Search

Attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) is a powerful method for probing interfacial chemical processes. However, SEIRAS-active nanostructured metallic thin films for the in situ analysis of electrochemical phenomena are often unstable under biased aqueous conditions. In this work, we present a surface-enhancing structure based on etched black Si internal reflection elements with Au-coatings for in situ electrochemical ATR-SEIRAS. Using electrochemical potential-dependent adsorption and desorption of 4-methoxypyridine on Au, we demonstrate that black Si-based substrates offer advantages over commonly used structures, such as electroless-deposited Au on Si and electrodeposited Au on ITO-coated Si, due to the combination of high stability, sensitivity, and conductivity. These characteristics are especially valuable for time-resolved measurements where stable substrates are required over extended times. Furthermore, the low sheet resistance of Au layers on black Si reduces the RC time constant of the electrochemical cell, enabling a significantly higher time resolution compared to that of traditional substrates. Thus, we employ black Si-based substrates in conjunction with rapid- and step-scan Fourier transform infrared (FTIR) spectroscopy to investigate the adsorption and desorption kinetics of 4-methoxypyridine during in situ electrochemical potential steps. Adsorption is shown to be diffusion-limited, which allows for the determination of the mean molecular area in a fully established monolayer. Moreover, no significant changes in the peak ratios of vibrational modes with different orientations relative to the molecular axis are observed, suggesting a single adsorption mode and no alteration of the average molecular orientation during the adsorption process. Overall, this study highlights the enhanced performance of black Si-based substrates for both steady-state and time-resolved in situ electrochemical ATR-SEIRAS, providing a powerful platform for kinetic and mechanistic investigations of electrochemical interfaces.

We demonstrate the epitaxial coating of GaN NWs with an epitaxial ZnO shell by atomic layer deposition at 300 °C. Scanning transmission electron microscopy proves a sharp and defect-free coherent interface. The strain in the core-shell structure due to the lattice mismatch and different thermal expansion coefficients of GaN and ZnO was analyzed using 4D-STEM strain mapping and Raman spectroscopy and compared to theoretical calculations. The results highlight the outstanding advantages of epitaxial shell growth using atomic layer deposition, e.g., conformal coating and precise thickness control.

The combination of molecular catalysts and semiconductor substrates in hybrid heterogeneous photo- or electrocatalytic devices could yield synergistic effects that result in enhanced activity and long-term stability. The extent of synergy strongly depends on the electronic interactions and energy level alignment between the molecular states and the valence and conduction band of the substrate. These properties of hybrid interfaces are investigated for a model system composed of protoporphyrin IX (PPIX) as a stand-in for molecular catalysts and a variety of semiconductor substrates. Monolayers of PPIX are deposited using Langmuir-Blodgett deposition. Their morphology is studied in dependence of the deposition surface pressure to achieve a high-quality, dense coverage. By making use of ultraviolet-visible spectroscopy and ultraviolet photoelectron spectroscopy, the band alignment is determined by the vacuum level and incorporates an interface dipole of 0.4 eV independent of the substrate. The HOMO, LUMO, and LUMO+1 levels were determined to be at 5.6, 3.7, and 2.7 eV below the vacuum level, respectively. The quenching of PPIX photoluminescence in dependence of the potential gradient between excited state and electron affinity of the semiconductor substrates is overall in good agreement with electron transfer processes occurring at very fast time scales on the order of femtoseconds. Nevertheless, deviations from this model become apparent for narrower band gap semiconductors, which points to an additional relevance of other processes, such as energy transfer. These findings highlight the importance of matching the semiconductor to the molecular catalyst to prevent undesirable deactivation pathways.

