Publications

Charge hopping and percolation in quantum dot (QD) solids has been widely studied, but the microscopic nature of the percolation process is not understood or determined. Here we present the first imaging of the charge percolation pathways in two-dimensional PbS QD arrays using Kelvin probe force microscopy (KPFM). We show that under dark conditions electrons percolate via in-gap states (IGS) instead of the conduction band, while holes percolate via valence band states. This novel transport behavior is explained by the electronic structure and energy level alignment of the individual QDs, which was measured by scanning tunneling spectroscopy (STS). Chemical treatments with hydrazine can remove the IGS, resulting in an intrinsic defect-free semiconductor, as revealed by STS and surface potential spectroscopy. The control over IGS can guide the design of novel electronic devices with impurity conduction, and photodiodes with controlled doping.

Abstract The use of a decal transfer lithography technique to fabricate elastomeric stamps with triangular cross‐sections, specifically triangular prisms and cones, is described. These stamps are used in demonstrations for several prototypical optical applications, including the fabrication of multiheight 3D photoresist patterns with near zero‐width features using near‐field phase shift lithography, fabrication of periodic porous polymer structures by maskless proximity field nanopatterning, embossing thin‐film antireflection coatings for improved device performance, and efficient fabrication of substrates for surface‐enhanced Raman spectroscopic sensing. The applications illustrate the utility of the triangular poly(dimethylsiloxane) decals for a wide variety of optics‐centric applications, particularly those that exploit the ability of the designed geometries and materials combinations to manipulate light–matter interactions in a predictable and controllable manner.

Significance Currently, the effect of branching of nanoparticles tens of nanometers in size on the mechanical properties of structural composites is not well understood due to the limited availability of branched nanoscale fillers. We report that branched nanofillers have the potential for optimization of nanocomposite Young’s modulus over their linear counterparts. Lattice spring model simulations reveal that the mechanism for this improvement involves the ability of branched nanoparticles to optimize the ratio of both filler and stiff interfacial bonds aligned with the tensile axis, as opposed to linear nanoparticles, which optimize only the filler bond orientation when parallel to the stretching axis. We believe this information could inform the design of nanocomposites with optimized mechanical properties for a variety of structural applications.

Extensive prior work has shown that colloidal inorganic nanocrystals coated with organic ligand shells can behave as artificial atoms and, as such, form superlattices with different crystal structures and packing densities. Although ordered superlattices present a high degree of long-range positional order, the relative crystallographic orientation of the inorganic nanocrystals with respect to each other tends to be random. Recent works have shown that superlattices can achieve orientational alignment through combinations of nanocrystal faceting and ligand modification, as well as selective metal particle attachment to particular facets. These studies have focused on the assembly of high-symmetry nanocrystals, such as cubes and cuboctahedra. Here, we study the assembly of elliptically faceted CdSe/CdS core/shell nanocrystals with one distinctive crystallographic orientation along the major elliptical axis. We show that the nanocrystals form an unexpectedly well-ordered translational superlattice, with a degree of order comparable to that achieved with higher-symmetry nanocrystals. Additionally, we show that, due to the particles' faceted shape, the superlattice is characterized by an orientational glass phase in which only certain orientations are possible due to entropically frustrated crystallization. In this phase, the nanocrystals do not exhibit a local orientational ordering but rather have distinct orientations that emerge at different locations within the same domain. The distinct orientations are a result of a facet-to-facet lock-in mechanism that occurs during the self-assembly process. These facet-to-facet alignments force the nanocrystals to tilt on different lattice planes forming different projections that we termed apparent polydispersity. Our experimental realization of an orientational glass phase for multifaceted semiconducting nanocrystals can be used to investigate how this phase is formed and how it can be utilized for potential optical, electrical, and thermal transport applications.

