Ultralarge atomically flat template-stripped Au surfaces for scanning probe microscopy

Hegner, Martin; Wagner, P.; Semenza, Giorgio

doi:10.1016/0039-6028(93)91474-4

Cited by 508 publications

(475 citation statements)

References 25 publications

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“…Substrates for CaCO 3 nucleation were prepared from evaporated gold on mica (Agilent Technologies) using the template-stripped gold method (48). Self-assembled monolayers were deposited on the gold by submerging the substrates in ethanol-based (200 proof anhydrous, Sigma-Aldrich), 1.5-mM solutions of the following five alkanethiols (Sigma-Aldrich): 16-Mercaptohexadecanoic acid (C16-COOH), 1,16-Hexadecanedithiol (C16-SH), 1,11-Undecanedithiol (C11-SH), 11-Mercaptoundecylphosphoric acid (C11-PO 4 ), or 11-Mercapto-1-undecanol (C11-OH), for 12-15 h.…”

Section: Methodsmentioning

confidence: 99%

Reconciling disparate views of template-directed nucleation through measurement of calcite nucleation kinetics and binding energies

Hamm

Giuffre

Han

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

136

173

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The physical basis for how macromolecules regulate the onset of mineral formation in calcifying tissues is not well established. A popular conceptual model assumes the organic matrix provides a stereochemical match during cooperative organization of solute ions. In contrast, another uses simple binding assays to identify good promoters of nucleation. Here, we reconcile these two views and provide a mechanistic explanation for template-directed nucleation by correlating heterogeneous nucleation barriers with crystal-substrate-binding free energies. We first measure the kinetics of calcite nucleation onto model substrates that present different functional group chemistries (carboxyl, thiol, phosphate, and hydroxyl) and conformations (C11 and C16 chain lengths). We find rates are substrate-specific and obey predictions of classical nucleation theory at supersaturations that extend above the solubility of amorphous calcium carbonate. Analysis of the kinetic data shows the thermodynamic barrier to nucleation is reduced by minimizing the interfacial free energy of the system, γ. We then use dynamic force spectroscopy to independently measure calcitesubstrate-binding free energies, ΔG b . Moreover, we show that within the classical theory of nucleation, γ and ΔG b should be linearly related. The results bear out this prediction and demonstrate that low-energy barriers to nucleation correlate with strong crystal-substrate binding. This relationship is general to all functional group chemistries and conformations. These findings provide a physical model that reconciles the long-standing concept of templated nucleation through stereochemical matching with the conventional wisdom that good binders are good nucleators. The alternative perspectives become internally consistent when viewed through the lens of crystal-substrate binding.B iological systems are unique in their ability to organize minerals into functional materials with complex patterns and architectures. A substantial body of evidence suggests specialized macromolecules, particularly proteins (1, 2) and carbohydrates (3, 4), provide preferential sites for nucleation to direct the placement, timing, and orientation of crystals (5), both intra-and extracellular. Within the biomineralization community, the conventional view of biologically directed nucleation is that macromolecular matrices present an interfacial match to the crystal lattice that assists in forming the crystal nucleus. This cooperative view of directed nucleation is rooted in the collective action of multiple residues that guide the organization of ions into a configuration defining the energetic minimum for the system. A series of in vitro observations have reinforced this picture by showing that highly ordered organic monolayers can control the location and orientation of calcite crystals precipitated from solution (6). In this approach, good templates are revealed through a direct functional assay, i.e., nucleation. Over the years, this view of mineralization, both in the context of natural stru...

