Nanostructured III-V semiconductors have emerged as one of the most promising materials systems for future optoelectronic applications. While planar III-V compounds are already at the center of the ongoing lighting revolution, where older light sources are replaced by modern white light LEDs, fabricating such materials in novel architectures, such as nanowires and quantum dots, creates new possibilities for optoelectronic applications. Not only do nanoscale structures allow the optically active III-V materials to be integrated with silicon microelectronics, but they also give rise to new fascinating properties inherent to the nanoscale.

One of the key parameters considered when selecting materials for applications in light-emitting and photovoltaic devices is the band gap energy. While alloying of conventional III-V materials provides a certain degree of band gap tunability, a significantly enhanced possibility of band gap engineering is offered by so-called dilute nitrides, where incorporation of a small percentage of nitrogen into III-V compounds causes a dramatic down-shift of the conduction band edge. In addition, nitrogen-induced splitting of the conduction band in dilute nitrides can be utilized in intermediate band solar cells, belonging to the next generation of photovoltaic devices.

For any material to be viable for optoelectronic applications, detailed knowledge of the electronic structure of the material, as well as a good understanding of carrier recombination processes is vital. For example, alloying may not only cause changes in the electronic structure but can also induce disorder. Disorder-induced potential fluctuations may alter charge carrier and exciton dynamics, and may even induce quantum confinement. Moreover, various defects in the material may introduce detrimental non-radiative (NR) states in the band gap deteriorating radiative efficiency. It is evident that, due to their different growth mechanisms, such properties could be markedly different in nanowires as compared to their planar counterparts. In this thesis, I aim to describe the electronic structure of dilute nitride nanowires, and its effects on the optical properties. Firstly, we investigate the electronic structure, and the structural and optical properties of novel GaNAsP nanowires, with a particular focus on the dominant recombination channels in the material. Secondly, we show how short-range fluctuations in the nitrogen content lead to the formation of quantum dots in dilute nitride nanowires, and investigate their electronic structure. Finally, we investigate the combined charge carrier and exciton dynamics of the quantum dots and effects of defects in their surroundings.

Before considering individual sources of NR recombination, it is instructive to investigate the overall effects of nitrogen incorporation on the structural properties of the nanowires. In Paper I, we show that nitrogen incorporation up to 0.16\% in Ga(N)AsP nanowires does not affect the overall structural quality of the material, nor does nitrogen degrade the good compositional uniformity of the nanowires. It is evident from our studies, however, that nitrogen incorporation has a strong and complex effect on recombination processes. We first show that nitrogen incorporation in GaNAsP nanowires reduces the NR recombination at room temperature as compared to the nitrogen-free nanowires (Paper I). This is in stark contrast to dilute nitride epilayers, where nitrogen incorporation enhances NR recombination. The reason for this difference is that in nanowires the surface recombination, rather than recombination via point defects, is the dominant NR recombination mechanism. We suggest that the nitrogen-induced suppression of the NR surface recombination in the nanowires is due to nitridation of the nanowire surface.

Another NR recombination channel common in III-V nanowires is caused by the presence of structural defects, such as rotational twin planes and stacking faults. Interestingly, while nitrogen incorporation does not appear to affect the density of such structural defects, increasing nitrogen incorporation reduces the NR recombination via the structural defects (Paper II). This is explained by competing trapping of excited carriers/excitons to the localized states characteristic to dilute nitrides, and at nitrogen-induced NR defects. This effect is, however, only present at cryogenic temperatures, while at room temperature the NR recombination via the structural defects is not the dominant recombination channel.

Importance of point defects in carrier recombination is highlighted in Paper III. Using the optically detected magnetic resonance technique, we show that gallium vacancies (V_Ga) that are formed within the nanowire volume act as efficient NR recombination centers, degrading optical efficiency of the Ga(N)AsP-based nanowires. Interestingly, while the defect formation is promoted by nitrogen incorporation, it is also readily present in ternary GaAsP nanowires. This contrasts with previous studies on planar structures, where V_Ga was not formed in the absence of nitrogen, unless subjected to irradiation by high-energy particles or heavy n-type doping. This, again, highlights how the defect formation is strikingly different in nanowires as compared to planar structures, likely due to the different growth processes.

Potential fluctuations in the conduction band, caused by non-uniformity of the nitrogen incorporation, is characteristic to dilute nitrides and is known to cause exciton/carrier localization. We find that in dilute nitride nanowires, such fluctuations at the short range cause three-dimensional quantum confinement of excitons, resulting in optically active quantum dots with spectrally ultranarrow and highly polarized emission lines (Paper IV). A careful investigation of such quantum dots reveals that their properties are strongly dependent on the host material (Papers V, VI). While the principal quantization axis of the quantum dots formed in the ternary GaNAs nanowires is preferably oriented along the nanowire axis (Paper V), it switches to the direction perpendicular to the nanowire axis in the quaternary GaNAsP nanowires (Paper VI). Another aspect illustrating the influence of the host material on the quantum-dot properties is the electronic character of the captured hole. In both alloys, we show coexistence of quantum dots where the captured holes are of either a pure heavy-hole character or a mixed light-hole and heavy-hole character. In the GaNAs quantum dots, the main cause of the light- and heavy-hole splitting is uniaxial tensile strain induced by a combination of lattice mismatch with the nanowire core and local alloy fluctuations (Paper V). In the GaNAsP quantum dots, however, we suggest that the main mechanism for the light- and heavy-hole splitting is local fluctuations in the P/As ratio (Paper VI).

Using time correlation single-photon counting, we show that the quantum dots in these dilute nitride nanowires behave as single photon emitters (Paper VI), confirming the three-dimensional quantum confinement of the emitters. Finally, since the quantum dots are formed by fluctuations mainly in the conduction band, only electrons are preferentially captured in the 0D confinement potential, whereas holes are expected to be mainly localized through the Coulomb interaction once an electron is captured by the quantum dot. In Paper VII, we investigate this rather peculiar capture mechanism, which we show to lead to unipolar, negative charging of the quantum dot. Moreover, we demonstrate that carrier capture by some quantum dots is strongly affected by the presence of defects in their local surroundings, which further alters the charge state of the quantum dot, where formation of the negatively charged exciton is promoted at the expense of its neutral counterpart. This underlines that the local surroundings of the quantum dots may greatly affect their properties and illustrates a possible way to exploit the defects for charge engineering of the quantum dots.

In summary, in this thesis work, we identify several important non-radiative recombination processes in dilute nitride nanowires that can undermine the potential of these novel nanostructures for future optoelectronic applications. The gained knowledge could be found useful for designing strategies to mitigate these harmful processes, thereby improving the efficiency of future light-emitting and photovoltaic devices based on these nanowires. Furthermore, we uncover a set of optically bright quantum dot single-photon emitters embedded in the dilute nitride nanowires, and reveal their unusual electronic structure with strikingly different confinement potentials between electrons and holes. Our findings open a new pathway for charge engineering of the quantum dots in nanowires, attractive for applications in e.g. quantum computation and optical switching.