Thesis (Ph. D.)--University of North Texas, August, 2008. / Title from title page display. Includes bibliographical references.

The ability to manipulate material response to dynamical processes depends on the extent of understanding of transport properties and their variation with chemical and structural features in materials. In this perspective, current work focuses on the thermal and electronic transport behavior of technologically important bulk and nanomaterials. Strontium titanate is a potential thermoelectric material due to its large Seebeck coefficient. Here, first principles electronic band structure and Boltzmann transport calculations are employed in studying the thermoelectric properties of this material in doped and deformed states. The calculations verified that excessive carrier concentrations are needed for this material to be used in thermoelectric applications. Carbon- and boron nitride-based nanomaterials also offer new opportunities in many applications from thermoelectrics to fast heat removers. For these materials, molecular dynamics calculations are used to evaluate lattice thermal transport. To do this, first, an energy moment term is reformulated for periodic boundary conditions and tested to calculate thermal conductivity from Einstein relation in various systems. The influences of the structural details (size, dimensionality) and defects (vacancies, Stone-Wales defects, edge roughness, isotopic disorder) on the thermal conductivity of C and BN nanostructures are explored. It is observed that single vacancies scatter phonons stronger than other type of defects due to unsatisfied bonds in their structure. In pristine states, BN nanostructures have 4-6 times lower thermal conductivity compared to C counterparts. The reason of this observation is investigated on the basis of phonon group velocities, life times and heat capacities. The calculations show that both phonon group velocities and life times are smaller in BN systems. Quantum corrections are also discussed for these classical simulations. The chemical and structural diversity that could be attained by mixing hexagonal boron nitride and graphene provide further avenues for tuning thermal and electronic properties. In this work, the thermal conductivity of hybrid graphene/hexagonal-BN structures: stripe superlattices and BN (graphene) dots embedded in graphene (BN) are studied. The largest reduction in thermal conductivity is observed at 50% chemical mixture in dot superlattices. The dot radius appears to have little effect on the magnitude of reduction around large concentrations while smaller dots are more influential at dilute systems.

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.

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.

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.