Hybrid inorganic/organic heterointerfaces are promising systems for next-generation photocatalytic, photovoltaic, and chemical-sensing applications. Their performance relies strongly on the development of robust and reliable surface passivation and functionalization protocols with (sub)molecular control. The structure, stability, and chemistry of the semiconductor surface determine the functionality of the hybrid assembly. Generally, these modification schemes have to be laboriously developed to satisfy the specific chemical demands of the semiconductor surface. The implementation of a chemically independent, yet highly selective, standardized surface functionalization scheme, compatible with nanoelectronic device fabrication, is of utmost technological relevance. Here, we introduce a modular surface assembly (MSA) approach that allows the covalent anchoring of molecular transition-metal complexes with sub-nanometer precision on any solid material by combining atomic layer deposition (ALD) and selectively self-assembled monolayers of phosphonic acids. ALD, as an essential tool in semiconductor device fabrication, is used to grow conformal aluminum oxide activation coatings, down to sub-nanometer thicknesses, on silicon surfaces to enable a selective step-by-step layer assembly of rhenium(I) bipyridine tricarbonyl molecular complexes. The modular surface assembly of molecular complexes generates precisely structured spatial ensembles with strong intermolecular vibrational and electronic coupling, as demonstrated by infrared spectroscopy, photoluminescence, and X-ray photoelectron spectroscopy analysis. The structure of the MSA can be chosen to avoid electronic interactions with the semiconductor substrate to exclusively investigate the electronic interactions between the surface-immobilized molecular complexes.

Magnetic anisotropy critically determines the utility of magnetic nanocrystals (NCs) in new nanomagnetism technologies. Using angular-dependent electron magnetic resonance (EMR), we observe magnetic anisotropy in isotropically arranged NCs of a nonmagnetic material. We show that the shape of the EMR angular variation can be well described by a simple model that considers magnetic dipole-dipole interactions between dipoles randomly located in the NCs, most likely due to surface dangling bonds. The magnetic anisotropy results from the fact that the energy term arising from the magnetic dipole-dipole interactions between all magnetic moments in the system is dominated by only a few dipole pairs, which always have an anisotropic geometric arrangement. Our work shows that magnetic anisotropy may be a general feature of NC systems containing randomly distributed magnetic dipoles., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Label-free detection of charged biomolecules, such as DNA, has experienced an increase in research activity in recent years, mainly to obviate the need for elaborate and expensive pretreatments for labeling target biomolecules. A promising label-free approach is based on the detection of changes in the electrical surface potential on biofunctionalized silicon field-effect devices. These devices require a reliable and selective immobilization of charged biomolecules on the device surface. In this work, self-assembled monolayers of phosphonic acids are used to prepare organic interfaces with a high density of peptide nucleic acid (PNA) bioreceptors, which are a synthetic analogue to DNA, covalently bound either in a multidentate ( ∥ PNA) or monodentate ( ⊥ PNA) fashion to the underlying silicon native oxide surface. The impact of the PNA bioreceptor orientation on the sensing platform's surface properties is characterized in detail by water contact angle measurements, atomic force microscopy, X-ray photoelectron spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. Our results suggest that the multidentate binding of the bioreceptor via attachment groups at the γ-points along the PNA backbone leads to the formation of an extended, protruding, and netlike three-dimensional metastructure. Typical "mesh" sizes are on the order of 8 ± 2.5 nm in diameter, with no preferential spatial orientation relative to the underlying surface. Contrarily, the monodentate binding provides a spatially more oriented metastructure comprising cylindrical features, of a typical size of 62 ± 23 × 12 ± 2 nm 2 . Additional cyclic voltammetry measurements in a redox buffer solution containing a small and highly mobile Ru-based complex reveal strikingly different insulating properties (ion diffusion kinetics) of these two PNA systems. Investigation by electrochemical impedance spectroscopy confirms that the binding mode has a significant impact on the electrochemical properties of the functional PNA layers represented by detectable changes of the conductance and capacitance of the underlying silicon substrate in the range of 30-50% depending on the surface organization of the bioreceptors in different bias potential regimes.

Solid-state quantum emitters embedded in a semiconductor crystal environment are potentially scalable platforms for quantum optical networks operated at room temperature. Prominent representatives are nitrogen-vacancy (NV) centers in diamond showing coherent entanglement and interference with each other. However, these emitters suffer from inefficient optical outcoupling from the diamond and from fluctuations of their charge state. Here, we demonstrate the implementation of regular n-type gallium nitride nanowire arrays on diamond as photonic waveguides to tailor the emission direction of surface-near NV centers and to electrically control their charge state in a p-i-n nanodiode. We show that the electrical excitation of single NV centers in such a diode can efficiently replace optical pumping. By the engineering of the array parameters, we find an optical read-out efficiency enhanced by a factor of 10 and predict a lateral NV-NV coupling 3 orders of magnitude stronger through evanescently coupled nanowire antennas compared to planar diamond not covered by nanowires, which opens up new possibilities for large-scale on-chip quantum-computing applications.

