It has been a long-standing goal to epitaxially integrate III-V alloys with Si substrates which can enable low-cost microelectronic and optoelectronic systems. Among the III-V alloys, gallium phosphide (GaP) is a strong candidate, especially for solar cells applications. Gallium phosphide with small lattice mismatch (~0.4%) to Si enables coherent/pseudomorphic epitaxial growth with little crystalline defect creation. The band offset between Si and GaP suggests that GaP can function as an electron-selective contact, and it has been theoretically shown that GaP/Si integrated solar cells have the potential to overcome the limitations of common a-Si based heterojunction (SHJ) solar cells.

Despite the promising potential of GaP/Si heterojunction solar cells, there are two main obstacles to realize high performance photovoltaic devices from this structure. First, the growth of the polar material (GaP) on the non-polar material (Si) is a challenge in how to suppress the formation of structural defects, such as anti-phase domains (APD). Further, it is widely observed that the minority-carrier lifetime of the Si substrates is significantly decreased during epitaxially growth of GaP on Si.

In this dissertation, two different GaP growth methods were compared and analyzed, including migration-enhanced epitaxy (MEE) and traditional molecular beam epitaxy (MBE). High quality GaP can be realized on precisely oriented (001) Si substrates by MBE growth, and the investigation of structural defect creation in the GaP/Si epitaxial structures was conducted using high resolution X-ray diffraction (HRXRD) and high resolution transmission electron microscopy (HRTEM).

The mechanisms responsible for lifetime degradation were further investigated, and it was found that external fast diffusors are the origin for the degradation. Two practical approaches including the use of both a SiNx diffusion barrier layer and P-diffused layers, to suppress the Si minority-carrier lifetime degradation during GaP epitaxial growth on Si by MBE were proposed. To achieve high performance of GaP/Si solar cells, different GaP/Si structures were designed, fabricated and compared, including GaP as a hetero-emitter, GaP as a heterojunction on the rear side, inserting passivation membrane layers at the GaP/Si interface, and GaP/wet-oxide functioning as a passivation contact. A designed of a-Si free carrier-selective contact MoOx/Si/GaP solar cells demonstrated 14.1% power conversion efficiency.

The development of high efficiency III-V solar cells is needed to meet the demands of a promising renewable energy source. Intermediate band solar cells (IBSCs) using semiconductor quantum dots (QDs) have been proposed to exceed the Shockley-Queisser efficiency limit [1]. The introduction of an IB in the forbidden gap of host material generates two additional carrier transitions for sub-bandgap photon absorption, leading to increased photocurrent of IBSCs while simultaneously allowing an open-circuit voltage of the highest band gap. To realize a high efficiency IBSC, QD structures should have high crystal quality and optimized electronic properties. This dissertation focuses on the investigation and optimization of the structural and optical properties of InAs/GaAsSb QDs and the development of InAs/GaAsSb QD-based IBSCs.

In the present dissertation, the interband optical transition and carrier lifetime of InAs/GaAsSb QDs with different silicon delta-doping densities have been first studied by time-integrated and time-resolved photoluminescence (PL). It is found that an optimized silicon delta-doping density in the QDs enables to fill the QD electronic states with electrons for sub-bandgap photon absorption and to improve carrier lifetime of the QDs.

After that, the crystal quality and QD morphology of single- and multi-stack InAs/GaAsSb QDs with different Sb compositions have been investigated by transmission electron microscopy (TEM) and x-ray diffraction (XRD). The TEM studies reveal that QD morphology of single-stack QDs is affected by Sb composition due to strain reducing effect of Sb incorporation. The XRD studies confirm that the increase of Sb composition increases the lattice mismatch between GaAs matrix and GaAsSb spacers, resulting in increase of the strain relaxation in GaAsSb of the multi-stack QDs. Furthermore, the increase of Sb composition causes a PL redshift and increases carrier lifetime of QDs.

Finally, the spacer layer thickness of multi-stack InAs/GaAsSb QDs is optimized for the growth of InAs/GaAsSb QD solar cells (QDSCs). The InAs/GaAsSb QDSCs with GaP strain compensating layer are grown and their device performances are characterized. The increase of GaP coverage is beneficial to improve the conversion efficiency of the QDSCs. However, the conversion efficiency is reduced when using a relatively large GaP coverage.

GaAs-based solar cells have attracted much interest because of their high conversion efficiencies of ~28% under one sun illumination. The main carrier recombination mechanisms in the GaAs-based solar cells are surface recombination, radiative recombination and non-radiative recombination. Photon recycling reduces the effect of radiative recombination and is an approach to obtain the device performance described by detailed balance theory. The photon recycling model has been developed and was applied to investigate the loss mechanisms in the state-of-the-art GaAs-based solar cell structures using PC1D software. A standard fabrication process of the GaAs-based solar cells is as follows: wafer preparation, individual cell isolation by mesa, n- and p-type metallization, rapid thermal annealing (RTA), cap layer etching, and anti-reflection coating (ARC). The growth rate for GaAs-based materials is one of critical factors to determine the cost for the growth of GaAs-based solar cells. The cost for fabricating GaAs-based solar cells can be reduced if the growth rate is increased without degrading the crystalline quality. The solar cell wafers grown at different growth rates of 14 μm/hour and 55 μm/hour were discussed in this work. The structural properties of the wafers were characterized by X-ray diffraction (XRD) to identify the crystalline quality, and then the as-grown wafers were fabricated into solar cell devices under the same process conditions. The optical and electrical properties such as surface reflection, external quantum efficiency (EQE), dark I-V, Suns-Voc, and illuminated I-V under one sun using a solar simulator were measured to compare the performances of the solar cells with different growth rates. Some simulations in PC1D have been demonstrated to investigate the reasons of the different device performances between fast growth and slow growth structures. A further analysis of the minority carrier lifetime is needed to investigate into the difference in device performances.