Neste trabalho, analisamos as propriedades estruturais, morfológicas e óticas de filmes finos de nitreto de índio, depositados em diferentes tipos de substratos (Si , safira-C, safira-A, safira-R, GaN/ safira e vidro) pelo método de deposição as s i s t ida por feixe de elétrons com energia de íons entre 100 e 1180 eV. A temperatura de substrato durante o processo de deposição variou da temperatura ambiente (TA) à 450oC, e ARR( I/A) ,que é a razão do f luxo de íons incidentes no feixe de íons relativa ao f luxo de átomos de In evaporados , de 0,8 até 4,5. O crescimento de InN cristalino foi fortemente influenciado pela orientação cristalográfica do substrato e os filmes sobre safira-C, safira-A e GaN/ safira foram os que apresentaram maior cristalinidade. O melhor valor de energia de íons foi de 100 eV para a formação de InN cristalino e sua cristalinidade aumentou com o aumento da temperatura do substrato. Não observamos influências de ARR( I/A) sobre a cristalinidade de InN e os filmes preparados em TA sobre GaN/ safira apresentaram InN amorfo. / In thi s work, we analyzed the structural , morphological and optical properties of thin indium nitride films grown on some types of subs t rate (Si , c-plane sapphire, a-plane sapphire, r -plane sapphire, GaN/ sapphire and glass ) by the ion beam as s is ted deposition method with ion energy of 100-1180 eV. The substrate temperature during deposition ranged from room temperature (RT) to 450oC and ARR ( I/A) , from 0.8 to 4.5. The growth of crystalline InN was strongly influenced by the crystallographic orientation of substrate and the films on c-plane sapphire, a-plane sapphire and GaN/ sapphire provided more favorable result s . The best value of ion energy was found to be 100 eV for the format ion of crystalline InN and this crystallization increased with increasing the substrate temperature. We found that influence of ARR( I/A) on the crystallization of InN was imperceptible and that the f ilm prepared at RT on the GaN/ sapphire was amorphous of InN.

The present work has been focused on the growth of Group III-nitride epitaxial layers and nanostructures on Si (111) substrates by plasma-assisted molecular beam epitaxy. Silicon is regarded as a promising substrate for III-nitrides, since it is available in large quantity, at low cost and compatible to microelectronics device processing. However, three-dimensional island growth is unavoidable for the direct growth of GaN on Si (111) because of the extreme lattice and thermal expansion coefficient mismatch. To overcome these difficulties, by introducing β-Si3N4 buffer layer, the yellow luminescence free GaN can be grow on Si (111) substrate. The overall research work carried out in the present study comprises of five main parts. In the first part, high quality, crack free and smooth surface of GaN and InN epilayers were grown on Si(111) substrate using the substrate nitridation process. Crystalline quality and surface roughness of the GaN and InN layers are extremely sensitive to nitridation conditions such as nitridation temperature and time. Raman and PL studies indicate that the GaN film obtained by the nitridation sequences has less tensile stress and optically good. The optical band gaps of InN are obtained between ~0.73 to 0.78 eV and the blueshift of absorption edge can be induced by background electron concentration. The higher electron concentration brings in the larger blueshift, due to a possible Burstein–Moss effect. InN epilayers were also grown on GaN/Si(111) substrate by varying the growth parameters such as indium flux, substrate temperature and RF power. In the second part, InGaN/Si, GaN/Si3N4/n-Si and InN/Si3N4/n-Si heterostructures were fabricated and temperature dependent electrical transport behaviors were studied. Current density-voltage plots (J-V-T) of InGaN/Si heterostructure revealed that the ideality factor and Schottky barrier height are temperature dependent and the incorrect values of the Richardson’s constant produced, suggests an inhomogeneous barrier at the heterostructure interface. The higher value of the ideality factor compared to the ideal value and its temperature dependence suggest that the current transport is primarily dominated by thermionic field emission rather than thermionic emission. The valence band offset of GaN/β-Si3N4/Si and InGaN/Si heterojunctions were determined by X-ray photoemission spectroscopy. InN QDs on Si(111) substrate by droplet epitaxy and S-K growth method were grown in the third part. Single-crystalline structure of InN QDs (droplet epitaxy) was