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In situ and online Raman spectroscopy - also known as Raman monitoring - offers the excellent opportunity among other possibilities for the evaluation of Raman spectra to investigate semiconductor layers during their growth without any interruption. Not only the surface properties of such layers can be studied, also simultaneously the substrate and the interface layer/substrate can be analysed. This study presents the analysis of growth processes of ZnS/sub x/Se/sub(1-x)/ and GaN layers as well the investigation of nitrogen doped ZnSe:N. Molecular beam epitaxy (MBE) was used for the fabrication of these layers. The analysis of the Raman spectra was focused on the chemical composition of the semiconductor material, the stress in layer and substrate, the incorporation of extraneous atoms like nitrogen radicals into a crystal, the doping and structural order of the semiconductor and as well on the crystalline and amorphous phase of the material. Additionally to the MBE growth processes, the temperature induced resonant Raman scattering of ZnS/sub x/Se/sub(1-x)/ and ZnSe:N and also the desorption, adsorption and phase transition of a-As, a-Se and Sb were studied. Further investigations were undertaken on the nitridation of GaAs(100) by means of a nitrogen plasma generated in an rf-plasma source. The properties and changes of the semiconductor layers and the substrate depending on the layer thickness during growth are evaluated. The results are compared with theoretical models (e.g. spatial correlation model and modified random-element-isodisplacement (MREI) model). / In situ- und online-Raman-Spektroskopie – oder auch Raman-Monitoring genannt – bietet unter anderem die ausgezeichnete Möglichkeit, das Wachstum von Halbleiterschichten ohne Unterbrechung zu verfolgen. Dabei können nicht nur die Oberflächeneigenschaften untersucht werden, sondern es können gleichzeitig auch Informationen über das Substrat und über die Grenzfläche Schicht/Substrat gemacht werden. In der vorliegenden Arbeit wurden die Wachstumsprozesse von ZnS/sub x/Se/sub(1-x)/- und GaN-Schichten sowie des stickstoffdotierten ZnSe:N untersucht. Zur Schichtherstellung wurde die Molekularstrahlepitaxie (MBE) verwendet. Das Hauptaugenmerk wurde dabei auf die chemische Zusammensetzung der Halbleitermaterialien, Verspannungen von Schicht und Substrat, auf den Einbau von Fremdatomen wie Stickstoffradikale in ein Kristall, die Dotierung und die strukturelle Ordnung der Halbleiter sowie deren kristalline und amorphe Phase gerichtet. Neben den MBE-Wachstumsprozessen wurden temperaturinduzierte resonante Raman-Streuung an ZnS/sub x/Se/sub(1-x)/ und ZnSe:N sowie Desorptions-, Adsorptions- und Phasenübergänge von a-As, a-Se und Sb studiert. Die Nitridierung von GaAs(100) mittels eines Stickstoffplasmas aus einer rf-Quelle wurde ebenso untersucht. Die Eigenschaften und Veränderungen der Halbleiterschichten und der Substrate während des Wachstums werden in Abhängigkeit von der Schichtdicke dargelegt. Die Ergebnisse werden mit entsprechenden theoretischen Modellen (z.B. Spatial-Correlation-Modell und Modified Random-Element-Isodisplacement (MREI)-Modell) verglichen.

