Sophia Buhbut

Built-in Quantum Dot Antennas in Dye-Sensitized Solar Cells

A new design of dye-sensitized solar cells involves colloidal semiconductor quantum dots that serve as antennas, funneling absorbed light to the charge separating dye molecules via nonradiative energy transfer. The colloidal quantum dot donors are incorporated into the solid titania electrode resulting in high energy transfer efficiency and significant improvement of the cell stability. This design practically separates the processes of light absorption and charge carrier injection, enabling us to optimize each of these separately. Incident photon-to-current efficiency measurements show a full coverage of the visible spectrum despite the use of a red absorbing dye, limited only by the efficiency of charge injection from the dye to the titania electrode. Time resolved luminescence measurements clearly relate this to Forster resonance energy transfer from the quantum dots to the dye. The presented design introduces new degrees of freedom in the utilization of quantum dot sensitizers for photovoltaic cells. In particular, it opens the way toward the utilization of new materials whose band offsets do not allow direct charge injection.

Quantum rod-sensitized solar cell: nanocrystal shape effect on the photovoltaic properties.

The effect of the shape of nanocrystal sensitizers in photoelectrochemical cells is reported. CdSe quantum rods of different dimensions were effectively deposited rapidly by electrophoresis onto mesoporous TiO(2) electrodes and compared with quantum dots. Photovoltaic efficiency values of up to 2.7% were measured for the QRSSC, notably high values for TiO(2) solar cells with ex situ synthesized nanoparticle sensitizers. The quantum rod-based solar cells exhibit a red shift of the electron injection onset and charge recombination is significantly suppressed compared to dot sensitizers. The improved photoelectrochemical characteristics of the quantum rods over the dots as sensitizers is assigned to the elongated shape, allowing the build-up of a dipole moment along the rod that leads to a downward shift of the TiO(2) energy bands relative to the quantum rods, leading to improved charge injection.

Design Rules for High-Efficiency Quantum-Dot-Sensitized Solar Cells: A Multilayer Approach

The effect of multilayer sensitization in quantum-dot (QD)-sensitized solar cells is reported. A series of electrodes, consisting of multilayer CdSe QDs were assembled on a compact TiO2 layer. Photocurrent measurements along with internal quantum efficiency calculation reveal similar electron collection efficiency up to a 100 nm thickness of the QD layers. Moreover, the optical density and the internal quantum efficiency measurements reveal that the desired surface area of the TiO2 electrode should be increased only by a factor of 17 compared with a compact electrode. We show that the sensitization of low-surface-area TiO2 electrode with QD layers increases the performance of the solar cell, resulting in 3.86% efficiency. These results demonstrate a conceptual difference between the QD-sensitized solar cell and the dye-based system in which dye multilayer decreases the cell performance. The utilization of multilayer QDs opens new opportunities for a significant improvement of quantum-dot-sensitized solar cells via innovative cell design.

Photo-Induced Dipoles: A New Method to Convert Photons into Photovoltage in Quantum Dot Sensitized Solar Cells

A high photovoltage is an essential ingredient for the construction of a high-efficiency quantum dot sensitized solar cell (QDSSC). In this paper we present a novel configuration of QDSSC which incorporates the photoinduced dipole (PID) phenomenon for improved open circuit voltage (Voc). This configuration, unlike previously studied ones with molecular dipoles, is based on a dipole moment which is created only under illumination and is a result of exciton dissociation. The generation of photodipoles was achieved by the creation of long-lived trapped holes inside a core of type-II ZnSe/CdS colloidal core/shell QDs, which are placed on top of the standard CdS QD sensitizer layer. Upon photoexcitation, the created photodipole negatively shifts the TiO2 energy bands, resulting in a photovoltage that is higher by ∼100 mV compared to the standard cell, without type-II QDs. The extra photovoltage gained diminishes the excessive overpotential losses caused by the energetic difference between the CdS sensitizer layer and the TiO2, without harming the charge injection processes. Moreover, we show that the extent of the additional photovoltage is controlled by the illumination intensity. This work provides new understanding regarding the operation mechanisms of photoelectrochemical cells, while presenting a new strategy for constructing a high-voltage QDSSCs. In addition, the PID effect has the potential to be implemented in other promising photovoltaic technologies.

Photophysics of Voltage Increase by Photoinduced Dipole Layers in Sensitized Solar Cells.

Significant overpotentials between the sensitizer and both the electron and hole conductors hamper the performance of sensitized solar cells, leading to a reduced photovoltage. We show that by using properly designed type-II quantum dots (QDs) between the sensitizer and the hole conductor in thin absorber cells, it is possible to increase the open circuit voltage (Voc) by more than 100 mV. This increase is due to the formation of a photoinduced dipole (PID) layer. Photogenerated holes in the type-II QDs are retained in the core for a relatively long time, allowing for the accumulation of a positively charged layer. Negative charges are, in turn, injected and accumulated in the TiO2 anode, creating a dipole moment, which negatively shifts the TiO2 conduction band relative to the electrolyte. We study this phenomenon using a unique TiO2/CdSe/(ZnSe:Te/CdS)/polysulfide system, where the formation of a PID depends on the color of the illumination. The PID concept thus introduces a new design strategy, where the operating parameters of the solar cell can be manipulated separately.

Controlling dye aggregation, injection energetics and catalytic recombination in organic sensitizer based dye cells using a single electrolyte additive

Organic dyes have been used extensively in recent years as sensitizers for Dye Sensitized Solar Cells (DSSCs) due to their high molar extinction coefficients, straightforward synthetic routes and readily available synthetic precursors. Though widely used, these dyes have some drawbacks, such as a tendency to aggregate and to catalyze electron recombination, thereby compromising both photovoltage and photocurrent. To circumvent the above-mentioned shortcomings of organic dyes, we adopt a novel strategy based on the addition of substituted benzene co-solvents to the electrolyte. This approach has several advantageous features which enhance cell performance: first, the substituted benzene molecules penetrate the dye layer to form stable complexes, thereby screening the excited state quenching and increasing the charge separation efficiency in the cell. Second, the benzene additive inhibits the catalytic recombination processes between electrons in TiO2 and the oxidized electrolyte, which increases the device Voc. Finally, despite not being adsorbed to the surface, the benzene derivatives shift the TiO2 conduction band positively, which improves the Jsc. SQ-1 sensitized DSSCs obtained using this strategy show a Jsc of 10.7 mA cm−2, a Voc of 657 mV and a total efficiency of 4.7% which is the best efficiency reported so far for such dyes in DSSCs.