Multifunctional Boron-Doped Diamond Colloidal AFM Probes.

Scanning probe microscopy techniques providing information on conductivity, chemical fluxes, and interfacial reactivity synchronized with topographical information have gained importance within the last decades. Herein, a novel colloidal atomic force microscopy (AFM) probe is presented using a spherical boron-doped diamond (BDD) electrode attached and electrically connected to a modified silicon nitride cantilever. These conductive spherical BDD-AFM probes allow for electrochemical force spectroscopy. The physical robustness of these bifunctional probes, and the excellent electrochemical properties of BDD renders this concept a unique multifunctional tool for a wide variety of scanning probe studies including conductive AFM, hybrid atomic force-scanning electrochemical microscopy, and tip-integrated chem/bio sensing.

Diamond Colloidal Probe Force Spectroscopy.

Diamond is a highly attractive coating material as it is characterized by a wide optical transparency window, a high thermal conductivity, and an extraordinary robustness due to its mechanical properties and its chemical inertness. In particular, the latter has aroused a great deal of interest for scanning probe microscopy applications in recent years. In this study, we present a novel method for the fabrication of atomic force microscopy (AFM) probes for force spectroscopy using robust diamond-coated spheres, i.e., colloidal particles. The so-called colloidal probe technique is commonly used to study interactions of single colloidal particles, e.g., on biological samples like living cells, or to measure mechanical properties like the Young's modulus. Under physiological measurement conditions, contamination of the particle often strongly limits the measurement time and often impedes reusability of the probe. Diamond as a chemically inert material allows treatment with harsh chemicals without degradation to refurbish the probe. Apart from that, the large surface area of spherical probes makes sensitive studies on surface interactions possible. This provides detailed insight into the interface of diamond with other materials and/or solvents. To fabricate such probes, silica microspheres were coated with a nanocrystalline diamond film and attached to tipless cantilevers. Measurements on soft polydimethylsiloxane (PDMS) show that the manufactured diamond spheres, even though possessing a rough surface, can be used to determine the Young's modulus from a Derjaguin-Muller-Toporov (DMT) fit. By means of force spectroscopy, they can readily probe force interactions of diamond with different substrate materials under varying conditions. The influence of the surface termination of the diamond was investigated concerning the interaction with flat diamond substrates in air. Additionally, measurements in solution, using varying salt concentrations, were carried out, which provide information on double-layer and van-der-Waals forces at the interface. The developed technique offers detailed insight into surface chemistry and physics of diamond with other materials concerning long and short-range force interactions and may provide a valuable probe for investigations under harsh conditions but also on biological samples, e.g., living cells, due to the robustness, chemical inertness, and biocompatibility of diamond.

GaN Nanowire Arrays for Efficient Optical Read-Out and Optoelectronic Control of NV Centers in Diamond.

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.

Electrically Conductive Diamond Membrane for Electrochemical Separation Processes.

Electrochemically switchable selective membranes play an important role in selective filtration processes such as water desalination, industrial waste treatment, and hemodialysis. Currently, membranes for these purposes need to be optimized in terms of electrical conductivity and stability against fouling and corrosion. In this paper, we report the fabrication of boron-doped diamond membrane by template diamond growth on quartz fiber filters. The morphology and quality of the diamond coating are characterized via SEM and Raman spectroscopy. The membrane is heavily boron doped (>10(21) cm(-3)) with >3 V potential window in aqueous electrolyte. By applying a membrane potential against the electrolyte, the redox active species can be removed via flow-through electrolysis. Compared to planar diamond electrodes, the ∼250 times surface enlargement provided by such a membrane ensures an effective removal of target chemicals from the input electrolyte. The high stability of diamond enables the membrane to not only work at high membrane bias but also to be self-cleaning via in situ electrochemical oxidation. Therefore, we believe that the diamond membrane presented in this paper will provide a solution to future selective filtration applications especially in extreme conditions.

Designing 3D Multihierarchical Heteronanostructures for High-Performance On-Chip Hybrid Supercapacitors: Poly(3,4-(ethylenedioxy)thiophene)-Coated Diamond/Silicon Nanowire Electrodes in an Aprotic Ionic Liquid.