Colloidal dodecene-passivated silicon (Si) nanocrystals were dispersed in hexane or chloroform and deposited onto substrates as face-centered cubic superlattices by slowly evaporating the solvent. The uniformity of the nanocrystals enables extended order; however, the solvent and the evaporation protocol significantly influence the self-assembly process, determining the morphology of the films, the extent of order, and the superlattice orientation on the substrate. Chloroform yielded superlattices with step-flow growth morphologies and (111) SL , (100) SL , and (110) SL orientations. Hexane led to mostly island morphologies when evaporated at room temperature with exclusively (111) SL orientations. Higher evaporation temperatures led to more extensive step-flow deposition. A model for the surface diffusion of nanocrystals adsorbed on the superlattice surface is developed.

Group III-nitride materials such as GaN nanowires are characterized by a spontaneous polarization within the crystal. The sign of the resulting sheet charge at the top and bottom facet of a GaN nanowire is determined by the orientation of the wurtzite bilayer of the different atomic species, called N and Ga polarity. We investigate the polarity distribution of heteroepitaxial GaN nanowires on different substrates and demonstrate polarity control of GaN nanowires on diamond. Kelvin Probe Force Microscopy is used to determine the polarity of individual selective area-grown and self-assembled nanowires over a large scale. At standard growth conditions, mixed polarity occurs for selective GaN nanowires on various substrates, namely on silicon, on sapphire and on diamond. To obtain control over the growth orientation on diamond, the substrate surface is modified by nitrogen and oxygen plasma exposure prior to growth, and the growth parameters are adjusted simultaneously. We find that the surface chemistry and the substrate temperature are the decisive factors for obtaining control of up to 93% for both polarity types, whereas the growth mode, namely selective area or self-assembled growth, does not influence the polarity distribution significantly. The experimental results are discussed by a model based on the interfacial bonds between the GaN nanowires, the termination layer, and the substrate.

We demonstrate the selective area growth of GaN-(Al,Ga)N core-shell nanowire heterostructures directly on Si(111). Photoluminescence spectroscopy on as-grown nanowires reveals a strong blueshift of the GaN band gap from 3.40 to 3.64 eV at room temperature. Raman measurements relate this shift to compressive strain within the GaN core. On the nanoscale, cathodoluminescence spectroscopy and scanning transmission electron microscopy prove the homogeneity of strain-related luminescence along the nanowire axis and the absence of significant fluctuations within the shell, respectively. A comparison of the experimental findings with numerical simulations indicates the absence of a significant defect-related strain relaxation for all investigated structures, with a maximum compressive strain of -3.4% for a shell thickness of 50 nm. The accurate control of the nanowire dimensions, namely, core diameter, shell thickness, and nanowire period, via selective area growth allows a specific manipulation of the resulting strain within individual nanowires on the same sample. This, in turn, enables a spatially resolved adjustment of the GaN band gap with an energy range of 240 meV in a one-step growth process.

The photoelectrochemical characterization of silicon carbide (SiC) electrodes is important for enabling a wide range of potential applications for this semiconductor. However, photocorrosion of the SiC surface remains a key challenge, because this process considerably hinders the deployment of this material into functional devices. In this report, we use cyclic voltammetry to investigate the stability of n-type 6H-SiC photoelectrodes in buffered aqueous electrolytes. For measurements in pure Tris buffer, photogenerated holes accumulate at the interface under anodic polarization, resulting in the formation of a porous surface oxide layer. Two possibilities are presented to significantly enhance the stability of the SiC photoelectrodes. In the first approach, redox molecules are added to the buffer solution to kinetically facilitate hole transfer to these molecules, and in the second approach, water oxidation in the electrolyte is induced by depositing a cobalt phosphate catalyst onto the semiconductor surface. Both methods are found to effectively suppress photocorrosion of the SiC electrodes, as confirmed by atomic force microscopy and X-ray photoelectron spectroscopy measurements. The presented study provides straightforward routes to stabilize n-type SiC photoelectrodes in aqueous electrolytes, which is essential for a possible utilization of this material in the fields of photocatalysis and multimodal biosensing.

