We report ultra-efficient multiple exciton generation (MEG) for single photon absorption in colloidal PbSe and PbS quantum dots (QDs). We employ transient absorption spectroscopy and present measurement data acquired for both intraband as well as interband probe energies. Quantum yields of 300% indicate the creation, on average, of three excitons per absorbed photon for PbSe QDs at photon energies that are four times the QD energy gap. Results indicate that the threshold photon energy for MEG in QDs is twice the lowest exciton absorption energy. We find that the biexciton effect, which shifts the transition energy for absorption of a second photon, influences the early time transient absorption data and may contribute to a modulation observed when probing near the lowest interband transition. We present experimental and theoretical values of the size-dependent interband transition energies for PbSe QDs. We present experimental and theoretical values of the size-dependent interband transition energies for PbSe QDs, and we also introduce a new model for MEG based on the coherent superposition of multiple excitonic states.

Multiple exciton generation (MEG) is a process whereby multiple electron-hole pairs, or excitons, are produced upon absorption of a single photon in semiconductor nanocrystals (NCs) and represents a promising route to increased solar conversion efficiencies in single-junction photovoltaic cells. We report for the first time MEG yields in colloidal Si NCs using ultrafast transient absorption spectroscopy. We find the threshold photon energy for MEG in 9.5 nm diameter Si NCs (effective band gap identical with Eg = 1.20 eV) to be 2.4 +/- 0.1Eg and find an exciton-production quantum yield of 2.6 +/- 0.2 excitons per absorbed photon at 3.4Eg. While MEG has been previously reported in direct-gap semiconductor NCs of PbSe, PbS, PbTe, CdSe, and InAs, this represents the first report of MEG within indirect-gap semiconductor NCs. Furthermore, MEG is found in relatively large Si NCs (diameter equal to about twice the Bohr radius) such that the confinement energy is not large enough to produce a large blue-shift of the band gap (only 80 meV), but the Coulomb interaction is sufficiently enhanced to produce efficient MEG. Our findings are of particular importance because Si dominates the photovoltaic solar cell industry, presents no problems regarding abundance and accessibility within the Earth's crust, and poses no significant environmental problems regarding toxicity.

We report an alternative synthesis and the first optical characterization of colloidal PbTe nanocrystals (NCs). We have synthesized spherical PbTe NCs having a size distribution as low as 7%, ranging in diameter from 2.6 to 8.3 nm, with first exciton transitions tuned from 1009 to 2054 nm. The syntheses of colloidal cubic-like PbSe and PbTe NCs using a PbO "one-pot" approach are also reported. The photoluminescence quantum yield of PbTe spherical NCs was measured to be as high as 52 +/- 2%. We also report the first known observation of efficient multiple exciton generation (MEG) from single photons absorbed in PbTe NCs. Finally, we report calculated longitudinal and transverse Bohr radii for PbS, PbSe, and PbTe NCs to account for electronic band anisotropy. This is followed by a comparison of the differences in the electronic band structure and optical properties of these lead salts.

We report nanocrystalline TiO2 solar cells sensitized with InAs quantum dots. InAs quantum dots of different sizes were synthesized and incorporated in solar cell devices. Efficient charge transfer from InAs quantum dots to TiO2 particles was achieved without deliberate modification of the quantum dot capping layer. A power conversion efficiency of about 1.7% under 5 mW/cm2 was achieved; this is relatively high for a nanocrystalline metal oxide solar cell sensitized with presynthesized quantum dots, but this efficiency could only be achieved at low light intensity. At one sun, the efficiency decreased to 0.3%. The devices are stable for at least weeks under room light in air.

Lithium‐rich manganese‐based layered oxides show great potential as high‐capacity cathode materials for lithium ion batteries, but usually exhibit a poor cycle life, gradual voltage drop during cycling, and low thermal stability in the highly delithiated state. Herein, a strategy to promote the electrochemical performance of this material by manipulating the electronic structure through incorporation of boracic polyanions is developed. As‐prepared Li[Li0.2Ni0.13Co0.13Mn0.54](BO4)0.015(BO3)0.005O1.925 shows a decreased M‐O covalency and a lowered O 2p band top compared with pristine Li[Li0.2Ni0.13Co0.13Mn0.54]O2. As a result, the modified cathode exhibits a superior reversible capacity of 300 mA h g−1 after 80 cycles, excellent cycling stability with a capacity retention of 89% within 300 cycles, higher thermal stability, and enhanced redox couple potentials. The improvements are correlated to the enhanced oxygen stability that originates from the tuned electronic structure. This facile strategy may further be extended to other high capacity electrode systems.

We report the absorption cross-section of colloidal InAs quantum dots of mean radii from 1.6 to 3.45 nm. We find excellent agreement between the measured results and calculated values based on a model of small-particle light absorption. The absorption cross-section per dot is 6.2 x 10(-16)R(3) cm(2) at 2.76 eV and 3.15 x 10(-16)R(1.28) cm(2) at the first-exciton absorption peak, with the dot radius R in nm. We find that the per-quantum-dot particle oscillator strength of the first-exciton transition is constant for all sizes studied. The radiative lifetime of the first exciton calculated from the oscillator strength increases with dot size and ranges from 4 ns for the smallest dots to 14 ns for the largest ones.

Femtosecond transient absorption spectroscopy has been used together with time-integrated photoluminescence (PL) measurements to study charge carrier relaxation in colloidal InP quantum dots (QDs). Measurements of band-edge photoinduced bleaching as well as PL intensity measurements indicate that the fraction of charge carriers relaxing to the band-edge states depends on excitation wavelength, with a markedly reduced relaxation efficiency observed for excitation well above the absorption edge. The results concur with previous research on CdSe and InP QDs, and suggest that with increasing excitation energy there arise relaxation pathways involving surface or external energy states exhibiting reduced radiative efficiency. Such highly excited carriers are either inhibited or deviated from reaching the band-edge states. Excitation intensity dependent measurements indicate that those charge carriers which contribute to the band-edge absorption bleaching also contribute proportionally to the time-integrated PL spectrum.

Pt is a classical catalyst that has been extensively used in fuel cell and solar cell electrodes, owing to its high catalytic activity, good conductivity, and stability. In conventional fiber-shaped solar cells, solid Pt wires are usually adopted as the electrode material. Here, we report a Pt nanoparticle-adsorbed carbon nanotube yarn made by solution adsorption and yarn spinning processes, with uniformly dispersed Pt nanoparticles through the porous nanotube network. We have fabricated TiO(2)-based dye-sensitized fiber solar cells with a Pt-nanotube hybrid yarn as counter electrode and achieved a power conversion efficiency of 4.85% under standard illumination (AM1.5, 100 mW/cm(2)), comparable to the same type of fiber cells with a Pt wire electrode (4.23%). Adsorption of Pt nanoparticles within a porous nanotube yarn results in enhanced Pt-electrolyte interfacial area and significantly reduced charge-transfer resistance across the electrolyte interface, compared to a pure nanotube yarn or Pt wire. Our porous Pt-nanotube hybrid yarns have the potential to reduce the use of noble metals, lower the device weight, and improve the solar cell efficiency.