Colloidal superlattices are fascinating materials made of ordered nanocrystals, yet they are rarely called “atomically precise.” That is unsurprising, given how challenging it is to quantify the degree of structural order in these materials. However, once that order crosses a certain threshold, constructive interference of X-rays diffracted by the nanocrystals dominates the diffraction pattern, offering a wealth of structural information. By treating nanocrystals as scattering sources forming a self-probing interferometer, we developed a multilayer diffraction method that enabled the accurate determination of nanocrystal size, interparticle spacing, and their fluctuations for samples of self-assembled CsPbBr<sub>3</sub> and PbS nanomaterials. The average nanocrystal displacement of 0.32-1.4 Å in the studied superlattices provides a figure of merit for their structural perfection and approaches the atomic displacement parameters found in traditional crystals. The method requires a laboratory-grade diffractometer and an open-source fitting algorithm for data analysis, providing a competitive alternative to resource-intensive synchrotron experiments.

Colloidal superlattices are fascinating materials made of ordered nanocrystals, yet they are rarely called “atomically precise.” That is unsurprising, given how challenging it is to quantify the degree of structural order in these materials. However, once that order crosses a certain threshold, constructive interference of X-rays diffracted by the nanocrystals dominates the diffraction pattern, offering a wealth of structural information. By treating nanocrystals as scattering sources forming a self-probing interferometer, we developed a multilayer diffraction method that enabled the accurate determination of nanocrystal size, interparticle spacing, and their fluctuations for samples of self-assembled CsPbBr 3 and PbS nanomaterials. The average nanocrystal displacement of 0.32-1.4 Å in the studied superlattices provides a figure of merit for their structural perfection and approaches the atomic displacement parameters found in traditional crystals. The method requires a laboratory-grade diffractometer and an open-source fitting algorithm for data analysis, providing a competitive alternative to resource-intensive synchrotron experiments.

Transient absorption (TA) is widely used to study the dynamics of various processes, such as trapping, nonradiative decay, or transferring of photoexcited carriers in semiconductor nanocrystals. TA spectra of these systems show photoinduced absorption (PA) features that appear lower in energy than those of the band edge, which have been attributed to sub-bandgap absorptions of photoexcited electrons and holes. Here, we perform atomistic, semiempirical pseudopotential calculations in CdSe nanostructures to compute oscillator strengths for sub-bandgap transitions of conduction band electrons, valence band holes, and surface-trapped holes. We find that sharper peaks in the infrared (IR) range and broader features in the near-IR range (0.5–1.0 eV) are due to near-band-edge transitions of electrons and holes, respectively. Additionally, we focus on the region from 1.45 to 1.9 eV (850–650 nm), in which broad features have been observed and assigned to the PA of holes populating surface traps of nanocrystals. While there has been experimental justification of this assignment, there has been little theoretical investigation. We find that, in this region of interest from 1.45 to 1.9 eV, oscillator strengths for transitions of trapped holes are significantly larger than those of electrons or valence band holes. We conclude that the low symmetry of localized surface trap states and optimal spatial overlap with highly oscillatory states deep in the valence band lead to large electric dipole matrix elements and increased oscillator strengths. Our results are consistent for CdSe and CdS cores, CdSe–CdS core–shell quantum dots, and CdSe nanorods.

Mechanical and Electrical Properties of CdTe Tetrapods Studied by Atomic Force Microscopy Liang Fang 1 , Jeong Young Park 1 , Yi Cui 2 , Paul Alivisatos 2 , Joshua Shcrier 3 , Byounghak Lee 3 , Lin-Wang Wang 3 , and Miquel Salmeron 1 * Molecular Foundry, Materials Science Division, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, California 94720 Chemistry Department, University of California at Berkeley, Berkeley, California 94720 Computational Research Division, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, California 94720 *Author to whom correspondence should be addressed. Electronic mail: mbsalmeron@lbl.gov Abstract The mechanical and electrical properties of CdTe tetrapod-shaped nanocrystals have been studied with atomic force microscopy. Tapping mode images of tetrapods deposited on silicon wafers revealed that they contact the surface with the ends of three arms. The length of these arms was found to be 130 ± 10 nm. A large fraction of the tetrapods had a shortened vertical arm as a result of fracture during sample preparation. Fracture also occurs when the applied load is a few nanonewtons. Compression experiments with the AFM tip indicate that tetrapods with the shortened vertical arm deform elastically when the applied force was less than 50 nN. Above 90 nN additional fracture events occurred that further shorted the vertical arm. Loads above 130 nN produced irreversible damage to the other arms as well. Current-voltage characteristics of tetrapods deposited on gold indicated semiconducting behavior with a current gap of ~2 eV at low loads (<50 nN) and a narrowing to about 1 eV at loads between 60 and 110 nN. Atomic calculation of the deformation suggests that the ends of the tetrapod arms are stuck during compression so that the deformations are due to bending modes. The reduction of the current gap is due to electrostatic effects, rather than strain deformation effects inside the tetrapod.