Photoactive reaction centers (RCs) are protein complexes in bacteria able to convert sunlight into other forms of energy with a high quantum yield. The photostimulation of immobilized RCs on inorganic electrodes result in the generation of photocurrent that is of interest for biosolar cell applications. This paper reports on the use of novel electrodes based on functional conductive nanocrystalline diamond onto which bacterial RCs are immobilized. A three-dimensional conductive polymer scaffold grafted to the diamond electrodes enables efficient entrapment of photoreactive proteins. The electron transfer in these functional diamond electrodes is optimized through the use of a ferrocene-based electron mediator, which provides significant advantages such as a rapid electron transfer as well as high generated photocurrent. A detailed discussion of the generated photocurrent as a function of time, bias voltage, and mediators in solution unveils the mechanisms limiting the electron transfer in these functional electrodes. This work featuring diamond-based electrodes in biophotovoltaics offers general guidelines that can serve to improve the performance of similar devices based on different materials and geometries.

In this work the position-controlled growth of GaN nanowires (NWs) on diamond by means of molecular beam epitaxy is investigated. In terms of growth, diamond can be seen as a model substrate, providing information of systematic relevance also for other substrates. Thin Ti masks are structured by electron beam lithography which allows the fabrication of perfectly homogeneous GaN NW arrays with different diameters and distances. While the wurtzite NWs are found to be Ga-polar, N-polar nucleation leads to the formation of tripod structures with a zinc-blende core which can be efficiently suppressed above a substrate temperature of 870 °C. A variation of the III/V flux ratio reveals that both axial and radial growth rates are N-limited despite the globally N-rich growth conditions, which is explained by the different diffusion behavior of Ga and N atoms. Furthermore, it is shown that the hole arrangement has no effect on the selectivity but can be used to force a transition from nanowire to nanotube growth by employing a highly competitive growth regime.

The modification of the diamond surface with organic molecules is a crucial aspect to be considered for any bioapplication of this material. There is great interest in broadening the range of linker molecules that can be covalently bound to the diamond surface. In the case of protein immobilization, the hydropathicity of the surface has a major influence on the protein conformation and, thus, on the functionality of proteins immobilized at surfaces. For electrochemical applications, particular attention has to be devoted to avoid that the charge transfer between the electrode and the redox center embedded in the protein is hindered by a thick insulating linker layer. This paper reports on the grafting of 6-phosphonohexanoic acid on OH-terminated diamond surfaces, serving as linkers to tether electroactive proteins onto diamond surfaces. X-ray photoelectron spectroscopy (XPS) confirms the formation of a stable layer on the surface. The charge transfer between electroactive molecules and the substrate is studied by electrochemical characterization of the redox activity of aminomethylferrocene and cytochrome c covalently bound to the substrate through this linker. Our work demonstrates that OH-terminated diamond functionalized with 6-phosphonohexanoic acid is a suitable platform to interface redox-proteins, which are fundamental building blocks for many bioelectronics applications.

The future exploitation of the exceptional properties of nanocrystal (NC) thin films deposited from liquid dispersions of nanoparticles relies upon our ability to produce films with improved electrical properties by simple and inexpensive means. Here, we demonstrate that the electronic conduction of solution-processed NC films can be strongly enhanced without the need of postdeposition treatments, via specific molecules adsorbed at the surfaces of adjacent NCs. This effect is demonstrated for Si NC films doped with the strong molecular oxidizing agent tetrafluoro-tetracyanoquinodimethane (F4-TCNQ). Density functional calculations were carried out with molecule-doped superlattice solid models. It is shown that, when populated by electrons, hybrid molecule/NC states edge (and may actually resonate with) the conduction-band states of the NC solid. This provides extra electronic connectivity across the NC network as the molecules effectively flatten the electronic potential barriers for electron transfer across the otherwise vacuum-filled network interstitialcies.

