Or colloïdal | EPFL Graph Search

L'or colloïdal est une suspension de nanoparticules d'or dans un milieu fluide qui peut être l'eau, un solvant organique ou un gel. Selon la taille et la concentration des particules en suspension, sa couleur varie du rouge vif (pour des particules de moins de 100 nanomètres), au jaunâtre (pour les particules les plus grosses). Connu depuis une époque reculée, l'or colloïdal fut à l'origine utilisé pour colorer le verre et la porcelaine. L'étude scientifique de ce mélange homogène ne débuta qu'avec les travaux de Michael Faraday dans les années 1850. En raison de leurs propriétés optiques, électroniques et de reconnaissance moléculaire uniques, les nanoparticules d'or font l'objet de recherches approfondies, avec de multiples domaines d'applications comme la microscopie électronique, l'électronique, les nanotechnologies, la science des matériaux et la nanomédecine. Les propriétés et les applications des nanoparticules d'or colloïdal dépendent de leur forme. Par exemple les particu

Scalable fabrication of functional nanostructures on stretchable substrates by capillary-assisted particle assembly and adhesion lithography

Shao-Chi Yu

The fabrication of metallic nanostructures on stretchable substrates enables specific applications that exploit the combination of the nano-scale phenomena and the mechanical tunability of the physical dimensions of the nanostructures. Due to the large difference in the thermal expansion coefficient between metals and polymer-based soft materials, patterning metallic nanostructures directly on a stretchable substrate is a known challenging task. In this thesis, scalable fabrications of metallic nanostructures on stretchable substrates by top-down and bottom-up methods are studied. Metallic nanostructures are first fabricated on Si substrates and subsequently transferred to stretchable substrates.In the first part of this thesis, fabrication of nanogap electrodes (NGEs) on a polydimethylsiloxane (PDMS) substrate using adhesion lithography is reported. With wafer-level processes, the nanogap is created on an Al sacrificial layer by separating two Au electrodes with an Al2O3 nanolayer. By etching the Al sacrificial layer, the NGEs are transferred to the PDMS substrate. Tunneling currents across the nanogap on PDMS are measured under various mechanical deformation statuses of the PDMS substrate. The electrical measurement results show that the nanogap distance is mechanically tunable in the quantum tunneling regime. The NGEs on PDMS might be eventually integrated with micro piezo-electric actuators to become miniaturized tunable NGEs, which could pave the way towards the application of an on-chip single-molecule detector. Apart from developing the fabrication process of the NGEs on PDMS, a yield study of the essential step of the adhesion lithography, e.g., the tape peeling process, is also conducted to understand the design principles of the NGEs. The yield of the wafer-level tape peeling process is larger than 80%.In the second part of this thesis, chip-level (~ 2 x 2 cm2) fabrication of ordered gold nanoparticles (AuNPs) on a PDMS substrate using capillary-assisted particle assembly (CAPA) technique is reported. AuNPs are first assembled on reusable Si templates with pre-defined topographical traps, and then transferred to the PDMS substrate by etching the Al sacrificial layer. The reusable assembly trap has the shape of the funnel which is designed for high assembly yield (> 90%) and precise particle placement (offset ~ 10 nm). The assembly yield, the particle position offset, the yield of the transfer process, and the reusability of the assembly template are systematically studied. Two functional AuNP structures are demonstrated using the reported fabrication process. The first structure is the plasmonic surface lattice resonance (SLR) arrays of 150 and 200 nm AuNP. The optical spectra of the AuNP arrays on PDMS are measured showing pitch-related SLR peaks that agree with the finite element method (FEM) simulation results. The second structure is the dimer of 200 nm AuNPs which has a nanogap between two AuNPs. By assembling two AuNPs in the same funnel-shaped trap, a nanogap is formed between two AuNPs. Combining Au electrodes fabricated using electron beam lithography and the lift-off process, NGEs are fabricated and successfully transferred to a PDMS substrate.

EPFL2022

Galvanic replacement reactions of Ga and In with Cu for the synthesis of bimetallic nanoparticles

