Luc Scheres

Organic Monolayers onto Oxide-Free Silicon with Improved Surface Coverage: Alkynes versus Alkenes

On H-Si(111), monolayer assembly with 1-alkenes results in alkyl monolayers with a Si-C-C linkage to the silicon substrate, while 1-alkynes yield alkenyl monolayers with a Si-C=C linkage. To investigate the influence of the different linkage groups on the final monolayer structure, organic monolayers were prepared from 1-alkenes and 1-alkynes with chain lengths from C(12) to C(18), and the final monolayer structures were studied in detail by static water contact angles measurements, ellipsometry, attenuated total reflectance infrared (ATR-IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The thicknesses, tilt angles, and packing densities of the alkyl monolayers are in good agreement with literature values, whereas increased thicknesses, reduced tilt angles, and improved packing densities were observed for the alkenyl monolayers. Finally, the surface coverages for alkyl monolayers were determined to be 50-55% (in line with literature values), while those for the alkenyl monolayers increased with the chain length from 55% for C(12) to as high as 65% for C(18)! The latter value is very close to the theoretical maximum of 69% obtainable on H-Si(111). Such enhanced monolayer quality and increased surface coverage of the alkenyl monolayers, in combination with the oxidation-inhibiting nature of the Si-C=C linkage, significantly increases the chance of successful implementation of organic monolayers on oxide-free silicon in molecular electronic and biosensor devices, especially in view of the importance of a defect-free monolayer structure and the corresponding stability of the monolayer-silicon interface.

Self-assembly of organic monolayers onto hydrogen-terminated silicon: 1-alkynes are better than 1-alkenes.

Recently, a new method for the preparation of high-quality organic monolayers with 1-alkynes at room temperature in the dark (i.e., without any external activation) was reported. To pinpoint the precise origin of this self-assembly process and to compare the reactivity of 1-alkenes and 1-alkynes toward hydrogen-terminated Si(111) [H-Si(111)], we followed the gradual formation of both monolayers at room temperature by static water contact angle measurements. Subsequently, attenuated total reflection infrared spectroscopy (ATR-IR) and X-ray photoelectron spectroscopy (XPS) were used to obtain detailed information about the structure and quality of the resulting monolayers. Our data clearly demonstrate that 1-alkynes are considerably more reactive toward H-Si(111) than 1-alkenes. 1-Alkynes are able to self-assemble into densely packed hydrophobic monolayers without any external activation (i.e., at room temperature under ambient light and even in the dark) whereas for 1-alkenes under the same conditions hardly any reactivity toward H-Si(111) was observed. The self-assembly of 1-alkynes on H-Si(111) at room temperature is explained by three factors: the higher nucleophilicity of 1-alkynes, which results in a facile attack at the electron-hole pairs at the H-Si surface and easy Si-C bond formation, the stabilization of the beta radical by delocalization over the double bond, and the lower-energy barrier encountered for H abstractions.

Molecular Electronics at Metal/Semiconductor Junctions. Si Inversion by Sub-Nanometer Molecular Films

Electronic transport across n-Si-alkyl monolayer/Hg junctions is, at reverse and low forward bias, independent of alkyl chain length from 18 down to 1 or 2 carbons! This and further recent results indicate that electron transport is minority, rather than majority carrier dominated, occurs via generation and recombination, rather than (the earlier assumed) thermionic emission, and, as such, is rather insensitive to interface properties. The (m)ethyl results show that binding organic molecules directly to semiconductors provides semiconductor/metal interface control options, not accessible otherwise.

Tuning the Electronic Communication between Redox Centers Bound to Insulating Surfaces

Controlling communication: The electronic communication between ferrocenyl centers bound to insulating silicon surfaces can be efficiently controlled; scanning electrochemical microscopy (SECM) shows that both the surface coverage of the electroactive units and the nature of the redox mediator allow for this control. The lateral charge propagation can be precisely tuned from an extremely slow to a very fast process

Charge transport across metal/molecular (alkyl) monolayer-Si junctions is dominated by the LUMO level

We compare the charge transport characteristics of heavy-doped p(++)- and n(++)-Si-alkyl chain/Hg junctions. Based on negative differential resistance in an analogous semiconductor-inorganic insulator/metal junction we suggest that for both p(++)- and n(++)-type junctions, the energy difference between the Fermi level and lowest unoccupied molecular orbital (LUMO), i.e., electron tunneling, controls charge transport. This conclusion is supported by results from photoelectron spectroscopy (ultraviolet photoemission spectroscopy, inverse photoelectron spectroscopy, and x-ray photoemission spectroscopy) for the molecule-Si band alignment at equilibrium, which clearly indicate that the energy difference between the Fermi level and the LUMO is much smaller than that between the Fermi level and the highest occupied molecular orbital (HOMO). Furthermore, the experimentally determined Fermi level - LUMO energy difference, agrees with the non-resonant tunneling barrier height, deduced from the exponential length attenuation of the current.

Molecular modeling of alkyl and alkenyl monolayers on hydrogen-terminated Si(111).