In this work, simulations of the electronic band structure of a p-GaN/n-ZnO heterointerface are presented. In contrast to homojunctions, an additional energy barrier due to the type-II band alignment hinders the flow of majority charge carriers in this heterojunction. Spontaneous polarization and piezoelectricity are shown to additionally affect the band structure and the location of the recombination region. Proposed as potential UV-LEDs and laser diodes, p-GaN/n-ZnO heterojunction nanowires were fabricated by plasma-assisted molecular beam epitaxy (PAMBE). Atomic resolution annular bright field scanning transmission electron microscopy (STEM) studies reveal an abrupt and defect-free heterointerface with a polarity inversion from N-polar GaN to Zn-polar ZnO. Photoluminescence measurements show strong excitonic UV emission originating from the ZnO-side of the interface as well as stimulated emission in the case of optical pumping above a threshold of 55 kW/cm(2).

For many applications of the nitrogen-vacancy (NV) center in diamond, the understanding and active control of its charge state is highly desired. In this work, we demonstrate the reversible manipulation of the charge state of a single NV center from NV(-) across NV(0) to a nonfluorescent, dark state by using an all-diamond in-plane gate nanostructure. Applying a voltage to the in-plane gate structure can influence the energy band bending sufficiently for charge state conversion of NV centers. These diamond in-plane structures can function as transparent top gates, enabling the distant control of the charge state of NV centers tens of micrometers away from the nanostructure.

We demonstrate the functionalization of n-type (100) and (111) 3C-SiC surfaces with organosilanes. Self-assembled monolayers (SAMs) of amino-propyldiethoxymethylsilane (APDEMS) and octadecyltrimethoxysilane (ODTMS) are formed via wet chemical processing techniques. Their structural, chemical, and electrical properties are investigated using static water contact angle measurements, atomic force microscopy, and X-ray photoelectron spectroscopy, revealing that the organic layers are smooth and densely packed. Furthermore, combined contact potential difference and surface photovoltage measurements demonstrate that the heterostructure functionality and surface potential can be tuned by utilizing different organosilane precursor molecules. Molecular dipoles are observed to significantly affect the work functions of the modified surfaces. Furthermore, the magnitude of the surface band bending is reduced following reaction of the hydroxylated surfaces with organosilanes, indicating that partial passivation of electrically active surface states is achieved. Micropatterning of organic layers is demonstrated by lithographically defined oxidation of organosilane-derived monolayers in an oxygen plasma, followed by visualization of resulting changes of the local wettability, as well as fluorescence microscopy following immobilization of fluorescently labeled BSA protein.

Platinum nanoparticles supported on n- and p-type gallium nitride (GaN) are investigated as novel hybrid systems for the electronic control of catalytic activity via electronic interactions with the semiconductor support. In situ oxidation and reduction were studied with high pressure photoemission spectroscopy. The experiments revealed that the underlying wide-band-gap semiconductor has a large influence on the chemical composition and oxygen affinity of supported nanoparticles under X-ray irradiation. For as-deposited Pt cuboctahedra supported on n-type GaN, a higher fraction of oxidized surface atoms was observed compared to cuboctahedral particles supported on p-type GaN. Under an oxygen atmosphere, immediate oxidation was recorded for nanoparticles on n-type GaN, whereas little oxidation was observed for nanoparticles on p-type GaN. Together, these results indicate that changes in the Pt chemical state under X-ray irradiation depend on the type of GaN doping. The strong interaction between the nanoparticles and the support is consistent with charge transfer of X-ray photogenerated free carriers at the semiconductor-nanoparticle interface and suggests that GaN is a promising wide-band-gap support material for photocatalysis and electronic control of catalysis.

We demonstrate the nucleation of self-assembled, epitaxial GaN nanowires (NWs) on (111) single-crystalline diamond without using a catalyst or buffer layer. The NWs show an excellent crystalline quality of the wurtzite crystal structure with m-plane faceting, a low defect density, and axial growth along the c-axis with N-face polarity, as shown by aberration corrected annular bright-field scanning transmission electron microscopy. X-ray diffraction confirms single domain growth with an in-plane epitaxial relationship of (10 ̅10)(GaN) [parallel] (01 ̅1)(Diamond) as well as some biaxial tensile strain induced by thermal expansion mismatch. In photoluminescence, a strong and sharp excitonic emission reveals excellent optical properties superior to state-of-the-art GaN NWs on silicon substrates. In combination with the high-quality diamond/NW interface, confirmed by high-resolution transmission electron microscopy measurements, these results underline the potential of p-type diamond/n-type nitride heterojunctions for efficient UV optoelectronic devices.

