How Depletion Layers Govern the Dynamic Plasmonic Response of In-Doped CdO Nanocrystals.

Doped metal oxide nanocrystals exhibit a localized surface plasmon resonance that is widely tunable across the mid- to near-infrared region, making them useful for applications in optoelectronics, sensing, and photocatalysis. Surface states pin the Fermi level and induce a surface depletion layer that hinders conductivity and refractive index sensing but can be advantageous for optical modulation. Several strategies have been developed to both synthetically and postsynthetically tailor the depletion layer toward particular applications; however, this understanding has primarily been advanced in Sn-doped In2O3 (ITO) nanocrystals, leaving open questions about generalizing to other doped metal oxides. Here, we quantitatively analyze the depletion layer in In-doped CdO (ICO) nanocrystals, which is shown to have an intrinsically wide depletion layer that leads to broad plasmonic modulation via postsynthetic chemical reduction and ligand exchange. Leveraging these insights, we applied depletion layer tuning to enhance the inherently weak plasmonic coupling in ICO nanocrystal superlattices. Our results demonstrate how an electronic band structure dictates the radial distribution of electrons and governs the response to postsynthetic modulation, enabling the design of tunable and responsive plasmonic materials.

Illuminating Disorder: Optical Properties of Complex Plasmonic Assemblies.

The optical properties of disordered plasmonic nanoparticle assemblies can be continuously tuned through the structural organization and composition of their colloidal building blocks. However, progress in the design and experimental realization of these materials has been limited by challenges associated with controlling and characterizing disordered assemblies and predicting their optical properties. This Perspective discusses integrated studies of experimental assembly of disordered optical materials, such as doped metal oxide nanocrystal gels and metasurfaces, with electromagnetic computations on large-scale simulated structures. The simulations prove vital for connecting experimental parameters to disordered structural motifs and optical properties, revealing structure-property relations that inform design choices. Opportunities are identified for optimizing optical property designs for disordered materials using computational inverse methods and tools from machine learning.

Singular and Nonsingular Transitions in the Infrared Plasmons of Nearly Touching Nanocube Dimers.

Narrow gaps between plasmon-supporting materials can confine infrared electromagnetic energy at the nanoscale, thus enabling applications in areas such as optical sensing. However, in nanoparticle dimers, the nature of the transition between touching (zero gap) and nearly nontouching (nonzero gap ≲15 nm) regimes is still a subject of debate. Here, we observe both singular and nonsingular transitions in infrared plasmons confined to dimers of fluorine-doped indium oxide nanocubes when moving from touching to nontouching configurations depending on the dimensionality of the contact region. Through spatially resolved electron energy-loss spectroscopy, we find a continuous spectral evolution of the lowest-order plasmon mode across the transition for finite touching areas, in excellent agreement with the simulations. This behavior challenges the widely accepted idea that a singular transition always emerges in the near-touching regime of plasmonic particle dimers. The apparent contradiction is resolved by theoretically examining different types of gap morphologies, revealing that the presence of a finite touching area renders the transition nonsingular, while one-dimensional and point-like contacts produce a singular behavior in which the lowest-order dipolar mode in the touching configuration, characterized by a net induced charge in each of the particles, becomes unphysical as soon as they are separated. Our results provide valuable insights into the nature of dimer plasmons in highly doped semiconductors.

Dual-Band Electrochromic Devices Utilizing Niobium Oxide Nanocrystals.

In this study, we realize functioning electrochromic devices based on colloidal niobium oxide nanocrystals, which show dual-band electrochromic behavior, with spectral selectivity between near-infrared and visible wavelengths. Minimally coloring vanadium oxide counter electrodes allow for full electrochromic devices that embody the dual-band electrochromic behavior of the niobium oxide component. The devices are fabricated using solution processing on both glass and flexible substrates, demonstrating that our platform has potential for the development of low-cost dual-band electrochromic devices for dynamic solar control in a variety of form factors and applications.

Wavelength Tunable Infrared Perfect Absorption in Plasmonic Nanocrystal Monolayers.

The ability to efficiently absorb light in ultrathin (subwavelength) layers is essential for modern electro-optic devices, including detectors, sensors, and nonlinear modulators. Tailoring these ultrathin films' spectral, spatial, and polarimetric properties is highly desirable for many, if not all, of the above applications. Doing so, however, often requires costly lithographic techniques or exotic materials, limiting scalability. Here we propose, demonstrate, and analyze a mid-infrared absorber architecture leveraging monolayer films of nanoplasmonic colloidal tin-doped indium oxide nanocrystals (ITO NCs). We fabricate a series of ITO NC monolayer films using the liquid-air interface method; by synthetically varying the Sn dopant concentration in the NCs, we achieve spectrally selective perfect absorption tunable between wavelengths of two and five micrometers. We achieve monolayer thickness-controlled coupling strength tuning by varying NC size, allowing access to different coupling regimes. Furthermore, we synthesize a bilayer film that enables broadband absorption covering the entire midwave IR region (λ = 3-5 µm). We demonstrate a scalable platform, with perfect absorption in monolayer films only hundredths of a wavelength in thickness, enabling strong light-matter interaction, with potential applications for molecular detection and ultrafast nonlinear optical applications.