On H-Si(111) surfaces monolayer formation with 1-alkenes results in alkyl monolayers with a Si-C-C linkage, while 1-alkynes yield alkenyl monolayers with a Si-C═C linkage. Recently, considerable structural differences between both types of monolayers were observed, including an increased thickness, improved packing, and higher surface coverage for the alkenyl monolayers. The precise origin thereof could experimentally not be clarified yet. Therefore, octadecyl and octadecenyl monolayers on Si(111) were studied in detail by molecular modeling via PCFF molecular mechanics calculations on periodically repeated slabs of modified surfaces. After energy minimization the packing energies, structural properties, close contacts, and deformations of the Si surfaces of monolayers structures with various substitution percentages and substitution patterns were analyzed. For the octadecyl monolayers all data pointed to a substitution percentage close to 50-55%, which is due the size of the CH(2) groups near the Si surface. This agrees with literature and the experimentally determined coverage of octadecyl monolayers. For the octadecenyl monolayers the minimum in packing energy per chain is calculated around 60% coverage, i.e., close to the experimentally observed value of 65% [Scheres et al. Langmuir 2010, 26, 4790], and this packing energy is less dependent on the substitution percentage than calculated for alkyl layers. Analysis of the chain conformations, close contacts, and Si surface deformation clarifies this, since even at coverages above 60% a relatively low number of close contacts and a negligible deformation of the Si was observed. In order to evaluate the thermodynamic feasibility of the monolayer structures, we estimated the binding energies of 1-alkenes and 1-alkynes to the hydrogen-terminated Si surface at a range of surface coverages by composite high-quality G3 calculations and determined the total energy of monolayer formation by adding the packing energies and the binding energies. It was shown that due to the significantly larger reaction exothermicity of the 1-alkynes, thermodynamically even a substitution percentage as high as 75% is possible for octadecenyl chains. However, because sterically (based on the van der Waals footprint) a coverage of 69% is the maximum for alkyl and alkenyl monolayers, the optimal substitution percentage of octadecenyl monolayers will be presumably close to this latter value, and the experimentally observed 65% is likely close to what is experimentally maximally obtainable with alkenyl monolayers.

Microcontact Printing onto Oxide‐Free Silicon via Highly Reactive Acid Fluoride‐Functionalized Monolayers

This work describes a new route for patterning organic monolayers on oxide-free silicon by microcontact printing (microCP) on a preformed, reactive, acid-fluoride-terminated monolayer. This indirect printing approach is fast and easily preserves the oxide-free and well-defined monolayer-silicon interface, which is the most important property for potential applications in biosensing and molecular electronics. Water-contact-angle measurements, ellipsometry, attenuated total reflection infrared spectroscopy, and X-ray photoelectron spectroscopy (XPS) demonstrate the formation of the initial acid-fluoride-terminated monolayers without upside-down attachment. Subsequent printing for twenty seconds with an N-hexadecylamine-inked poly(dimethylsiloxane) stamp results in well-defined 5-microm N-hexadecylamide dots, as evidenced by atomic force microscopy and scanning electron microscopy. Printing with a flat stamp allows investigation of the efficiency of amide formation by microCP and water-contact-angle measurements, ellipsometry, and XPS reveal the quantitative conversion of the acid fluoride groups to the corresponding amide within twenty seconds. The absence of silicon oxide, even after immersion in water for 16 h, demonstrates that the oxide-free monolayer-silicon interface is easily preserved by this patterning route. Finally, it is shown by fluorescence microscopy that complex biomolecules, like functionalized oligo-DNA, can also be immobilized on the oxide-free silicon surface via microCP.

Ambient Surface Analysis of Organic Monolayers using Direct Analysis in Real Time Orbitrap Mass Spectrometry

A better characterization of nanometer-thick organic layers (monolayers) as used for engineering surface properties, biosensing, nanomedicine, and smart materials will widen their application. The aim of this study was to develop direct analysis in real time high-resolution mass spectrometry (DART-HRMS) into a new and complementary analytical tool for characterizing organic monolayers. To assess the scope and formulate general interpretation rules, DART-HRMS was used to analyze a diverse set of monolayers having different chemistries (amides, esters, amines, acids, alcohols, alkanes, ethers, thioethers, polymers, sugars) on five different substrates (Si, Si3N4, glass, Al2O3, Au). The substrate did not play a major role except in the case of gold, for which breaking of the weak Au-S bond that tethers the monolayer to the surface, was observed. For monolayers with stronger covalent interfacial bonds, fragmentation around terminal groups was found. For ester and amide-terminated monolayers, in situ hydrolysis during DART resulted in the detection of ions characteristic of the terminal groups (alcohol, amine, carboxylic acid). For ether and thioether-terminated layers, scission of C-O or C-S bonds also led to the release of the terminal part of the monolayer in a predictable manner. Only the spectra of alkane monolayers could not be interpreted. DART-HRMS allowed for the analysis of and distinction between monolayers containing biologically relevant mono or disaccharides. Overall, DART-HRMS is a promising surface analysis technique that combines detailed structural information on nanomaterials and ultrathin films with fast analyses under ambient conditions.

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

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.

Photothermal micro- and nanopatterning of organic/silicon interfaces.

Photothermal laser processing of organic monolayers on oxide-free silicon substrates under ambient conditions is investigated. Organic monolayers on Si(100) and Si(111) substrates are prepared via hydrosilylation of H-terminated silicon samples in neat 1-hexadecene and 1-hexadecyne, respectively. Laser processing at lambda = 514 nm and a 1/e(2) spot diameter of 2.6 microm results in local decomposition of the monolayers and oxidation of the exposed substrate. In agreement with the high thermal and chemical stability of these monolayers, a thermokinetic analysis of the data from experiments at distinct laser powers and pulse lengths points to a highly activated process. As a result, processing is strongly nonlinear and allows for subwavelength patterning, with line widths between 0.4 and 1.4 microm. Most remarkably, upon fabrication of dense line patterns, narrow organic monolayer stripes with sharp edges and lateral dimensions of 80 nm are formed. This opens up new perspectives in photothermal engineering of organic/silicon interfaces, e.g., for hybrid microelectronic and sensor applications.