739 publications from this institution
Structural transformations in CdSe nanocrystals are studied using high pressure x-ray diffraction and high pressure optical absorption at room temperature. The nanocrystals undergo a wurtzite to rock salt transition analogous to that observed in bulk CdSe. Both the thermodynamics and the kinetics of the transformation, however, are significantly different in finite size. The nanocrystal phase transition pressures vary from 3.6 to 4.9 GPa for crystallites ranging from 21 to 10 Å in radius, respectively, in comparison to a value of 2.0 GPa for bulk CdSe. The size dependent data can be modeled using thermodynamics when surface energies are accounted for. Surface energies calculated in this way can be used to understand the dynamic microscopic path followed by atoms during the phase transition. X-ray diffraction data also shows that unlike bulk CdSe, crystalline domain size is conserved upon multiple transition in the nanocrystals, indicating that the transition only nucleates once in each nanocrystal.
Silicon nanoparticles have the promise to surpass the theoretical efficiency limit of single-junction silicon photovoltaics by the creation of a "phonon bottleneck,"a theorized slowing of the cooling rate of hot optical phonons that in turn reduces the cooling rate of hot carriers in the material. Verifying the presence of a phonon bottleneck in silicon nanoparticles requires simultaneous resolution of electronic and structural changes at short timescales. Here, extreme ultraviolet transient absorption spectroscopy is used to observe the excited-state electronic and lattice dynamics in polycrystalline silicon nanoparticles following 800 nm photoexcitation, which excites carriers with 0.35 ± 0.03 eV excess energy above the Δ1 conduction band minimum. The nanoparticles have nominal 100 nm diameters with crystalline grain sizes of about ∼16 nm. The extracted carrier?phonon and phonon?phonon relaxation times of the nanoparticles are compared to those for a silicon (100) single-crystal thin film at similar carrier densities (2 × 1019 cm?3for the nanoparticles and 6 × 1019 cm?3for the film). The measured carrier? phonon and phonon?phonon scattering lifetimes for the polycrystalline nanoparticles are 870 ± 40 fs and 17.5 ± 0.3 ps, respectively, versus 195 ± 20 fs and 8.1 ± 0.2 ps, respectively, for the silicon thin film. The reduced scattering rates observed in the nanoparticles are consistent with the phonon bottleneck hypothesis.
