Controlling the morphology of nanoparticle-polymer composite films for potential use in solar cells

  • Rhys Rhodes

Student thesis: Phd


This thesis presents an investigation into the factors affecting the morphology of hybrid inorganic / organic photoactive layers used in photovoltaic cells. Although optimisation of the organic (polymer) phase has received substantial attention, research into the morphology of the inorganic phase (semiconducting nanocrystals) remains limited. It is believed that there is a strong link between the morphology of the final photoactive film and the quality of the initial nanocrystal dispersion. To this end, two nanocrystal systems were investigated; zinc oxide (ZnO) and lead sulphide (PbS). ZnO nanocrystals were synthesised and found to possess reproducible characteristics. It was determined that colloid stability was initially dependent upon the presence of acetate groups bound to the surface, which in turn required a small quantity of methanol to be present in the organic dispersant. It was also discovered that while methanol evaporated readily from the surface of the nanocrystals, another molecule, 1-propylamine (1-PA), did not. Further investigations showed that while methanol only weakly physisorbed to the surface of ZnO nanocrystals, 1-PA formed strong, dative covalent bonds with Zn2+, preventing evaporation despite a low boiling point. Subsequent investigations into the effects of different ligands upon colloid stability found that amine-based groups typically possessed superior stabilising capabilities compared to alcohol-based analogues. The characteristics of nanocrystal / polymer blends were also investigated. It was determined that the nanocrystal dispersion became unstable at higher concentrations of polymer due to depletion aggregation. Films of nanocrystal / polymer blends were cast from dispersions containing either alcohol or amine-based ligands, and it was observed that dispersions stabilised with 1-PA possessed smooth morphologies on the micrometer scale. Investigations at the nanometer scale, however, revealed aggregates large enough to favour recombination.The latter half of this thesis regards the characterisation of PbS nanocrystals and investigations into triggered aggregation. It was determined that while PbS nanocrystals possessed reproducible characteristics, the stabilising molecule, oleic acid (OA) was insulating. The effects of exchanging the OA groups for a shorter ligand, butylamine (BA) were investigated.Finally, PbS nanocrystals were treated with a bidentate ligand, 1,2-ethanedithiol (EDT) to induce triggered aggregation. It was observed that the system was highly sensitive to the concentration of EDT in dispersion, forming small, relatively dispersed aggregates at low [EDT], and micrometer-sized crystalline structures at high [EDT]. The characterisation and entrapment of these nanocrystal structures within semi-conducting polymer films is also discussed.
Date of Award1 Aug 2012
Original languageEnglish
Awarding Institution
  • The University of Manchester
SupervisorBrian Saunders (Supervisor)


  • Semi-conducting polymers
  • Triggered aggregation
  • Hybrid solar cells
  • Colloid science
  • Morphology
  • Photovoltaic cells
  • Nanocrystals
  • Colloid dispersions
  • Zinc oxide
  • Lead sulphide

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