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DOE OSTI2020

Mapping Competitive Reduction upon Charging in LiNi 0.8 Co 0.15 Al 0.05 O 2 Primary Particles

Side reactions involving surface reduction play a critical role in the failure of LiNi 0.8 Co 0.15 Al 0.05 O 2 to reach its theoretical capacity as a cathode material for Li-ion batteries. While macroscopic consequences are known, the underlying nanoscopic mechanisms are not fully elucidated. By coupling X-ray spectroscopy with several X-ray microscopy modalities, we have spatially resolved the extent of Ni oxidation at several states of charge and uncovered heterogeneity that is hidden when considering ensemble measurements alone. The use of morphologically controlled particles enabled high-resolution imaging of these materials, uncovering gradients of Ni oxidation states within individual primary particles. At high states of charge, these gradients revealed regions of possible oxygen deficiency extending deeper into the particle than previously observed. Surface-sensitive X-ray coupled scanning tunneling microscopy allows oxidation states to be measured at the material's surface, showing predominantly Ni II in the first atomic layer and mixtures of Ni II with Ni III /Ni IV already appearing 1.5 nm into the particle. These results reveal the subtle interplay between irreversible surface transformations and the bulk reactions that ultimately define function, which will refine strategies of surface passivation that are key to overcoming current performance limitations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Quantum-enhanced detection of viral cDNA via luminescence resonance energy transfer using upconversion and gold nanoparticles

Abstract The COVID-19 pandemic has profoundly impacted global economies and healthcare systems, revealing critical vulnerabilities in both. In response, our study introduces a sensitive and highly specific detection method for cDNA, leveraging Luminescence Resonance Energy Transfer (LRET) between upconversion nanoparticles (UCNPs) and gold nanoparticles (AuNPs), and achieves a detection limit of 242 fM for SARS-CoV-2 cDNA. This innovative sensing platform utilizes UCNPs conjugated with one primer and AuNPs with another, targeting the 5′ and 3′ ends of the SARS-CoV-2 cDNA, respectively, enabling precise differentiation of mismatched cDNA sequences and significantly improving detection specificity. Through rigorous experimental analysis, we established a quenching efficiency range from 10.4 % to 73.6 %, with an optimal midpoint of 42 %, thereby demonstrating the superior sensitivity of our method. Our work uses SARS-CoV-2 cDNA as a model system to demonstrate the potential of our LRET-based detection method. This proof-of-concept study highlights the adaptability of our platform for future diagnostic applications. Instrumental validation confirms the synthesis and formation of AuNPs, addressing the need for experimental verification of the preparation of nanomaterial. Our comparative analysis with existing SARS-CoV-2 detection methods revealed that our approach provides a low detection limit and high specificity for target cDNA sequences, underscoring its potential for targeted COVID-19 diagnostics. This study demonstrates the superior sensitivity and adaptability of using UCNPs and AuNPs for cDNA detection, offering significant advances in rapid, accessible diagnostic technologies. Our method, characterized by its low detection limit and high precision, represents a critical step forward in developing next-generation biosensors for managing current and future viral outbreaks. By adjusting primer sequences, this platform can be tailored to detect other pathogens, contributing to the enhancement of global healthcare responsiveness and infectious disease control.

Esmaeili, Shahriar [Institute for Quantum Science ↗

DOE OSTI2022

Ligand Coverage and Exciton Delocalization Control Chiral Imprinting in Perovskite Nanoplatelets

Chiral perovskites have generated significant recent interest, yet little is known about how their chiro-optical properties arise. In this study, chiral methylammonium lead halide perovskite nanoplatelets (NPLs) with varied halide and ligand compositions are prepared using direct synthetic methods. Circular dichroism (CD) and 1 H NMR studies find a non-linear relationship between the chiroptical properties and the ratio of chiral phenylethylammonium (PEA) to achiral octylamine (OA) ligands on the NPL surface. We use density functional theory (DFT) computations and a chiral imprinted particle-in-a-box model to rationalize the experimentally observed CD spectra and find that the saturation point of the induced chirality depends on the size of the perovskite exciton relative to the size of the ligands. Temperature-dependent CD and 1 H NMR studies, combined with DFT analysis, show that both the CD intensity and sign depend strongly on the structure and orientation of the ligands. Furthermore, this work reveals the complex nature of chiral imprinting in perovskite nanostructures and establishes a simple physical model for ligand-induced chiral imprinting to guide the further development of chiral materials.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Two-Dimensional Siloxene Nanosheets: Impact of Morphology and Purity on Electrochemistry