Despite the central role of light absorption and the subsequent generation of free charge carriers in organic and hybrid organic-inorganic photovoltaics, the precise process of this initial photoconversion is still debated. We employ a novel broadband (UV-Vis-NIR) transient absorption spectroscopy setup to probe charge generation and recombination in the thin films of the recently suggested hybrid material combination poly(3-hexylthiophene)/silicon (P3HT/Si) with 40 fs time resolution. Our approach allows for monitoring the time evolution of the relevant transient species under various excitation intensities and excitation wavelengths. Both in regioregular (RR) and regiorandom (RRa) P3HT, we observe an instant (<40 fs) creation of singlet excitons, which subsequently dissociate to form polarons in 140 fs. The quantum yield of polaron formation through dissociation of delocalized excitons is significantly enhanced by adding Si as an electron acceptor, revealing ultrafast electron transfer from P3HT to Si. P3HT/Si films with aggregated RR-P3HT are found to provide free charge carriers in planar as well as in bulk heterojunctions, and losses are due to nongeminate recombination. In contrast for RRa-P3HT/Si, geminate recombination of bound carriers is observed as the dominant loss mechanism. Site-selective excitation by variation of pump wavelength uncovers an energy transfer from P3HT coils to aggregates with a 1/e transfer time of 3 ps and reveals a factor of 2 more efficient polaron formation using aggregated RR-P3HT compared to disordered RRa-P3HT. Therefore, we find that polymer structural order rather than excess energy is the key criterion for free charge generation in hybrid P3HT/Si solar cells.

The exact band alignment at organic/inorganic semiconductor heterojunctions is influenced by a variety of properties and is difficult to predict. For organic/inorganic bilayer heterojunctions made of poly(3-hexylthiophene) (P3HT) and n-type 6H-SiC, the band alignment is determined via current-voltage measurements. For this purpose, a model equivalent circuit, combining thermionic emission and space-charge-limited current effects, is proposed which describes the behavior of the heterojunction very well. From the fitting parameters, an interface barrier height of 1.1 eV between the lowest unoccupied molecular orbital (LUMO) of P3HT and the conduction band (CB) of 6H-SiC is determined. In addition, from the maximum open circuit voltage of 6H-SiC/P3HT diodes, a difference of 0.9 eV between the highest occupied molecular orbital (HOMO) of P3HT and the CB of 6H-SiC is deduced. These two values determine the alignment of the energy bands of 6H-SiC relative to the HOMO and LUMO of P3HT. The 6H-SiC/P3HT bilayer heterojunction exhibits an open circuit voltage of ~0.5 V at room temperature, which makes such a materials system a potential candidate for bulk heterojunction hybrid solar cells with 6H-SiC nanoparticles.

A critical bottleneck for the widespread use of single layer graphene is the absence of a facile method of chemical modification which does not diminish the outstanding properties of the two-dimensional sp(2) network. Here, we report on the direct chemical modification of graphene by photopolymerization with styrene. We demonstrate that photopolymerization occurs at existing defect sites and that there is no detectable disruption of the basal plane conjugation of graphene. This method thus offers a route to define graphene functionality without degrading its electronic properties. Furthermore, we show that photopolymerization with styrene results in self-organized intercalative growth and delamination of few layer graphene. Under these reaction conditions, we find that a range of other vinyl monomers exhibits no reactivity with graphene. However, we demonstrate an alternative route by which the surface reactivity can be precisely tuned, and these monomers can be locally grafted via electron-beam-induced carbon deposition on the graphene surface.

