Wave function engineering for ultrafast charge separation and slow charge recombination in type II core/shell quantum dots.

Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.
Journal of the American Chemical Society (Impact Factor: 11.44). 06/2011; 133(22):8762-71. DOI: 10.1021/ja202752s
Source: PubMed

ABSTRACT The size dependence of optical and electronic properties of semiconductor quantum dots (QDs) have been extensively studied in various applications ranging from solar energy conversion to biological imaging. Core/shell QDs allow further tuning of these properties by controlling the spatial distributions of the conduction-band electron and valence-band hole wave functions through the choice of the core/shell materials and their size/thickness. It is possible to engineer type II core/shell QDs, such as CdTe/CdSe, in which the lowest energy conduction-band electron is largely localized in the shell while the lowest energy valence-band hole is localized in the core. This spatial distribution enables ultrafast electron transfer to the surface-adsorbed electron acceptors due to enhanced electron density on the shell materials, while simultaneously retarding the charge recombination process because the shell acts as a tunneling barrier for the core localized hole. Using ultrafast transient absorption spectroscopy, we show that in CdTe/CdSe-anthraquinone (AQ) complexes, after the initial ultrafast (~770 fs) intra-QD electron transfer from the CdTe core to the CdSe shell, the shell-localized electron is transferred to the adsorbed AQ with a half-life of 2.7 ps. The subsequent charge recombination from the reduced acceptor, AQ(-), to the hole in the CdTe core has a half-life of 92 ns. Compared to CdSe-AQ complexes, the type II band alignment in CdTe/CdSe QDs maintains similar ultrafast charge separation while retarding the charge recombination by 100-fold. This unique ultrafast charge separation and slow recombination property, coupled with longer single and multiple exciton lifetimes in type II QDs, suggests that they are ideal light-harvesting materials for solar energy conversion.

  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Even though previously reported CdTe/CdSe type-II core/shell QD sensitizers possess intrinsic superior optoelectronic properties (such as wide absorption range, fast charge separation, and slow charge recombination) in serving as light absorbers, the efficiency of the resultant solar cell is still limited by the relatively low photovoltage. To further enhance photovoltage and cell efficiency accordingly, ZnTe/CdSe type-II core/shell QDs with much larger conduction band (CB) offset in comparison with that of CdTe/CdSe (1.22 eV vs 0.27 eV) are adopted as sensitizers in the construction of quantum dot sensitized solar cells (QDSCs). The augment of band offset produces an increase of the charge accumulation across the QD/TiO2 interface under illumination and induces stronger dipole effects, therefore bringing forward an upward shift of the TiO2 CB edge after sensitization and resulting in enhancement of the photovoltage of the resultant cell devices. The variation of relative chemical capacitance, Cμ, between ZnTe/CdSe and reference CdTe/CdSe cells extracted from impedance spectroscopy (IS) characterization under dark and illumination conditions clearly demonstrates that, under light irradiation conditions, the sensitization of ZnTe/CdSe QDs upshifts the CB edge of TiO2 by the level of ∼50 mV related to that in the reference cell and results in the enhancement of Voc of the corresponding cell devices. In addition, charge extraction measurements have also confirmed the photovoltage enhancement in the ZnTe/CdSe cell related to reference CdTe/CdSe cell. Furthermore, transient grating (TG) measurements have revealed a faster electron injection rate for the ZnTe/CdSe-based QDSCs in comparison with the CdSe cells. The resultant ZnTe/CdSe QD-based QDSCs exhibit a champion power conversion efficiency of 7.17% and a certified efficiency of 6.82% under AM 1.5G full one sun illumination, which is, as far as we know, one of the highest efficiencies for liquid-junction QDSCs.
    ACS Nano 01/2015; · 12.03 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: The absorption of photons through the direct generation of spatially separated excitons at dot-ligand interfaces is proposed as a promising strategy for tailoring the optical gap of small silicon quantum dots independent of their size. This removes a primary drawback for the use of very small dots in broad range of applications. For instance, the strategy can be applied to solar energy technologies to align the absorption of such dots with the peak of the solar spectrum. The key is to establish both a Type-II energy level alignment and a strong electronic coupling between the dot and ligand. Our first principles analysis indicates that connecting conjugated organic ligands to silicon quantum dots using vinyl connectivity can satisfy both requirements. For a prototype assembly of 2.6 nm dots, we predict that triphenylamine termination will result in a 0.47 eV redshift along with an enhanced near-edge absorption character. Robustness analyses of the influence of oxidation on absorption and of extra alkyl ligands reveal that the control of both factors is important in practical applications.
    Physical Chemistry Chemical Physics 08/2014; · 4.20 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Femtosecond time-resolved absorption and picosecond time-resolved emission studies have been carried out to study the indirect type exciton of CdS/ZnSe core/shell quantum dots (QDs). The CdS/ZnSe core/shell QD samples are synthesized with increasing thickness of ZnSe shell on CdS core QDs. In these CdS/ZnSe core/shell samples, a new energy band lower than the energy gap of both the CdS core and ZnSe shell has been observed and attributed to indirect bandgap transitions from the valence band of the ZnSe shell to the conduction band of the CdS core. The transient PL studies have revealed that the indirect type exciton, e(CdS)/h(ZnSe) due to photoexcitation of this low-energy band, endures less carrier trapping than selective excitation of the CdS core and charge transfer in the staggered photoexcited state. Femtosecond transient absorption studies have revealed that carrier trapping is as fast as 100 fs and interfacial charge recombination slows down with increasing ZnSe shell thickness on the CdS QD in CdS/ZnSe core/shell QDs.
    The Journal of Physical Chemistry C 05/2013; 117(21):10901–10908. · 4.84 Impact Factor


Available from