Aqueous-phase linker-assisted attachment of cysteinate(2-)-capped cdse quantum dots to TiO2 for quantum dot-sensitized solar cells.

We have synthesized water-dispersible cysteinate(2-)-capped CdSe nanocrystals and attached them to TiO2 using one-step linker-assisted assembly. Room-temperature syntheses yielded CdSe magic-sized clusters (MSCs) exhibiting a narrow and intense first excitonic absorption band centered at 422 nm. Syntheses at 80 °C yielded regular CdSe quantum dots (RQDs) with broader and red-shifted first excitonic absorption bands. Cysteinate(2-)-capped CdSe MSCs and RQDs adsorbed to bare nanocrystalline TiO2 films from aqueous dispersions. CdSe-functionalized TiO2 films were incorporated into working electrodes of quantum dot-sensitized solar cells (QDSSCs). Short-circuit photocurrent action spectra of QDSSCs corresponded closely to absorptance spectra of CdSe-functionalized TiO2 films. Power-conversion efficiencies were (0.43±0.04)% for MSC-functionalized TiO2 and (0.83±0.11)% for RQD-functionalized TiO2. Absorbed photon-to-current efficiencies under white-light illumination were approximately 0.3 for both MSC- and RQD-based QDSSCs, despite the significant differences in the electronic properties of MSCs and RQDs. Cysteinate(2-) is an attractive capping group and ligand, as it engenders water-dispersibility of CdSe nanocrystals with a range of photophysical properties, enables facile all-aqueous linker-assisted attachment of nanocrystals to TiO2, and promotes efficient interfacial charge transfer.

Attachment of CdSe nanoparticles to TiO2 via aqueous linker-assisted assembly: influence of molecular linkers on electronic properties and interfacial electron transfer.

CdSe nanoparticles (NPs) capped with cysteinate (Cys), 3-mercaptopropionate (MP), and mercaptosuccinate (MS) were adsorbed to TiO(2) from basic aqueous dispersions. Native capping groups served as molecular linkers to TiO(2). Thus, the materials-assembly chemistry was simplified and made more reproducible and environmentally benign. The electronic properties of CdSe and the electron-transfer reactivity at CdSe-linker-TiO(2) interfaces varied with the structure and functionality of the capping groups. Cys-capped CdSe NPs exhibited a narrow and intense first excitonic absorption band centered at 422 nm, suggesting that they were magic-sized nanocrystals (MSCs) with diameters less than 2 nm. MP- and MS-capped CdSe NPs had broader and lower-energy absorption bands, which are typical of regular quantum dots. Photocurrent action spectra of nanocrystalline TiO(2) films functionalized with Cys-CdSe, MP-CdSe, and MS-CdSe overlaid closely with absorption spectra, indicating that excitation of CdSe gave rise to the injection of electrons into TiO(2). Under white-light illumination, the global energy-conversion efficiency for Cys-capped CdSe ((0.45 ± 0.11)%) was 1.2-to-6-fold greater than for MP- and MS-capped CdSe. Similarly, the absorbed photon-to-current efficiency was 1.3-to-3.3-fold greater. These differences arose from linker-dependent variations of electron-injection and charge-recombination reactivity. Transient absorption measurements indicated that electron injection from Cys-capped CdSe was more efficient than from MS-capped CdSe. In addition, charge recombination at CdSe-MS-TiO(2) interfaces was complete within hundreds of nanoseconds, whereas the charge-separated-state lifetime at CdSe-Cys-TiO(2) interfaces was on the order of several microseconds. Thus, Cys-capped CdSe MSCs are readily attached to TiO(2) and exhibit unusual electronic properties and desirable electron-transfer reactivity.

Influence of solvation and the structure of adsorbates on the kinetics and mechanism of dimerization-induced compositional changes of mixed monolayers on TiO(2).

Mixed monolayers of thiol-terminated (T) and methyl-terminated (Me) carboxylic acids on nanocrystalline TiO(2) films underwent dimerization-induced compositional changes. At short reaction times, the compositions of mixed monolayers were kinetically controlled and mirrored the compositions of coadsorption solutions. On time scales up to several hours, well after the establishment of saturation surface coverages, the monolayers relaxed to thermodynamically controlled compositions through the displacement of Me by T. Equilibration was driven by the formation of intermolecular disulfide bonds between thiol groups of adsorbed T, which yielded polydentate dimeric adsorbates that were bound more strongly than monomeric adsorbates to TiO(2). The rate of compositional changes increased with decreasing solvent viscosity and decreasing alkyl chain length of T, suggesting that the rate of adsorption of T to TiO(2) strongly influenced the overall kinetics under certain conditions. Steric bulk within adsorbates and the strength of surface-attachment interactions also influenced the rate of compositional changes. A kinetic model, derived on the basis of Langmuir adsorption and desorption kinetics, accounts for key aspects of the mixed-monolayer compositional changes. The rate-determining step in the overall mechanism involved either the adsorption of T or the formation of disulfide bonds, depending on the conditions under which monolayers were prepared. Our findings illustrate that dimerization and other intermolecular interactions between adsorbates may dramatically influence the composition and terminal functionalization of mixed monolayers.