Two-dimensional (2D) siloxene (Si 6 O 3 H 6 ) has shown promise as a negative electrode material for Li-ion batteries due to its high gravimetric capacity and superior mechanical properties under (de)lithiation compared to bulk Si. Here, in this work, we prepare purified siloxene nanosheets through the removal of bulk Si contaminants, use ultrasonication to control the lateral size and thickness of the nanosheets, and probe the effects of the resulting morphology and purity on the electrochemistry. The thin siloxene nanosheets formed after 4 h of ultrasonication deliver an average capacity of 810 mA h/g under a 1000 mA/g rate over 200 cycles with a capacity retention of 76%. Interestingly, the purified siloxene shows lower initial capacity but superior capacity retention over extended cycling. The 2D morphology benefit is illustrated where the parent siloxene nanosheet morphology and structure were largely maintained based on operando optoelectrochemistry, in situ Raman, ex situ scanning electron microscopy, and ex situ transmission electron microscopy. Furthermore, the purified siloxene-based electrode free from crystalline Si impurity experiences the least expansion upon (de)lithiation as visualized by cross-section electron microscopy of samples recovered post-cycling.

25 ENERGY STORAGE↗

DOE OSTI2023

Immediate effects of acute Mars mission equivalent doses of SEP and GCR radiation on the murine gastrointestinal system-protective effects of curcumin-loaded nanolipoprotein particles (cNLPs)

Introduction: Missions beyond low Earth orbit (LEO) will expose astronauts to ionizing radiation (IR) in the form of solar energetic particles (SEP) and galactic cosmic rays (GCR) including high atomic number and energy (HZE) nuclei. The gastrointestinal (GI) system is documented to be highly radiosensitive with even relatively low dose IR exposures capable of inducing mucosal lesions and disrupting epithelial barrier function. IR is also an established risk factor for colorectal cancer (CRC) with several studies examining long-term GI effects of SEP/GCR exposure using tumor-prone APC mouse models. Studies of acute short-term effects of modeled space radiation exposures in wildtype mouse models are more limited and necessary to better define charged particle- induced GI pathologies and test novel medical countermeasures (MCMs) to promote astronaut safety. Methods: In this study, we performed ground-based studies where male and female C57BL/6J mice were exposed to γ-rays, 50 MeV protons, or 1 GeV/n Fe-56 ions at the NASA Space Radiation Laboratory (NSRL) with histology and immunohistochemistry endpoints measured in the first 24 h post-irradiation to define immediate SEP/GCR-induced GI alterations. Results: Our data show that unlike matched γ-ray controls, acute exposures to protons and iron ions disrupts intestinal function and induces mucosal lesions, vascular congestion, epithelial barrier breakdown, and marked enlargement of mucosa-associated lymphoid tissue. We also measured kinetics of DNA double-strand break (DSB) repair using gamma-H2AX- specific antibodies and apoptosis via TUNEL labeling, noting the induction and disappearance of extranuclear cytoplasmic DNA marked by gamma-H2AX only in the charged particle-irradiated samples. We show that 18 h pre-treatment with curcumin-loaded nanolipoprotein particles (cNLPs) delivered via IV injection reduces DSB-associated foci levels and apoptosis and restore crypt villi lengths. Discussion: These data improve our understanding of physiological alterations in the GI tract immediately following exposures to modeled space radiations and demonstrates effectiveness of a promising space radiation MCM.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2021

Theory of the effect of external stress on the activated dynamics and transport of dilute penetrants in supercooled liquids and glasses

