Raman scattering in InN films and nanostructures

Studies of lattice dynamics devoted to wurtzite InN are presented. Raman scattering experiments on both InN thin films and nanometric islands grown by Metal–Organic Vapor Phase Epitaxy (MOVPE) were performed at room temperature. From the Raman spectra recorded from InN films under hydrostatic pressure up to 13 GPa, linear pressure coefficients and the corresponding Grüneisen parameters for both E₂ and A₁(LO) phonons were extracted for the wurtzite structure up to 11 GPa, close to the starting pressure of the hexagonal to rock-salt phase transition of InN. Spectra at higher pressure suggest that InN undergoes a gradual phase transition, and the reverse transition exhibits a strong hysteresis effect during the downstroke. Then, we discuss recent results on large single InN islands grown on GaN buffer layers, obtained by spatially resolved micro-Raman measurements. The magnitude of the residual strain is estimated, using a recent determination of phonon deformation potentials. It is found to vary linearly as a function of island height.     

Microstructural assessment of InN-on-GaN films grown by plasma-assisted MBE

The structural properties of InN thin films, grown by rf plasma-assisted molecular beam epitaxy on Ga-face GaN/Al₂O₃(0001) substrates, were investigated by means of conventional and high resolution electron microscopy. Our observations showed that a uniform InN film of total thickness up to 1 μm could be readily grown on GaN without any indication of columnar growth. A clear epitaxial orientation relationship of , was determined. The quality of the InN film was rather good, having threading dislocations as the dominant structural defect with a density in the range of 10⁹–10¹⁰ cm⁻². The crystal lattice parameters of wurtzite InN were estimated by electron diffraction analysis to be a=0.354 nm and c=0.569 nm, using Al₂O₃ as the reference crystal. Heteroepitaxial growth of InN on GaN was accomplished by the introduction of a network of three regularly spaced misfit dislocation arrays at the atomically flat interface plane. The experimentally measured distance of misfit dislocations was 2.72 nm. This is in good agreement with the theoretical value derived from the in-plane lattice mismatch of InN and GaN, which indicated that nearly full relaxation of the interfacial strain between the two crystal lattices was achieved.     

Epitaxial growth of InN on nearly lattice-matched (Mn,Zn)Fe2O4

We have grown InN films on nearly lattice-matched (Mn,Zn)Fe₂O₄ (111) substrates at low temperatures by pulsed laser deposition (PLD) and investigated their structural properties. InN films grown at substrate temperatures above 400 °C show poor crystallinity, and their in-plane epitaxial relationship is [10-10]InN//[11-2](Mn,Zn)Fe₂O₄, which means that their lattice mismatch is quite large (11%). By contrast, high quality InN films with flat surfaces can be grown at growth temperatures lower than 150 °C with the ideal in-plane epitaxial relationship of [11-20]InN//[11-2](Mn,Zn)Fe₂O₄, which produces lattice mismatches of as low as 2.0%. X-ray reflectivity measurements have revealed that the thickness of the interfacial layer between the InN and the substrates is reduced from 14 to 8.4 nm when the growth temperature is decreased from 400 °C to room temperature. This suppression of the interface reactions by reducing the growth temperature is probably responsible for the improvement in crystalline quality. These results indicate that the use of (Mn,Zn)Fe₂O₄ (111) substrates at low growth temperatures allows us to achieve nearly lattice matched epitaxial growth of InN.     

Growth of InN films on (1 1 1)GaAs substrates by reactive magnetron sputtering

Indium nitride (InN) films were grown on (1 1 1)GaAs substrates by reactive magnetron sputtering using an indium target. It was found that the crystal quality of InN films depends strongly on the substrate temperature and sputtering gas pressure, and highly c-axis preferred wurtzite InN films can be obtained at growth temperature as low as 100°C. Based on these results, the growth mechanism of InN films in the reactive magnetron sputtering was discussed.     

