A primary motivation of research in photovoltaic technology is to obtain higher efficiency photovoltaic devices at reduced cost of production so that solar electricity can be cost competitive. The majority of photovoltaic technologies are based on p-n junction, with efficiency potential being much lower than the thermodynamic limits of individual technologies and thereby providing substantial scope for further improvements in efficiency. The thesis explores photovoltaic devices using new physical processes that rely on thin layers and are capable of attaining the thermodynamic limit of photovoltaic technology. Silicon heterostructure is one of the candidate technologies in which thin films induce a minority carrier collecting junction in silicon and the devices can achieve efficiency close to the thermodynamic limits of silicon technology. The thesis proposes and experimentally establishes a new theory explaining the operation of silicon heterostructure solar cells. The theory will assist in identifying the optimum properties of thin film materials for silicon heterostructure and help in design and characterization of the devices, along with aiding in developing new devices based on this technology. The efficiency potential of silicon heterostructure is constrained by the thermodynamic limit (31%) of single junction solar cell and is considerably lower than the limit of photovoltaic conversion (~ 80 %). A further improvement in photovoltaic conversion efficiency is possible by implementing a multiple quasi-fermi level system (MQFL). A MQFL allows the absorption of sub band gap photons with current being extracted at a higher band-gap, thereby allowing to overcome the efficiency limit of single junction devices. A MQFL can be realized either by thin epitaxial layers of alternating higher and lower band gap material with nearly lattice matched (quantum well) or highly lattice mismatched (quantum dot) structure. The thesis identifies the material combination for quantum well structure and calculates the absorption coefficient of a MQFl based on quantum well. GaAsSb (barrier)/InAs(dot) was identified as a candidate material for MQFL using quantum dot. The thesis explains the growth mechanism of GaAsSb and the optimization of GaAsSb and GaAs heterointerface.