Tobias Hanrath

In spite of recent doubts carrier multiplication does occur in PbSe nanocrystals.

Efficient carrier multiplication has been reported for several semiconductor nanocrystals: PbSe, PbS, PbTe, CdSe, InAs, and Si. Some of these reports have been challenged by studies claiming that carrier multiplication does not occur in CdSe, CdTe, and InAs nanocrystals, thus raising legitimate doubts concerning the occurrence of carrier multiplication in the remaining materials. Here, conclusive evidence is given for its occurrence in PbSe nanocrystals using femtosecond transient photobleaching. In addition, it is shown that a correct determination of carrier-multiplication efficiency requires spectral integration over the photobleach feature. The carrier multiplication efficiency we obtain is significantly lower than what has been reported previously, and it remains an open question whether it is higher in nanocrystals than it is in bulk semiconductors.

Thermally Induced Structural Evolution and Performance of Mesoporous Block Copolymer-Directed Alumina Perovskite Solar Cells

Structure control in solution-processed hybrid perovskites is crucial to design and fabricate highly efficient solar cells. Here, we utilize in situ grazing incidence wide-angle X-ray scattering and scanning electron microscopy to investigate the structural evolution and film morphologies of methylammonium lead tri-iodide/chloride (CH3NH3PbI3–xClx) in mesoporous block copolymer derived alumina superstructures during thermal annealing. We show the CH3NH3PbI3–xClx material evolution to be characterized by three distinct structures: a crystalline precursor structure not described previously, a 3D perovskite structure, and a mixture of compounds resulting from degradation. Finally, we demonstrate how understanding the processing parameters provides the foundation needed for optimal perovskite film morphology and coverage, leading to enhanced block copolymer-directed perovskite solar cell performance.

SnSe Nanocrystals: Synthesis, Structure, Optical Properties, and Surface Chemistry

The colloidal synthesis of SnSe nanoparticles is accomplished through the injection of bis[bis(trimethylsilyl)amino]tin(II) into hot trioctylphosphine:selenium in the presence of oleylamine. Through the manipulation of reaction temperature particles are grown with the average diameter reliably tuned to 4-10 nm. Quantum confinement is examined by establishing a relationship between particle size and band gap while the in depth growth dynamics are illuminated through UV-vis-NIR spectroscopy. Surface chemistry effects are explored, including the demonstration of useful ligand exchanges and the development of routes toward anisotropic particle growth. Finally, transient current-voltage properties of SnSe nanocrystal films in the dark and light are examined.

Photogenerated Exciton Dissociation in Highly Coupled Lead Salt Nanocrystal Assemblies

Internanocrystal coupling induced excitons dissociation in lead salt nanocrystal assemblies is investigated. By combining transient photoluminescence spectroscopy, grazing incidence small-angle X-ray scattering, and time-resolved electric force microscopy, we show that excitons can dissociate, without the aid of an external bias or chemical potential gradient, via tunneling through a potential barrier when the coupling energy is comparable to the exciton binding energy. Our results have important implications for the design of nanocrystal-based optoelectronic devices.

Predicting Nanocrystal Shape through Consideration of Surface-Ligand Interactions

Density functional calculations for the binding energy of oleic acid-based ligands on Pb-rich {100} and {111} facets of PbSe nanocrystals determine the surface energies as a function of ligand coverage. Oleic acid is expected to bind to the nanocrystal surface in the form of lead oleate. The Wulff construction predicts the thermodynamic equilibrium shape of the PbSe nanocrystals. The equilibrium shape is a function of the ligand surface coverage, which can be controlled by changing the concentration of oleic acid during synthesis. The different binding energy of the ligand on the {100} and {111} facets results in different equilibrium ligand coverages on the facets, and a transition in the equilibrium shape from octahedral to cubic is predicted when increasing the ligand concentration during synthesis.

Controlling Nanocrystal Superlattice Symmetry and Shape-Anisotropic Interactions through Variable Ligand Surface Coverage

The assembly of colloidal nanocrystals (NCs) into superstructures with long-range translational and orientational order is sensitive to the molecular interactions between ligands bound to the NC surface. We illustrate how ligand coverage on colloidal PbS NCs can be exploited as a tunable parameter to direct the self-assembly of superlattices with predefined symmetry. We show that PbS NCs with dense ligand coverage assemble into face-centered cubic (fcc) superlattices whereas NCs with sparse ligand coverage assemble into body-centered cubic (bcc) superlattices which also exhibit orientational ordering of NCs in their lattice sites. Surface chemistry characterization combined with density functional theory calculations suggest that the loss of ligands occurs preferentially on {100} than on reconstructed {111} NC facets. The resulting anisotropic ligand distribution amplifies the role of NC shape in the assembly and leads to the formation of superlattices with translational and orientational order.

