Hybrid solar cells with tert-butylthiol exchanged CdSe multipod acceptors and novel semi-random P3HTT-DPP and alternating PCDTBT copolymer donors were studied, giving high performance devices with power conversion efficiencies >3%.

Degenerately doped metal-oxide nanocrystals (NCs) show localized surface plasmon resonances (LSPRs) that are tunable via their tunable excess charge-carrier densities. Modulation of excess charge carriers has also been used to control magnetism in colloidal doped metal-oxide NCs. The addition of excess delocalized conduction-band (CB) electrons can be achieved through aliovalent doping or by postsynthetic techniques such as electrochemistry or photodoping. Here, we examine the influence of charge-compensating aliovalent dopants on the potentials of excess CB electrons in freestanding colloidal degenerately doped oxide NCs, both experimentally and through modeling. Taking Sn 4+ :In 2 O 3 (ITO) NCs as a model system, we use spectroelectrochemical techniques to examine differences between aliovalent doping and photodoping. We demonstrate that whereas photodoping introduces excess CB electrons by raising the Fermi level relative to the CB edge, aliovalent impurity substitution introduces excess CB electrons by stabilizing the CB edge relative to an externally defined Fermi level. Significant differences are thus observed electrochemically between spectroscopically similar delocalized CB electrons compensated by aliovalent dopants and those compensated by surface cations (e.g., protons) during photodoping. Theoretical modeling illustrates the very different potentials that arise from charge compensation via aliovalent substitution and surface charge compensation. Spectroelectrochemical titrations allow the ITO NC band-edge stabilization as a function of Sn 4+ doping to be quantified. Extremely large capacitances are observed in both In 2 O 3 and ITO NCs, making these NCs attractive for reversible charge-storage applications.

We present a spectroscopic study of colloidal PbSe quantum dots (QDs) that have been photodoped to introduce excess delocalized conduction-band (CB) electrons. High-quality absorption spectra are obtained for these degenerately doped QDs with excess electron concentrations up to ∼10 cm. At the highest doping levels, electrons have completely filled the 1S orbitals of the CB and partially populated the higher-energy 1P orbitals. Spectroscopic changes observed as a function of carrier concentration permit an unambiguous assignment of the second excitonic absorption maximum to 1P-1P transitions. At intermediate doping levels, a clear absorption feature appears between the first two excitonic maxima that is attributable to parity-forbidden 1S-1P excitations, which become observable because of electrostatic symmetry breaking. Redshifts of the main excitonic absorption features with increased carrier concentration are also analyzed. The Coulomb stabilization energies of both the 1S-1S and 1P-1P excitons in n-doped PbSe QDs are remarkably similar to those observed for multiexcitons with the same electron count. The origins of these redshifts are discussed.

Leveraging recent advances in electron energy monochromation and aberration correction, we record the spatially resolved infrared plasmon spectrum of individual tin-doped indium oxide nanocrystals using electron energy-loss spectroscopy (EELS). Both surface and bulk plasmon responses are measured as a function of tin doping concentration from 1−10 atomic percent. These results are compared to theoretical models, which elucidate the spectral detuning of the same surface plasmon resonance feature when measured from aloof and penetrating probe geometries. We additionally demonstrate a unique approach to retrieving the fundamental dielectric parameters of individual semiconductor nanocrystals via EELS. This method, devoid from ensemble averaging, illustrates the potential for electron-beam ellipsometry measurements on materials that cannot be prepared in bulk form or as thin films.

Carrier-doped semiconductor nanocrystals (NCs) offer strong plasmonic responses at frequencies beyond those accessible by conventional plasmonic nanoparticles. Like their noble metal analogues, these emerging materials can harness free space radiation and confine it to the nanoscale but at resonance frequencies that are natively infrared and spectrally tunable by carrier concentration. In this work we combine monochromated STEM-EELS and theoretical modeling to investigate the capability of colloidal indium tin oxide (ITO) NC pairs to form hybridized plasmon modes, providing an additional route to influence the IR plasmon spectrum. These results demonstrate that ITO NCs may have greater coupling strength than expected, emphasizing their potential for near-field enhancement and resonant energy transfer in the IR region.