verified by TEM and the chemical bonding configurations of InN QDs were examined by XPS. The interdigitated electrode pattern was created and (I-V) characteristics of InN QDs were studied in a metal–semiconductor–metal configuration in the temperature range of 80–300 K. The I-V characteristics of lateral grown InN QDs were explained by using the trap model. A systematic manipulation of the morphology, optical emission and structural properties of InN/Si (111) QDs (S-K method) is demonstrated by changing the growth kinetics parameters such as flux rate and growth time. The growth kinetics of the QDs has been studied through the scaling method and observed that the distribution of dot sizes, for samples grown under varying conditions, has followed the scaling function. In the fourth part, InN nanorods (NRs) were grown on Si(111) and current transport properties of NRs/Si heterojunctions were studied. The rapid rise and decay of infrared on/off characteristics of InN NRs/Si heterojunction indicate that the device is highly sensitive to the IR light. Self-aligned GaN nanodots were grown on semi-insulating Si(111) substrate. The interdigitated electrode pattern was created on nanodots using photolithography and dark as well as UV photocurrent were studied. Surface band gaps of InN QDs were estimated from scanning tunneling spectroscopy (STS) I-V curves in the last part. It is found that band gap is strongly dependent on the size of InN QDs. The observed size-dependent STS band gap energy blueshifts as the QD’s diameter or height was reduced.

We present the results of GaInNAs/GaAs quantum dot structures with GaAsN barrier layers grown by solid source molecular beam epitaxy. Extension of the emission wavelength of GaInNAs quantum dots by ~170nm was observed in samples with GaAsN barriers in place of GaAs. However, optimization of the GaAsN barrier layer thickness is necessary to avoid degradation in luminescence intensity and structural property of the GaInNAs dots. Lasers with GaInNAs quantum dots as active layer were fabricated and room-temperature continuous-wave lasing was observed for the first time. Lasing occurs via the ground state at ~1.2μm, with threshold current density of 2.1kA/cm[superscript 2] and maximum output power of 16mW. These results are significantly better than previously reported values for this quantum-dot system. / Singapore-MIT Alliance (SMA)

Since the initial breakthroughs in structural quality and p-type conductivity in GaN during the late 1980s, the group-III nitride material system has attracted an enormous amount of interest because of its properties and applications in both electronics and optoelectronics. Although blue light-emitting diodes have been commercialized based on this success, much less progress has been made in ultraviolet emitters, green emitters, and photovoltaics. This lack of development has been attributed to insufficient structural and electrical material quality, which is directly linked to the growth of the material. The objective of this work is to expand the understanding of III-nitride growth towards the improvement of current device capabilities and the facilitation of novel device designs. Group-III nitride thin films are grown by molecular-beam epitaxy in a pulsed, metal-rich environment. The growths of nitride binaries and ternaries are observed in situ by transient reflection high-energy electron diffraction (RHEED) intensities, which respond to the behavior of atoms on the growing surface. By analyzing and interpreting these RHEED signatures, a comprehensive understanding of nitride thin film growth is obtained. The growth kinetics of unintentionally doped GaN by metal-rich MBE are elucidated, and a novel method of in situ growth rate measurement is discovered. This technique is expanded to InN, highlighting the similarity in molecular-beam epitaxy growth kinetics between III-nitride binaries. The growth of Mg-doped GaN is then explored to increase Mg incorporation and electrical activation. The growth of InxGa1-xN alloys are investigated with the goal of eliminating phase separation, which enables single-phase material for use in photovoltaics. Finally, the growth of unintentionally doped and Mg-doped AlGaN is investigated towards higher efficiency light emitting diodes. These advancements in the understanding of III-nitride growth will address several critical problems and enable devices relying on consistent growth in production, single-phase material, and practical hole concentrations in materials with high carrier activation energies.