The growth temperatures dependence of optical and electrical properties of InN films

InN films grown on sapphire at different substrate temperatures from 550°C to 700°C by metalorganic chemical vapor deposition were investigated. The low-temperature GaN nucleation layer with high-temperature annealing (1100°C) was used as a buffer for main InN layer growth. X-ray diffraction and Raman scattering measurements reveal that the quality of InN films can be improved by increasing the growth temperature to 600°C. Further high substrate temperatures may promote the thermal decomposition of InN films and result in poor crystallinity and surface morphology. The photoluminescence and Hall measurements were employed to characterize the optical and electrical properties of InN films, which also indicates strong growth temperature dependence. The InN films grown at temperature of 600°C show not only a high mobility with low carrier concentration, but also a strong infrared emission band located around 0.7 eV. For a 600 nm thick InN film grown at 600°C, the Hall mobility achieves up to 938 cm²/Vs with electron concentration of 3.9 × 10¹⁸ cm⁻³. Supported by the National Basic Research Program of China (Grant No. 2006CB6049), the National Natural Science Foundation of China (Grant Nos. 6039072, 60476030 and 60421003), the Great Fund of the Ministry of Education of China (Grant No. 10416), the Specialized Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20050284004), and the Natural Science Foundation of Jiangsu Province of China (Grant Nos. BK2005210 and BK2006126)     

Temperature effects on optical properties of InN thin films

Transmission measurements have been carried out on InN thin films grown by radio frequency magnetron sputtering on a sapphire (0001) substrate at 10–300 K. With the aid of a novel procedure developed for analyzing the transmission spectra, the effect of temperature on optical properties, such as the absorption coefficient, band-gap, Urbach bandtail characteristics, refractive index and extinction coefficient, of InN thin films has been determined. The wavelength and temperature dependence of the absorption coefficient in both the Urbach and intrinsic absorption regions has been described by a series of empirical formulae. The temperature dependence of the refractive index dispersion below the band-gap is also found to follow a Sellmeier equation. These formulae are very useful for the characterization and device design of InN films. The free-electron concentration in the InN thin film determined here is also found to be in good agreement with that obtained from infrared reflection measurements. PACS 78.66.Fd; 78.40.Fy; 78.20.Bh; 78.20.Ci     

Influence of sputtering power and Ar–N2 flow on the structure and optical properties of indium nitride films prepared by magnetron sputtering

ABSTRACT

This paper discusses the deposition of indium nitride (InN) thin films on Si (100) substrates by using pulsed DC magnetron sputtering. Effects of varying sputtering power and Ar–N₂ flow ratio on the structural, morphological, and optical properties of indium nitride (InN) films were investigated. The structural characterization indicated nanocrystalline InN film with preferred orientation towards (101) plane that exhibited the optimum crystalline quality at 130?W and for 40:60 Ar–N₂ ratio. The surface morphology of InN, as observed through FESEM, contained irregularly shaped nanocrystals with size that increases with higher sputtering power and Ar:N₂ flow ratio. The optical properties of InN films were studied using ellipsometer at room temperature. The band gap of InN was decreased with the increase of sputtering power to 130?W, whereas an increase in the band gap was noticed with the increase of the Ar:N₂ flow ratio.     

Structural and optical characterisation of InN layers grown by MOCVD

In the following, we report investigations of the dependencies of the structural, optical and electrical characteristics of InN thin films grown by MOCVD on the growth temperature. The layer thicknesses range from 70 to 400 nm. Their carrier concentrations range from 7×10¹⁸ to 4×10¹⁹ cm⁻³. Hall mobility values from 150 to 1300 cm²/V/s were determined in these films. The variation of the growth temperature and V/III ratio brought about different growth modes and rates. Using TEM, in addition to measuring layer thickness, we also determined the growth mode along with the structural quality of the InN layers. The surface roughness was obtained from AFM measurements. The layer crystalline quality was also investigated by means of X-ray diffraction in the rocking mode. Photoluminescence measurements performed at room temperature and at 7 K gave emission at around 0.7 eV.     

Effect of carrier concentration of InN on the transport behavior of InN/GaN heterostructure based Schottky junctions

We present the study involving the dependence of carrier concentration of InN films, grown on GaN templates using the plasma assisted molecular beam epitaxy system, on growth temperature. The influence of InN carrier concentration on the electrical transport behavior of InN/GaN heterostructure based Schottky junctions is also discussed. The optical absorption edge of InN film was found to be strongly dependent on carrier concentration, and was described by Kane's k.p model, with non-parabolic dispersion relation for carrier in the conduction band. The position of the Fermi-level in InN films was modulated by the carrier concentration in the InN films. The barrier height of the heterojunctions as estimated from I–V characteristic was also found to be dependent on the carrier concentration of InN.     

