Nanoparticle sensitisation of solid-state nanocrystalline solar cell

Over the past fifteen years dye-sensitised nanocrystalline solar cells have been the subject of intense research and development efforts. These systems provide a technically and economically credible alternative to classical p-n junction solar cells, reaching over 10 % certified efficiency under standard solar illumination conditions (AM 1.5, 1000 W/m2). Recently, the liquid electrolyte, commonly used in these dye-sensitised solar cells, could successfully be replaced by a novel solid hole-conducting material (spiro-OMeTAD). The absence of volatile solvents and corrosive components like iodine presents a clear advantage of these solid-state devices over their photoelectrochemical counterparts. Yet, their maximum overall efficiency of about 3 % clearly lacks behind the performance features of classical dye-sensitized solar cells. The objective of this work is the replacement of the usually used sensitiser (transition metal complexes and organic dyes) by quantum-dots. It was motivated by the possibility to achieve panchromatic light absorption due to the size-dependent properties of the quantum-dots. Some studies have been published using quantum-dots of inorganic low-bandgap semiconductors as sensitisers for mesoporous wide bandgap semiconductor electrodes in conjunction with liquid electrolytes. These systems often suffer from corrosion and photo-corrosion mainly due to the aggressive nature of the electrolyte employed. Solid-state organic-inorganic heterojunctions might provide the desired environment for quantum-dot sensitisation, as the environment is much less aggressive. A large variety of inorganic quantum-dot materials like PbS, CdS, PbSe and CdSe were scrutinized for their use as sensitisers. All particles were synthesised in situ on the TiO2 surface using two different techniques: dip-coating and chemical bath deposition. Lead sulphide was the most investigated due to its superior photovoltaic characteristics. High Resolution Transmission Electron Microscopy (HRTEM) of PbS sensitised TiO2 electrodes fabricated via dip-coating clearly showed the distinct particles on the surface of the semiconductor. The electron transfer dynamics following optical excitation of quantum-dot sensitized TiO2/spiro-OMeTAD heterojunctions were thoroughly studied. Fluorescence spectroscopy was used to prove the possible electron injection from the PbS into the TiO2. Nanosecond laser spectroscopy was applied to monitor the interfacial recombination of the injected electron and the oxidised hole-conductor. Femtosecond laser spectroscopy allowed measuring the ultra-fast kinetics in the system, including electron trapping, exciton recombination and PbS regeneration. An overall efficiency of 0.5 % at 0.1 sun (AM 1.5) has been reached with such systems. Chemical bath deposition (CBD) of PbS leads to the formation of a layer rather than distinct particles on the TiO2. Solar cells fabricated via CBD exhibited open-circuit voltages which were generally 100 mV higher then those of comparable devices made via dip-coating. The PbS layer acts as blocking layer, hindering the contact between TiO2 and the hole-conductor. This technique allowed achieving devices highly linear with respect to the illumination power. Different strategies were pursued to impede interfacial recombination, among which the introduction of self-assembled monolayers at the interface between the organic and inorganic phases was proven to be the most efficient. Nanosecond laser spectroscopy showed a strong decrease of the interfacial recombination kinetic rates in the presence of hexadecylmalonic acid or decylphosphonic acid monolayers. Short-circuit currents could be raised by a factor two to four using such type of molecules. The overall efficiency of the device could be strongly increased, reaching 1 % at 0.1 Sun (AM 1.5). CBD was also used to deposit PbSe and CdSe layers at the surface of TiO2. Fluorescence spectroscopy was used to probe electron injection from CdSe quantum dots to TiO2. Generally it was observed that metal sulfides were more efficient in sensitizing TiO2/OMeTAD heterojunctions then the respective selenides.

Grätzel, Michael
Lausanne, EPFL
Other identifiers:
urn: urn:nbn:ch:bel-epfl-thesis3017-8

 Record created 2005-03-16, last modified 2018-03-17

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