In this research the growth of InN epilayers by high-pressure chemical vapor deposition (HPCVD) and structural, optical properties of HPCVD grown InN layers has been studied. We demonstrated that the HPCVD approach suppresses the thermal decomposition of InN, and therefore extends the processing parameters towards the higher growth temperatures (up to 1100K for reactor pressures of 15 bar, molar ammonia and TMI ratios around 800, and a carrier gas flow of 12 slm). Structural and surface morphology studies of InN thin layers have been performed by X-ray diffraction, low energy electron diffraction (LEED), auger electron spectroscopy (AES), high-resolution electron energy loss spectroscopy (HREELS) and atomic force microscopy (AFM). Raman spectroscopy, infrared reflection, transmission, photoluminescence spectroscopy studies have been carried out to investigate the structural and optical properties of InN films grown on sapphire and GaN/sapphire templates. InN layers grown on a GaN (0002) epilayer exhibit single-phase InN (0002) X-ray diffraction peaks with a full width at half maximum (FWHM) around 200 arcsec. Auger electron spectroscopy confirmed the cleanliness of the surface, and low energy electron diffraction yielded a 1×1 hexagonal pattern indicating a well-ordered surface. The plasmon excitations are shifted to lower energies in HREEL spectra due to the higher carrier concentration at the surface than in the bulk, suggesting a surface electron accumulation. The surface roughness of samples grown on GaN templates is found to be smoother (roughness of 9 nm) compared to the samples grown on sapphire. We found that the deposition sometimes led to the growth of 3 dimensional hexagonal InN pyramids. Results obtained from Raman and IR reflectance measurements are used to estimate the free carrier concentrations, which were found in the range from mid 10^18 cm-3 to low 10^20 cm-3. The optical absorption edge energy calculated from the transmission spectra is 1.2 eV for samples of lower electron concentration. The Raman analysis revealed a high-quality crystalline layer with a FWHM for the E2(high) peak around 6.9 cm^-1. The results presented in our study suggest that the optimum molar ratio might be below 800, which is due to the efficient cracking of the ammonia precursor at the high reactor pressure and high growth temperature.

Indium nitride has many applications as a semiconductor. High quality films of indium nitride can be grown using Chemical Vapour Deposition (CVD) and Atomic Layer Deposition (ALD), but the availability of precursors and knowledge of the underlaying chemical reactions is limited. In this study the gas phase decomposition of a new indium precursor, N,N-dimethyl-N',N''-diisopropylguanidinate, has been investigated by quantum chemical methods for use in both CVD and ALD of indium nitride. The computations showed significant decomposition at around 250°C, 3 mbar indicating that the precursor is unstable at ALD conditions. A computational study of the surface chemical mechanism of the adsorption of trimethylindium and ammonia on indium nitride was also performed as a method development for other precursor surface mechanism studies. The results show, in accordance with experimental data, that the low reactivity of ammonia is a limiting factor in thermal ALD growth of indium nitride with trimethylindium and ammonia.

Das Wachstum von monolagen dünnen Schichten von InN und GaN/InN auf ZnO wurde untersucht. Ebenso der Einfluss der Verspannung, welche durch das Substrat bedingt ist, auf den Indiumgehalt von (In, Ga)N Heterostrukturen, welche auf GaN und ZnO gewachsen wurden. Alle Proben wurden mittels Molekularstrahlepitaxy gewachsen. Es wurde eine Prozedur entwickelt zum Glühen von ZnO Substraten, um glatte Oberflächen mit Stufenfluss-Morphologie zu erhalten, welche sich für das Wachstum von monolage-dünnen Heterostrukturen eignen. Solche Zn-ZnO und O-ZnO Oberflächen konnten produziert werden, wenn die Proben bei 1050 °C in einer O2 Atmosphäre bei 1 bar für eine Stunde geglüht wurden. Reflection high energy electron diffraction wurde eingesetzt, um in situ den Wachstumsmodus und die Entwicklung des a-Gitterabstandes zu untersuchen. Die kritische Schichtdicke, ab welcher ein Übergang im Wachstumsmodus von glattem zu rauhem Wachstum statt findet, war für das Wachstum von InN auf ZnO geringer als 2 ML und setzt gemeinsam mit dem Beginn der Relaxation ein. Für das Wachstum von GaN auf monolagen-dünnem InN/ZnO konnte gezeigt werden, dass höchstens wenige ML abgeschieden werden können, bevor Relaxation eintritt und/oder eine Vermischung zu (In, Ga)N stattfindet. Untersuchungen durch Röntgenbeugung und Raman Spektroskopie geben Hinweise darauf, dass das Abscheidung