Solid‐phase epitaxy of InOx Ny alloys via thermal oxidation of InN films on yttria‐stabilized zirconia

The characteristics of InO_x N_y alloy films prepared via thermal oxidation of InN epitaxial films with In‐ or N‐polarities grown on nearly lattice‐matched, yttria‐stabilized zirconia (YSZ) substrates are investigated. The InN films were oxidized to InO_x N_y with a gradual change in O/N composition by annealing in air. Structural analysis revealed that the temperature for phase transition from wurtzite structure depends on the polarity of InN, and N‐polar InO_x N_y films can retain their wurtzite structure even at higher temperatures compared with the case of In‐polar films. Furthermore, changes in the valence band structure and optical characteristics of the InO_x N_y alloys take place via thermal oxidation. These results indicate that InO_x N_y grown via thermal oxidation of N‐polar InN on YSZ can be considered as an alloy semiconductor for optoelectronic devices. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation and transport properties of Ba1−x Sr x CuO2+δ infinite layer films grown by molecular-beam epitaxy

Thin films of Ba_1–x Sr _x CuO₂₊ in the infinite layer structure were prepared by molecular beam epitaxy on SrTiO₃ substrates. Excellent in-plane order during growth was shown by RHEED. The lattice constant inc-direction was determined by x-ray diffraction. It changed from 0.404 nm to 0.345 nm whenx increased from 0 to 1. The film surfaces were smooth with some outgrowths as revealed by atomic force microscopy. Excellent crystal structure and epitaxy of the films was demonstrated by high resolution transmission electron microscopy. The room temperature dc resistivities of the films varied from 10^–3 cm to 10² cm, depending onx and on the oxidation conditions during growth. The resistivities of most films showed negative temperature coefficients and obeyed the conduction model of variable range hopping at low temperatures. In the composition rangex=0.5–0.8, however, an anomalous resistance dependence on temperature was observed in many samples. The resistivities started to deviate from the monotonic behaviour just below 200 K and in some cases dropped remarkably at temperatures below 140 K.     

Low temperature thermoelectric properties of Cu intercalated TiSe2: a charge density wave material

Y₂O₃ nanoparticles and nanorods have been firstly synthesized in bulk Ti-Y films prepared by magnetron sputtering on Si (100) substrates at different temperatures. X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDS) are used to characterize the structure, morphology, and composition of the as-synthesized nanoparticles and nanorods. The mechanical properties of the sputtered films are investigated using nanoindentation techniques. The results indicate that both the nanoparticles and nanorods have a pure cubic Y₂O₃ structure resulting from the reaction of Y atoms with the residual O₂ in the vacuum chamber, and are free from defects and dislocations with uniform diameters of about 30 nm. The Y₂O₃ nanoparticles mainly distribute at the grain boundaries of the Ti matrix and the nanorods have lengths ranging from 250 nm to more than 1 μm with the growth direction parallel to the (002) plane. As the growth temperature elevates, the nanoparticles turn to be coarsening while more and longer nanorods are inclined to form. Compared with the Ti film, the TiY films have a remarkable increase in hardness, but do not exhibit expected increase in elastic modulus. Finally, the growth mechanism is also briefly discussed.     

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.     

Growth, structure and electrical properties of tungsten oxide nanorods

Tungsten trioxide has shown good sensing properties towards various gases. Recently thin nanostructured WO₃ films have been tested. Due to their large surface area to volume ratio they exhibit good sensitivity depending on the grain size. However in conventional WO₃ thin films the average grain size exceeds the thickness of the surface space charge layer, so the electrical conduction is mainly controlled by the carriers transport across the grain boundaries. An alternative way seems to be in a monocrystalline material with nanometric dimensions. Our objective is to fabricate nanosized tungsten oxide rods and to test their sensing properties under gas adsorption. In this work, we focus on the growth, the structure and the electrical properties of tungsten nanorods. The tungsten oxide nanorods were grown by vapour transport from a WO₃ layer onto a substrate (Mica). The nanorods growth was controlled by the temperature gradient between the WO₃ layer and the substrate. Their morphology was investigated by AFM and their structure by TED and TEM. We have investigated the conductivity of the WO₃ nanorods with a technique derived from Atomic Force Microscopy operating in contact mode with a conductive tip (Resiscope).     