We generalize the self-consistent cooperative hopping theory for a dilute spherical penetrant or tracer activated dynamics in dense metastable hard sphere fluids and glasses to address the effect of external stress, the consequences of which are systematically established as a function of matrix packing fraction and penetrant-to-matrix size ratio. All relaxation processes speed up under stress, but the difference between the penetrant and matrix hopping (alpha relaxation) times decreases significantly with stress corresponding to less time scale decoupling. A dynamic crossover occurs at a critical “slaving onset” stress beyond which the matrix activated hopping relaxation time controls the penetrant hopping time. This characteristic stress increases (decreases) exponentially with packing fraction (size ratio) and can be well below the absolute yield stress of the matrix. Below the slaving onset, the penetrant hopping time is predicted to vary exponentially with stress, differing from the power law dependence of the pure matrix alpha time due to system-specificity of the stress-induced changes in the penetrant local cage and elastic barriers. An exponential growth of the penetrant alpha relaxation time with size ratio under stress is predicted, and at a fixed matrix packing fraction, the exponential relation between penetrant hopping time and stress for different size ratios can be collapsed onto a master curve. Direct connections between the short- and long-time activated penetrant dynamics and between the penetrant (or matrix) alpha relaxation time and matrix thermodynamic dimensionless compressibility are also predicted. The presented results should be testable in future experiments and simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Field-Driven Out-of-Equilibrium Collective Patterns for Swarm Micro-Robotics

Soft robotics has been rapidly advancing, offering significant improvements over traditional rigid robotic systems through the use of compliant materials that enhance adaptability and interaction with the environment. However, current approaches face critical challenges, including the reliance on complex “top-down” fabrication techniques and the difficulty of wireless powering and control at the microscale. Swarm robotics introduces a paradigm shift, leveraging collective dynamics to achieve cooperative and adaptable behaviors among multiple robotic units. Inspired by nature, this “bottom-up” approach enables swarm robots to execute task-specific reconfigurations, enhancing flexibility and robustness. Field-driven active colloids emerge as a promising platform for swarm microrobotics, capable of self-propulsion and self-organization into dynamic collective patterns under external field excitation and manipulation. These systems mimic biologically inspired swarm behaviors, such as flocking and vortex formation, providing a versatile foundation for designing innovative swarm microrobots. Here, this review discusses the principles of electric and magnetic field-driven collective self-organization, focusing on the particle dynamics, the emergence of collective swarm patterns, and illustrative examples of functional swarm microrobots. It concludes with future perspectives on harnessing these systems for adaptive, scalable, and multifunctional microrobotic applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2020

High-performance light-driven heterogeneous CO 2 catalysis with near-unity selectivity on metal phosphides

Akin to single-site homogeneous catalysis, a long sought-after goal is to achieve reaction site precision in heterogeneous catalysis for chemical control over patterns of activity, selectivity and stability. Herein, we report on metal phosphides as a class of material capable of realizing these attributes and unlock their potential in solar-driven CO 2 hydrogenation. Selected as an archetype, Ni 12 P 5 affords a structure based upon highly dispersed nickel nanoclusters integrated into a phosphorus lattice that harvest light intensely across the entire solar spectral range. Motivated by its panchromatic absorption and unique linearly bonded nickel-carbonyl-dominated reaction route, Ni 12 P 5 is found to be a photothermal catalyst for the reverse water gas shift reaction, offering a CO production rate of 960 ± 12 mmol g cat –1 h –1 , near 100% selectivity and long-term stability. Successful extension of this idea to Co2P analogs implies that metal phosphide materials are poised as a universal platform for high-rate and highly selective photothermal CO 2 catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Effect of Charged Block Length Mismatch on Double Diblock Polyelectrolyte Complex Micelle Cores

Polyelectrolyte complex micelles are hydrophilic nanoparticles that self-assemble in aqueous environments due to associative microphase separation between oppositely charged blocky polyelectrolytes. In this work, we employ a suite of physical characterization tools to examine the effect of charged block length mismatch on the equilibrium structure of double diblock polyelectrolyte complex micelles (D-PCMs) by mixing a diverse library of peptide and synthetic charged-neutral block polyelectrolytes with a wide range of charged block lengths (25–200 units) and chemistries. Early work on D-PCMs suggested that this class of micelles can only be formed from blocky polyelectrolytes with identical charged block lengths, a phenomenon referred to as chain length recognition. Here, we use salt annealing to create PCMs at equilibrium, which shows that chain length recognition, a longstanding hurdle to repeatable self-assembly from mismatched polyelectrolytes, can be overcome. Interestingly, D-PCM structure–property relationships display a range of values that vary systematically with the charged block lengths and chemical identity of constituent polyelectrolyte pairings and cannot be described by generalizable scaling laws. We discuss the interdependent growth behavior of the radius, ionic pair aggregation number, and density in the micelle core for three chemically distinct diblock pairings and suggest a potential physical mechanism that leads to this unique behavior. By comparing the results of these D-PCMs to the scaling laws recently developed for single diblock polyelectrolyte complex micelles (S-PCMs: diblock + homopolymer), we observe that D-PCM design schemes reduce the size and aggregation number and restrict their growth to a function of charged block length relative to S-PCMs. Understanding these favorable attributes enables more predictive use of a wider array of charged molecular building blocks to anticipate and control macroscopic properties of micelles spanning countless storage and delivery applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