We present an approach for the thermally activated formation of alkene-derived self-assembled monolayers on oxygen-terminated single and polycrystalline diamond surfaces. Chemical modification of the oxygen and hydrogen plasma-treated samples was achieved by heating in 1-octadecene. The resulting layers were characterized using X-ray photoelectron spectroscopy, thermal desorption spectroscopy, atomic force microscopy, Fourier transform infrared spectroscopy, and water contact angle measurements. This investigation reveals that alkenes selectively attach to the oxygen-terminated sites via covalent C-O-C bonds. The hydrophilic oxygen-terminated diamond is rendered strongly hydrophobic following this reaction. The nature of the process limits the organic layer growth to a single monolayer, and FTIR measurements reveal that such monolayers are dense and well ordered. In contrast, hydrogen-terminated diamond sites remain unaffected by this process. This method is thus complementary to the UV-initiated reaction of alkenes with diamond, which exhibits the opposite reactivity contrast. Thermal alkylation increases the range of available diamond functionalization strategies and provides a means of straightforwardly forming single organic layers in order to engineer the surface properties of diamond.

A lithographic method to generate reactive thiol groups on functionalized synthetic diamond for biosensor and molecular electronic applications is developed. We demonstrate that ultrananocrystalline diamond (UNCD) thin films covalently functionalized with surface-generated thiol groups allow controlled thiol-disulfide exchange surface hybridization processes. The generation of the thiol functional head groups was obtained by irradiating phenylsulfonic acid (PSA) monolayers on UNCD surfaces. The conversion of the functional headgroup of the self-assembled monolayer was verified by using X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and fluorescence microscopy. Our findings indicate the selective generation of reactive thiol surface groups. Furthermore, we demonstrate the grafting of yeast cytochrome c to the thiol-modified diamond surface and the electron transfer between protein and electrode.

Enzyme-modified field effect transistors (ENFETs) were realized using surface-conductive single-crystalline diamond films. The enzymes penicillinase and acetylcholinesterase were immobilized onto the active area of diamond-based electrolytic solution gated FETs, using different organic linker molecules and cross-linking chemistries. The active area of the devices was patterned to generate enzyme-modified regions next to surface-conductive regions. Penicillinase was chosen as a robust model system, but the main focus of the present paper is on acetylcholinesterase, an enzyme essential for many neuronal signal transduction processes. All the different ENFETs show a clear and specific response to the corresponding substrate, penicillin and acetylcholine. The device response is based on the pH sensitivity of the surface-conductive active area and is enabled by the local pH change induced during the enzymatic reaction. The devices demonstrate promising stability and characteristic variations of the enzymatic activity with measurement conditions. Furthermore, the results from the ENFET measurements were compared with the results of spectrophotometric experiments, carried out with enzymes immobilized on diamond substrates and also with free enzymes in solution. This allows an analysis of the enzyme kinetics, as well as qualitative comparison of the different functionalization methods employed in this study.

We have investigated the electrochemical interface between diamond electrodes and aqueous electrolytes using electrochemical techniques such as cyclic voltammetry and ac impedance spectroscopy. High-quality CVD-grown boron-doped polycrystalline diamond electrodes and IIa single crystalline natural diamond electrodes have been used in this study. In the case of hydrogen-terminated diamond electrodes, the electrochemical interface is dominated by the electrochemical double layer. Frequency-dependent impedance spectroscopy reveals a potential regime in which the contribution of ion adsorption becomes relevant. We have conducted experiments to evaluate the effect of pH and ionic strength on the double layer. Our results suggest that only ions resulting from water auto-dissociation, i.e., hydroxide and hydronium ions, are responsible for ion adsorption and, thus, able to modify the charge at the double layer. In contrast, no effect of the adsorption of several dissolved ions (such as Na+, K+, Cl-) has been observed On the basis of the electrochemical characterization of H-terminated diamond surfaces, we also discuss the phenomenon of the surface conductivity in diamond, as well as the pH sensitivity of the diamond surface. The influence of the O2/OH- and H2/H3O+ redox couples on the origin of the surface conductivity is discussed.

We investigate the origin of the surface conductivity of H-terminated diamond films immersed in aqueous electrolyte. We demonstrate that in contrast to the in air situation, charge transfer across the diamond interface does not govern the surface conductivity in aqueous electrolyte when a gate electrode controls the diamond/electrolyte interfacial potential. Instead, this almost ideally polarizable interface allows the capacitive charging of the surface. This description resolves the observed disagreement of the pH sensitivity of the diamond surface conductivity in air and in aqueous electrolyte.