Structural Control of Plasmon Resonance in Molecularly Linked Metal Oxide Nanocrystal Gel Assemblies.

Nanocrystal gels exhibit collective optical phenomena based on interactions among their constituent building blocks. However, their inherently disordered structures have made it challenging to understand, predict, or design properties such as optical absorption spectra that are sensitive to the coupling between the plasmon resonances of the individual nanocrystals. Here, we bring indium tin oxide nanocrystal gels under chemical control and show that their infrared absorption can be predicted and systematically tuned by selecting the nanocrystal sizes and compositions and molecular structures of the link-mediating surface ligands. Thermoreversible assemblies with metal-terpyridine links form reproducible gel architectures, enabling us to derive a plasmon ruler that governs the spectral shifts upon gelation, predicated on the nanocrystal and ligand compositions. This empirical guide is validated using large-scale, many-bodied simulations to compute the optical spectra of gels with varied structural parameters. Based on the derived plasmon ruler, we design and demonstrate a nanocrystal mixture whose spectrum exhibits distinctive line narrowing upon assembly.

Dipolar Ligands Tune Plasmonic Properties of Tin-Doped Indium Oxide Nanocrystals.

Surface functionalization with dipolar molecules is known to tune the electronic band alignment in semiconductor films and colloidal quantum dots. Yet, the influence of surface modification on plasmonic nanocrystals and their properties remains little explored. Here, we functionalize tin-doped indium oxide nanocrystals (ITO NCs) via ligand exchange with a series of cinnamic acids with different electron-withdrawing and -donating dipolar characters. Consistent with previous reports on semiconductors, we find that withdrawing (donating) ligands increase (decrease) the work function caused by an electrostatic potential shift across the molecular layer. Quantitative analyses of the plasmonic extinction spectra reveal that varying the ligand molecular dipole affects the near-surface depletion layer, with an anticorrelated trend between the electron concentration and electronic volume fraction, factors that are positively correlated in as-synthesized NCs. Electronic structure engineering through surface modification provides access to distinctive combinations of plasmonic properties that could enable optoelectronic applications, sensing, and hot electron-driven processes.

Hierarchically Doped Plasmonic Nanocrystal Metamaterials.

Assembling plasmonic nanocrystals in regular superlattices can produce effective optical properties not found in homogeneous materials. However, the range of these metamaterial properties is limited when a single nanocrystal composition is selected for the constituent meta-atoms. Here, we show how continuously varying doping at two length scales, the atomic and nanocrystal scales, enables tuning of both the frequency and bandwidth of the collective plasmon resonance in nanocrystal-based metasurfaces, while these features are inextricably linked in single-component superlattices. Varying the mixing ratio of indium tin oxide nanocrystals with different dopant concentrations, we use large-scale simulations to predict the emergence of a broad infrared spectral region with near-zero permittivity. Experimentally, tunable reflectance and absorption bands are observed, owing to in- and out-of-plane collective resonances. These spectral features and the predicted strong near-field enhancement establish this multiscale doping strategy as a powerful new approach to designing metamaterials for optical applications.

Plasmonic Response of Complex Nanoparticle Assemblies.

Optical properties of nanoparticle assemblies reflect distinctive characteristics of their building blocks and spatial organization, giving rise to emergent phenomena. Integrated experimental and computational studies have established design principles connecting the structure to properties for assembled clusters and superlattices. However, conventional electromagnetic simulations are too computationally expensive to treat more complex assemblies. Here we establish a fast, materials agnostic method to simulate the optical response of large nanoparticle assemblies incorporating both structural and compositional complexity. This many-bodied, mutual polarization method resolves limitations of established approaches, achieving rapid, accurate convergence for configurations including thousands of nanoparticles, with some overlapping. We demonstrate these capabilities by reproducing experimental trends and uncovering far- and near-field mechanisms governing the optical response of plasmonic semiconductor nanocrystal assemblies including structurally complex gel networks and compositionally complex mixed binary superlattices. This broadly applicable framework will facilitate the design of complex, hierarchically structured, and dynamic assemblies for desired optical characteristics.

Modular mixing in plasmonic metal oxide nanocrystal gels with thermoreversible links.