A versatile and robust hierarchically multifunctionalized nanostructured material made of poly(3,4-(ethylenedioxy)thiophene) (PEDOT)-coated diamond@silicon nanowires has been demonstrated to be an excellent capacitive electrode for supercapacitor devices. Thus, the electrochemical deposition of nanometric PEDOT films on diamond-coated silicon nanowire (SiNW) electrodes using N-methyl-N-propylpyrrolidinium bis((trifluoromethyl)sulfonyl)imide ionic liquid displayed a specific capacitance value of 140 F g(-1) at a scan rate of 1 mV s(-1). The as-grown functionalized electrodes were evaluated in a symmetric planar microsupercapacitor using butyltrimethylammonium bis((trifluoromethyl)sulfonyl)imide aprotic ionic liquid as the electrolyte. The device exhibited extraordinary energy and power density values of 26 mJ cm(-2) and 1.3 mW cm(-2) within a large voltage cell of 2.5 V, respectively. In addition, the system was able to retain 80% of its initial capacitance after 15 000 galvanostatic charge-discharge cycles at a high current density of 1 mA cm(-2) while maintaining a Coulombic efficiency around 100%. Therefore, this multifunctionalized hybrid device represents one of the best electrochemical performances concerning coated SiNW electrodes for a high-energy advanced on-chip supercapacitor.

Active and fast charge-state switching of single NV centres in diamond by in-plane Al-Schottky junctions.

In this paper, we demonstrate an active and fast control of the charge state and hence of the optical and electronic properties of single and near-surface nitrogen-vacancy centres (NV centres) in diamond. This active manipulation is achieved by using a two-dimensional Schottky-diode structure from diamond, i.e., by using aluminium as Schottky contact on a hydrogen terminated diamond surface. By changing the applied potential on the Schottky contact, we are able to actively switch single NV centres between all three charge states NV+, NV0 and NV- on a timescale of 10 to 100 ns, corresponding to a switching frequency of 10-100 MHz. This switching frequency is much higher than the hyperfine interaction frequency between an electron spin (of NV-) and a nuclear spin (of 15N or 13C for example) of 2.66 kHz. This high-frequency charge state switching with a planar diode structure would open the door for many quantum optical applications such as a quantum computer with single NVs for quantum information processing as well as single 13C atoms for long-lifetime storage of quantum information. Furthermore, a control of spectral emission properties of single NVs as a single photon emitters - embedded in photonic structures for example - can be realized which would be vital for quantum communication and cryptography.

Diamond-Based Supercapacitors: Realization and Properties.

In this Spotlight on Applications, we describe our recent progress on the fabrication of surface-enlarged boron-doped polycrystalline diamond electrodes, and evaluate their performance in supercapacitor applications. We begin with a discussion of the fabrication methods of porous diamond materials. The diamond surface enlargement starts with a top-down plasma etching method. Although the extra surface area provided by surface roughening or nanostructuring provides good outcome for sensing applications, a capacitance value <1 mF cm-2 or a surface-enlargement factor <100 fail to meet the requirement of a practical supercapacitor. Driven by the need for large surface areas, we recently focused on the tempated-growth method. We worked on both supported and free-standing porous diamond materials to enhance the areal capacitance to the "mF cm-2" range. With our newly developed free-standing diamond paper, areal capacitance can be multiplied by stacking multilayers of the electrode material. Finally, considering the fact that there is no real diamond-based supercapacitor device up to now, we fabricated the first prototype pouch-cell device based on the free-standing diamond paper to evaluate its performance. The results reveal that the diamond paper is suitable for operation in high potential windows (up to 2.5 V) in aqueous electrolyte with a capacitance of 0.688 mF cm-2 per layer of paper (or 0.645 F g-1). Impedance spectroscopy revealed that the operation frequency of the device exceeds 30 Hz. Because of the large potential window and the ability to work at high frequency, the specific power of the device reached 1 × 105 W kg-1. In the end, we made estimations on the future target performance of diamond supercapacitors based on the existing information.

Electrostatic Self-Assembly of Diamond Nanoparticles onto Al- and N-Polar Sputtered Aluminum Nitride Surfaces.

Electrostatic self-assembly of diamond nanoparticles (DNPs) onto substrate surfaces (so-called nanodiamond seeding) is a notable technique, enabling chemical vapor deposition (CVD) of nanocrystalline diamond thin films on non-diamond substrates. In this study, we examine this technique onto differently polarized (either Al- or N-polar) c-axis oriented sputtered aluminum nitride (AlN) film surfaces. This investigation shows that Al-polar films, as compared to N-polar ones, obtain DNPs with higher density and more homogeneously on their surfaces. The origin of these differences in density and homogeneity is discussed based on the hydrolysis behavior of AlN surfaces in aqueous suspensions.

Appropriate salt concentration of nanodiamond colloids for electrostatic self-assembly seeding of monosized individual diamond nanoparticles on silicon dioxide surfaces.

