Optimization of band structure and quantum-size-effect tuning for two-photon absorption enhancement in quantum dots.

The two-photon absorption, 2PA, cross sections of PbS quantum dots, QDs, are theoretically and experimentally investigated and are shown to be enhanced with increasing quantum confinement. This is in contrast to our previous results for CdSe and CdTe QDs where the reduced density of states dominated and resulted in a decrease in 2PA with a decrease in QD size. Qualitatively this trend can be understood by the highly symmetric distribution of conduction and valence band states in PbS that results in an accumulation of allowed 2PA transitions in certain spectral regions. We also measure the frequency nondegenerate 2PA cross sections that are up to five times larger than for the degenerate case. We use a k·p four-band envelope function formalism to model the increasing trend of the two-photon cross sections due to quantum confinement and also due to resonance enhancement in the nondegenerate case.

Role of symmetry breaking on the optical transitions in lead-salt quantum dots.

The influence of quantum confinement on the one- and two-photon absorption spectra (1PA and 2PA) of PbS and PbSe semiconductor quantum dots (QDs) is investigated. The results show 2PA peaks at energies where only 1PA transitions are predicted and 1PA peaks where only 2PA transitions are predicted by the often used isotropic k x p four-band envelope function formalism. The first experimentally identified two-photon absorption peak coincides with the energy of the first one photon allowed transition. This first two-photon peak cannot be explained by band anisotropy, verifying that the inversion symmetry of the wave functions is broken and relaxation of the parity selection rules has to be taken into account to explain optical transitions in lead-salt QDs. Thus, while the band anisotropy of the bulk semiconductor plays a role in the absorption spectra, especially for the more anisotropic PbSe QDs, a complete model of the absorption spectra, for both 1PA and 2PA, must also include symmetry breaking of the quantum confined wave functions. These studies clarify the controversy of the origin of spectral features in lead-salt QDs.

Colloidal quantum-dot photodetectors exploiting multiexciton generation.

Multiexciton generation (MEG) has been indirectly observed in colloidal quantum dots, both in solution and the solid state, but has not yet been shown to enhance photocurrent in an optoelectronic device. Here, we report a class of solution-processed photoconductive detectors, sensitive in the ultraviolet, visible, and the infrared, in which the internal gain is dramatically enhanced for photon energies Ephoton greater than 2.7 times the quantum-confined bandgap Ebandgap. Three thin-film devices with different quantum-confined bandgaps (set by the size of their constituent lead sulfide nanoparticles) show enhancement determined by the bandgap-normalized photon energy, Ephoton/Ebandgap, which is a clear signature of MEG. The findings point to a valuable role for MEG in enhancing the photocurrent in a solid-state optoelectronic device. We compare the conditions on carrier excitation, recombination, and transport for photoconductive versus photovoltaic devices to benefit from MEG.

Highly luminescent lead sulfide nanocrystals in organic solvents and water through ligand exchange with poly(acrylic acid).

Hydrophobic lead sulfide quantum dots (PbS/OA) synthesized in the presence of oleic acid were transferred from nonpolar organic solvents to polar solvents such as alcohols and water by a simple ligand exchange with poly(acrylic acid) (PAA). Ligand exchange took place rapidly at room temperature When a colloidal solution of PbS/OA in tetrahydrofuran (THF) was treated with excess PAA, the PbS/PAA nanocrystals that formed were insoluble in hexane and toluene but could be dissolved in methanol or water, where they formed colloidal solutions that were stable for months. Ligand exchange was accompanied by a small blue shift in the band-edge absorption, consistent with a small reduction in particle size. While there was a decrease in quantum yield associated with ligand exchange and transfer to polar solvents, as is commonly found for colloidal quantum dots, the quantum yields determined were impressively high: PbS/OA in toluene (82%) and in THF (58%); PbS/PAA in THF (42%) and in water (24%). The quantum yields for the PbS/PAA solutions decreased over time as the solutions were allowed to age in the presence of air.

Megahertz-frequency large-area optical modulators at 1.55 microm based on solution-cast colloidal quantum dots.

We report the realization of large-area, communications-wavelength electro-optic modulators made via simple solution-casting onto an arbitrary substrate. The devices employ colloidal quantum dots synthesized in, and processed from, the solution phase. Devices exhibit greater than 30% modulation depth at the 1.55 microm eye-safe wavelengths of interest in free-space optical communications. The devices retain considerable modulation depth beyond 1 MHz.

Carrier relaxation dynamics in lead sulfide colloidal quantum dots.

We report transient absorption saturation measurements on lead sulfide colloidal nanocrystals at the first and second exciton energies and fit the results to a model incorporating intraband and interband relaxation processes. We study in detail the Auger recombination from the first excited state, which takes place when more than one electron-hole pair is excited in a dot. We find an Auger coefficient of 4.5 x 10(-30) cm6/s for dots of 5.5 nm diameter, and observe saturation of the absorption bleaching when the (8-fold degenerate) first level is filled. We develop a model for the absorption dynamics using Poisson statistics and find a good fit with our experimental measurements.

Nucleotide-directed growth of semiconductor nanocrystals.

We engineer colloidal quantum dot nanocrystals through the choice of biomolecular ligands responsible for nanoparticle nucleation, growth, stabilization, and passivation. We systematically vary the presence of, and thereby elucidate the role of, phosphate groups and a multiplicity of functionalities on the mononucleotides used as ligands. The results provide the basis for synthesis of nanoparticles using precisely controlled synthetic oligonucleotide sequences.

Synthesis and optical properties of thiol-stabilized PbS nanocrystals.

Thiol-capped water-soluble PbS nanocrystals (NCs) stabilized with 1-thioglycerol, dithioglycerol, or a mixture of 1-thioglycerol/dithioglycerol (TGL/DTG) were prepared via one-stage synthesis at room temperature. We found that NCs stabilized with a TGL/DTG mixture show efficient and stable infrared photoluminescence centered in the second "biological window" (1050-1200 nm). Under optimized conditions, full width at half-maximum of the PL emission peak was from 70 to 100 nm. PbS NCs were stable to precipitation and aggregation for the time period from 2 to 3 months when stored in the dark under room temperature. Room-temperature photoluminescence quantum efficiency of NCs was from 7 to 10%. When NCs were stored at 37 degrees C, their PL emission red-shifted, consistent with the NC growth.