Phenanthrene-Fused-Quinoxaline as a Key Building Block for Highly Efficient and Stable Sensitizers in Copper-Electrolyte-Based Dye-Sensitized Solar Cells

Dye-sensitized solar cells (DSSCs) based on Cu-II/I bipyridyl or phenanthroline complexes as redox shuttles have achieved very high open-circuit voltages (V-OC, more than 1 V). However, their short-circuit photocurrent density (J(SC)) has remained modest. Increasing the J(SC) is expected to extend the spectral response of sensitizers to the red or NIR region while maintaining efficient electron injection in the mesoscopic TiO2 film and fast regeneration by the Cu-I complex. Herein, we report two new D-A-pi-A-featured sensitizers termed HY63 and HY64, which employ benzothiadiazole (BT) or phenanthrene-fused-quinoxaline (PFQ), respectively, as the auxiliary electron-withdrawing acceptor moiety. Despite their very similar energy levels and absorption onsets, HY64-based DSSCs outperform their HY63 counterparts, achieving a power conversion efficiency (PCE) of 12.5 %. PFQ is superior to BT in reducing charge recombination resulting in the near-quantitative collection of photogenerated charge carriers.

Formate as Anti-Oxidation Additives for Pb-Free FASnI(3) Perovskite Solar Cells

Jaeki Jeong, Jinhyun Kim, Jiyoun Seo

Pb-free Sn-based perovskite solar cells (PSCs) have significant potential for application in photovoltaic devices because oftheir suitable bandgap, low exciton binding energy, high carrier mobility, and long diffusion length. However, their performance is hampered by several issues. Sn-based perovskites are highly susceptible to oxidation, which induces a high concentration of defects and degrades the chemical stability of the perovskite crystals. Herein, the anion formate (HCOO-) can effectively suppress the oxidation of Sn in the pure formamidinium tin triiodide (FASnI(3)) perovskite without using A-site cationic additives. Moreover, the presence of formate results in a uniform pinhole-free perovskite film with a low trap density, reduced charge carrier recombination, and improved charge extraction. Density functional theory calculations show that formate-treated FASnI(3) has improved stability against oxidative Sn degradation. The formate-treated PSC achieves a power conversion efficiency of 12.11% at a high open-circuit voltage of 0.71 V. The device exhibits improved stability in ambient air in which it maintained over 80% of its initial power conversion efficiency after 180 min because oxidation is inhibited owing to the strong interaction between Sn and formate.

WILEY-V C H VERLAG GMBH2022

Linear and Time-Resolved THz Spectroscopy of Photonic and Charge Transporting Systems

Jan Cornelius Brauer

Photo-induced charge separation and charge transport are fundamental processes in many energy conversion techniques, where light is converted into chemical energy (PEC), into electrical energy (solar cells) or in the opposite sense if electrical energy is converted into light (LEDs). In all cited examples, charge carriers have either to be transported towards an interface where they can undergo radiative recombination, trigger a chemical reaction, or they have to be evacuated from the interface as free charge carriers to be able to perform work in an external electrical circuit. In this work the charge generation dynamics and transport is studied using THz time domain spectroscopy and complimentary techniques on systems finding application in dye sensitized solar cells and PEC cells for water splitting. The functioning of a dye sensitized solar cell is based on the kinetic competition between several reactions, i.e. electron injection, dye-regeneration, electron back- reaction and charge extraction. Accordingly the rates of all of these reactions have to be optimized in order to optimize the cell performance. This requires a good understanding of the underlying mechanism of these processes. In photochemical cells, the encountered processes are in a way similar. After initial excitation, the generated charges have to be separated and have to reach either the interface to the electrolyte or the external circuit before being annihilated by recombining. Knowing the diffusion length and carrier lifetime in a specific material might therefore be helpful to optimize the film morphology, i. e. the aspect ratio. Chapter 1 gives an overview over the functioning of DSCs and PEC cells and summarizes some theoretical aspects of the processes encountered in these devices. Chapter 2 is devoted to the description of the experimental tools used and built in this work. In chapter 3, charge transport in a liquid molecular hole conductor, 10- methylphenoxazine, is investigated. The transport is rationalized using a model taking into account ionic diffusion and intermolecular hole transfer, i. e. hopping. It is found that the conduction occurs principally by hopping, as the HTM cation seems to be mainly present in an ion-paired form with the anion from the doping agent. Hopping of charge requires molecular vibration to bring acceptor and donor molecule in electronic resonance. Two vibrational modes of the HTM cation and neutral molecules that might be coupled to charge transport are observed. In chapter 4, electron injection from a dye into the conduction band of TiO2 films is investigated by monitoring the appearance of the free electron. This signal is compared to the signal arising from direct UV excitation of the TiO2. In addition to previous studies done in the group, the effect of dye aggregation leading to decelerated electron injection is investigated. Comparing the THz signal amplitude to the injected charge carrier concentration, the THz mobility in TiO2 films was found to be 0.1-0.15 cm2V-1s-1 and constant over the investigated charge carrier concentrations. Furthermore the influence of sintering temperature of the TiO2 film has been addressed in a preliminary study. In chapter 5, the influence of liquid electrolytes, of a solid state hole conducting material and of the commonly used additives Li+ and tBP on the charge generation dynamics have been investigated. While in this work the presence of an electrolyte/HTM has not shown any influence on the electron injection dynamics, the generation of the free electron seems to be strongly dependent on the molecular surrounding. This discrepancy is discussed in terms of a coulombic bound electron- hole pair as an intermediate state in the electron injection dynamics. Chapter 6 contains a study on the charge carrier dynamics in cuprous oxide, being used as material for photoelectrochemical water splitting. The wavelength and fluence dependence on the charge carrier lifetime, mobility and diffusion length was studied. The strong dependence of the charge carrier lifetime is discussed in terms of trapping mediated recombination.

EPFL2012

Influence of nitrogen dopants on N-doped TiO2 electrodes and their applications in dye-sensitized solar cells

Wei Guo, Ulf Anders Hagfeldt

Three different types of nanocryst., N-doped TiO2 electrodes were synthesized using several nitrogen dopants through wet methods. The obtained nanocryst., N-doped TiO2 electrodes possessed different crystallite sizes, surface areas, and N-doping amts. Characterizations were performed to reveal the nitrogen-doping processes for the wet methods using ammonia, urea, and triethylamine as the nitrogen dopants. Addnl., a high conversion efficiency of 8.32% was achieved by the dye-sensitized solar cells, based on the N-doped TiO2 electrodes. For instance, in comparison with the com. P25 (5.76%) and pure anatase TiO2 electrodes (7.14%), significant improvements (44% and 17%, resp.) in the efficiencies were obtained. The findings also indicated that the ammonia nitrogen dopant was more efficient than other two nitrogen dopants. The electron transports, electron lifetimes, and charge recombination in the dye-sensitized N-doped TiO2 solar cells also differed from those in the pure TiO2-based dye-sensitized solar cells (DSCs). Specifically, an enhanced photocurrent of ∼36% in N-doped DSCs resulted from the synergistic effects of the high dye uptake and the efficient electron transport. Moreover, the relation between charge and voltage revealed that less charge was needed to get a high open-circuit voltage in the N-doping films.

2011

Linear and Time-Resolved THz Spectroscopy of Photonic and Charge Transporting Systems

Jan Cornelius Brauer

EPFL2012