Penta-twinned Gold Research Articles

In situ atomic observations of aggregation growth and evolution of penta-twinned gold nanocrystals

The twin boundaries and inherent lattice strain of five-fold twin (5-FT) structures offer a promising and innovative approach to tune nanocrystal configurations and properties, enriching nanomaterial performance. However, a comprehensive understanding of the nonclassical growth models governing 5-FT nanocrystals remains elusive, largely due to the constraints of their small thermodynamically stable size and complex twin configurations. Here, we conducted in situ investigations to elucidate the atomic-scale mechanisms driving size-dependent and twin configuration-related aggregation phenomena between 5-FT and other nanoparticles at the atomic scale. Our results reveal that surface diffusion significantly shapes the morphology of aggregated nanoparticles, promoting the symmetrical formation of 5-FT, especially in smaller nanoparticles. Moreover, the inherent structural characteristics of 5-FT mitigate the dominance of surface diffusion in its morphological evolution, retarding the aggregation evolution process and fostering intricate twin structures. These findings contribute to advancing our capacity to manipulate the configuration of twinned particles, enabling more predictable synthesis of functional nanomaterials for advanced engineering applications.

Single Crystal and Pentatwinned Gold Nanorods Result in Chiral Nanocrystals with Reverse Handedness.

Handedness is an essential attribute of chiral nanocrystals, having a major influence on their properties. During chemical growth, the handedness of nanocrystals is usually tuned by selecting the corresponding enantiomer of chiral molecules involved in asymmetric growth, often known as chiral inducers. We report that, even using the same chiral inducer enantiomer, the handedness of chiral gold nanocrystals can be reversed by using Au nanorod seeds with either single crystalline or pentatwinned structure. This effect holds for chiral growth induced both by amino acids and by chiral micelles. Although it was challenging to discern the morphological handedness for L-cystine-directed particles, even using electron tomography, both cases showed circular dichroism bands of opposite sign, with nearly mirrored chiroptical signatures for chiral micelle-directed growth, along with quasi-helical wrinkles of inverted handedness. These results expand the chiral growth toolbox with an effect that might be exploited to yield a host of interesting morphologies with tunable optical properties.

Single Crystal and Pentatwinned Gold Nanorods Result in Chiral Nanocrystals with Reverse Handedness

AbstractHandedness is an essential attribute of chiral nanocrystals, having a major influence on their properties. During chemical growth, the handedness of nanocrystals is usually tuned by selecting the corresponding enantiomer of chiral molecules involved in asymmetric growth, often known as chiral inducers. We report that, even using the same chiral inducer enantiomer, the handedness of chiral gold nanocrystals can be reversed by using Au nanorod seeds with either single crystalline or pentatwinned structure. This effect holds for chiral growth induced both by amino acids and by chiral micelles. Although it was challenging to discern the morphological handedness for L‐cystine‐directed particles, even using electron tomography, both cases showed circular dichroism bands of opposite sign, with nearly mirrored chiroptical signatures for chiral micelle‐directed growth, along with quasi‐helical wrinkles of inverted handedness. These results expand the chiral growth toolbox with an effect that might be exploited to yield a host of interesting morphologies with tunable optical properties.

Electromigration Lifetime of Penta-Twinned Gold Nanowires: Implications for Flexible Electronics

Electromigration Lifetime of Penta-Twinned Gold Nanowires: Implications for Flexible Electronics

Regulated synthesis of an Au NB-DT@Ag bimetallic core-molecule-shell nanostructure for reliable SERS detection.

In recent research, anisotropic plasmonic core-shell nanomaterials have gained a lot of attention in surface-enhanced Raman scattering (SERS) due to their brilliant uniformity and optical properties. Herein, a bimetallic core-molecule-shell (CMS) composite nanorod SERS substrate nanomaterial (Au NB-DT@Ag NRs) was designed and synthesized under precise regulation. The inner core is gold nanobipyramids (Au NBs), which possess superior plasmonic properties. Uniform Au NBs of five different sizes were fabricated via a penta-twinned gold seed mediated growth method. The length varied from 160 to 62 nm and the corresponding diameter varied from 60 to 23 nm while the longitudinal surface plasmonic resonance (SPR) changed from 908 to 715 nm. The SERS activity of five Au NBs were compared and the optimally sized one with a length of 78 nm and width of 28 nm was set as the inner core. After modification with the Raman reporter (DT), different amounts of silver were deposited on the surface of Au NB-DTs to form an Au NB-DT@Ag nanocomposite. The shape of the nanostructure gradually became a rod and lengthened while the longitudinal SPR wavelength varied from 733 nm to 664 nm with an increase in the amount of silver nitrate added. The Au NB-DT@Ag NRs with the best SERS activity (b-3) could realize the quantitative detection of the toxic dyes malachite green (MG) and crystal violet (CV) of concentrations as low as 5 × 10-9 M, showing good reproducibility and stability. This work offers a new design strategy for a SERS substrate for reliable quantitative SERS detection applications.

