Suppressing recombination in perovskite solar cells via surface engineering of TiO2 ETL

Hybrid perovskite solar cells (PSCs) have gained significant attention owing to their excellent physicochemical and photovoltaic properties. PSCs typically consist of a perovskite light absorber sandwiched between two carrier selective layers optimized with respect to optimal band alignment and low interfacial recombination. The quality of the perovskite layer and interfaces play major roles in the fabrication of high-performance PSCs. In the present work, we systematically investigate the planar structure PSCs based on TiO2 and TiO2/ZnO electron transport layers (ETLs), which provide deeper insight into the charge recombination and accumulation mechanisms. We show that the double-layer structure of TiO2/ZnO ETL improves the optical and morphology properties of perovskite film leading to superior device performance. From the ideality factor, EIS and IMVS results, a suppressed recombination in TiO2/ZnO PSCs is achieved, which is due to improved grain size of perovskite absorber layer grown on ZnO nanocrystals (NCs). Additionally, we find that the ZnO NCs improve the shunt resistance and quality of the perovskite and suppress the recombination. The present study provides a novel strategy to improve the device performance of PSCs along with a detail investigation procedure to understand the physical mechanism.

A Material Approach to Dye-Sensitized Solar Cells

Philippe Pierre Labouchère

With growing concerns on future energy supplies, solar energy appears as an energy source whose potential remains to be tapped at a large scale. In the last two decades, dye-sensitized solar cells (DSCs) have been considered as a competitive means to convert solar energy into electricity thanks to their low manufacturing and environmental costs, simple fabrication and high efficiency. Indeed, record efficiencies as high as 13% have been obtained for liquid DSCs and recently, solid-state DSCs using solid hole transport materials as well as perovskite materials as sensitizers have showed efficiencies above 17%. From a physical point of view, charge carrier generation in a DSC takes place in a photoactive light harvester chemisorbed on a mesoscopic semiconductor oxide. Due to the excellent electronic overlap, the exciton separation occurs by the injection of the excited electrons and holes from the dye into the conduction band of the semiconductor and redox electrolyte, respectively. A high surface area mesoscopic photoanode is necessary to ensure a high-density bulk heterojunction and efficient light harvesting in the visible part of the solar spectrum due to effective dye loading. This implies that the DSC has a large, heterogeneous interface through which photogenerated electrons may be intercepted as a result of the slow electron transport. The latter is governed by an ambipolar diffusion mechanism controlled by trap-limited hopping through a long path to the transparent conductive electrode. It is however hindered by the low electron mobility in anatase TiO2 nanoparticles and the multiple grain boundaries in the mesoporous film. The work conducted during this thesis aimed at developing new architectures for the electrodes of DSCs using notably atomic layer deposition (ALD) and inverse opal host-guest structures with different semiconducting metal oxides. First, using a self-assembled polymeric template and ALD, we fabricated a porous ZnO inverse opal backbone. Advantages are numerous: a high electronic mobility of ZnO, a precise control of the metal oxide deposition using ALD and in situ growth of ZnO nanowires at low temperatures. Besides increasing the surface area available for photoactive dye molecules, single-crystal nanowires offer a defect-free path for photoinjected electrons. However, because of the relative instability of ZnO in acidic environments, a TiO2 overlayer was deposited by ALD. This proved to increase the recombination resistance of photogenerated electrons and increased their lifetime in the porous film. This host-guest approach was further transposed to three related fields in photo-electrochemistry using different ALD precursors. For water splitting, a niobium-doped tin oxide inverse opal backbone was constructed, which served as a host for hematite deposited by atmospheric pressure chemical vapour deposition or ALD. In the field of plasmonics, a TiO2 inverse opal host was made to act as a scaffold for silver nanoparticles. For solid-state DSCs, we strived to achieve an ultra-thin ZnO inverse opal, which acted as a host for perovskite crystals. Finally, we studied the effect of very thin TiO2 and ZnO overlayers deposited by ALD on top of mesoporous ZnO and TiO2, respectively. We were able to accurately monitor the thickness of overlayers and study the effects on photovoltaic parameters such as transport and recombination rates of photogenerated electrons, photocurrent, photovoltage, fill factor and efficiency.

EPFL2014

Light Harvesting and Charge Recombination in CH3NH3PbI3 Perovskite Solar Cells Studied by Hole Transport Layer Thickness Variation

Mohammad Ibrahim Dar, Michael Graetzel, Robin Humphry-Baker, Nevena Vaskova Marinova, Mohammad Khaja Nazeeruddin, Wolfgang Richard Tress, Shaik Mohammed Zakeeruddin

A tailored optimization of perovskite solar cells requires a detailed understanding of the processes limiting the device efficiency. Here, we study the role of the hole transport layer (HTL) spiro-MeOTAD and its thickness in a mesoscopic TiO2-based solar cell architecture. We find that a sufficiently thick (200 nm) HTL not only increases the charge carrier collection efficiency but also the light harvesting efficiency. This is due to an enhanced reflection of a smooth HTL/Au electrode interface. The rough CH3NH3PbI3 perovskite surface requires an HTL thickness of >400 nm to avoid surface recombination and guarantee a high-Open-circuit voltage. Analyses of the electroluminescence efficiency and the diode ideality factor show that the open-circuit voltage becomes completely limited by trap-assisted recombination in the perovskite for a thick HTL. Thus, spiro-MeOTAD is a very good HTL choice from the device physics' point of view. The fill factor analyzed by the Suns-V-oc method is not transport limited, but trap-recombination limited as well. Consequently, a further optimization of the device has to focus on defects in the polycrystalline perovskite film.

American Chemical Society2015

A Material Approach to Dye-Sensitized Solar Cells

Philippe Pierre Labouchère

EPFL2014