Self-assembly and Mesocrystal Formation via Non-classical Crystallisation

New materials can be fabricated using small scaled building blocks as a repetition unit. Nanoparticles with their unique size-tuneable properties from quantum confinement can especially be utilised to form two- and three-dimensional ordered assemblies to introduce them into what would normally be considered to be incompatible matrices. Furthermore, new collective properties that derive from the ordered arrangement of the building blocks, are accomplished. Additionally, different materials can be combined by mixing different building blocks during self-assembly, so that size ranges and material combinations that are difficult to achieve by other means can be formed. The arrangement of small particles into highly ordered arrangements can be realised via self-assembly. To achieve such assemblies, highly monodisperse nanoparticular building blocks with a size distribution below 5 % have to be synthesised. The production and variation in the size of both lead chalcogenide and noble metal nanoparticles is presented in this work. Moreover, the syntheses of multicomponential nanoparticles (PbSe/PbS and Au/PbS) are investigated. Non-classical crystallisation methodologies with their varyious self-assembly mechanisms are used for the formation of highly symmetrical mesocrystals and supracrystals. Analogous to classical crystallisation methods and their formation processes the interparticle interactions, attractive as well as repulsive, determine the resulting crystalline structure. Variation of the environmental parameters consequently leads to structural variation due to the changing interparticle interactions. In contrast to classical crystallisation the length scale of the interparticle forces stays constant as the size dimension of the self-assembled building unit is changed. Two different non-classical crystallisation pathways are investigated in this work. One pathway focuses on the slow destabilisation of nanoparticles in organic media by the addition of a non-solvent. In this approach optimisation of parameters for the formation of highly symmetrical three-dimensional mesostructures are studied. Furthermore, to shine some light onto the mechanism of self-assembly, the intrinsic arrangement of the building units in a mesocrystal and the steps of non-solvent addition are analysed. The mechanistic investigations explain the differences observed in mesocrystal formation between metal and semiconductor nanoparticles. The lower homogeneity of the building units of the metal nanoparticles leads to smaller and less defined superstructures in comparison to semiconductor building blocks. Another pathway of non-classical crystallisation is the usage of electrostatic interactions as the driving force for self-assembly and supracrystal formation. Therefore, the building blocks are transferred into aqueous media and stabilised with oppositely charged ligands. The well-know procedure for metal nanoparticles was adapted for semiconductor materials. The lower stability of these nanoparticles in aqueous solution induces an agglomeration of the semiconductor nanoparticles without including oppositely charged metal nanoparticles. The destabilisation effect can be increased by the addition of equally charged metal nanoparticles in a salting out type process. In comparison to the slow formation of mesocrystals achieved via destabilisation in an organic media (up to 4 weeks), the salting out procedure takes place within two hours, but the faster agglomeration causes a less well defined assembly of the building units in the mesocrystals. Moreover, the arrangement of semiconductor nanoparticles with organic molecules such as polymers and proteins was investigated in order to use the nanoparticles as a light harvesting component. In combination with the directly bound polymer the charge carrier may be directly transferred to the conductive thiophene-based polymer, so that infrared light can be transformed into an electrical signal for use in further applications such as solar cells. The advantage of the nanoparticle-protein system is the self-assembly across a liquid-liquid interface and additionally a Förster resonance energy transfer can occur at this phase boundary. Hence, it is possible to transfer highly energetic photons directly to biological samples without destroying the biological material