The popularity of III-nitride materials has taken up the semiconductor industry to newer applications because of their remarkable properties. In addition to having a direct and wide band gap of 3.4 eV, a very fascinating property of GaN is the band gap tuning from 0.7 to 6.2 eV by alloying with Al or In. The most common orientation to grow optoelectronic devices out of these materials are the polar c-plane which are strongly affected by the intrinsic spontaneous and piezoelectric polarization fields. Devices grown in no polar orientation such as (1 0 –1 0) m-plane or (1 1 –2 0) a-plane have no polarization in the growth direction and are receiving a lot of focus due to enhanced behaviour. The first part of this thesis deals with the development of non-polar epimGaN films of usable quality, on an m-plane sapphire by plasma assisted molecular beam epitaxy. Growth conditions such as growth temperature and Ga/N flux ratio were tuned to obtain a reasonably good crystalline quality film. MSM photodetectors were fabricated from (1 0 -1 0) m-GaN, (1 1 -2 0) a-GaN and semipolar (1 1 -2 2) GaN films and were compared with the polar (0 0 0 2) c-GaN epilayer. Later part of the thesis investigated (1 0 -1 0) InN/ (1 0 -1 0) GaN heterostructures. Further, we could successfully grow single composition nonpolar a-plane InxGa1-xN epilayers on (1 1 -2 0) GaN / (1 -1 0 2) sapphire substrate. This thesis focuses on the growth and characterisation of nonpolar GaN, InxGa1-xN and InN by plasma assisted molecular beam epitaxy and on their photodetection potential. Chapter 1 explains the motivation of this thesis work with an introduction to the III-nitride material and the choice of the substrate made. Polarization effect in the polar, nonpolar and semipolar oriented growth is discussed. Fabrication of semiconductor photodetectors and its principle is explained in details. Chapter 2 discusses the various experimental tools used for the growth and characterisation of the film. Molecular beam epitaxy technique is elaborately explained along with details of the calibration for the BEP of various effusion cells along with growth temperature at the substrate. Chapter 3 discusses the consequence of nitridation on bare m-sapphire substrate. Impact of nitridation step prior to the growth of GaN film over (1 0 -1 0) m-sapphire substrate was also studied. The films grown on the nitridated surface resulted in a nonpolar (1 0 -1 0) orientation while without nitridation caused a semipolar (1 1 -2 2) orientation. Room temperature photoluminescence study showed that nonpolar GaN films have higher value of compressive strain as compared to semipolar GaN films, which was further confirmed by room temperature Raman spectroscopy. The room temperature UV photodetection of both films was investigated by measuring the I-V characteristics under UV light illumination. UV photodetectors fabricated on nonpolar GaN showed better characteristics, including higher external quantum efficiency, compared to photodetectors fabricated on semipolar GaN. Chapter 4 focuses on the optimization and characterisation of nonpolar (1 0 -1 0) m-GaN on m-sapphire by molecular beam epitaxy. A brief introduction to the challenges in growing a pure single phase nonpolar (1 0 -1 0) GaN on (1 0 -1 0) sapphire without any other semipolar GaN growth is followed by our results achieving the same. Effect of the growth temperature and Ga/N ratio on the structural and optical properties of m-GaN epilayers was studied and the best condition was obtained for the growth temperature of 7600C and nitrogen flow of 1 sccm. Strain in the film was quantitatively measured using Raman spectroscopy and qualitatively analyzed by RSM. Au/ nonpolar GaN schottky diode was fabricated and temperature dependent I-V characteristics showed rectifying nature. Chapter 5 demonstrates the growth of (1 0 -1 0) m-InN / (1 0 -1 0) m-GaN / (1 0 -1 0) m-sapphire substrate. Nonpolar InN layer was grown at growth temperature ranging from 3900C to 440C to obtain a good quality film at 4000C. An in-plane relationship was established for the hetrostructures using phi-scan and a perfect alignment was found for the epilayers. RSM images on the asymmetric plane revealed highly strained layers. InN band gap was found to be around 0.8 eV from absorption spectra. The valance band offset value is calculated to be 0.93 eV for nonpolar m-plane InN/GaN heterojunctions. The heterojunctions form in the type-I straddling configuration with a conduction band offsets of 1.82 eV. Chapter 6 focuses on the optimization of nonpolar (1 1 -2 0) a-GaN on (1 -1 0 2) r-sapphire by molecular beam epitaxy. Effect of the growth temperature and Ga/N ratio on the structural and optical properties of a-GaN epilayers was studied and the best condition was obtained for the growth temperature of 7600C and nitrogen flow of 1 sccm. An in-plane orientation relationship is found to be [0 0 0 1] GaN || [-1 1 0 1] sapphire and [-1 1 0 0] GaN || [1 1 -2 0] sapphire for nonpolar GaN on r-sapphire substrate. Strain in the film was quantitatively measured using Raman spectroscopy and qualitatively analyzed by RSM. UV photo response of a-GaN film was measured after fabricating an MSM structure over the film with Au. EQE of the photodetectors fabricated in the (0 0 0 2) polar and (1 1 -2 0) nonpolar growth directions were compared in terms of responsively, nonpolar a-GaN showed the best sensitivity at the cost of comparatively slow response time. Chapter 7 demonstrates the growth of non-polar (1 1 -2 0) a-plane InGaN epilayers on a-plane (1 1 -2 0) GaN/ (1 -1 0 2) r-plane sapphire substrate using PAMBE. The high resolution X-ray diffraction (HRXRD) studies confirmed the orientation of the films and the compositions to be In0.19Ga0.81N, In0.21Ga0.79N and In0.23Ga0.77N. The compositions of the films were controlled by the growth parameters such as growth temperature and indium flux. Effect of variation of Indium composition on the strain of the epilayers was analyzed from the asymmetric RSM images. Further, we report the growth of self-assembled non-polar high indium clusters of In0.55Ga0.45N over non-polar (1 1 -2 0) a-plane In0.17Ga0.83N epilayer grown on a-plane (1 1 -2 0) GaN / (1 -1 0 2) r-plane sapphire substrate. The structure hence grown when investigated for photo-detecting properties, showed sensitivity to both infrared and ultraviolet radiations due to the different composition of InGaN region. Chapter 8 concludes with the summary of present investigations and the scope for future work.

Through the history of mankind, novel materials have played a key role in techno- logical progress. As we approach the limits of scaling it becomes difficult to squeeze out any more extensions to Moore’s law by just reducing device feature sizes. It is important to look for an alternate semiconductor to silicon in order to continue making the progress predicted by Moore’s law. Among the various semiconductor options being explored world-wide, the III-nitride semiconductor material system has certain unique characteristics that make it one of the leading contenders. We explore the III-nitride semiconductor material system for the unique advantages that it offers over the other alternatives available to us. This thesis studies the device applications of epitaxial III-nitride films and nanos- tructures grown using plasma assisted molecular beam epitaxy (PAMBE) The material characterisation of the PAMBE grown epitaxial III-nitrides was car- ried out using techniques like high resolution X-ray diffraction (HR-XRD), field emis- sion scanning electron microscopy (FESEM), room temperature photoluminescence (PL) and transmission electron microscopy (TEM). The epitaxial III-nitrides were then further processed to fabricate devices like Schottky diodes, photodetectors and surface acoustic wave (SAW) devices. The electrical charcterisation of the fabricated devices was carried out using techniques like Hall measurement, IV and CV measure- ments on a DC probe station and S-parameter measurements on a vector network analyser connected to an RF probe station. We begin our work on Schottky diodes by explaining the motivation for adding an interfacial layer in a metal-semiconductor Schottky contact and how high-k di- electrics like HfO2 have been relatively unexplored in this application. We report the work carried out on the Pt/n-GaN metal-semiconductor (MS) Schottky and the Pt/HfO2/n-GaN metal-insulator-semiconductor (MIS) Schottky diode. We report an improvement in the diode parameters like barrier height (0.52 eV to 0.63 eV), ideality factor (2.1 to 1.3) and rectification ratio (35.9 to 98.9 @2V bias) after the introduction of 5 nm of HfO2 as the interfacial layer. Temperature dependent I-V measurements were done to gain a further understanding of the interface. We observe that the barrier height and ideality factor exhibit a temperature dependence. This was attributed to inhomogeneities at the interface and by assuming a Gaussian distribution of barrier heights. UV and IR photodetectors using III-nitrides are then studied. Our work on UV photodetectors describes the growth of epitaxial