The Role of Secondary Particle Structures in Surface Phase Transitions of Ni-Rich Cathodes

Nanometer-thick reconstruction layers on layered cathode surfaces have been widely observed on both pristine and cycled materials. However, the mechanisms of reconstruction and the role that these structures play in electrochemical performance are not fully understood. From a crystallographic perspective, such surface reconstruction layers result from cation site-mixing between Li and transition-metal ions, but it remains far from clear as to what the critical factors are that control such cation mixing for various cathode chemistries. In this paper, we report observations on surface transformations during cycling of a Ni-rich cathode-oxide that are governed by direct contact with the liquid electrolyte. Specifically, within a secondary particle, the three-dimensional hierarchical aggregate of primary particles leads to the formation of grain boundaries of different characteristics, including open grain boundaries that allow the permeation of liquid electrolyte, and closed grain boundaries that exclude liquid electrolyte penetration. Upon battery cycling, surfaces in direct contact with the liquid electrolyte showed a surface reconstruction layer while the surfaces that did not have contact with the electrolyte showed no such reconstructions. In addition, the critical role of oxygen in reconstruction of grain boundaries is demonstrated, and the unexpected oxygen depletion at twin boundaries result in severe phase transitions. The present work provides further insights into phase transitions at solid-solid and solid-liquid interfaces within secondary cathode particles and suggests strategies for mitigating surface/interfacial degradation.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Controlling morphology in hybrid isotropic/patchy particle assemblies

Brownian dynamics is used to study self-assembly in a hybrid system of isotropic particles (IPs), combined with anisotropic building blocks that represent special “designer particles.” Those are modeled as spherical patchy particles (PPs) with binding only allowed between their patches and IPs. In this study, two types of PPs are considered: Octahedral PPs (Oh-PPs) and Square PPs (Sq-PPs), with octahedral and square arrangements of patches, respectively. The self-assembly is additionally facilitated by the simulated annealing procedure. Here, the resultant structures are characterized by a combination of local correlations in cubatic ordering and a symmetry-specific variation of bond orientation order parameters (SymBOPs). By varying the PP/IP size ratio, we detected a sharp crossover between two distinct morphologies in both types of systems. High symmetry phases, NaCl crystal for Oh-PP and square lattice for Sq-PP, are observed for larger size ratios. For the smaller ones, the dominant morphologies are significantly different, e.g., Oh-PPs form a compact amorphous structure with predominantly face-to-face orientation of neighboring PPs. Unusually, for a morphology without a long-range order, it is still possible to identify well organized coherent clusters of this structure, thanks to the adoption of our SymBOP-based characterization.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2021

Identification of Brillouin Zones by In-Plane Lasing from Light-Cone Surface Lattice Resonances

Periodic optical structures can control the flow of light, which has facilitated applications in optical fibers, laser cavities, and biochemical sensors. The first Brillouin zone (BZ) in reciprocal space can describe all the electromagnetic fields localized inside a photonic lattice. However, photonic lattices also exhibit radiative losses from light scattering, but the radiated fields are not captured by the first BZ. In a two-dimensional lattice, the in-plane wavevectors of photonic modes are limited by the so-called light cone, which depicts free-photon dispersion relations in the surrounding medium. Here we show that projection of the light cone on extended BZs provides a geometric method to observe radiated electromagnetic fields of photonic lattice modes. We developed a coupled dipole radiation theory to reveal how lattice geometry and dipole orientation affect the angular distributions of the radiated fields. Using dye molecules as local dipole emitters to excite and probe the optical modes, we experimentally identified high-order BZ edges through directional, in-plane lasing emission.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Size-Resolved Elemental Composition of Respiratory Particles in Three Healthy Subjects