der nominalen Struktur 100x(1 ML InN/2 MLs GaN) vermutlich zum Wachstum von (In, Ga)N führte. Die chemische Zusammensetzung war für alle Proben sehr ähnlich mit einem indium Gehält von etwa x: 0.36 und einem Relaxationsgrad von 65% - 73% für Proben, die auf ZnO gewachsen wurde und 95% für Wachstum auf 300 nm In0.19Ga0.81N/GaN. Ein unbeabsichtigter Unterschied im V/III-Verhältnis während des Wachstums von (In, Ga)N Heterostrukturen, auf welchen die Anwesenheit von Metalltröpchen auf manchen Proben hinwies, lies auf einen möglichen Einfluss auf das Relaxationsverhalten und die Oberflächenrauhigkeit schließen. / Several thin InN and GaN/InN films and (In, Ga)N heterostructures were grown using molecular beam epitaxy to investigate their growth mode. InN and GaN/InN films were grown on ZnO substrates and (In, Ga)N heterostructures were grown on (In, Ga)N buffers and ZnO substrates. Fabricating the heterostructures on two different types of substrates was a means of strain engineering to possibly increase the indium content in the (In, Ga)N layers. An annealing procedure was established to treat ZnO substrate to gain smooth, stepped surfaces suitable for ML thin heterostructure devices. Reflection high energy electron diffraction was used to investigate in situ the growth mechanism and evolution of the a-lattice spacing. The critical layer thickness for growth mode transition of InN from smooth to rough is below 2 MLs and fairly coincides with the onset of main relaxation. The deposition of GaN on ML thin InN/ZnO shows that at best a few MLs can be deposited before relaxation and/or intermixing into (In, GaN) takes place. Investigations by X-ray diffraction and Raman spectroscopy indicate that the deposition of a nominal structure of 100x(1 ML InN/2 MLs GaN) seems to result in the growth of (In, Ga)N instead. The average chemical composition was similar for all samples with an indium content close to x: 0.36 and a degree of relaxation between 65%-73% for samples grown on ZnO and 95% for the sample grown on 300 nm In0.19Ga0.81N/GaN pseudo-substrate. The surface was probed with atomic force microscopy and showed that starting with smooth surfaces with root mean square roughness around 0.2 nm there was a considerable roughening during growth and surfaces with grain like morphology and a roughness around 2 to 3 nm was produced. Unintentional differences in V/III ratio during growth of (In, Ga)N heterostructures, indicated by the presence of droplets on some of the sample surfaces, were possible, impacting on the sample relaxation behavior and the surface roughness.

Group III-nitride semiconductors have received much research attention and witnessed a significant development due to their ample applications in solid-state lighting and high-power/high-frequency electronics. Numerous growth methods were explored to achieve device quality epitaxial III-nitride semiconductors. Among the growth methods for III-nitride semiconductors, molecular beam epitaxy provides advantages such as formation of abrupt interfaces and in-situ monitoring of growth. The present research work focuses on the growth and characterizations of III-nitride based epitaxial films, nanostructures and heterostructures on c-sapphire substrate using plasma-assisted molecular beam epitaxy system. The correlation between structural, optical and electrical properties of III-nitride semiconductors would be extremely useful. The interfaces of the metal/semiconductor and semiconductor heterostructures are very important in the performance of semiconductor devices. In this regard, the electrical transport studies of metal/semiconductor and semiconductor heterostructures have been carried out. Besides, studies involved with the defect induced room temperature ferromagnetism of GaN films and InN nano-structures have also been carried out. The thesis is organized in eight different chapters and a brief overview of each chapter is given below. Chapter 1 provides a brief introduction on physical properties of group III-nitride semiconductors. It also describes the importance of III-nitride heterostructures in the operation of optoelectronic devices. In addition, it also includes the current strategy of the emergence of room temperature ferromagnetism in III-nitride semiconductors. Chapter 2 deals with the basic working principles of molecular beam epitaxy system and different characterization tools employed in the present work. Chapter 3 describes the growth of GaN films on c-sapphire by plasma-assisted molecular beam epitaxy. The effects of N/Ga flux ratio on structural, morphological and optical properties have been studied. The flux ratio plays a major role in controlling crystal quality, morphology and emission properties