Group III-Nitrides (GaN, InN & AlN) are considered one of the most important class of semiconducting materials after Si and GaAs. The excellent optical and electrical properties of these nitrides result in numerous applications in lighting, lasers, and high-power/high-frequency devices. Due to the lack of cheap bulk III- Nitride substrates, GaN based devices have been developed on foreign substrates like Si, sapphire and SiC. These technologies have been predominantly developed on the so called Ga-polarity epitaxial stacks with growth in the [0001] direction of GaN. It is this orientation that grows most easily on sapphire by metal organic chemical vapor deposition (MOCVD), the most common combination of substrate and deposition method used thus far. The opposite [000¯1] or N-polar orientation, very different in properties due to the lack of an inversion centre, offers several ad- vantages that could be exploited for better electronic and optoelectronic devices. However, its growth is more challenging and needs better understanding. The aim of the work reported in this dissertation was a systematic investigation of the relation between the various growth parameters which control polarity, surface roughness and mosaicity of GaN on non-miscut sapphire (0001) wafers for power electronics and lighting applications, with emphasis on the realization of N-polar epitaxial layers. GaN is grown on sapphire (0001) in a two-step process, which involves the deposition of a thin low temperature GaN nucleation layer (NL) on surface modified sapphire followed by the growth of high temperature device quality GaN epitaxial layer. The processing technique used is MOCVD. Various processing methods for synthesis of GaN layers are described with particular em- phasis on MOCVD method. The effect of ex situ cleaning followed by an in situ cleaning on the surface morphology of sapphire (0001) wafers is discussed. The characterization tools used in this dissertation for studying the chemical bond nature of nitrided sapphire surface and microstructural evolution (morphological and structural) of GaN layers are described in detail. The effect of nitridation temperature (TN) on structural transformation of non- miscut sapphire (0001) surface has been explored. The structural evolution of nitrided layers at different stages of their process like as grown stage and thermal annealing stage is investigated systematically. The chemical bond environment information of the nitrided layers have been examined by x-ray photoelectron spectroscopy (XPS). It is found that high temperature nitridation (TN ≥ 800oC) results in an Al-N tetrahedral bond environment on sapphire surface. In contrast, low temperature nitridation (TN = 530oC) results in a complex Al-O-N environment on sapphire surfaces. Microstructural evolution of low temperature GaN NLs has been studied at every stage of processing by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Surface roughness evolution and island size distribution of NLs measured from AFM are discussed. It is found that NLs processed on sapphire wafers nitrided at (TN ≥ 800oC) showed strong wurtzite [0002] orientation with sub-nanometre surface roughness. In contrast, NLs processed at (TN = 530oC) showed zinc blende phase in the as grown stage with higher surface roughness, but acquired a greater degree of wurtzite [0002] orientation after thermal annealing prior to high temperature GaN growth. Polarity, surface quality and crystal quality of subsequently grown high temperature GaN epitaxial layers is described in relation to the structure of the trans- formed nitrided layers. Higher nitridation temperatures (TN ≥ 800oC) consistently yield N-polar GaN whereas lower nitridation temperatures (TN = 530oC) yield Ga-polar GaN. It is found that the relative O atom concentration levels in nitrided layers control the density of inversion domains in N-polar GaN. The effect of various growth parameters (NH3 flow rate, growth temperature, NL thickness) on surface morphology and mosaicity of both Ga & N-polar GaN layers is discussed in detail. We report device quality N-polar GaN epitaxial layers on non-miscut sapphire (0001) wafers by careful optimization of growth temperature. It is found that lower growth temperatures (800oC) are favorable for obtaining smooth N- polar GaN layers. In contrast, N-polar GaN layers grown at higher temperatures (1000 to 1080oC) are rough with hexagonal hillocks.

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.

