaN/GaN HEMT on silicon (001) substrate with noticeably better transport and electrical characteristics than previously reported. The heterostructure has been grown by molecular beam epitaxy. The 2D electron gas formed at the AlGaN/GaN interface exhibits a sheet carrier density of 8×10¹² cm⁻² and a Hall mobility of 1800 cm²/V s at room temperature. High electron mobility transistors with a gate length of 4 μm have been processed and DC characteristics have been achieved. A maximum drain current of more than 500 mA/mm and a transconductance g_m of 120 mS/mm have been obtained. These results are promising and open the way for making efficient AlGaN/GaN HEMT devices on Si(001).     

Epitaxial growth of 4H–SiC{0001} and reduction of deep levels

Homoepitaxial growth of 4H–SiC{0001} by hot-wall chemical vapor deposition (CVD) and characterization of deep levels in both n- and p-type epilayers have been investigated. On 4 off-axis 4H–SiC(0001), formation of macrosteps can be reduced by decreasing the C/Si ratio during CVD, though the growth condition leads to the increase in nitrogen incorporation. The 4H–SiC() face is promising, owing to its very smooth surface morphology even on 4 off-axis substrates and to its superior quality of the oxide/SiC interface. Deep level transient spectroscopy measurements in the wide temperature range from 100 K to 820 K on both n- and p-type 4H–SiC epilayers have revealed almost all the deep levels located in the whole energy range of the bandgap. Thermal annealing at 1350–1700 C of epilayers has resulted in reduction of deep level concentrations by one order of magnitude.     

The effect of the aminating temperature on the synthesis of gallium nitride nanowires doped with magnesium

GaN nanowires doped with Mg have been synthesized at different temperature through ammoniating the magnetron-sputtered Ga₂O₃/Au layered films deposited on Si substrates. X-ray diffraction (XRD), Scanning electron microscope (SEM), high-resolution TEM (HRTEM) equipped with an energy-dispersive X-ray (EDX) spectrometer and photoluminescence (PL) were used to analyze the structure, morphology, composition and optical properties of the as-synthesized sample. The results show that the ammoniating temperature has a great impact on the properties of GaN. The optimally ammoniating temperature of Ga₂O₃/Au layer is 900 C for the growth of GaN nanowires(NWs). The band gap emission (358 nm) relative to that (370 nm) of undoped GaN NWs has an apparent blueshift, which can be ascribed to the doping of Mg. Finally, the growth mechanism is also briefly discussed.