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Section: Methodsmentioning

confidence: 99%

Reconciling disparate views of template-directed nucleation through measurement of calcite nucleation kinetics and binding energies

Hamm

Giuffre

Han

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

136

173

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“…After cooling and right before an experiment the surface is peeled off and the freshly exposed polymer surface is used for the force measurement. The same technique can also be used for gold or other materials which can be sputtered or evaporated [26,27]. First the material is deposited onto mica or a silicon wafer.…”

Section: Overviewmentioning

confidence: 99%

Force measurements with the atomic force microscope: Technique, interpretation and applications

Butt

Cappella

Kappl

2005

Surface Science Reports

3,245

2,949

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“…The process is based on a modified template-stripping procedure that was introduced by Butt [266][267] and Hegner [268][269] independently. A naturally flat surface such as Mica or a polished silicon wafer is used as a template onto which gold is evaporated.…”

Section: Introduction: Laterally Patterned Ultraflat Substratesmentioning

confidence: 99%

“…Originally developed for scanning tunneling microscopy imaging, [266][267][268][269] these substrates have been extensively used as electrodes for the electrochemical characterization of self-assembled tethered lipid bilayer membranes [270][271][272] Recently, similar surfaces have been employed for the construction of high quality plasmonic materials [273][274] and as substrates for the patterning of graphene. [275] Using two different surface materials in a similar approach adds to the versatility of the produced substrates as different properties of the patterning materials can be exploited individually.…”

Section: Introduction: Laterally Patterned Ultraflat Substratesmentioning

confidence: 99%

Surface Patterning with Colloidal Monolayers

Vogel

2012

Springer Theses

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This thesis focuses on the controlled assembly of monodisperse polymer colloids into ordered two-dimensional arrangements. These assemblies, commonly referred to as colloidal monolayers, are subsequently used as masks for the generation of arrays of complex metal nanostructures on solid substrates.The motivation of the research presented here is twofold. First, monolayer crystallization methods were developed to simplify the assembly of colloids and to produce more complex arrangements of colloids in a precise way. Second, various approaches to colloidal lithography are designed with the aim to include novel features or functions to arrays of metal nanostructures.The air/water interface was exploited for the crystallization of colloidal monolayer architectures as it combines a two-dimensional confinement with a high lateral mobility of the colloids that is beneficial for the creation of high long range order. A direct assembly of colloids is presented that provides a cheap, fast and conceptually simple methodology for the preparation of ordered colloidal monolayers. The produced two-dimensional crystals can be transformed into nonclose-packed architectures by a plasma-induced size reduction step, thus providing valuable masks for more sophisticated lithographic processes. Finally, the controlled co-assembly of binary colloidal crystals with defined stoichiometries on a Langmuir trough is introduced and characterized with respect to accessible configurations and size ratios.Several approaches to lithography are presented that aim at introducing different features to colloidal lithography. First, using metal-complex containing latex particles, the synthesis of which is described as well, symmetric arrays of metal nanoparticles can be created by controlled combustion of the organic material of the colloids. The process does not feature an inherent limit in nanoparticle size and is able to produce complex materials as will be demonstrated for FePt alloy particles. Precise control over both size and spacing of the particle array is presented.Second, two lithographic processes are introduced to create sophisticated nanoparticle dimer units consisting of two crescent shaped nanostructures in close proximity; essentially by using a single colloid as mask to generate two structures simultaneously. Strong coupling processes of the parental plasmon resonances of the two objects are observed that are accompanied by high near-field enhancements. A plasmon hybridization model is elaborated to explain all polarization dependent shifts of the resonance positions. Last, a technique to produce laterally patterned, ultra-flat substrates without surface topographies by embedding gold nanoparticles in a silicon dioxide matrix is applied to construct robust and re-usable sensing architectures and to introduce an approach for the nanoscale patterning of solid supported lipid bilayer membranes.

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Ultralarge atomically flat template-stripped Au surfaces for scanning probe microscopy

Cited by 508 publications

References 25 publications

Reconciling disparate views of template-directed nucleation through measurement of calcite nucleation kinetics and binding energies

Reconciling disparate views of template-directed nucleation through measurement of calcite nucleation kinetics and binding energies

Force measurements with the atomic force microscope: Technique, interpretation and applications

Surface Patterning with Colloidal Monolayers

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