Gelation offers a powerful strategy to assemble plasmonic nanocrystal networks incorporating both the distinctive optical properties of constituent building blocks and customizable collective properties. Beyond what a single-component assembly can offer, the characteristics of nanocrystal networks can be tuned in a broader range when two or more components are intimately combined. Here, we demonstrate mixed nanocrystal gel networks using thermoresponsive metal-terpyridine links that enable rapid gel assembly and disassembly with thermal cycling. Plasmonic indium oxide nanocrystals with different sizes, doping concentrations, and shapes are reliably intermixed in linked gel assemblies, exhibiting collective infrared absorption that reflects the contributions of each component while also deviating systematically from a linear combination of the spectra for single-component gels. We extend a many-bodied, mutual polarization method to simulate the optical response of mixed nanocrystal gels, reproducing the experimental trends with no free parameters and revealing that spectral deviations originate from cross-coupling between nanocrystals with distinct plasmonic properties. Our thermoreversible linking strategy directs the assembly of mixed nanocrystal gels with continuously tunable far- and near-field optical properties that are distinct from those of the building blocks or mixed close-packed structures.

Highly Responsive Plasmon Modulation in Dopant-Segregated Nanocrystals.

Electron transfer to and from metal oxide nanocrystals (NCs) modulates their infrared localized surface plasmon resonance (LSPR), revealing fundamental aspects of their photophysics and enabling dynamic optical applications. We synthesized and chemically reduced dopant-segregated Sn-doped In2O3 NCs, investigating the influence of radial dopant segregation on LSPR modulation and near-field enhancement (NFE). We found that core-doped NCs show large LSPR shifts and NFE change during chemical titration, enabling broadband modulation in LSPR energy of over 1000 cm-1 and of peak extinction over 300%. Simulations reveal that the evolution of the LSPR spectra during chemical reduction results from raising the surface Fermi level and increasing the donor defect density in the shell region. These results establish dopant segregation as a useful strategy to engineer the dynamic optical modulation in plasmonic semiconductor NC heterostructures going beyond what is possible with conventional plasmonic metals.

Synthetic Control of Intrinsic Defect Formation in Metal Oxide Nanocrystals Using Dissociated Spectator Metal Salts.

Crystallographic defects are essential to the functional properties of semiconductors, controlling everything from conductivity to optical properties and catalytic activity. In nanocrystals, too, defect engineering with extrinsic dopants has been fruitful. Although intrinsic defects like vacancies can be equally useful, synthetic strategies for controlling their generation are comparatively underdeveloped. Here, we show that intrinsic defect concentration can be tuned during the synthesis of colloidal metal oxide nanocrystals by the addition of metal salts. Although not incorporated in the nanocrystals, the metal salts dissociate at high temperatures, promoting the dissociation of carboxylate ligands from metal precursors, leading to the introduction of oxygen vacancies. For example, the concentration of oxygen vacancies can be controlled up to 9% in indium oxide nanocrystals. This method is broadly applicable as we demonstrate by generating intrinsic defects in metal oxide nanocrystals of various morphologies and compositions.

Effective Hard-Sphere Repulsions between Oleate-Capped Colloidal Metal Oxide Nanocrystals.

Nanocrystal interactions in solvent influence colloidal stability and dictate self-assembly outcomes. Small-angle X-ray scattering is used to study how dilute oleate-capped In2O3 nanocrystals with 7-19 nm core diameters interact when dispersed in a series of nonpolar solvents. Osmotic second virial coefficient analysis finds toluene-dispersed nanocrystals in this size range interact like effective hard spheres with diameters comprising the inorganic core and a ligand-solvent corona with a core-size independent thickness. Hard-sphere-like structure factors are similarly observed for nanocrystals with a 9.7 nm core diameter dispersed in all the solvents investigated. Nanocrystal hydrodynamic diameters from dynamic light scattering measurements correlate with thermodynamic diameters obtained from the osmotic second virial coefficient analysis for all samples. The ability to prepare nanoscale building blocks of different sizes, and dispersed in a variety of solvents, with effective hard-sphere repulsions provides a foundation for assembly, where secondary linking or depletant molecules can be deliberately added to customize interactions to form superstructures such as gel networks or superlattices.

Symmetry-breaking in patch formation on triangular gold nanoparticles by asymmetric polymer grafting.