of GaN films. The dislocation density is found to increase with increase in N/Ga flux ratio. The surface morphologies of the films as seen by scanning electron microscopy show pits on the surface and found that the pit density on the surface increases with flux ratio. The room temperature photoluminescence study reveals the shift in band-edge emission towards the lower energy with increase in N/Ga flux ratio. This is believed to arise from the reduction in compressive stress in the GaN films as it is evidenced by room temperature Raman study. The transport studies on the Pt/GaN Schottky diodes showed a significant increase in leakage current with an increase in N/Ga ratio and is found to be caused by the increase in dislocation density in the GaN films. Chapter 4 deals with the fabrication and characterization of Au/GaN Schottky diodes. The temperature dependent current–voltage measurements have been used to determine the current transport mechanism in Schottky diodes. The barrier height (φb) and the ideality factor (η) are estimated from the thermionic emission model and are found to be temperature dependent in nature, indicating the existence of barrier height inhomogeneities at the Au/GaN interface. The conventional Richardson plot of ln(Is/T2) versus 1/kT gives Richardson constant value of 3.23×10-5 Acm-2 K-2, which is much lower than the known value of 26.4 Acm-2 K-2 for GaN. Such discrepancy of Richardson constant value was attributed to the existence of barrier height inhomogeneities at the Au/GaN interface. The modified Richardson plot of ln(Is/T2)-q2σs2/2k2T2 versus q/kT, by assuming a Gaussian distribution of barrier heights at the Au/GaN interface, provides the Schottky barrier height of 1.47 eV and Richardson constant value of 38.8 Acm-2 K-2 which is very close to the theatrical value of Richardson constant. The temperature dependence of barrier height is interpreted on the basis of existence of the Gaussian distribution of the barrier heights due to the barrier height inhomogeneities at the Au/GaN interface. Chapter 5 addresses on the influence of GaN underlayer thickness on structural, electrical and optical properties of InN thin films grown using plasma-assisted molecular beam epitaxy. The high resolution X-ray diffraction study reveals superior crystalline quality for the InN film grown on thicker GaN film. The electronic and optical properties seem to be greatly influenced by the structural quality of the films, as can be evidenced from Hall measurement and optical absorption spectroscopy. Also, we present the studies involving the dependence of structural, electrical and optical properties of InN films, grown on thicker GaN films, on growth temperature. The optical absorption edge of InN film is found to be strongly dependent on carrier concentration. Kane’s k.p model is used to describe the dependence of optical absorption edge on carrier concentration by considering the non-parabolic dispersion relation for carrier in the conduction band. Chapter 6 deals with the analysis of the temperature dependent current transport mechanisms in InN/GaN heterostructure based Schottky junctions. The barrier height (φb) and the ideality factor (η) of the InN/GaN Schottky junctions are found to be temperature dependent. The temperature dependence of the barrier height indicates that the Schottky barrier height is inhomogeneous in nature at the heterostructure interface. The higher value of the ideality factor and its temperature dependence suggest that the current transport is primarily dominated by thermionic field emission (TFE) other than thermionic emission (TE). The room temperature barrier height and the ideality factor obtained by TFE model are 1.43 eV and 1.21, respectively. Chapter 7 focuses on the defect induced room temperature ferromagnetism in Ga deficient GaN epitaxial films and InN nano-structures grown on c-sapphire substrate by using plasma-assisted molecular beam epitaxy. The observed yellow emission peak in room temperature photoluminescence spectra and the peak positioning at 300 cm-1 in Raman spectra confirms the existence of Ga vacancies in GaN films. The ferromagnetism in Ga deficient GaN films is believed to originate from the polarization of the unpaired 2p electrons of nitrogen surrounding the Ga vacancy. The InN nano-structures of different size are grown on sapphire substrate, the structural and magnetic properties are studied. The room temperature magnetization measurement of InN nano-structures exhibits the ferromagnetic behavior. The saturation magnetization is found to be strongly dependent on the size of the nano-structures. Finally, Chapter 8 gives the summary of the present work and the scope for future work in this area of research.