Monosized (∼4 nm) diamond nanoparticles arranged on substrate surfaces are exciting candidates for single-photon sources and nucleation sites for ultrathin nanocrystalline diamond film growth. The most commonly used technique to obtain substrate-supported diamond nanoparticles is electrostatic self-assembly seeding using nanodiamond colloidal suspensions. Currently, monodisperse nanodiamond colloids, which have a narrow distribution of particle sizes centering on the core particle size (∼4 nm), are available for the seeding technique on different substrate materials such as Si, SiO2, Cu, and AlN. However, the self-assembled nanoparticles tend to form small (typically a few tens of nanometers or even larger) aggregates on all of those substrate materials. In this study, this major weakness of self-assembled diamond nanoparticles was solved by modifying the salt concentration of nanodiamond colloidal suspensions. Several salt concentrations of colloidal suspensions were prepared using potassium chloride as an inserted electrolyte and were examined with respect to seeding on SiO2 surfaces. The colloidal suspensions and the seeded surfaces were characterized by dynamic light scattering and atomic force microscopy, respectively. Also, the interaction energies between diamond nanoparticles in each of the examined colloidal suspensions were compared on the basis of the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. From these investigations, it became clear that the appropriate salt concentration suppresses the formation of small aggregates during the seeding process owing to the modified electrostatic repulsive interaction between nanoparticles. Finally, monosized (<10 nm) individual diamond nanoparticles arranged on SiO2 surfaces have been successfully obtained.

Tuned NV emission by in-plane Al-Schottky junctions on hydrogen terminated diamond.

The negatively charged nitrogen-vacancy (NV) centre exhibits outstanding optical and spin properties and thus is very attractive for applications in quantum optics. Up to now an active control of the charge state of near-surface NV centres is difficult and the centres switch in an uncontrolled way between different charge states. In this work, we demonstrate an active control of the charge state of NV centres (implanted 7 nm below the surface) by using an in-plane Schottky diode geometry from aluminium on hydrogen terminated diamond in combination with confocal micro-photoluminescence measurements. The partial quenching of NV-photoluminescence caused by the hole accumulation layer of the hydrogen terminated surface can be recovered by applying reverse bias potentials on this diode, i.e. the NV(0) charge state is depleted while the NV(-) charge state is populated. This charge state conversion is caused by the bias voltage affected modulation of the band bending in the depletion region which shifts the Fermi level across the NV charge transition levels.

Diamond nanoelectrode arrays for the detection of surface sensitive adsorption.

Nanocrystalline diamond nanoelectrode arrays (NEAs) have been applied to investigate surface-sensitive adsorption phenomena at the diamond-liquid interface. The adsorption of neutral methyl viologen (MV(0) ) was used as a model system. The adsorption of MV(0) was examined on hydrogen- and oxygen-terminated surfaces. On the hydrogenated nanoelectrode surface, a sharp anodic stripping peak was observed upon oxidation of MV(0) , revealing strong adsorption of MV(0) . In contrast, a sigmoidal voltammogram was recorded with an oxygenated electrode surface, indicating there was no MV(0) adsorption. The changes in the shapes of these voltammograms are due to the drastic changes that occur in the diffusion profiles during the transition. The diffusion profile changes from hemispherical diffusion on oxygen-terminated surfaces to thin-layer electrochemistry upon adsorption on hydrogen-terminated surfaces. Different types and concentrations of buffer solutions were then used to vary the interaction of MV(0) with diamond NEAs. The results suggest that the adsorption of MV(0) on hydrogen-terminated diamond NEAs is controlled by hydrophobic interactions. Therefore, diamond NEAs are ideal for the study of adsorption phenomena at the liquid-solid interface with voltammetry.

Diamond decorated with copper nanoparticles for electrochemical reduction of carbon dioxide.

Electrochemical CO2 reduction has been investigated on a planar diamond electrode in aqueous and nonaqueous solutions. On a diamond electrode decorated with copper nanoparticles, CO2 reduction starts from -0.1 V versus a normal hydrogen electrode (NHE) when a mixture of water and ionic liquid ([H2O] = 10 µM) is used. The current density reaches 5.1 ± 0.1 mA cm(-2) for CO2 reduction at a potential of -1.3 V versus NHE. The main products are formic acid and formaldehyde. Moreover, the electrode system is stable and has a long lifetime. It is thus promising to be applied in the future for mass production of industrial chemicals and liquid fuels using CO2 as the source of raw material.

Electrochemistry of nanocrystalline 3C silicon carbide films.

Silicon carbide (SiC) films have been used frequently for high-frequency and powder devices but have seldom been applied as the electrode material. In this paper, we have investigated the electrochemical properties of the nanocrystalline 3C-SiC film in detail. A film with grain sizes of 5 to 20 nm shows a surface roughness of about 30 nm. The resistivity of the film is in the range of 3.5-6.2 kΩ cm. In 0.1 M H(2)SO(4) solution, the film has a double-layer capacitance of 30-35 µF cm(-2) and a potential window of 3.0 V if an absolute current density of 0.1 mA cm(-2) is defined as the threshold. Its electrochemical activity was examined by using redox probes of [Ru(NH(3))(6)](2+/3+) and [Fe(CN)(6)](3-/4-) in aqueous solutions and by using redox probes of quinone and ferrocene in nonaqueous solutions. Diffusion-controlled, quasi-reversible electrode processes were achieved in four cases. The surface chemistry of the nanocrystalline 3C-SiC film was studied by electrochemical grafting with 4-nitrobenzenediazonium salts. The grafting was confirmed by time-of-flight secondary ion mass spectroscopy. All these results confirm that the nanocrystalline 3C-SiC film is promising for use as an electrode material.