GaN films. Au nanoparticles were fabricated on these films using thermal evaporation and annealing. Al nanostruc- tures were fabricated using nanosphere lithography. Plasmonic enhancement using these metallic nanostructures was explored by fabricating metal-semiconductor-metal (MSM) photodetectors. We observed plasmonic enhancement of photocurrent in both cases. To obtain greater improvement, we etched down on the GaN film using reac tive ion etching (RIE). This resulted in further increase in photocurrent along with a reduction in dark current which was attributed to creation of new trap states. IR photodetectors studied in this thesis are InN quantum dots whose density can be controlled by varying the indium flux during growth. We observe that increase in InN quantum dot density results in increase in photocurrent and decrease in dark current in the fabricated IR photodetectors. We then explore the advantages that InGaN offers as a material that supports surface acoustic waves and fabricate InGaN based surface acoustic wave devices. We describe the growth of epitaxial In0.23 Ga0.77 N films on GaN template using molecular beam epitaxy. Material characterisation was carried out using HR-XRD, FESEM, PL and TEM. The composition was determined from HR-XRD and PL measurements and both results matched each other. This was followed by the fabrication of interdigited electrodes with finger spacing of 10 µm. S-parameter results showed a transmission peak at 104 MHz with an insertion loss of 19 dB. To the best of our knowledge, this is the first demonstration of an InGaN based SAW device. In summary, this thesis demonstrates the practical advantages of epitaxially grown film and nanostructured III-nitride materials such as GaN, InN and InGaN using plasma assisted molecular beam epitaxy for Schottky diodes, UV and IR photodetec- tors and surface acoustic wave devices.

Ce travail est consacré à l’étude de la génération de deuxième harmonique (SHG) dans des guides d’ondes de Nitrure d’éléments III. Un des buts principaux de ce travail, était d’identifier les origines des pertes à la propagation dans les guides d’ondes GaN et de fortement les réduire dans des guides présentant des possibilités d’accord de phase, pour améliorer l’efficacité de la SHG. Nous avons fait un progrès très important dans cette direction et avons fabriqué des guides d’ondes plans de GaN épitaxiés sur des substrats de saphir avec des pertes à la propagation inférieure à 1dB/cm dans le visible. Dans ces guides d’ondes à faibles pertes, il a été possible d’obtenir un processus de SHG efficace en utilisant l’accord de phase modal. Nous avons obtenu 2% de conversion entre une pompe dans le proche infrarouge et un harmonique dans le visible, ce qui correspond à une efficacité de conversion normalisée de 0,15%W-1cm-2. Les pertes à la propagation et l’efficacité de conversion obtenues sont les meilleurs résultats rapportés jusqu'ici pour des guides d’ondes plan en GaN. De plus, nous avons étudié des guides d’ondes de Nitrure d’éléments III épitaxiés sur des substrats de Si, dont la fabrication demande de relever plusieurs défis, mais qui ouvrent des possibilités intéressantes. La première est la possibilité de graver sélectivement les nitrures ou le Si, ce que nous avons utilisé pour développer une plate-forme permettant la fabrication d’objets suspendus comme des micro-disques, des guides d’ondes et des micro-disques couplés à un guide d’ondes. Cette plate-forme a permis la première démonstration de SHG doublement résonante en utilisant un accord de phase modal entre des modes de galerie du micro-disque. Bien que toutes les expériences que nous avons exécutées aient été faites dans une région spectrale limitée, l’étude numérique présentée dans ce manuscrit démontre la grande adaptabilité de cette plate-forme basée sur la possibilité de faire varier la composition des guides d’ondes AlGaN de GaN pur à AlN pur. La deuxième possibilité liée à l’épitaxie de nitrures d’éléments III sur Si, est qu'en la combinant avec des techniques de report, on peut jouer avec des guides nitrures d’éléments III sur SiO2. Nos résultats numériques révèlent le potentiel complet des guides d’ondes d’AlGaN en démontrant qu’en utilisant différentes combinaisons de mode et en jouant sur la composition et la géométrie des guides d’ondes, il est possible d’obtenir un signal de deuxième harmonique dans l’ultra-violet, le visible ou le proche-infrarouges. Ces résultats montrent aussi, que pour améliorer encore l’efficacité de la SHG, on doit fabriquer des guides d’ondes canaux