The chemical composition of respiratory particles is of interest because the viability of any viruses and bacteria in the particles has been shown to depend on this factor. Here, using computer controlled scanning electron microscopy/energy dispersive X-ray spectroscopy (CCSEM/EDX), we analyzed the size-resolved chemical composition of greater than 35,000 individual respiratory particles collected from three healthy human subjects, quantitatively at nanometer-scale spatial resolution. The desiccated particles ranged in size from 0.05 to 4.4 μm, and the mode of the size distribution was approximately 0.1 μm. Particles were heterogeneous in composition, with approximately 42% of them containing a carbon atomic percentage greater than 95% and approximately 53% of them containing a Na + P + K + Cl percentage greater than 5%. Based on the particles’ elemental composition, we classified them into five categories: 48%–56% of the total number were carbonaceous, mostly organic; 40%–50% Na-rich salt; 0.3%–0.5% P-rich salt; 0.1–0.8% K-rich salt; and 1%–2.5% mixed salt. The number ratio of Na-rich salt particles to carbonaceous particles increased with increasing particle size; particles larger than approximately 2 μm were dominated by Na-rich salt. Size-dependent differences in the chemical composition of respiratory particles may have important implications for the efficiency of airborne transmission of respiratory pathogens.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2023

Theoretical Analysis of Resonant Tunneling Enhanced Field Emission

In this paper, we develop an exact analytical quantum theory for field emission from surfaces with a nearby quantum well, by solving the one-dimensional time-independent Schrödinger equation. The quantum well, which may be introduced by ions, atoms, nanoparticles, etc., is simplified as a square potential well with depth H, width d, and distance to the surface L. The theory is used to analyze the effects of the quantum well (d, H, and L), the cathode properties (work function W and Fermi energy E F ), and dc field F. It is found that the quantum well can lead to resonant tunneling enhanced field emission up to several orders of magnitude larger than that from bare cathode surfaces. In the meantime, the electron-emission-energy spectrum is significantly narrowed. The strong enhancement region is bounded by the conditions eFL + H ≥ W + C and eFL ≤ W, with e being the elementary charge (positive) and C a constant dependent on dc field F. It is also found that the linear shift of resonance peaks in the electron-emission-energy spectrum with dc field F follows ε p =ε p⁢0 –e⁢FL, with ε p⁢0 being approximately the eigenenergies for electrons confined in a square potential well without a dc field. Finally, the theory provides insights for the design of high-efficiency field emitters, which can produce a high current and highly collimated electron beams.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2021

Forced Crowding of Colloids by Thermophoresis and Convection in a Custom Liquid Clusius–Dickel Microdevice

Here, we report a study demonstrating that simultaneous induction of a steady-state convection current and temperature gradient in a confined geometry can be an effective way to force crowding of dissolved particulates. To investigate this thermogravitationally driven concentration of particles in-situ, we developed a micro-device capable of sustaining controlled transverse temperature gradients within a 5 cm long, 0.1 mm inner diameter capillary that allowed visualization of particle movement with standard optical microscopy. Experiments were conducted on two material systems representative of nano-scale small molecules and micro-scale particles. With the small molecules (aromatic dyes, 530-790 g/mol, 1-1.5 nm) thermophoretic and gravitational effects in the micro-device resulted in an asymmetrical 2x concentration change along the capillary height over 3 days. In contrast, the concentration change under similar conditions for 40-micron diameter latex colloids is 50-fold in 30 minutes. This dramatic difference in separation times is consistent with simulations and models of thermophoresis where the thermophoretic effect scales with particle size. Induced crowding of particulates leads to formation of accumulation and depletion zones in at the bottom and top of the capillary respectively. Both the concentration of dye molecules over time in the depletion zone and spatial distribution of colloids over the entire capillary length were found to be good fits to simple first-order exponential decay functions. Furthermore, these results suggest potential applications of thermogravitational separation in developing new functional materials via thermophoretic and convective effects.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Ligand-Controlled Energetics and Charge Transfer in Pure and Doped Nanocrystals

