Metallization of colloidal crystals

Ehlen, Ali; Lopez-Rios, Hector; Cruz, Mónica Olvera de la

doi:10.1103/physrevmaterials.5.115601

Cited by 6 publications

(13 citation statements)

References 48 publications

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“…Experiments and molecular simulations showed how the electron equivalents can break their distribution symmetry around the atom equivalents and move in the superlattice in a way resembling the behavior of electrons in metals. 38,[66][67][68][69][70][71] Similar intra-lattice mobility has also been observed in aggregates of gold NPs decorated with a high density of positively charged groups. Cl − counterions coassembled with NP decorated with a high-density of (11-mercaptoundecyl)-N,N,N -trimethylammonium (TMA) groups, generating colloidal superclusters with semiconductive properties useful to build chemoelectronic circuits.…”

Section: Introductionsupporting

confidence: 62%

“…Pioneering works have shown how the selectivity of DNA interactions can be exploited to assemble NPs functionalized with single-stranded DNA into a variety of superstructures with symmetries typical of a metallic crystal. 38,[66][67][68][69][70][71] As "atom equivalents", the NPs in such supercrystals are surrounded by the smaller particles, which keep them together as superelectron equivalents. Experiments and molecular simulations showed how the electron equivalents can break their distribution symmetry around the atom equivalents and move in the superlattice in a way resembling the behavior of electrons in metals.…”

Section: Introductionmentioning

confidence: 99%

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Supramolecular Semiconductivity through Emerging Ionic Gates in Ion-Nanoparticle Superlattices

Lionello

Perego

Gardin

et al. 2022

Preprint

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The self-assembly of nanoparticles driven by small molecules or ions may produce colloidal superlattices with properties reminiscent of those of metals or semiconductors. However, to what extent the properties of such supramolecular crystals actually resemble those of atomic materials often remains unclear. Here, we present coarse-grained molecular simulations explicitly demonstrating how a behavior evocative of that of semiconductors may emerge in a colloidal superlattice. As a case study, we focus on gold nanoparticles bearing positively charged groups that self-assemble into FCC crystals via mediation of citrate counterions. In silico ohmic experiments show how the dynamically diverse behavior of the ions in different superlattice domains allows the opening of conductive ionic gates above certain levels of applied electric fields. The observed binary conductive/non-conductive behavior is reminiscent of that of conventional semiconductors; however, at a supramolecular level, crossing the “band-gap” requires a sufficient electrostatic stimulus to break the electrostatic interactions and make ions diffuse throughout the superlattice’s cavities.

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Section: Introductionsupporting

confidence: 62%

Section: Introductionmentioning

confidence: 99%

Supramolecular Semiconductivity through Emerging Ionic Gates in Ion-Nanoparticle Superlattices

Lionello

Perego

Gardin

et al. 2022

Preprint

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“…Snapshots of the lattice verify the fact that the small NPs are located at the interstitial sites before the rapid lattice expansion (Figure C), as is characteristic of ionic compounds, and after the expansion the small NPs become delocalized (Figure D). Meanwhile, the lattice in the metallic state experiences larger vibration and distortion while maintaining the fcc structure, which is also found in NPs with grafted linkers interacting with large NPs. , On the basis of the equilibrium configurations of the crystal, we further divide the fcc phase in Figure F into the ionic and metallic states (Figure E).…”

Section: Resultsmentioning

confidence: 99%

“…When the strength of the interactions between the two components is reduced by decreasing the number of grafted DNA chains on the smaller NPs and/or by increasing the temperature, the smaller NPs undergo a transition from localized to delocalized from the interstitial sites and roam the crystal maintaining the integrity of lattice formed by the larger NPs, as electrons do in metals. This way of bonding appears in molecular dynamics (MD) simulations of coassemblies of asymmetric NPs even when electrostatic interactions are not included. − The transition from localized to delocalized small components, termed metallization , hereafter referred also as the ionic to metallic transition , was predicted to exist in cubic and various noncubic functionalized colloidal crystal lattices, some of which have been obtained experimentally . The metallization behavior has also been seen in two-dimensional lattices …”