présentant un isolement optique parfait du substrat de Si et une inversion de polarité précisément placée dans le cœur du guide d’ondes. Dans une telle structure on pourrait profiter simultanément du confinement de la puissance, de l’accord de phase modal et d’un recouvrement optimisé des modes en interaction. Dans ce cas, nos calculs montrent que l’efficacité de conversion pourrait atteindre 100%W-1cm-2. Au cours de ce travail nous avons pu tester des guides canaux et des guides présentant une inversion de polarité dans le cœur. La qualité des flancs des guides canaux s’est avérée être tout à fait encourageante, mais leur performance non linéaire sont restées très limitées, principalement à cause de fortes pertes à la propagation dues au couplage avec le substrat absorbant et à la forte rugosité de surface des couches inversées. Les structures utilisant les techniques de report, n'ont pu être testées car elles ont cassé en cour de fabrication. L'obtention de guides optimisés exige de progresser encore pour réaliser des couches de confinement optique plus épaisses et/ou d’adapter la technique de report à ces matériaux. / This work is dedicated to the study of the second harmonic generation (SHG) in III-Nitride waveguides. One of the main goals of this work, was to identify the origins of the propagation losses in GaN waveguides, and to strongly reduce them in waveguides presenting some phase matching possibilities, in order to improve the SHG efficiency. We have made a very important progress in this direction, and fabricated by hetero-epitaxy GaN planar waveguides on sapphire substrates with propagation losses below 1dB/cm in the visible spectral region. These low-loss waveguides were used for the demonstration of an efficient second harmonic generation process using modal phase matching. We obtained 2% of power conversion from the near-infrared to the visible spectral regions with a normalized efficiency of 0.15%W-1cm-2. The obtained propagation losses and conversion efficiency are the best-reported results so far for GaN planar waveguides. In addition, we have studied epitaxial III-nitride waveguides on Si substrates, which are very challenging to fabricate, but opens new interesting opportunities. The first one is the possibility to etch selectively the nitrides or the Si. The selective chemical etching was used to develop a platform allowing the fabrication of suspended objects such as micro-disks, waveguides and micro-disks coupled to a waveguide. This platform has allowed the first demonstration of doubly resonant SHG using phase matching between the whispering gallery modes of a micro-disk. Although all the experiments we performed were done in a limited spectral region, the numerical study presented in this manuscript demonstrates the large adaptability of this platform based on the possibility of varying the composition of AlGaN waveguides from pure GaN to pure AlN. The second opportunity of epitaxial III-nitrides layers on Si is the possibility to combine them with report technologies to obtain III-nitride waveguides on SiO2. Our numerical results reveal the full potential of AlGaN waveguides by demonstrating that using different mode combinations and playing with waveguides composition and geometry, it is possible to obtain a second harmonic signal in the ultraviolet, the visible or the near-infrared spectral regions. These results also demonstrate, that to further improve the SHG efficiency, one has to fabricate ridge waveguides presenting a perfect optical isolation from the Si substrate and a polarity inversion precisely positioned in the core of the waveguide. In these structures one could benefit simultaneously from the power confinement, the modal phase matching and an optimized overlap of the interacting modes. In this case, we calculate that the conversion efficiencies could be as high as 100%W-1cm-2. Both ridge waveguides and polarity inversion were tested in this work. The quality of the ridges was quite encouraging, but their nonlinear performance remained limited mainly because of the high propagation losses due to the coupling with the absorbing substrate and to the roughness of the surface of the epitaxial inverted layers. The structures fabricated using the report technique, haven’t been tested, as they were broken during their fabrication. Getting fully optimized waveguides requires further progresses in realizing thicker optical buffer layers and/or adapting the report technique to these materials.

No description available.

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.