Synthesizing patchy particles with predictive control over patch size, shape, placement and number has been highly sought-after for nanoparticle assembly research, but is fraught with challenges. Here we show that polymers can be designed to selectively adsorb onto nanoparticle surfaces already partially coated by other chains to drive the formation of patchy nanoparticles with broken symmetry. In our model system of triangular gold nanoparticles and polystyrene-b-polyacrylic acid patch, single- and double-patch nanoparticles are produced at high yield. These asymmetric single-patch nanoparticles are shown to assemble into self-limited patch‒patch connected bowties exhibiting intriguing plasmonic properties. To unveil the mechanism of symmetry-breaking patch formation, we develop a theory that accurately predicts our experimental observations at all scales-from patch patterning on nanoparticles, to the size/shape of the patches, to the particle assemblies driven by patch‒patch interactions. Both the experimental strategy and theoretical prediction extend to nanoparticles of other shapes such as octahedra and bipyramids. Our work provides an approach to leverage polymer interactions with nanoscale curved surfaces for asymmetric grafting in nanomaterials engineering.

Dynamics of equilibrium-linked colloidal networks.

Colloids that attractively bond to only a few neighbors (e.g., patchy particles) can form equilibrium gels with distinctive dynamic properties that are stable in time. Here, we use a coarse-grained model to explore the dynamics of linked networks of patchy colloids whose average valence is macroscopically, rather than microscopically, constrained. Simulation results for the model show dynamic hallmarks of equilibrium gel formation and establish that the colloid-colloid bond persistence time controls the characteristic slow relaxation of the self-intermediate scattering function. The model features re-entrant network formation without phase separation as a function of linker concentration, centered at the stoichiometric ratio of linker ends to nanoparticle surface bonding sites. Departures from stoichiometry result in linker-starved or linker-saturated networks with reduced connectivity and shorter characteristic relaxation times with lower activation energies. Underlying the re-entrant trends, dynamic properties vary monotonically with the number of effective network bonds per colloid, a quantity that can be predicted using Wertheim's thermodynamic perturbation theory. These behaviors suggest macroscopic in situ strategies for tuning the dynamic response of colloidal networks.

Aqueous transfer of colloidal metal oxide nanocrystals via base-driven ligand exchange.

A general method is developed for removal of native nonpolar oleate ligands from colloidal metal oxide nanocrystals of varying morphologies and compositions. Ligand stripping occurs by phase transfer into potassium hydroxide solution, yielding stable aqueous dispersions with little nanocrystal aggregation and without significant changes to the nanomaterials' physical or chemical properties. This method enables facile fabrication of conductive films of ligand-free nanocrystals.

Contact Conductance Governs Metallicity in Conducting Metal Oxide Nanocrystal Films.

Although colloidal nanoparticles hold promise for fabricating electronic components, the properties of nanoparticle-derived materials can be unpredictable. Materials made from metallic nanocrystals exhibit a variety of transport behavior ranging from insulators, with internanocrystal contacts acting as electron transport bottlenecks, to conventional metals, where phonon scattering limits electron mobility. The insulator-metal transition (IMT) in nanocrystal films is thought to be determined by contact conductance. Meanwhile, criteria are lacking to predict the characteristic transport behavior of metallic nanocrystal films beyond this threshold. Using a library of transparent conducting tin-doped indium oxide nanocrystal films with varied electron concentration, size, and contact area, we assess the IMT as it depends on contact conductance and show how contact conductance is also key to predicting the temperature-dependence of conductivity in metallic films. The results establish a phase diagram for electron transport behavior that can guide the creation of metallic conducting materials from nanocrystal building blocks.

Assembling Inorganic Nanocrystal Gels.

Inorganic nanocrystal gels retain distinct properties of individual nanocrystals while offering tunable, network-structure-dependent characteristics. We review different mechanisms for assembling gels from colloidal nanocrystals including (1) controlled destabilization, (2) direct bridging, (3) depletion, as well as linking mediated by (4) coordination bonding or (5) dynamic covalent bonding, and we highlight how each impacts gel properties. These approaches use nanocrystal surface chemistry or the addition of small molecules to mediate inter-nanocrystal attractions. Each method offers advantages in terms of gel stability, reversibility, or tunability and presents new opportunities for the design of reconfigurable materials and fueled assemblies.

Colorimetric quantification of linking in thermoreversible nanocrystal gel assemblies.

Nanocrystal gels can be responsive, tunable materials, but designing their structure and properties is challenging. By using reversibly bonded molecular linkers, gelation can be realized under conditions predicted by thermodynamics. However, simulations have offered the only microscopic insights, with no experimental means to monitor linking leading to gelation. We introduce a metal coordination linkage with a distinct optical signature allowing us to quantify linking in situ and establish structural and thermodynamic bases for assembly. Because of coupling between linked indium tin oxide nanocrystals, their infrared absorption shifts abruptly at a chemically tunable gelation temperature. We quantify bonding spectroscopically and use molecular simulation to understand temperature-dependent bonding motifs, revealing that gel formation is governed by reaching a critical number of effective links that extend the nanocrystal network. Microscopic insights from our colorimetric linking chemistry enable switchable gels based on thermodynamic principles, opening the door to rational design of programmable nanocrystal networks.