[Formulae and special characters can not be reproduced here. Please see the pdf version of the Abstract for an accurate reproduction.] Indium nitride is an important III-V nitride semiconductor with many potential applications such as in high frequency transistors, laser diodes and photo voltaic cells. The mobility and peak drift velocity of this material are predicted to be extremely high and superior to that of gallium nitride. However, many material properties such as the origin of the n-type conductivity and the electronic band gap are not well understood. Moreover, there is limited information on the stoichiometry and the level of impurity contaminations in the films from different growth techniques. The n-type conductivity observed for as-grown indium nitride films has long been attributed to nitrogen vacancies, implying that the material is nitrogen deficient. A band gap value around 2 eV, as measured by the optical absorption method, is suggested by some authors to be a result of the formation of an InNIn2O3 alloy. Alternatively, the observation of a lower absorption edge, suggesting a band gap around 0.7 eV, may be caused by Mie scattering at indium clusters that may form during film growth. Secondary ion mass spectroscopy and x-ray techniques provide only qualitative composition information. The quantitative interpretation of the results relies on calibration samples which are not available for indium nitride. In Rutherford backscattering spectroscopy, while quantitative, the carbon, nitrogen and oxygen signals cannot be separated unless the film is very thin ([tilde]150 nm). However, with heavy ion Elastic Recoil Detection (ERD) analysis all the elements in indium nitride films can be fully separated even for a film thickness of [tilde] 800 nm. In this work, indium nitride films from different growth techniques have been analysed with ERD using 200 MeV 197Au projectiles. The observed nitrogen depletion during the ERD analysis was monitored as a function of projectile fluence using a gas ionisation detector with a large solid angle. Different models have been tested and it has been shown that the bulk molecular recombination model accurately describes the nitrogen depletion so that the original nitrogen-to- indium ratio can be measured with an accuracy of [plus or minus]3 [percent]. The correlation of nitrogen depletion rate and stopping power of the projectile ion has been investigated. The study has shown that the rate of depletion is slower for low-Z projectiles. It has been shown that for a film with good structural properties, no loss of nitrogen occurs during the ERD analysis with low-Z projectiles such as 42 MeV 32S. Thus, the original nitrogen-to-indium ratio can be obtained without any theoretical modelling, and with a precision of better than [plus or minus]1 [percent]. All the indium nitride films studied in this work, for which X-ray diffraction shows no metallic indium, are nitrogen-rich which is contradictory to expectation. Therefore, the common assertion that nitrogen vacancies are the cause of n-type conductivity in as-grown films is diffcult to explain. Instead, the existence of In vacancies, N antisites and interstitial N2 may be speculated. The carbon and oxygen contamination is an issue for films grown by all common growth techniques. However, the suggested correlation of oxygen content in the film with the apparent band gap is not supported by the ERD results. Instead, a correlation between nitrogen-to-indium ratio and the measured band gap has been observed for films grown by RF-sputtering. This work reports the implantation of radioisotope probes using negative ions. The 111In/Cd probe was selected for this work as it is a common Perturbed Angular Correlation (PAC) probe and ideally suited for the study of indium nitride. For the synthesis of the probe 111In/Cd, several possibilities, such as the production of 111In/Cd via nuclear fusion evaporation reactions and from commercially available 111InCl3 solutions, were explored. Different materials, including powders of Al2O3 and In2O3, were investigated as a carrier for the probe in the ion source of the radioisotope implanter. It has been established that combining the 111InCl3 solution as the source and In2O3 powder as the carrier material gives optimum implantation efficiency. The radioisotope implanter facility has been developed to a stage that the radioisotope probe 111In/Cd can be routinely implanted into materials as molecular 111InO?? ions. An implantation rate of 3x10 4[th] Becquerel per hour has been demonstrated. Measurements on different materials (Ag, In, Ni, Si, InP) have shown that condensed matter spectroscopies such as Low Temperature Nuclear Orientation, Nuclear Magnetic Resonance on Oriented Nuclei (NMRON) and Perturbed Angular Correlation can be reliably performed. NMRON measurements on silver indicate a new resonance