Photothermally Induced Microchemical Functionalization of Organic Monolayers

Klingebiel, Benjamin; Schröter, Anja; Franzka, Steffen; Hartmann, Nils

doi:10.1002/cphc.200900278

Cited by 16 publications

(20 citation statements)

References 31 publications

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“…[ 23 ] Zhu and co‐workers [ 24 ] achieved local functionalization with polymer by plasma‐induced graft polymerization in a 12 µm thick hourglass‐shaped nanochannel by functionalization of one conical side with poly( N ‐isopropylacrylamide) and the other side with acrylic acid. Other possibilities of a local functionalization of surfaces are contactless electrofunctionalization induced by polarization of the pore membrane in an electric field, [ 25 ] surface patterning using click chemistry directed by scanning electrochemical microscopy, [ 26 ] photothermally induced, [ 27 ] microcontact printing, [ 28 ] photolithographic patterning from reactive silane monolayer [ 29 ] or by using a masking/unmasking technique. [ 30 ] Selective molecular‐assembly patterning which uses oxide contrast of SiO 2 and TiO 2 produced by photolithography and etching [ 31 ] can be used to create patterns with biochemical functionality in simple dip‐and‐rinse steps as shown by Blättler et al [ 32 ] Besides the requirement of sophisticated equipment, a drawback of these techniques is the difficulty in achieving local multifunctionalization within the nanopores.…”

Section: Introductionmentioning

confidence: 99%

Wetting‐Controlled Localized Placement of Surface Functionalities within Nanopores

Ochs

Mohammadi²,

Vogel³

et al. 2020

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Mimicking such functional control in synthetic nanopores requires precise control of structure and local placement of surface functionality. Such precisely prepared materials with nanoscale control on structure and functionalization would allow, for example, new perspectives in sensing. [1] Further strategies mimicking the functionality of biological channels include dynamic curvature nanochannel-based membranes to regulate ionic transport [2] or flexible elastomer-based microchannels for microfluidic devices. [3] Already today nanoscopically structured materials play a crucial role in applications such as sensors or lab on chip devices, [4] separation, [4d] catalysis, [5] and for the developing of new materials, for example for applications in tissue engineering [6] or for the control of surface wettability. [7] Traditionally, nanostructures are fabricated using top-down approaches like photolithography, ink-jet printing or electrospinning. Alternatively, bottom-up methods, which are based on the self-assembly of molecules or larger building blocks, can yield defined structures with high resolution. [8] Periodic, nanostructured materials are for example accessible through the self-assembly of colloidal building blocks, which can yield macroscopic areas of wellordered colloidal crystals. [9] Such colloidal crystals can be further used as templates to generate inorganic, interconnected nanopore arrays by backfilling with a sol-gel precursor and subsequent removal of the templating particles. [9a,10] In two dimensions, the resulting porous materials are known as inverse colloidal monolayers and their wettability can be adjusted by pore opening angle and surface functionalization. [7e,11] Such structures are ideal model pores due to their uniformity, adjustable pore size and ordered structure.A key step toward multifunctional nanopores with nanolocal control, is the ability to precisely position different functionalities into individual pores. [1a] Therefore, it is necessary to develop strategies for a nanoscale control in manufacturing and functionalization of porous materials. This enables nanopore design with multiple functional and responsive units, individually and precisely placed into each nanopore. [1b] To date, functionalization of porous silica materials is mainly based on postsynthetic functionalization strategies like grafting of silanes from gas or liquid phase or cocondensation of functional building blocks. [12] These approaches generally result in a homogenous functionalization without In the context of sensing and transport control, nanopores play an essential role. Designing multifunctional nanopores and placing multiple surface functionalities with nanoscale precision remains challenging. Interface effects together with a combination of different materials are used to obtain local multifunctionalization of nanoscale pores within a model pore system prepared by colloidal templating. Silica inverse colloidal monolayers are first functionalized with a gold layer to create a hybrid porous ...

