Group III-A nitrides (GaN, AlN, InN and alloys) are materials of considerable contemporary interest and currently enable a wide variety of optoelectronic and high-power, high-frequency electronic applications. All of these applications utilize device structures that employ a single or multiple hetero-junctions, with material compositions varying across the interface. For example, the workhorse of GaN based electronic devices is the high electron mobility transistor (HEMT) which is usually composed of an AlGaN/GaN hetero-junction, where a two-dimensional electron gas (2DEG) is formed due to differences in polarization between the two layers. In addition to such hetero-junctions in the same material family, formation of hetero-interfaces in nitrides begins right from the epitaxy of the very first layer due to the lack of native substrates for their growth. The consequences of such "dissimilar" hetero-junctions typically manifest as large defect densities at this interface which in turn gives rise to defective films. Additionally, if the substrate is also a semiconductor, the electrical properties at such dissimilar semiconductor-nitride hetero-junctions are particularly important in terms of their influence on the performance of nitride devices. Nevertheless, the large defect densities at such dissimilar 3D-3D semiconductor interfaces, which translate into more trap states, also prevents them from being used as active device layers to say nothing of reliability considerations arising because of these defects. Recently, the advent of 2D materials such as graphene and MoS2 has opened up avenues for Van der Waal’s epitaxy of these layered films with practically any other material. Such defect-free integration enables dissimilar semiconductor hetero-junctions to be used as active device layers with carrier transport across the 2D-3D hetero-interface. This thesis deals with hetero-epitaxial growth platforms for reducing defect densities, and the material and electrical properties of dissimilar hetero-junctions with the group III-A nitride material system.