Charge separation in contact systems with CdSe quantum dot layers

Abstract: Quantum dot (QD) solar cells are a fast developing area in the field of solution processed photovoltaics. Central aspects for the application of QDs in solar cells are separation and transport of charge carriers in the QD layers and the formation of charge selective contacts. Even though efficiencies of up to 7% were reached in QD solar cells, these processes are not yet fully understood. In this thesis the mechanisms of charge separation, transport and recombination in CdSe QD layers and layer systems were studied. Charge separation was measured via surface photovoltage (SPV) at CdSe QD layers with thicknesses in the range of monolayers. To determine the influence of interparticle distance of QDs and trap states on the surface of QDs on charge separation, QDs with four different surfactant layers were studied. Layers of CdSe QDs were prepared on ITO, Si, SiO2 and CdS by dip coating under inert atmosphere. The layers were characterized by Rutherford backscattering spectrometry, UV-vis spectroscopy, step profilometry and scanning electron microscopy to determine the areal density, the absorption and thickness of CdSe QD monolayers.


SPV measurements show that initial charge separation from the CdSe QDs on ITO only happened from the first monolayer of QDs. Electrons, photo-excited in the first monolayer of CdSe QDs, were trapped on the ITO surface. The remaining free holes were trapped in surface states and/or diffused into the neighboring QD layers. The thick surfactant layer (1.6 nm) of pristine QDs had to be reduced by washing and/or ligand exchange for separation of photo-excited charge carriers. Both, interparticle distance and trap density, influenced the processes of charge separation and recombination. SPV
transients of CdSe monolayers could be described by a single QD approximation model, based on Miller-Abrahams hopping of holes between the delocalized excitonic state, traps on the surface of the QD and the filled trap on the ITO surface (recombination). The values of QD-ITO distance and trap density, determined with the simulation were consistent with transmission electron microscopy and photoluminescence measurements. The separation and diffusion of charge carriers was limited due to trapping of charge carriers. Smaller interparticle distances led to faster decays in CdSe QD monolayers. However the increase of traps, which resulted in a slower decay dominated and led to longer decay times of SPV transients of modified CdSe QD layers. By deposition of CdSe QDs on CdS a heterojunction was created. The CdS layer served as acceptor for electrons excited in CdSe QDs. Furthermore a CdSe QD/CdTe nanoparticle heterojunction was realized by successive electrophoretic deposition. CdSe QDs acted as electron acceptors, whereas CdTe nanoparticles acted as electron donors. Charge separation was dominated by the CdSe QD/CdTe nanoparticle interphase, as inverted layer stacking of CdSe QDs and CdTe nanoparticles gave an inverted SPV signal.


Autor: Zillner, Elisabeth Franziska
Erstellt am25.03.2013
PhDthesis.pdf 

Freie Universität Berlin