High temperature growth of InN on various substrates by plasma-assisted pulsed laser deposition

InN has attracted much attention due to its optical and electrical properties that make it suitable for the fabrication of infrared optical devices and high-speed electronic devices. In this work we report on the structural properties and morphology of InN thin films grown on different substrates by radiofrequency plasma beam assisted pulsed laser deposition. Sapphire and silicon substrates were considered for the growth of these films. The influence of substrate type and growth parameters on the morphology and structural properties of the resulting InN thin films is discussed. The structural analysis of the samples was performed by means of X-ray diffraction. The morphology of the thin films was investigated through atomic force microscopy. Although growth of InN from a metallic In target using nitrogen radiofrequency plasma assisted pulsed laser deposition was achieved for all the samples, growth conditions were found to play an important role on the crystal quality of the resulting thin films.     

Morphology transition of ZnO films with DMZn flow rate in MOCVD process

We used a metal-organic chemical vapor deposition (MOCVD) method to grow ZnO films on MgAl₂O₄ (1 1 1) substrate, and succeeded in preparing films with microstructures from well-aligned ZnO nanorods to continuous and dense films by adjusting the ratio of the input rates of oxygen and zinc sources (VI/II). At the growth temperature of 350 °C, the ZnO nanorods were formed under a low flow rate of a zinc precursor. On the other hand, continuous and dense ZnO films were formed under a high flow rate of the zinc precursor. There is a transition zone at medium zinc precursor flow rate, where nanorods transform to dense films. We proved that the height of ZnO nanorods and the thickness of ZnO dense films both increase with zinc flow rate, and are consistent with the mass-transport mechanism for ZnO growth. The XRD spectra of the sample in the transition zone show both (0 0 2) and (1 0 1) peaks, where (1 0 1) peaks are formed only in the transition zone. We consider that there are (0 0 2) and (1 0 1) ZnO grains in the early growth stage of dense ZnO films.     

Synthesis of VO2 (B) nanorods for Li battery application

Vanadium dioxide nanorods were synthesized through a hydrothermal reaction from V₂O₅ xerogel, poly(vinyl pyrrolidone) (PVP) and lithium perchlorate (LiClO₄). The prepared samples were characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical discharge–charge cycling in lithium battery. SEM images reveal the nanorods to have dimensions on the order of 1–3 μm in length and 10–50 nm in diameter. The measured initial discharge capacity of the lithium battery with a cathode made of VO₂ (B) nanorods was 152 mA h/g.     

Dielectric constant and current transport for HfO2 thin films on ITO

The dielectric constant and leakage current mechanisms for HfO₂ thin films deposited on indium–tin–oxide using reactive rf sputtering deposition were examined. Indium–tin–oxide was selected as the bottom metal as it is of interest as an electrode in transparent field-effect transistor development. The dielectric constant of HfO₂ films was approximately 20 and did not vary significantly with deposition conditions. Temperature-dependent leakage current measurements indicate that Schottky emission is the dominant transport mechanism in films deposited at low temperature and/or low oxygen pressure. The HfO₂/indium–tin–oxide barrier height was extracted to be 1.1±0.2 eV. Films deposited at high temperature and/or oxygen pressure deviate from the Schottky emission model, presumably due to the formation of polycrystalline material with grain boundary conduction. PACS  73.61.Ng; 73.50.Lw; 77.55.+f     

Growth of InN thin films on ZnO substrate by plasma-assisted molecular beam epitaxy

We have studied the microstructure property of InN epitaxial films grown on ZnO substrate by plasma-assisted molecular beam epitaxy. We found that the In₂O₃ compound was produced on ZnO substrate and many pits were formed on the InN films when InN was directly grown on ZnO substrate with the N/In flux ratio less than 40. We demonstrated that the quality of InN film was significantly improved when the In₂O₃ layer was used as a buffer to prevent the reaction between In and the ZnO substrate.