Section: Introductionmentioning

confidence: 99%

“…Experimentally, the crystals are assembled in a colloid suspension that determines the composition of the compound, which we hypothesize it should change at the ionic–metallic transition. Simulations and analysis of the ionic–metallic transition in colloidal crystals, ,,, however, do not consider molecular and/or atomic exchange between the crystals and the surroundings. That is, the simulations consider an isolated crystalline phase whose composition does not react to changes in the temperature or the solution conditions, whereas the composition of the assembled crystals should be an outcome of the experimental conditions, instead of a controlling parameter.…”

Section: Introductionmentioning

confidence: 99%

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Superionic Colloidal Crystals: Ionic to Metallic Bonding Transitions

Lin

Cruz

2022

J. Phys. Chem. B

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Size-asymmetric binary charged colloidal solutions can assemble into ionic colloidal crystals. These are often stabilized by ionic-type bonding, where the components with smaller size and charge sit at fixed points within the lattice of large particles. Here, we study the transition termed ionic to metallic bonding transition, by which the lattice of the smaller component melts while the crystal of the large particles is preserved, as in metallic bonding. We simulate a charged colloidal crystal in equilibrium with a solution containing small colloidal particles and counterions using the Coulomb interaction between the finite-size components. We find ionic to metallic first-order transitions by increasing either the temperature or the concentration of the small particles in the solution. The transition is accompanied by a lattice expansion and increased absorption of small particles into the crystal. We compute the free energies of the ionic and metallic states using the Madelung constant and Wigner–Seitz cell approaches, respectively, combined with the quasi-harmonic lattice model. The calculation reproduces the simulated transition and reveals that the enthalpic gain is more pronounced than the entropic gain in the transition from ionic to metallic bonding when material is exchanged with the solution.

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Self-Assembling of Nonadditive Mixtures Containing Patchy Particles with Tunable Interactions

Matos,

Escobedo

2023

J. Phys. Chem. B

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Mixtures of nanoparticles (NPs) with hybridizing grafted DNA or DNA-like strands have been of particular interest because of the tunable selectivity provided for the interactions between the NP components. A richer self-assembly behavior would be accessible if these NP-NP interactions could be designed to give nonadditive mixing (in analogy to the case of molecular components). Nonadditive mixing occurs when the mixed-state volume is smaller (negative) or larger (positive) than the sum of the individual components’ volumes. However, instances of nonadditivity in colloidal/NP mixtures are rare, and systematic studies of such mixtures are nonexistent. This work focuses on patchy NPs whose patches (coarsely representing grafted hybridizing DNA strands) not only encode selectivity across components but also impart a tunable nonadditivity by varying their extent of protrusion. To guide the exploration of the relationship between phase behavior and nonadditivity for different patches’ designs, the NP–NP potential of mean force (PMF) and a nonadditive parameter were first calculated. For one-patch NPs, different lamellar morphologies were predominantly observed. In contrast, for mixtures of two-patch NPs and (fully grafted) spherical particles, a rich phase behavior was found depending on patch–patch angle and degree of nonadditivity, resulting in phases such as the gyroid, cylinder, honeycomb, and two-layered crystal. Our results also show that both minimum positive nonadditivity and multivalent interactions are necessary for the formation of ordered network mesophases in the class of models studied.

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Metallization of colloidal crystals

Cited by 6 publications

References 48 publications

Supramolecular Semiconductivity through Emerging Ionic Gates in Ion-Nanoparticle Superlattices

Supramolecular Semiconductivity through Emerging Ionic Gates in Ion-Nanoparticle Superlattices

Superionic Colloidal Crystals: Ionic to Metallic Bonding Transitions

Self-Assembling of Nonadditive Mixtures Containing Patchy Particles with Tunable Interactions

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