In this work, a facile method for the preparation of structured and functional polymer grafts on diamond surfaces is described. Uniform poly(styrene) (PS) grafts with a thickness of approximately 110 nm were created directly onto oxidized ultrananocrystalline diamond (UNCD) surfaces by the self-initiated photografting and photopolymerization of bulk styrene with UV irradiation. The stable covalent bonding of the PS grafts allows polymer analogue reactions with drastic reaction conditions without noticeable detachment of the polymer coating. Thus, various functionalities, such as nitro, sulfonic, and aminomethyl groups have been successfully incorporated to the polymer grafts. Furthermore, the reactivity contrast between hydrogenated and oxidized UNCD surfaces allows for the preparation of structured polymer grafts. Finally, we have demonstrated the good reactivity and accessibility of the incorporated pendant functional groups.

Charge build-up at the solid/aqueous interface is a ubiquitous phenomenon that determines the properties of interfacial electrical double layers. Due to its unique properties, the surface of diamond offers an attractive platform to investigate charging mechanisms in aqueous solutions. We investigate the surface charge by studying the ion sensitivity of H-terminated single crystalline diamond surface conductive layers. The effect of monovalent and divalent salts has been probed at different pH values. For a pH above 3.5, increasing the ionic strength results in a decrease of the surface conductivity, in contrast to the results obtained for pH below 3.5. Electrokinetic experiments are in good agreement with the surface conductivity measurements, showing an isoelectric point at pH 3.5 for the H-terminated diamond surface. We discuss the results in terms of the Coulombic screening by electrolyte ions of the surface potential, which is induced by a pH-dependent surface charge. The origin of this surface charge is discussed in terms of charge regulation by amphoteric hydroxyl surface groups and unsymmetrical adsorption of hydroxide and hydronium ions induced by the hydrophobic nature of the H-terminated diamond surface. This surface charge can have important consequences for processes governed by the diamond/aqueous interface, such as electron transfer to charged redox molecules, adsorption of charged molecules and proteins, and ion sensitivity.

We have investigated the formation of self-assembled monolayers (SAMs) of 4'-nitro-1,1-biphenyl-4-diazonium tetrafluoroborate (NBD) onto ultrananocrystalline diamond (UNCD) thin films. In contrast to the common approach to modify diamond and diamond-like substrates by electrografting, the SAM was formed from the saturated solution of NBD in acetonitrile by pure chemical grafting. Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and near edge X-ray absorption fine structure spectroscopy (NEXAFS) have been used to verify the direct covalent attachment of the 4'-nitro-1,1-biphenyl (NB) SAM on the diamond substrate via stable C-C bonds and to estimate the monolayer packing density. The results confirm the presence of a very stable, homogeneous and dense monolayer. Additionally, the terminal nitro group of the NB SAM can be readily converted into an amino group by X-ray irradiation as well as electrochemistry. This opens the possibility of in situ electrochemical modification as well as the creation of chemical patterns (chemical lithography) in the SAM on UNCD substrates and enables a variety of consecutive chemical functionalization for sensing and molecular electronics applications.

Horseradish peroxidase (HRP) has been immobilized on the surface of functionalized nanocrystalline diamond (NCD) thin films. The structure of the modified NCD surface as well as the electrochemical behavior of the whole system was characterized by impedance spectroscopy and cyclic voltammetry. The proximity of HRP heme groups to the NCD surface allowed direct electron transfer between them, resulting in two separated one-electron-transfer peaks at 0.05 V and 0.29 V vs Ag/AgCl, corresponding to the cathodic and anodic process, respectively. The heterogeneous electron-transfer constant for both processes was calculated to be 0.066 s(-1), the charge-transfer coefficient alpha = 0.49, and the immobilized enzymatic layer about 2.10(-10) mol/cm2. The modified NCD electrode was used as a third-generation biosensor for hydrogen peroxide determination showing a linear response in the 0.1-45 mM H2O2 range, at +0.05 V vs Ag/AgCl.