Laia Castilla Amorós

The need for efficient and selective catalysts, capable of driving important conversions to build a more sustainable society, encourages the development of synthetic approaches towards new nanomaterials. Cu-based bimetallic nanoparticles (NPs) promise to fulfill this gap by selectively producing energy-dense products via CO2 electroreduction (CO2RR). However, as small variations in its composition and configuration can enormously affect the catalyst performance, the vast diversity of bimetallic NPs challenges systematic catalyst evaluation. Colloidal bimetallic NPs serve as an ideal platform for the exploration of composition-configuration-property relationships, necessary for rational catalyst design. Although an extensive library of noble metal bimetallic NPs exists, much less has been done regarding non-noble Cu-based bimetallic NPs despite their potential as catalysts for CO2RR. The aim of this thesis is to advance in the synthesis of Cu-based NPs, with focus on Cu-Ga and Cu-In, which have been predicted or demonstrated to possess interesting catalytic properties.The thesis starts with an introduction on bimetallic NPs and the different colloidal approaches to synthesize them. Galvanic replacement reactions (GRRs) are discussed more in details, as they are the synthetic approach of choice for the Cu-Ga and Cu-In NPs. Ga and In belong to a family of liquid metals; thus, information on their general properties is also provided. The first two experimental chapters focus on the reactivity and surface chemistry of Ga NPs. Chapter 3 demonstrates that Ga NPs react with a copper-amine complex to form anisotropic Cu-Ga nanodimers (NDs). Mechanistic studies reveal that a GRR takes place. Yet, the ND morphology differs from the more typical hollow core@shell structures obtained from GRRs. This unusual morphology is attributed to the liquid nature of Ga NPs and to the presence of a native oxide shell. This discovery fostered a follow up study, which is discussed in Chapter 4. The effect of the chemical nature of the capping ligand on the oxide thickness and reactivity of the Ga NPs is investigated. The thickness of the oxide skin is found to greatly depend on the ligands. Specifically, amines and carboxylic acids promote thicker oxide shells while thiols and phosphines hinder its growth. The reaction between Ga NPs with different oxide thickness and the copper precursor leads to a surprising result, while thicker oxides cause the formation of NDs, isolated Cu NPs form with thinner oxides.Chapter 5 turns towards Cu-In NPs. Following the same synthetic scheme, In NPs with different sizes are exploited as sacrificial seeds for the GRR. Cu-In NPs with an unprecedented variety of morphologies and elemental distributions are obtained: spherical Cu11In9 intermetallic and patchy phase-segregated Cu-In NPs, as well as Cu-Cu11In9 and Cu-In NDs. Segregation of the two metals occurs as the GRR progresses, with time or with higher copper precursor concentration. Comparing the obtained results with the Cu-In phase diagram reveals that the bigger seeds stabilize the bulk-like Cu-Cu11In9 configuration before their complete segregation into Cu-In NDs. Aiding in the development of more predictive synthetic approaches.Finally, Chapter 6 concludes by summarizing the significance of the achievements, which advance the knowledge on underexplored bimetallic NPs and on the GRR when applied beyond noble metals. An outlook on future developments is also provided.

EPFL2022

Synthesis of carbon nanotubes and characterization of nanotubes as atomic force microscopy tips

Yanki Keles

This thesis describes the synthesis of carbon nanotubes (CNTs) by chemical vapor deposition (CVD) and the evaluation of them as tips of atomic force microscope (AFM) probes. Both arc-discharge and CVD grown nanotubes were investigated as AFM tips. Two methods were used to produce nanotube tipped AFM probes: (i) nanotubes were directly grown on the apex of AFM probes by CVD and (ii) pre-grown nanotubes were mechanically attached onto the apex of AFM probes. The first part of the thesis describes experiments that sought to control the growth of carbon nanotubes by chemical vapor deposition. The effects of various parameters e.g. catalyst, the carbon source, the addition of hydrogen and the growth temperature, on carbon nanotube growth were investigated. Ethylene was found to lead to better quality nanotubes than the acetylene. Grown nanotubes' quality was found to improve upon flow of hydrogen during the synthesis. Nanotubes synthesized on 3 nm iron film at 840°C using ethylene and hydrogen led to utilizable carbon nanotube tipped AFM probes. The second part of the thesis focuses on the mechanical production of nanotube tipped AFM probes in high resolution electron microscopes using nanomanipulators. Scanning electron microscopy (SEM) was found to be more convenient than transmission electron microscopy (TEM) to carry out the nanomanipulation process. Both arc-discharge and CVD grown nanotubes were successfully attached onto the AFM probes using a custom made nanomanipulator. Nanotubes were glued onto the probes by focused electron beam (FEB) induced amorphous carbon deposits. FEB irradiation deposited amorphous carbon performed more reliable attachment on CVD nanotubes than the arc-discharge nanotubes. The last part of the thesis describes tapping mode AFM measurements done using nanotube tipped AFM probes. Different nanotube tipped probes were investigated as AFM tips for scanning colloidal gold particles with different diameters and gratings from Digital Instruments™ AFMs. High resolution AFM images were obtained by arc-discharge nanotube tips. CVD grown nanotubes were shown to be more resilient to tip crashes than the arc-discharge grown nanotubes. However, all the AFM images acquired from the scans by CVD nanotubes had the same kind of ringing artifact, in good agreement with a previously reported data about the artifacts of the CVD nanotube tipped AFM probes. Open ends of the CVD nanotubes, lack of crystallinity and the defects in their structure are suggested to be the reason for these artifacts.

EPFL2006

Scalable fabrication of functional nanostructures on stretchable substrates by capillary-assisted particle assembly and adhesion lithography

Shao-Chi Yu

EPFL2022

Galvanic replacement reactions of Ga and In with Cu for the synthesis of bimetallic nanoparticles

Laia Castilla Amorós

EPFL2022

Synthesis of carbon nanotubes and characterization of nanotubes as atomic force microscopy tips

Yanki Keles

EPFL2006