We investigate the early stages of cesium lead bromide perovskite formation through absorption spectroscopy of stopped-flow reactions, high-throughput mapping, and direct synthesis and titration of potential precursor species. Calorimetric and spectroscopic measurements of lead bromide complex titrations combined with theoretical calculations suggest that bromide complexes with higher coordination numbers than previously considered for nonpolar systems can better explain observed behaviors. Synthesis mapping of binary lead halides reveals multiple lead bromide species with absorption peaks higher than 300 nm, including a previously observed species with a peak at 313 nm and two species with peaks at 345 and 370 nm that also appear as reaction intermediates during the formation of lead bromide perovskites. Based on theoretical calculations of excitonic energies that match within 50 meV, we give a preliminary assignment of these species as two-dimensional magic-sized clusters with side lengths of 2, 3, and 4 unit cells. Kinetic measurements of the conversion of benzoyl bromide precursor are connected to stopped-flow measurements of product formation and demonstrate that the formation of complexes and magic-sized clusters (i.e., nucleation) is controlled by precursor decomposition, whereas the growth rate of 2D and 3D perovskites is significantly slower.

In conventional spectroscopy, transitions between electronic levels are governed by the electric dipole selection rule because electric quadrupole, magnetic dipole, and coupled electric dipole-magnetic dipole transitions are forbidden in a far field. We demonstrated that by using nanostructured electromagnetic fields, the selection rules of absorption spectroscopy could be fundamentally manipulated. We also show that forbidden transitions between discrete quantum levels in a semiconductor nanorod structure are allowed within the near-field of a noble metal nanoparticle. Atomistic simulations analyzed by an effective mass model reveal the breakdown of the dipolar selection rules where quadrupole and octupole transitions are allowed. Our demonstration could be generalized to the use of nanostructured near-fields for enhancing light-matter interactions that are typically weak or forbidden.

Colloidal nanocrystal/DNA conjugates hold the promise of becoming powerful probes for biological diagnostics as well as versatile building blocks for nanotechnology. To fully realize this potential, it is important to precisely control the number of oligonucleotides bound to the nanocrystal. Here we demonstrate electrophoretic isolation of 5 and 10 nm gold nanocrystals bearing discrete numbers of single-stranded DNA (1−5). The potential use of these discrete conjugates in the fabrication of novel nanostructures is discussed.

Compositional and interfacial control in heterojunction thin films is critical to the performance of complex devices that separate or combine charges. For high performance, these applications require epitaxially matched interfaces, which are difficult to produce. Here, we present a new architecture for producing low-strain, single-crystalline heterojunctions using self-assembly and in-film cation exchange of colloidal nanorods. A systematic set of experiments demonstrates a cation exchange procedure that lends precise control over compositional depths in a monolayer film of vertically aligned nanorods. Compositional changes are reflected by electrical performance as rectification is induced, quenched, and reversed during cation exchange from CdS to Cu(2)S to PbS. As an additional benefit, we achieve this single-crystal architecture via an inherently simple and low-temperature wet chemical process, which is general to a variety of chemistries. This permits ensemble measurement of transport through a colloidal nanoparticle film with no interparticle charge hopping.