Publications

Scientific Machine Learning of 2D Perovskite Nanosheet Formation

We apply a scientific machine learning framework to aid the prediction and understanding of nanomaterial formation processes via a joint spectral-kinetic model. We apply this framework to study nucleation and growth of 2D perovskite nanosheets. Colloidal nanomaterials have size-dependent optical properties, and can be observed in situ, all of which make them a good model for understanding the complex processes of nucleation, growth and phase transformation of 2D perovskites. Our results demonstrate that this model nanomaterial can form through two processes at the nanoscale: either via a layer-by-layer chemical exfoliation process from lead bromide nanocrystals or via direct nucleation from precursors. We utilize a phenomenological kinetic analysis to study the exfoliation process and scientific machine learning to study the direct nucleation and growth, and discuss the circumstances under which it is more appropriate to use phenomenological or more complex machine learning models. Data for both analysis techniques are collected through in-situ spectroscopy in a stopped flow chamber, incorporating over 500,000 spectra taken under more than 100 different conditions. More broadly, our research shows that the ability to utilize and integrate traditional kinetics and machine learning methods will greatly assist the understanding of complex chemical systems.

Precise Tuning of Surface Quenching for Luminescence Enhancement in Core–Shell Lanthanide-Doped Nanocrystals

Lanthanide-doped nanocrystals are of particular interest for the research community not only due to their ability to shape light by downshifting, quantum cutting, and upconversion but also because novel optical properties can be found by the precise engineering of core-shell nanocrystals. Because of the large surface area-to-volume ratio of nanocrystals, the luminescence is typically suppressed by surface quenching. Here, we demonstrate a mechanism that exploits surface quenching processes to improve the luminescence of our core-shell lanthanide-doped nanocrystals. By carefully tuning the shell thickness of inert β-NaLuF₄ around β-NaYF₄ nanocrystals doped with Yb³⁺ and Er³⁺, we unravel the relationship between quantum yield and shell thickness, and quantify surface quenching rates for the relevant Er³⁺ and Yb³⁺ energy levels. This enhanced understanding of the system's dynamics allowed us to design nanocrystals with a surface quenching-assisted mechanism for bright NIR to NIR downshifting with a distinctive efficiency peak for an optimized shell thickness.

Controlled Assembly of Hybrid Bulk−Heterojunction Solar Cells by Sequential Deposition

This work presents a technique to create ordered and easily characterized hybrid nanocrystal-polymer composites by sequential deposition of tetrapod-shaped cadmium telluride (CdTe) nanocrystals and poly(3-hexlythiophene). With controlled fabrication and composite morphology, these devices offer several advantages over traditional co-deposited hybrid cells and provide a model system for detailed investigation into the operation of bulk-heterojunction cells.

Hole Transfer Dynamics from a CdSe/CdS Quantum Rod to a Tethered Ferrocene Derivative

Hole transfer between a CdSe/CdS core/shell semiconductor nanorod and a surface-ligated alkyl ferrocene is investigated by a combination of ab initio quantum chemistry calculations and electrochemical and time-resolved photoluminescence measurements. The calculated driving force for hole transfer corresponds well with electrochemical measurements of nanorods partially ligated by 6-ferrocenylhexanethiolate. The calculations and the experiments suggest that single step hole transfer from the valence band to ferrocene is in the Marcus inverted region. Additionally, time-resolved photoluminescence data suggest that two-step hole transfer to ferrocene mediated by a deep trap state is unlikely. However, the calculations also suggest that shallow surface states of the CdS shell could play a significant role in mediating hole transfer as long as their energies are close enough to the nanorod highest occupied molecular orbital energy. Regardless of the detailed mechanism of hole transfer, our results suggest that holes may be extracted more efficiently from well-passivated nanocrystals by reducing the energetic driving force for hole transfer, thus minimizing energetic losses.

Ultrafast Dynamics in CdSe Nanocrystals

Influence of three-dimensional nanoparticle branching on the Young’s modulus of nanocomposites: Effect of interface orientation

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.

Light-emitting diodes made from cadmium selenide nanocrystals and a semiconducting polymer

Precursor Chemistry of Lead Bromide Perovskite Nanocrystals

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.

Multilayer Diffraction Reveals That Colloidal Superlattices Approach the Structural Perfection of Single Crystals

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.

AutoDetect-mNP: An Unsupervised Machine Learning Algorithm for Automated Analysis of Transmission Electron Microscope Images of Metal Nanoparticles

The synthesis quality of artificial inorganic nanocrystals is most often assessed by transmission electron microscopy (TEM) for which new high-throughput advances have dramatically increased both the quantity and information richness of metal nanoparticle (mNP) characterization. Existing automated data analysis algorithms of TEM mNP images generally adopt a supervised approach, requiring a significant effort in human preparation of labelled data that reduces objectivity, efficiency, and generalizability. We have developed an unsupervised algorithm AutoDetect-mNP for automated analysis of TEM images that objectively extracts morphological information of convex mNPs from TEM images based on their shape attributes, requiring little to no human input in the process. The performance of AutoDetect-mNP is tested on two datasets of bright field TEM images of Au nanoparticles with different shapes, demonstrating that the algorithm is quantitatively reliable, and can thus serve as a generalizable measure of the morphology distributions of any mNP synthesis. The AutoDetect-mNP algorithm will aid in future developments of high-throughput characterization of newly synthesized mNPs, and the future advent of time-resolved TEM studies that can investigate reaction mechanisms of mNP synthesis and reactivity.

