Alexey Y. Koposov

CdSe Quantum-Dot-Sensitized Solar Cell with ∼100% Internal Quantum Efficiency

We have constructed and studied photoelectrochemical solar cells (PECs) consisting of a photoanode prepared by direct deposition of independently synthesized CdSe nanocrystal quantum dots (NQDs) onto a nanocrystalline TiO(2) film (NQD/TiO(2)), aqueous Na(2)S or Li(2)S electrolyte, and a Pt counter electrode. We show that light harvesting efficiency (LHE) of the NQD/TiO(2) photoanode is significantly enhanced when the NQD surface passivation is changed from tri-n-octylphosphine oxide (TOPO) to 4-butylamine (BA). In the PEC the use of NQDs with a shorter passivating ligand, BA, leads to a significant enhancement in both the electron injection efficiency at the NQD/TiO(2) interface and charge collection efficiency at the NQD/electrolyte interface, with the latter attributed mostly to a more efficient diffusion of the electrolyte through the pores of the photoanode. We show that by utilizing BA-capped NQDs and aqueous Li(2)S as an electrolyte, it is possible to achieve ∼100% internal quantum efficiency of photon-to-electron conversion, matching the performance of dye-sensitized solar cells.

Heavily doped n-type PbSe and PbS nanocrystals using ground-state charge transfer from cobaltocene

Colloidal nanocrystals (NCs) of lead chalcogenides are a promising class of tunable infrared materials for applications in devices such as photodetectors and solar cells. Such devices typically employ electronic materials in which charge carrier concentrations are manipulated through “doping;” however, persistent electronic doping of these NCs remains a challenge. Here, we demonstrate that heavily doped n-type PbSe and PbS NCs can be realized utilizing ground-state electron transfer from cobaltocene. This allows injecting up to eight electrons per NC into the band-edge state and maintaining the doping level for at least a month at room temperature. Doping is confirmed by inter- and intra-band optical absorption, as well as by carrier dynamics. Finally, FET measurements of doped NC films and the demonstration of a p-n diode provide additional evidence that the developed doping procedure allows for persistent incorporation of electrons into the quantum-confined NC states.

Role of solvent-oxygen ion pairs in photooxidation of CdSe nanocrystal quantum dots

Understanding the mechanisms for photodegradation of nanocrystal quantum dots is an important step toward their application in real-world technologies. A usual assumption is that photochemical modifications in nanocrystals, such as their photooxidation, are triggered by absorption of a photon in the dot itself. Here, we demonstrate that, contrary to this commonly accepted picture, nanocrystal oxidation can be initiated by photoexcitation of solvent-oxygen ion pairs that relax to produce singlet oxygen, which then reacts with the nanocrystals. We make this conclusion on the basis of photolysis studies of solutions of CdSe nanocrystals. Our measurements indicate a sharp spectral onset for photooxidation, which depends on solvent identity and is 4.8 eV for hexane and 3.4 eV for toluene. Importantly, the photooxidation onset correlates with the position of a new optical absorption feature, which develops in a neat solvent upon its exposure to oxygen. This provides direct evidence that nanocrystal photooxidation is mediated by excitation of solvent-oxygen pairs and suggests that the stability of the nanocrystals is defined by not only the properties of their surfaces (as has been commonly believed) but also the properties of their environment, that is, of the surrounding solvent or matrix.

Quantum dot sensitized solar cell

Photoelectrochemical solar cells (PECs) have been constructed and studied, the cells comprising a photoanode prepared by direct deposition of independently synthesized nanocrystal quantum dots (NQDs) onto a nanocrystalline metal oxide film, aqueous electrolyte and a counter electrode. It has been shown that the light harvesting efficiency (LHE) of the NQD/metal oxide photoanode is significantly enhanced when the NQD surface passivation is changed to a smaller ligand (e.g. butylamine (BA)). In the PEC the use of NQDs with a shorter passivating ligand leads to a significant enhancement in both the electron injection efficiency at the NQD/metal oxide interface and charge collection efficiency at the NQD/electrolyte interface.

Effect of organic passivation on photoinduced electron transfer across the quantum dot/TiO2 interface

We report a study of the internal quantum efficiency (IQE) of CdSe quantum-dot (QD)-sensitized solar cells prepared by direct adsorption of pre-synthesized QDs, passivated with either tri-n-octylphosphine oxide (TOPO) or n-butylamine (BA), onto a nanocrystalline TiO(2) film.