The research in this award period initially focused on the spectroscopy and dynamics of spherical CdSe nanocrystals and CdSe nanoplatelets. In the later part of the grant period we turned our attention to InP-based nanocrystals. It has long been believed that the transient absorption signal from approximately spherical CdSe nanocrystals is dominated by conduction band state filling. However, this long-held belief has recently been challenged, based on femtosecond absorption measurements. However, the recent studies challenging the conventional wisdom do not account of finite rates of spin-lattice relaxation. Our work showed that this is a crucial error and that the recent results are misinterpreted, that is, the previous prevailing wisdom is correct. Another study focused on CdSe nanocrystal photochemistry used transient absorption (TA) spectroscopy to determine the spatial extents of CdSe nanoplatelet (NPL) excitons. Our work shows that the spatial extents of the excitons in the NPLs are far less than the physical dimension of the NPL. Using a model developed to understand the transient absorption spectroscopy, we obtain an average excitonic area of 21.2 ± 2.5 nm 2 , independent of the nanoplatelet size. Our work on InP/ZnSe and InP/ZnS core/shell nanocrystals shows that when there is a small lattice mismatch (InP-ZnSe, 3.5%) a coherent core-shell interface is obtained. In contrast, the InP-ZnS lattice mismatch is much larger, 8.3%. In this case, the experimental results showed best agreement with calculations in which lattice strain is ignored, indicating that the interfaces in InP/ZnS nanocrystals are largely incoherent.

14 SOLAR ENERGY↗

DOE OSTI2023

Ferroelectric Polarization in BaTiO 3 Nanocrystals Controls Photoelectrochemical Water Oxidation and Photocatalytic Hydrogen Evolution

Ferroelectric (FE) semiconductors such as BaTiO 3 support a remnant polarization after the application of an electric field that can promote the separation of photogenerated charge carriers. Here, we demonstrate FE-enhanced photocatalytic hydrogen evolution and photoelectrochemical water oxidation with barium titanate nanocrystals for the first time. Nanocrystals of the ferroelectric tetragonal structure type were obtained by a hydrothermal synthesis from TiO 2 and barium hydroxide in 63% yield. BaTiO 3 nanocrystal films on tantalum substrates exhibit water oxidation photocurrents of 0.141 mA cm –2 at 1.23 V RHE under UV light (60 mW cm –2 ) illumination. Electric polarization at 52.8 kV cm –1 normal to the film plane increases the photocurrent by a factor of 2 or decreases it by a factor of 3.5, depending on the field polarity. It also shifts the onset potential by –0.15 or +0.09 V and it modifies the surface photovoltage signal. Lastly, exposure to an electric field increases the H 2 evolution rate of Pt/BaTiO 3 by a factor of ~1.5, and it raises the selectivity of photodeposition of silver onto the (001) facets of the nanocrystal. All FE enhancements can be removed by heating samples above the Curie temperature of BaTiO 3 . Furthermore, these findings can be explained by FE dipole-induced changes to the potential drop across the space charge layer of the material. The ability to use the ferroelectric effect to enhance hydrogen evolution and water oxidation is of potential interest for the development of improved solar energy for fuel conversion systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Size-Resolved Shape Evolution in Inorganic Nanocrystals Captured via High-Throughput Deep Learning-Driven Statistical Characterization

Precise size and shape control in nanocrystal synthesis is essential for utilizing nanocrystals in various industrial applications, such as catalysis, sensing, and energy conversion. However, traditional ensemble measurements often overlook the subtle size and shape distributions of individual nanocrystals, hindering the establishment of robust structure–property relationships. In this study, we uncover intricate shape evolutions and growth mechanisms in Co 3 O 4 nanocrystal synthesis at a subnanometer scale, enabled by deep-learning-assisted statistical characterization. By first controlling synthetic parameters such as cobalt precursor concentration and water amount then using high resolution electron microscopy imaging to identify the geometric features of individual nanocrystals, this study provides insights into the interplay between synthesis conditions and the sizedependent shape evolution in colloidal nanocrystals. Utilizing population-wide imaging data encompassing over 441,067 nanocrystals, we analyze their characteristics and elucidate previously unobserved size-resolved shape evolution. This high-throughput statistical analysis is essential for representing the entire population accurately and enables the study of the size dependency of growth regimes in shaping nanocrystals. Our findings provide experimental quantification of the growth regime transition based on the size of the crystals, specifically (i) for faceting and (ii) from thermodynamic to kinetic, as evidenced by transitions from convex to concave polyhedral crystals. Additionally, we introduce the concept of an “onset radius,” which describes the critical size thresholds at which these transitions occur. This discovery has implications beyond achieving nanocrystals with desired morphology; it enables finely tuned correlation between geometry and material properties, advancing the field of colloidal nanocrystal synthesis and its applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