Ultrafast Laser-Induced Formation of Hollow Gold Nanorods and Their Optical Properties.

Laser irradiation has been shown to be an efficient means to modify structures and shapes of plasmonic nanoparticles for tuning their properties. Thermomechanical deformations of single-crystal and penta-twinned gold nanorods by femtosecond laser irradiations have been studied by classical molecular dynamics simulations. It is demonstrated that hollow gold nanorods could be formed by femtosecond laser irradiations under certain conditions of maximum temperatures in nanorods by laser heating and cooling rates due to the extrinsic solvent. For a given maximum temperature and cooling rate, a larger cavity is induced in the irradiated single-crystal nanorod. The results also indicate that at the same cooling rate a higher threshold of maximum temperature can be required for producing the cavity in the twinned nanorod. The optical spectra of the laser-irradiated gold nanorods are calculated, and the shifts in the surface plasmon resonance peak of the nanorods are illustrated due to the thermal reshaping and the plasmon hybridization mechanism. Moreover, we show the formation of the hollow gold nanorod possessing the surface plasmon resonance peak in the second near-infrared window and a relatively small aspect ratio (∼2.8), which is highly desirable and suitable for serving as agents in biomedical imaging and photothermal therapy applications.

Symmetry Breaking in Seed-Mediated Silver Nanorod Growth Induced by Dimethyl Sulfoxide

Engineering symmetry breaking in seed-mediated growth is a fundamental challenge to produce colloidal nanocrystals with controlled morphologies and properties. In this work, we show a simple, aqueous approach to breaking the inversion symmetry of silver nanorods by restricting growth to one end of the pentatwinned gold bipyramid seed. Controlled addition of dimethyl sulfoxide (DMSO) allows us to tune both the symmetry and the length and width of the objects. Simulations and experiments demonstrate the adsorption of DMSO, which displaces interfacial water, reduces binding of surfactant and chloride ions at the gold surface, and slows down the deposition kinetics of silver. Besides showing the potential of DMSO for controlling the synthesis of complex nanostructures, this work opens new perspectives for the study of the physical properties of noncentrosymmetric nanoparticles, e.g., by controlling their plasmon modes and their second-harmonic generation efficiency.

A universal route with fine kinetic control to a family of penta-twinned gold nanocrystals.

Some of the major difficulties hindering the synthesis of different types of colloidal nanocrystals are their complex synthetic methods and the lack of a universal growth mechanism in one system. Herein, we propose a general strategy of kinetically controlled seed-mediated growth to synthesize a family of penta-twinned gold nanocrystals. Specifically, different kinds of penta-twinned nanocrystals (truncated penta-twinned decahedra, truncated bipyramids, bipyramids, truncated bipyramids with tips, star-like penta-twinned nanocrystals, decahedra with concave edges, and decahedra) with tunable sizes and high purity were readily achieved in one system solely by tailoring the deposition kinetics of adatoms on different sites of decahedral seeds. The controllable deposition kinetics can be realized by changing the ratio of reductant/gold precursors (R), which dictates whether horizontal or vertical features along the 5-fold axis direction of Au decahedral seeds are produced. Additionally, the selective growth of a second metal (silver) on penta-twinned gold seeds can be reached through minor modification of R, which opens a new avenue for mechanistic investigation by visualizing the seed localization within the final particles. The present work demonstrates a general paradigm for the kinetic growth of penta-twinned crystals and would be extended to the synthesis of other families of nanocrystals.