frequency of 75.08 MHz for 111InAg at 8.0 T. The local lattice environment of indium nitride thin films has been investigated with PAC spectroscopy. Several methods of introducing a radioisotope probe into a host material have been investigated for indium nitride. The thermal diffusion of the radioisotope probe 111In/Cd into indium nitride at a temperature below the dissociation temperature (about 550 [degrees] C) was not possible. The probe was, however, successfully introduced into indium nitride films with ion implantation techniques. Recoil implantation at MeV energies following fusion evaporation reactions and ion implantation at keV energies, both have been investigated for indium nitride films. An interaction frequency of v = 28 MHz has been measured for the 111In/Cd probe in indium nitride. This result is consistent with that obtained for indium nitride bulk grains. The PAC results suggest that all types of indium nitride films have a highly disordered lattice which could only be partially improved by annealing. Furnace annealing in nitrogen atmosphere above 400 [degrees] C resulted in the dissociation of the film. However, such dissociation could be avoided with rapid thermal annealing up to 600 [degrees] C. More detailed defect studies with PAC require the availability of better material. This study has also shown that indium nitride is highly sensitive to ion beam irradiation. Severe depletion of nitrogen during exposure to ions with MeV and KeV energies is an issue for the ion beam characterisation and processing of indium nitride.

The objective of this dissertation is to shed light on the physical properties of InN epilayers grown by High-Pressure Chemical Vapor Deposition (HPCVD) for optical device applications. Physical properties of HPCVD grown InN layers were investigated by X-ray diffraction, Raman scattering, infrared reflection spectroscopies, and atomic force microscopy. The dependencies of physical properties as well as surface morphologies of InN layers grown either directly on sapphire substrates or on GaN/sapphire templates on varied growth conditions were studied. The effect of crucial growth parameters such as growth pressure, V/III molar ratio, precursor pulse separation, substrate material, and mass transport along the flow direction on the optical and structural properties, as well as on the surface morphologies were investigated separately. At present, growth of high-quality InN material by conventional growth techniques is limited due to low dissociation temperature of InN (~600 ºC) and large difference in the partial pressures of TMI and NH3 precursors. In this research, HPCVD technique, in which ambient nitrogen is injected into reaction zone at super-atmospheric growth pressures, was utilized to suppress surface dissociation of InN at high temperatures. At high pressures, long-range and short-range orderings indicate that c-lattice constant is shorter and E2(high) mode frequency is higher than those obtained from low-pressure growth techniques, revealing that InN structure compressed either due to a hydrostatic pressure during the growth or thermal contraction during the annealing. Although the influence of varied growth parameters usually exhibit consistent correlation between long-range and short-range crystalline orderings, inconsistent correlation of these indicate inclination of InN anisotropy. InN layers, grown directly on α-sapphire substrates, exhibit InN (1 0 1) Bragg reflex. This might be due to a high c/a ratio of sapphire-grown InN epilayers compared to that of GaN/sapphire-grown InN epilayers. Optical analysis indicates that free carrier concentration, ne, in the range of 1–50 × 1018 cm–3 exhibits consistent tendency with longitudinal-optic phonon. However, for high ne values, electrostatic forces dominate over inter-atomic forces, and consistent tendency between ne and LO phonon disappears. Structural results reveal that growth temperature increases ~6.6 ºC/bar and V/III ratio affects indium migration and/or evaporation. The growth temperature and V/III ratio of InN thin films are optimized at ~850 ºC and 2400 molar ratio, respectively. Although high in-plane strain and c/a ratio values are obtained for sapphire-grown epilayers, FWHM values of long-range and short-range orderings and free carrier concentration value are still lower than those of GaN/sapphire-grown epilayers. Finally, vibrational and optical properties of chalcopyrite ZGP crystal on the (001), (110), and (10) crystalline planes were investigated by Raman scattering and infrared (IR) reflection spectroscopies. Raman scattering exhibits a nonlinear polarizability on the c-plane, and a linear polarizability on the a- and b-planes of ZGP crystal. Also, birefringence of ZGP crystal was calculated from the hydrostatic pressure difference between (110) and (10) crystalline planes for mid-frequency B2(LO) mode.