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We report on the effect of ligand exchange of copper sulphide selenide aswell as copper selenide nanocrystals with the organic pi-system Cobaltbeta-tetraaminophthalocyanine and analyse changes in the structural, optical aswell as electric properties of thin films of these hybrid materials. A strongligand interaction with the surface of the nanocrystals is revealed by UV-visabsorption and Raman spectroscopy. Grazing-incidence small-angle X-rayscattering studies show a significant contraction in the interparticle distanceupon ligand exchange. For copper-deficient copper selenide, this contractionhas a negligible effect on electric transport, while for copper-deficientcopper sulphide selenide, the conductivity increases by eight orders ofmagnitude and results in metal-like temperature-dependent transport. We discussthese differences in the light of varying contributions of electronic vs. ionictransport in the two materials and highlight their effect on the stability ofthe transport properties under ambient conditions. With photocurrentmeasurements, we demonstrate high optical responsivities of 200-400 A W-1 forthe phthalocyanine-capped copper sulphide selenide and emphasize the beneficialrole of the organic pi-system in this respect, which acts as an electroniclinker and an optical sensitizer at the same time.

Dye-Sensitized Ternary Copper Chalcogenide Nanocrystals: Optoelectronic Properties, Air Stability and Photosensitivity