Bromide Causes Facet-Selective Atomic Addition in Gold Nanorod Syntheses

The aspect ratio-dependent properties of gold nanorods are used in a variety of applications, but the cause of anisotropic nanorod growth remains unclear. Measurements utilizing single-crystal electrodes were collected to determine what additive(s) in pentatwinned gold nanorod syntheses are responsible for facet-selective atomic addition. With cetyltrimethylammonium in the absence of bromide, the rate of atomic addition to Au(100) and Au(111) single crystals was the same, and isotropic nanoparticles were produced. The addition of increasing concentrations of bromide suppressed the rate of atomic addition to Au(100) relative to Au(111) and increased the aspect ratio of gold nanorods. Bromide was a more effective passivator of Au(100) in the absence of cetyltrimethylammonium, indicating cetyltrimethylammonium does not cause facet-selective atomic addition. Cetyltrimethylammonium surfactant is still necessary for gold nanorod growth because it reduces the rate of gold ion reduction and stabilizes suspended nanoparticles against aggregation.

PH Regulated Synthesis of Monodisperse Penta-Twinned Gold Nanoparticles with High Yield

Making different types of nanoparticles (NPs) in the same system is important not only for simplifying the synthesis but for reaching a universal growth mechanism and improving reproducibility. Here we show that different types of penta-twinned NPs (spheroid, bipyramid, and decahedron) with adjustable sizes can be prepared in one system with high purity by simply varying the initial pH of the growth solution. The generality of this method has been demonstrated with a variety of enols as a reductant, including ascorbic acid. The effect of pH was mainly attributed to the regulation of the reduction potential of reductants (RPRs), which determines the atomic deposition preference on the penta-twinned seed surface due to the lattice strain energy at the twin boundary and then the way it grows into final products. This method of controlling the atomic deposition by regulating the RPRs could be useful for the synthesis of other nanoparticles through the seed-mediated method.

Atomistic simulation of the measurement of mechanical properties of gold nanorods by AFM

Mechanical properties of nanoscale objects can be measured with an atomic force microscope (AFM) tip. However, the continuum models typically used to relate the force measured at a certain indentation depth to quantities such as the elastic modulus, may not be valid at such small scales, where the details of atomistic processes need to be taken into account. On the other hand, molecular dynamics (MD) simulations of nanoindentation, which can offer understanding at an atomistic level, are often performed on systems much smaller than the ones studied experimentally. Here, we present large scale MD simulations of the nanoindentation of single crystal and penta-twinned gold nanorod samples on a silicon substrate, with a spherical diamond AFM tip apex. Both the sample and tip sizes and geometries match commercially available products, potentially linking simulation and experiment. Different deformation mechanisms, involving the creation, migration and annihilation of dislocations are observed depending on the nanorod crystallographic structure and orientation. Using the Oliver-Pharr method, the Young’s moduli of the (100) terminated and (110) terminated single crystal nanorods, and the penta-twinned nanorod, have been determined to be 103 ± 2, 140 ± 4 and 108 ± 2 GPa, respectively, which is in good agreement with bending experiments performed on nanowires.

High-Yield Seeded Growth of Monodisperse Pentatwinned Gold Nanoparticles through Thermally Induced Seed Twinning.

We show that thermal treatment of small Au seeds results in extensive twinning and a subsequent drastic improvement in the yield (>85%) of formation of pentatwinned nanoparticles (NPs), with preselected morphology (nanorods, bipyramids, and decahedra) and aspect ratio. The "quality" of the seeds thus defines the yield of the obtained NPs, which in the case of nanorods avoids the need for additives such as Ag+ ions. This modified seeded growth method also improves reproducibility, as the seeds can be stored for extended periods of time without compromising the quality of the final NPs. Additionally, minor modification of the seeds with Pd allows their localization within the final particles, which opens new avenues toward mechanistic studies. Together, these results represent a paradigm shift in anisotropic gold NP synthesis.

Breathing mode vibrations and elastic properties of single-crystal and penta-twinned gold nanorods.

The acoustic vibrations of individual single-crystal and penta-twinned gold nanorods with widths from ∼7 to ∼26 nm are studied using atomic-level simulations and finite element calculations. It is demonstrated that the continuum model in the limit of an infinite rod length could be used to describe the breathing periods of nanorods with an aspect ratio as small as ∼2.5, in combination with bulk material elastic constants. The elastic moduli of gold nanorods are determined via their atomistically simulated extensional periods and the dispersion relation based on long-wavelength approximation. The twinned nanorods become stiffer as the width is reduced, which is in contrast to the size dependence of the modulus in single-crystal nanorods. Further finite element calculations for the breathing periods of nanorods are performed using isotropic elastic constants of bulk gold. We find that the breathing vibrations of the penta-twinned nanorods are more affected by the crystal structure effect than those of single-crystal nanorods, because a smaller range of crystal directions perpendicular to the long axis is involved in the breathing vibrations of twinned nanorods.