Group III-nitride semiconductors are well suited for the fabrication of devices including visible-ultraviolet light emitting diodes, high-temperature and high-frequency devices. The wurtzite III-nitride based heterostructures grown along polar c-direction have large internal electric fields due to discontinuities in spontaneous and piezoelectric polarizations. For optoelectronic devices, such as light-emitting diodes and laser diodes, the internal electric field is deleterious as it causes a spatial separation of electron and hole wave functions in the quantum wells, which decreases emission efficiency. Growth of GaN-based heterostructures in alternative orientations, which have reduced (semipolar) or no polarization (nonpolar) in the growth direction, has been a major area of research in the last few years. The correlation between structural, optical and transport properties of semipolar and nonpolar III-nitride would be extremely useful. The thesis focuses on the growth and characterizations of semipolar and nonpolar III-nitride heterostructures by plasma-assisted molecular beam epitaxy. Chapter 1 provides a brief introduction to the III-nitride semiconductors. The importance of semipolar and nonpolar III-nitride heterostructures over conventional polar heterostructures has been discussed. Chapter 2 deals with the descriptions of molecular beam epitaxy system and working principles of different characterization tools used in the present work. Chapter 3 addresses the molecular beam epitaxial growth of nonpolar (1 1 -2 0) and semipolar (1 1 -2 2) GaN on sapphire substrates. An in-plane orientation relationship is found to be [0 0 0 1] GaN || [-1 1 0 1] sapphire and [-1 1 0 0] GaN || [1 1 -2 0] sapphire for nonpolar GaN on r-sapphire substrates. Effect of growth temperature on structural, morphological and optical properties of nonpolar GaN has been studied. The growth temperature plays a major role in controlling crystal quality, morphology and emission properties of nonpolar a-plane GaN. The a-plane GaN shows crystalline anisotropy nature and it has reduced with increase in the growth temperature. The surface roughness was found to decrease with increase in growth temperature and film grown at 760°C shows reasonably smooth surface with roughness 3.05 nm. Room temperature photoluminescence spectra show near band emission peak at 3.434 -3.442 eV. The film grown at 800 ºC shows broad yellow luminescence peak at 2.2 eV. Low temperature photoluminescence spectra show near band emission at 3.483 eV along with defect related emissions. Raman spectra exhibit blue shift due to compressive strain in the film. An in-plane orientation relationship is found to be [1 -1 00] GaN || [1 2-1 0] sapphire and [-1 -1 2 3] GaN || [0 0 0 1] sapphire for semipolar GaN on m-plane sapphire substrates. The surface morphology of semipolar GaN film is found to be reasonably smooth with pits on the surface. Room temperature photoluminescence shows the near band emission (NBE) at 3.432 eV, which is slightly blue shifted compared to the bulk GaN. The Raman E2 (high) peak position observed at 569.1 cm1. Chapter 4 deals with the fabrication and characterizations of Au/nonpolar and Au/semipolar GaN schottky diodes. The temperature-dependent current–voltage measurements have been used to determine the current mechanisms in Schottky diodes fabricated on nonpolar a-plane GaN and semipolar GaN epilayers. The barrier height (φb) and ideally factor (η) estimated from the thermionic emission model are found to be temperature dependent in nature indicate the deviations from the thermionic emission (TE) transport mechanism. Low temperature I-V characteristics of Au/ GaN Schottky diode show temperature independent tunnelling parameter. Barrier heights calculated from XPS are found to be 0.96 eV and 1.13 eV for Au/nonpolar GaN and Au/semipolar GaN respectively. Chapter 5 demonstrates the growth of InN on r-sapphire substrates with and without GaN buffer layer. InN film and nanostructures are grown on r-sapphire without GaN buffer layer and they are highly oriented along (0002) direction. The electron microscopy study confirms the nanostructures are vertically aligned and highly oriented along the (0001) direction. The Raman studies of InN nanostructures show the SO modes along with the other possible Raman modes. The band gap of InN nanostructures is found to be 0.82 eV. InN grown with a-plane GaN buffer shows nonpolar orientated growth. Growth temperature dependent studies of nonpolar a-plane InN epilayers are carried out. The valence band offset value is calculated to be 1.31 eV for nonpolar a-plane InN/GaN heterojunctions. The heterojunctions form in the type-I straddling configuration with a conduction band offsets of 1.41 eV. Chapter 6 deals with the temperature dependent I-V characteristics of the nonpolar a-plane (1 1 -2 0) InN/GaN heterostructures. The measured values of barrier height and ideality factor from the TE model show the temperature dependent variation. The double Gaussian distribution has mean barrier height values ( ϕb ) of 1.17 and 0.69 eV with standard deviation (σs ) of 0.17 and 0.098 V, respectively. The modified Richardson plot ln (Is/T2)-q2σ2/2k2T2 ) versus q/kT in the temperature range of 350 – 500 K, yielded the Richardson constant of 19.5 A/cm2 K2 which is very close to the theoretical value of 24 A/cm2 K2 for n-type GaN. The tunneling parameters E0 found to be temperature independent at low temperature range (150 –300 K). Chapter 7 concludes with the summary of present investigations and the scope for future work.