Semiconductor Nanorod Liquid Crystals and Their Assembly on a Substrate

The macroscopic alignment and superlattice structures of CdSe nanorods in a nematic liquid‐crystalline (LC) phase are determined by the phases that form prior to complete solvent evaporation (e.g., vortex structures in linear arrays, see Figure). By controlling the phase of the LC solution and its orientation using pretreated surfaces or external fields, it may be possible to achieve fine control of order in deposited nanorod films.

From Quanta to the Continuum: Opportunities for Mesoscale Science

This report explores the opportunity and defines the research agenda for mesoscale science—discovering, understanding, and controlling interactions among disparate systems and phenomena to reach the full potential of materials complexity and functionality. The ability to predict and control mesoscale phenomena and architectures is essential if atomic and molecular knowledge is to blossom into a next generation of technology opportunities, societal benefits, and scientific advances.. The body of this report outlines the need, the opportunities, the challenges, and the benefits of mastering mesoscale science.

Dynamics of Nanoscale Dendrite Formation in Solution Growth Revealed Through in Situ Liquid Cell Electron Microscopy

Formation mechanisms of dendrite structures have been extensively explored theoretically, and many theoretical predictions have been validated for micro- or macroscale dendrites. However, it is challenging to determine whether classical dendrite growth theories are applicable at the nanoscale due to the lack of detailed information on the nanodendrite growth dynamics. Here, we study iron oxide nanodendrite formation using liquid cell transmission electron microscopy (TEM). We observe "seaweed"-like iron oxide nanodendrites growing predominantly in two dimensions on the membrane of a liquid cell. By tracking the trajectories of their morphology development with high spatial and temporal resolution, it is possible to explore the relationship between the tip curvature and growth rate, tip splitting mechanisms, and the effects of precursor diffusion and depletion on the morphology evolution. We show that the growth of iron oxide nanodendrites is remarkably consistent with the existing theoretical predictions on dendritic morphology evolution during growth, despite occurring at the nanoscale.

Electronic Structure of Cobalt Nanocrystals Suspended in Liquid

The electronic structure of cobalt nanocrystals suspended in liquid as a function of size has been investigated using in-situ x-ray absorption and emission spectroscopy. A sharp absorption peak associated with the ligand molecules is found that increases in intensity upon reducing the nanocrystal size. X-ray Raman features due to d-d and to charge-transfer excitations of ligand molecules are identified. The study reveals the local symmetry of the surface of {var_epsilon}-Co phase nanocrystals, which originates from a dynamic interaction between Co nanocrystals and surfactant + solvent molecules.

Novel inorganic materials for solution-processed electronics

Vacancy Coalescence during Oxidation of Iron Nanoparticles

In the present work, we analyze the geometry and composition of the nanostructures obtained from the oxidation of iron nanoparticles. The initial oxidation of iron takes place by outward diffusion of cations through the growing oxide shell. This net material flow is balanced by an opposite flow of vacancies, which coalesce at the metal/oxide interface. Thus, the partial oxidation of colloidal iron nanoparticles leads to the formation of core−void−shell nanostructures. Furthermore, the complete oxidation of iron nanoparticles in the 3−8 nm size range leads to the formation of hollow iron oxide nanoparticles. We analyze the size and temperature range in which vacancy coalescence during oxidation of amine-stabilized iron nanoparticles takes place. Maghemite is the crystallographic structure obtained from the complete oxidation of iron nanoparticles under our synthetic conditions.

Nanocrystals as Model Systems for Pressure-Induced Structural Phase Transitions

Research Article| January 01, 2001 Nanocrystals as Model Systems for Pressure-Induced Structural Phase Transitions Keren Jacobs; Keren Jacobs Department of Chemistry, University of California–Berkeley, Berkeley, California 94720 Search for other works by this author on: GSW Google Scholar A. Paul Alivisatos A. Paul Alivisatos Department of Chemistry, University of California–Berkeley, Berkeley, California 94720 Search for other works by this author on: GSW Google Scholar Author and Article Information Keren Jacobs Department of Chemistry, University of California–Berkeley, Berkeley, California 94720 A. Paul Alivisatos Department of Chemistry, University of California–Berkeley, Berkeley, California 94720 Publisher: Mineralogical Society of America First Online: 09 Mar 2017 © The Mineralogical Society Of America Reviews in Mineralogy and Geochemistry (2001) 44 (1): 59–72. https://doi.org/10.2138/rmg.2001.44.02 Article history First Online: 09 Mar 2017 Cite View This Citation Add to Citation Manager Share Icon Share Facebook Twitter LinkedIn Email Permissions Search Site Citation Keren Jacobs, A. Paul Alivisatos; Nanocrystals as Model Systems for Pressure-Induced Structural Phase Transitions. Reviews in Mineralogy and Geochemistry 2001;; 44 (1): 59–72. doi: https://doi.org/10.2138/rmg.2001.44.02 Download citation file: Ris (Zotero) Refmanager EasyBib Bookends Mendeley Papers EndNote RefWorks BibTex toolbar search Search Dropdown Menu toolbar search search input Search input auto suggest filter your search All ContentBy SocietyReviews in Mineralogy and Geochemistry Search Advanced Search An understanding of first-order pressure-induced structural transitions is relevant to many research areas in geological and planetary sciences because it involves the study of materials exposed to high pressures. For example, solid-solid transitions in silicates are responsible for the seismic discontinuities in the earth’s mantle (Chudinovskikh and Boehler 2001) and may play a role in plate tectonics and deep earthquakes (Kirby et al. 1991). In geological applications, models of structural transition kinetics simulate rock formation taking place over millions of years (Shekar and Rajan 2001). Despite their importance in earth science applications, the microscopic... You do not have access to this content, please speak to your institutional administrator if you feel you should have access.

Semiconductor Nanocrystals: Opportunities to Create New Materials Through