Controlled Living Nanowire Growth: Precise Control over the Morphology and Optical Properties of AgAuAg Bimetallic Nanowires.

Inspired by the concept of living polymerization reaction, we are able to produce silver–gold–silver nanowires with a precise control over their total length and plasmonic properties by establishing a constant silver deposition rate on the tips of penta-twinned gold nanorods used as seed cores. Consequently, the length of the wires increases linearly in time. Starting with ∼210 nm × 32 nm gold cores, we produce nanowire lengths up to several microns in a highly controlled manner, with a small self-limited increase in thickness of ∼4 nm, corresponding to aspect ratios above 100, whereas the low polydispersity of the product allows us to detect up to nine distinguishable plasmonic resonances in a single colloidal solution. We analyze the spatial distribution and the nature of the plasmons by electron energy loss spectroscopy and obtain excellent agreement between measurements and electromagnetic simulations, clearly demonstrating that the presence of the gold core plays a marginal role, except for relatively short wires or high-energy modes.

Substrate Induced Symmetry Breaking in Penta-twinned Gold Nanorod Probed by Free Electron Impact

Cathodoluminescence (CL) spectroscopy and imaging in a high resolution scanning electron microscope (SEM) is used to probe and directly map the localized surface plasmon resonance (LSPR) modes of a penta-twinned gold nanorod deposited on a silicon substrate. Finite-difference time-domain simulation of CL enables us to gain insight into the origin of the plasmon modes. Our experimental results and simulations demonstrate that the substrate plays a very crucial role in the observed plasmonic property of gold nanorod. We have shown that, in the visible domain of the spectrum, the plasmon mode gets split into two distinct peaks due to substrate induced hybridization of in-plane and out-of-plane modes. With increasing the refractive index of the substrate, the intensity of these hybridized modes increases. We provide a detailed analysis on the origin and coupling of various plasmon modes mediated by the substrate.

Growth of pentatwinned gold nanorods into truncated decahedra

The growth mechanism from pentatwinned (PTW) gold nanorods into truncated quasi-decahedral particles when a gold salt (HAuCl₄) is reduced by N, N-dimethylformamide (DMF) in the presence of poly(vinylpyrrolidone), was elucidated through a combination of different techniques, including transmission and scanning electron microscopy, high resolution TEM and selected area electron diffraction. Particles with intermediate shapes between the original pentatwinned Au nanorods, used as seeds, and the final quasi-decahedral particles were obtained by simply tuning the [HAuCl₄] to [seeds] ratio. From the thorough structural analysis of all the intermediate morphologies obtained, it was concluded that gradual morphology changes are related to the preferential growth of higher energy crystallographic facets. As a result of the particle growth and concomitant decreased anisotropy, a progressive blue-shift of the surface plasmon resonance bands of the nanoparticles was registered by vis-NIR extinction spectroscopy.

The formation of penta-twinned gold particles

The formation of gold particles containing five radially arranged twin boundaries (called penta-twinned particles) has been investigated by means of high-resolution transmission electron microscopy. The particles were produced by evaporation of gold in helium at low pressure (0.5 kPa). The processes involved in the formation of the particles are deduced from the experimentally observed size distribution, the characteristic particle morphologies and the frequency of different particle structures. The penta-twinned particles are suggested to be formed by the collision and rearrangement of small single crystals in the helium atmosphere.

The structure of small penta-twinned gold particles

The structure of small penta-twinned gold particles

The structure of small penta-twinned gold particles

The structural features of penta-twinned gold particles (size between 2 and 6 nm) generated by gas evaporation have been investigated by high resolution TEM. Penta-twinned particles differ from quasi-crystals in the following way: the five coherent twin boundaries separating the twin oriented segments do not join up along a common edge. The lattice parameter is reduced by 4 – 5 % in comparison to that of bulk gold. The formation of the penta-twinned particles is proposed to occur by particle collision. The particles were observed to be crystalline at ambient temperature.