On the Dual Roles of Ligands in the Synthesis of Colloidal Metal Nanostructures

Ortiz, Nancy; Skrabalak, Sara E.

doi:10.1021/la404539p

Cited by 101 publications

(104 citation statements)

References 75 publications

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“…Such reducing and capping effects of the amine are frequently found in the literature. 24,27,35 For this reason, the multiple growth rates of Cu during thermal heating in the 1:1 and 1:2 ink-printed films containing the insufficient HA amount were induced, leading to the wide particle size distribution, low film density, and low electrical conductivity. On the other hand, a single-route growth of Cu with a relatively slow growth rate proceeded in 1:3 ink with enough HA content, which led to the narrow particle size distribution, high film density, and high electrical conductivity.…”

Section: Resultsmentioning

confidence: 99%

Effect of the Amine Concentration on Phase Evolution and Densification in Printed Films Using Cu(II) Complex Ink

Choi

Hong

2015

Langmuir

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The nucleation and growth behavior of Cu nanoparticles during thermal heating of Cu(II) complex inks for printed Cu metallization were investigated, particularly focusing on the effects of the amine concentration on the microstructure evolution and electrical conductivity. Herein, the dual effects of hexylamine as a reducing agent dissociating the carboxyl group from the precursor and a capping agent hindering the subsequent growth of Cu nuclei were confirmed. On the basis of such dual effects of amine, the sufficient complexation of the Cu(II) precursor with a high amine concentration in the ink led to the single-route growth of Cu nanoparticles during thermal heating, which resulted in the dense film with a narrow particle size distribution exhibiting a high electrical conductivity. The electrical conductivity of the film could be further enhanced by a reducing atmosphere with formic acid. Significantly, the understanding of the ink chemistry and the nucleation and growth kinetics in the metal ion complex or metal-organic decomposition (MOD) ink can provide the design rules for the formulation of the solution-type inks to control the microstructure of printed metallization.

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Section: Resultsmentioning

confidence: 99%

Effect of the Amine Concentration on Phase Evolution and Densification in Printed Films Using Cu(II) Complex Ink

Choi

Hong

2015

Langmuir

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“…oleic acid (~0.13 mmol) and oleylamine (0.09 mmol). As discussed herein, these ligands can be involved in molecular complexes formed from the metal precursor [4,[23][24][25][26]. As a result, metallic Pt nanoparticles of 4.5 AE 0.8 nm were prepared at 230 C under argon via the reduction of Pt(acac) 2 (0.07 mmol).…”

Section: Size Control In the Presence Of Conventional Stabilisers In Ilsmentioning

confidence: 99%

Size Control of Monodisperse Metal Nanocrystals in Ionic Liquids

Lignier

2015

Ionic Liquids (ILs) in Organometallic Catalysis

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During the last decade, a great interest in the preparation of uniform nanocrystals has offered efficient synthetic strategies to precisely engineer metal, metal oxide and alloy at the nanoscale. Due to their physicochemical properties, ionic liquids (ILs) simultaneously demonstrated their potential in different areas such as nanocrystal synthesis, catalysis and energy. As a result, ionic liquids have been employed for the preparation of monodisperse nanocrystals and the control of their size. This chapter highlights the most promising methods for the synthesis of uniform nanocrystals in ionic liquids which act as a solvent, stabiliser, reducing agent and even precursor. As a result, successful preparations of nanoparticles in the presence of ILs are now available for both noble and earth-abundant elements such as gold, platinum, iridium, silver, palladium, ruthenium, rhodium, copper, nickel, cobalt and iron.The formation mechanisms of these nanocrystals are discussed as well as our mechanistic understanding in conventional organic and aqueous solvents. In addition, the IL approach is compared to leading methods in conventional solvents to make possible the identification of general principles for most metallic elements. By analogy with conventional solvents, these strategies can be adapted to the preparation of semiconductor nanocrystals. These achievements are going to drive the identification of relationships between the nature of ILs components, the physicochemical properties of ILs, the formation of nanocrystals in ILs and the resulting performances of these nano-objects.

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“…[1][2][3][4][5] Understanding the role of ligands in controlling surface properties in plasmonic metal nanocrystal growth has therefore received considerable attention. [6][7][8][9][10] Traditionally, ligand is well-known as capping agent, shapedirect reagent, mediator of reduction kinetics, and even as reducing agent, e.g. in metal crystal growth/engineering for its interaction with the surface of crystal facets, where facets with preferred ligand binding are less exposed and thus grow slower during the metal deposition, as exemplified from different colloidal synthesis such as CTAB-gold NR, 6-7 PVP-silver nanocube, 8 PVPgold nanostar system.…”

Section: Introductionmentioning

confidence: 99%

Engineering Structural Diversity in Gold Nanocrystals by Ligand-Mediated Interface Control

Wang

Sentosun

et al. 2015

Chem. Mater.

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Surface and interface control is fundamentally important for crystal growth engineering, catalysis, surface enhanced spectroscopies, and self-assembly, among other processes and applications. Understanding the role of ligands in regulating surface properties of plasmonic metal nanocrystals during growth has received considerable attention. However, the underlying mechanisms and the diverse functionalities of ligands are yet to be fully addressed. In this contribution, we report a systematic study of ligand-mediated interface control in seeded growth of gold nanocrystals, leading to diverse and exotic nanostructures with an improved surface enhanced Raman scattering (SERS) activity. Three dimensional transmission electron microscopy (3D TEM) revealed an intriguing gold shell growth process mediated by the bifunctional ligand 1,4-benzenedithiol (BDT), which leads to a unique crystal growth mechanism as compared to other ligands, and subsequently to the concept of interfacial energy control mechanism. Volmer-Weber growth mode was proposed to be responsible for BDT-mediated seeded growth, favoring the strongest interfacial energy and generating an asymmetric island growth pathway with internal crevices/gaps. This additionally favors incorporation of BDT at the plasmonic nanogaps, thereby generating strong SERS activity with a maximum efficiency for a core-semishell configuration obtained along seeded growth. Numerical modeling was used to explain this observation. Interestingly, the same strategy can be used to engineer the structural diversity of this system, by using gold nanoparticle seeds with various sizes and shapes, and varying the [Au 3+ ]/[Au 0 ] ratio. This rendered a series of diverse and exotic plasmonic nanohybrids such as semishell-coated gold nanorods, with embedded Raman-active tags and Janus surface with distinct surface functionalities. These would greatly enrich the plasmonic nanostructure toolbox for various studies and applications such as anisotropic nanocrystal engineering, SERS, and high-resolution Raman bioimaging or nanoantenna devices.

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On the Dual Roles of Ligands in the Synthesis of Colloidal Metal Nanostructures

Cited by 101 publications

References 75 publications

Effect of the Amine Concentration on Phase Evolution and Densification in Printed Films Using Cu(II) Complex Ink

Effect of the Amine Concentration on Phase Evolution and Densification in Printed Films Using Cu(II) Complex Ink

Size Control of Monodisperse Metal Nanocrystals in Ionic Liquids

Engineering Structural Diversity in Gold Nanocrystals by Ligand-Mediated Interface Control

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