Diamond nanophotonics.

We demonstrate the coupling of single color centers in diamond to plasmonic and dielectric photonic structures to realize novel nanophotonic devices. Nanometer spatial control in the creation of single color centers in diamond is achieved by implantation of nitrogen atoms through high-aspect-ratio channels in a mica mask. Enhanced broadband single-photon emission is demonstrated by coupling nitrogen-vacancy centers to plasmonic resonators, such as metallic nanoantennas. Improved photon-collection efficiency and directed emission is demonstrated by solid immersion lenses and micropillar cavities. Thereafter, the coupling of diamond nanocrystals to the guided modes of micropillar resonators is discussed along with experimental results. Finally, we present a gas-phase-doping approach to incorporate color centers based on nickel and tungsten, in situ into diamond using microwave-plasma-enhanced chemical vapor deposition. The fabrication of silicon-vacancy centers in nanodiamonds by microwave-plasma-enhanced chemical vapor deposition is discussed in addition.

Fractional surface termination of diamond by electrochemical oxidation.

The crystalline form of sp(3)-hybridized carbon, diamond, offers various electrolyte-stable surface terminations. The H-termination-selective attachment of nitrophenyl diazonium, imaged by AFM, shows that electrochemical oxidation can control the fractional hydrogen/oxygen surface termination of diamond on the nanometer scale. This is of particular interest for all applications relying on interfacial electrochemistry, especially for biointerfaces.

Integrated all-diamond ultramicroelectrode arrays: optimization of faradaic and capacitive currents.

Integrated all-diamond ultramicroelectrode arrays (UMEAs) were fabricated using standard photolithography processes. The array consisted of typically 45 ultramicroelectrodes with a diameter of 10 µm and with a center-to-center spacing of 60 µm. The quasi-reference and counter electrodes were made from conductive diamond and were integrated on a 5 × 5 mm(2) chip. On the UMEA, a high ratio of faradaic current to capacitive current was achieved on heavily boron-doped and hydrogen-terminated diamond surfaces at slow scan rates and in high concentration of supporting electrolyte. A sensitive and reproducible detection of dopamine was achieved on hydrogen-terminated diamond UMEA at slow scan rates. The detection limit of dopamine in the presence of ascorbic acid was 1.0 nM, which is 50-100 times lower than that obtained on the macrosized boron-doped diamond electrodes. This array is promising for sensitive and reproducible detection of analytes in solutions with low detection limits.

The creation of a biomimetic interface between boron-doped diamond and immobilized proteins.

Immobilization of proteins on a solid electrode is to date done by chemical cross-linking or by addition of an adjustable intermediate. In this paper we introduce a concept where a solid with variable surface properties is optimized to mediate binding of the electron-transfer protein Cytochrome c (Cyt c) by mimicking the natural binding environment. It is shown that, as a carbon-based material, boron-doped diamond can be adjusted by simple electrochemical surface treatments to the specific biochemical requirements of Cyt c. The structure and functionality of passively adsorbed Cyt c on variously terminated diamond surfaces were characterized in detail using a combination of electrochemical techniques and atomic force microscopy with single-molecule resolution. Partially oxidized diamond allowed stable immobilization of Cyt c together with high electron transfer activity, driven by a combination of electrostatic and hydrophobic interactions. This surface mimics the natural binding partner, where coarse orientation is governed by electrostatic interaction of the protein's dipole and hydrophobic interactions assist in formation of the electron transfer complex. The optimized surface mediated electron transfer kinetics around 100 times faster than those reported for other solids and even faster kinetics than on self-assembled monolayers of alkanethiols.

Nanocrystalline 3C-SiC electrode for biosensing applications.

Silicon carbide has been proved as a candidate for power and high-frequency devices. In this paper, we show the application of nanocrystalline 3C-SiC as an electrochemical electrode and its electrochemical functionalization for biosensing applications. SiC electrodes show a wider potential window and lower background current than glassy carbon electrodes. The surface can be electrochemically functionalized with diazonium salts, as confirmed by electrochemical techniques and X-ray photoelectron spectroscopy. The nitrophenyl film is used as linker layer to bond DNA molecule to SiC. These results show that 3C-SiC can be an interesting transducer material for applications in electro- and bioelectrochemical applications.