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Section: Introductionmentioning

confidence: 99%

Wetting‐Controlled Localized Placement of Surface Functionalities within Nanopores

Ochs

Mohammadi²,

Vogel³

et al. 2020

Small

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“…For processing, laser‐beam lithography can use either photochemical or photothermal reactions or a combination thereof to achieve the desired patterning 59. In photochemical laser patterning, direct or substrate‐mediated electronic excitations are used for processing.…”

Section: Introductionmentioning

confidence: 99%

Micro‐ and Nanopatterning of Functional Organic Monolayers on Oxide‐Free Silicon by Laser‐Induced Photothermal Desorption

Scheres

Klingebiel

Maat

et al. 2010

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The photothermal laser patterning of functional organic monolayers, prepared on oxide-free hydrogen-terminated silicon, and subsequent backfilling of the laser-written lines with a second organic monolayer that differs in its terminal functionality, is described. Since the thermal monolayer decomposition process is highly nonlinear in the applied laser power density, subwavelength patterning of the organic monolayers is feasible. After photothermal laser patterning of hexadecenyl monolayers, the lines freed up by the laser are backfilled with functional acid fluoride monolayers. Coupling of cysteamine to the acid fluoride groups and subsequent attachment of Au nanoparticles allows easy characterization of the functional lines by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Depending on the laser power and writing speed, functional lines with widths between 1.1 μm and 250 nm can be created. In addition, trifluoroethyl-terminated (TFE) monolayers are also patterned. Subsequently, the decomposed lines are backfilled with a nonfunctional hexadecenyl monolayer, the TFE stripes are converted into thiol stripes, and then finally covered with Au nanoparticles. By reducing the lateral distance between the laser lines, Au-nanoparticle stripes with widths close to 100 nm are obtained. Finally, in view of the great potential of this type of monolayer in the field of biosensing, the ease of fabricating biofunctional patterns is demonstrated by covalent binding of fluorescently labeled oligo-DNA to acid-fluoride-backfilled laser lines, which--as shown by fluorescence microscopy--is accessible for hybridization.

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“…Further patterning methods include ink-jet printing [14,15], nanografting [16] and even near-field lithography [17]. Because it allows rapid prototyping and patterning of large areas with high precision, laser machining has been used by various groups to pattern SAMs [18][19][20][21][22][23][24][25]. Even though alkanethiol SAMs on gold have emerged as a standard [2], patterning schemes for SAMs of thiolated molecules on copper surfaces are of considerable interest because copper is extensively used in the electronics industry.…”

Section: Introductionmentioning

confidence: 99%

Patterned self-assembled monolayers of alkanethiols on copper nanomembranes by submerged laser ablation

Rhinow

Hampp

2012

Appl. Phys. A

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Self-assembled monolayers (SAMs) of alkanethiols are major building blocks for nanotechnology. SAMs provide a functional interface between electrodes and biomolecules, which makes them attractive for biochip fabrication. Although gold has emerged as a standard, copper has several advantages, such as compatibility with semiconductors. However, as copper is easily oxidized in air, patterning SAMs on copper is a challenging task. In this work we demonstrate that submerged laser ablation (SLAB) is well-suited for this purpose, as thiols are exchanged in-situ, avoiding air exposition. Using different types of ω-substituted alkanethiols we show that alkanethiol SAMs on copper surfaces can be patterned using SLAB. The resulting patterns were analyzed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Both methods indicate that the intense laser beam promotes the exchange of thiols at the copper surface. Furthermore, we present a procedure for the production of free-standing copper nanomembranes, oxidation-protected by alkanethiol SAMs. Incubation of copper-coated mica in alkanethiol solutions leads to SAM formation on both surfaces of the copper film due to intercalation of the organic molecules. Corrosion-protected copper nanomembranes were floated onto water, transferred to electron microscopy grids, and

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Photothermally Induced Microchemical Functionalization of Organic Monolayers

Cited by 16 publications

References 31 publications

Wetting‐Controlled Localized Placement of Surface Functionalities within Nanopores

Wetting‐Controlled Localized Placement of Surface Functionalities within Nanopores

Micro‐ and Nanopatterning of Functional Organic Monolayers on Oxide‐Free Silicon by Laser‐Induced Photothermal Desorption

Patterned self-assembled monolayers of alkanethiols on copper nanomembranes by submerged laser ablation

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