In situ and online Raman spectroscopy - also known as Raman monitoring - offers the excellent opportunity among other possibilities for the evaluation of Raman spectra to investigate semiconductor layers during their growth without any interruption. Not only the surface properties of such layers can be studied, also simultaneously the substrate and the interface layer/substrate can be analysed. This study presents the analysis of growth processes of ZnS/sub x/Se/sub(1-x)/ and GaN layers as well the investigation of nitrogen doped ZnSe:N. Molecular beam epitaxy (MBE) was used for the fabrication of these layers. The analysis of the Raman spectra was focused on the chemical composition of the semiconductor material, the stress in layer and substrate, the incorporation of extraneous atoms like nitrogen radicals into a crystal, the doping and structural order of the semiconductor and as well on the crystalline and amorphous phase of the material. Additionally to the MBE growth processes, the temperature induced resonant Raman scattering of ZnS/sub x/Se/sub(1-x)/ and ZnSe:N and also the desorption, adsorption and phase transition of a-As, a-Se and Sb were studied. Further investigations were undertaken on the nitridation of GaAs(100) by means of a nitrogen plasma generated in an rf-plasma source. The properties and changes of the semiconductor layers and the substrate depending on the layer thickness during growth are evaluated. The results are compared with theoretical models (e.g. spatial correlation model and modified random-element-isodisplacement (MREI) model). / In situ- und online-Raman-Spektroskopie – oder auch Raman-Monitoring genannt – bietet unter anderem die ausgezeichnete Möglichkeit, das Wachstum von Halbleiterschichten ohne Unterbrechung zu verfolgen. Dabei können nicht nur die Oberflächeneigenschaften untersucht werden, sondern es können gleichzeitig auch Informationen über das Substrat und über die Grenzfläche Schicht/Substrat gemacht werden. In der vorliegenden Arbeit wurden die Wachstumsprozesse von ZnS/sub x/Se/sub(1-x)/- und GaN-Schichten sowie des stickstoffdotierten ZnSe:N untersucht. Zur Schichtherstellung wurde die Molekularstrahlepitaxie (MBE) verwendet. Das Hauptaugenmerk wurde dabei auf die chemische Zusammensetzung der Halbleitermaterialien, Verspannungen von Schicht und Substrat, auf den Einbau von Fremdatomen wie Stickstoffradikale in ein Kristall, die Dotierung und die strukturelle Ordnung der Halbleiter sowie deren kristalline und amorphe Phase gerichtet. Neben den MBE-Wachstumsprozessen wurden temperaturinduzierte resonante Raman-Streuung an ZnS/sub x/Se/sub(1-x)/ und ZnSe:N sowie Desorptions-, Adsorptions- und Phasenübergänge von a-As, a-Se und Sb studiert. Die Nitridierung von GaAs(100) mittels eines Stickstoffplasmas aus einer rf-Quelle wurde ebenso untersucht. Die Eigenschaften und Veränderungen der Halbleiterschichten und der Substrate während des Wachstums werden in Abhängigkeit von der Schichtdicke dargelegt. Die Ergebnisse werden mit entsprechenden theoretischen Modellen (z.B. Spatial-Correlation-Modell und Modified Random-Element-Isodisplacement (MREI)-Modell) verglichen.