The demands for faster, smaller, and less expensive electronic equipments are basically the driving forces for improving the speed and increasing the packing density of microelectronic components. Down-scaling of the devices is the principal method to realize these requests. For future CMOS devices, new materials are required in the transistor structure to enable further scaling and improve the transistor performance. This thesis focuses on novel metal gate and high-κ dielectric materials for future CMOS technologies. Specifically, TiN and ZrN gate electrode materials were studied with respect to work function and thermal stability. High work function, suitable for pMOS transistors, was extracted from both C-V and I-V measurements for PVD and ALD TiN in TiN/SiO2/Si MOS capacitor structures. ZrNx/SiO2/Si MOS capacitors exhibited n-type work function when the low-resistivity ZrNx was deposited at low nitrogen gas flow. Further, variable work function by 0.6 eV was achieved by reactive sputter depositing TiNx or ZrNx at various nitrogen gas flow. Both metal-nitride systems demonstrate a shift in work function after RTP annealing, which is discussed in terms of Fermi level pinning due to extrinsic interface states. Still, the materials are promising in a gate last process as well as show potential as complementary gate electrodes. The dielectric constant of as-deposited (Ta2O5)1-x(TiO2)x thin films is around 22, whereas that of AlN is about 10. The latter is not dependent on the degree of crystallinity or on the measurement frequency up to 10 GHz. Both dielectrics exhibit characteristics appropriate for integrated capacitors. Finally, utilization of novel materials were demonstrated in strained SiGe surface-channel pMOSFETs with an ALD TiN/Al2O3 gate stack. The transistors were characterized with standard I-V, charge pumping, and low-frequency noise measurements. Correlation between the mobility and the oxide charge was found. Improved transistor performance was achieved by conducting low-temperature water vapor annealing, which reduced the negative charge in the Al2O3.

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.

A transparent conductive electrode (TCE) is an important component in many of our modern optoelectronic devices like photovoltaics, light emitting diodes and touch screens. These devices require good current injection and spreading as well as a high transparency. In this thesis we explore the use of graphene as an alternative to the current widely used indium tin oxide (ITO) as TCE in gallium nitride (GaN) based light emitting diodes (LEDs). Monolayer crystalline graphene can be produced on copper foils using chemical vapor deposition (CVD), where metals (especially copper) has a catalysing effect on the formation of graphene. However, transfer of graphene from copper foils is not suitable for an industrial scale and it results in a poor contact with the target substrate. We investigate the possibility of directly integrating graphene on GaN-based LEDs by using plasma-enhanced chemical vapor deposition (PECVD). We try to obtain the optimal conditions under these catalyst-free circumstances and propose a recipe adapted for the setup that we used. We will also study ideas of using a metal (we tried copper and nickel) to assist the direct growth that could help to increase the fraction of sp2 carbon bonds and reduce the sheet resistance. The metals are evaporated onto our samples either before or after we grow a carbon film to either assist the growth or rearrange the carbon respectively. The focus was not on trying to optimize the conditions for one metal treatment but rather to briefly explore multiple methods to find a suitable path for further studies. The direct grown pristine carbon films shows indications from Raman measurements of being nanocrystalline graphene with a sheet resistance ranging from about 20-50 kΩ/sq having a transmittance of approximately 96 % at 550 nm. A transmittance at this level is closely related to the value of an ideal monolayer graphene, which indicates that our carbon films could be close to one atom in thickness while being visually homogeneous and complete in coverage. Due to the use of a temperature close to the melting point of copper we struggled to keep the assisting copper from evaporating too fast or staying homogeneous after the treatment. Nickel has a higher melting temperature, but it appears as if this metal might be diffusing into the GaN substrate which changes the properties of both the GaN and carbon film. Even though the metal treatments that we tested did not provide any noticeable improvements, there is need for further investigations to obtain suitable treatment conditions. We suggest that the treatments involving copper are a more promising path to pursue as nickel seem to cause unavoidable intermixing problems.

published_or_final_version / Physics / Doctoral / Doctor of Philosophy

published_or_final_version / abstract / toc / Physics / Master / Master of Philosophy

published_or_final_version / abstract / Physics / Master / Master of Philosophy

published_or_final_version / Electrical and Electronic Engineering / Doctoral / Doctor of Philosophy

published_or_final_version / Physics / Master / Master of Philosophy