Solution-processed nanocrystal quantum dot tandem solar cells.

J.J.C., W.N.W., and R.S.H. contributed equally to this work. This work was supported in part by Award No. KUS-C1-018-02, made by King Abdullah University of Science and Technology (KAUST). J.J.C. acknowledges support from the NSF IGERT fellowship. W.N.W. and R.S.H. acknowledge support from undergraduate research fellowships from the Cornell Engineering Learning Initiative and the KAUST-CU center. Y.F.L. acknowledges fellowship from Agency of Science, Technology and Research (A*STAR), Singapore. J.L.L. and J.A.M. acknowledge support from the U.S. National Science Foundation through grants DMR-1006633 and DMR-0706508. J.J. acknowledges funding through the Flexible Electronics Theme of the CSIRO Future Manufacturing Flagship, aCSIRO Office of Chief Executive Postdoctoral Fellowship and the Australian Department of Innovation, Industry, Science and Research, International Science Linkage Grant, CG100059. The authors thank Prof. Rene A. J. Janssen and David Moore for a critical reading of the manuscript and useful discussions.

Shape-anisotropy driven symmetry transformations in nanocrystal superlattice polymorphs.

Despite intense research efforts by research groups worldwide, the potential of self-assembled nanocrystal superlattices (NCSLs) has not been realized due to an incomplete understanding of the fundamental molecular interactions governing the self-assembly process. Because NCSLs reside naturally at length-scales between atomic crystals and colloidal assemblies, synthetic control over the properties of constituent nanocrystal (NC) building blocks and their coupling in ordered assemblies is expected to yield a new class of materials with remarkable optical, electronic, and vibrational characteristics. Progress toward the formation of suitable test structures and subsequent development of NCSL-based technologies has been held back by the limited control over superlattice spacing and symmetry. Here we show that NCSL symmetry can be controlled by manipulating molecular interactions between ligands bound to the NC surface and the surrounding solvent. Specifically, we demonstrate solvent vapor-mediated NCSL symmetry transformations that are driven by the orientational ordering of NCs within the lattice. The assembly of various superlattice polymorphs, including face-centered cubic (fcc), body-centered cubic (bcc), and body-centered tetragonal (bct) structures, is studied in real time using in situ grazing incidence small-angle X-ray scattering (GISAXS) under controlled solvent vapor exposure. This approach provides quantitative insights into the molecular level physics that controls solvent-ligand interactions and assembly of NCSLs. Computer simulations based on all-atom molecular dynamics techniques confirm several key insights gained from experiment.

Confined-but-connected quantum solids via controlled ligand displacement.

Confined-but-connected quantum dot solids (QDS) combine the advantages of tunable, quantum-confined energy levels with efficient charge transport through enhanced electronic interdot coupling. We report the fabrication of QDS by treating self-assembled films of colloidal PbSe quantum dots with polar nonsolvents. Treatment with dimethylformamide balances the rates of self-assembly and ligand displacement to yield confined-but-connected QDS structures with cubic ordering and quasi-epitaxial interdot connections through facets of neighboring dots. The QDS structure was analyzed by a combination of transmission electron microscopy and wide-angle and small-angle X-ray scattering. Excitonic absorption signatures in optical spectroscopy confirm that quantum confinement is preserved. Transport measurements show significantly enhanced conductivity in treated films.

Charge transport and localization in atomically coherent quantum dot solids

Epitaxial attachment of quantum dots into ordered superlattices enables the synthesis of quasi-two-dimensional materials that theoretically exhibit features such as Dirac cones and topological states, and have major potential for unprecedented optoelectronic devices. Initial studies found that disorder in these structures causes localization of electrons within a few lattice constants, and highlight the critical need for precise structural characterization and systematic assessment of the effects of disorder on transport. Here we fabricated superlattices with the quantum dots registered to within a single atomic bond length (limited by the polydispersity of the quantum dot building blocks), but missing a fraction (20%) of the epitaxial connections. Calculations of the electronic structure including the measured disorder account for the electron localization inferred from transport measurements. The calculations also show that improvement of the epitaxial connections will lead to completely delocalized electrons and may enable the observation of the remarkable properties predicted for these materials.