This paper presents a method to distinguish graphene from graphite in powdered samples by analysing the Raman 2D band symmetry.

We demonstrate a highly efficient, single-step, cathodic exfoliation process of graphite to produce single- to few-layer graphene with a yield of over 70% from natural graphite flakes.

Mechanical and electrical losses induced by an electrode material greatly influence the performance of bulk acoustic wave (BAW) resonators. Graphene as a conducting and virtually massless 2D material is a suitable candidate as an alternative electrode material for BAW resonators which reduces electrode induced mechanical losses. In this publication we show that graphene acts as an active top electrode for solidly mounted BAW resonators (BAW-SMR) at 2.1 GHz resonance frequency. Due to a strong decrease of mass loading and its remarkable electronic properties, graphene demonstrates its ability as an ultrathin conductive layer. In our experiments we used an optimized graphene wet transfer on aluminum nitride-based solidly mounted resonator devices. We achieved more than a triplication of the resonator’s quality factor Q and a resonance frequency close to an ‘unloaded’ resonator without metallization. Our results reveal the direct influence of both, the graphene quality and the graphene contacting via metal structures, on the performance characteristic of a BAW resonator. These findings clearly show the potential of graphene in minimizing mechanical losses due to its virtually massless character. Moreover, they highlight the advantages of graphene and other 2D conductive materials for alternative electrodes in electroacoustic resonators for radio frequency applications.

The two-dimensional and virtually massless character of graphene attracts great interest for radio frequency devices, such as surface and bulk acoustic wave resonators. Due to its good electric conductivity, graphene might be an alternative as a virtually massless electrode by improving resonator performance regarding mass-loading effects. We report on an optimization of the commonly used wet transfer technique for large-area graphene, grown via chemical vapor deposition, onto aluminum nitride (AlN), which is mainly used as an active, piezoelectric material for acoustic devices. Today, graphene wet transfer is well-engineered for silicon dioxide (SiO2). Investigations on AlN substrates reveal highly different surface properties compared to SiO2 regarding wettability, which strongly influences the quality of transferred graphene monolayers. Both physical and chemical effects of a plasma treatment of AlN surfaces change wettability and avoid large-scale cracks in the transferred graphene sheet during desiccation. Spatially-resolved Raman spectroscopy reveals a strong strain and doping dependence on AlN plasma pretreatments correlating with the electrical conductivity of graphene. In our work, we achieved transferred crack-free large-area (40 × 40 mm2) graphene monolayers with sheet resistances down to 350 Ω/sq. These achievements make graphene more powerful as an eco-friendly and cheaper replacement for conventional electrode materials used in radio frequency resonator devices.

A cathodic electrochemical method for the exfoliation of graphite to produce hydrogenated graphenic flakes is introduced. The resulting solutions consist of micrometer-sized and predominantly 1–4 layers thick hydrogenated graphenic flakes. In contrast to oxygenation, chemisorption of hydrogen avoids the formation of structural vacancy defects in the exfoliated flakes. Thermal desorption of hydrogen therefore results in graphenic flakes with a low defect density and consequently good electrical conductivity. Cathodic electrochemical exfoliation offers a remarkably simple and effective technique for the production of high quality graphene flakes and their hydrogenated relatives.

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.

Nano-structured electrodes become promising materials for a vast number of applications such as bio-chemical sensing and supercapacitors. We introduce a new concept to generate surface enlarged diamond electrodes, so-called “diamond foam”. To obtain diamond foam electrodes, SiO2 spheres were used for heavily boron-doped (1021 cm− 3) nano-crystalline diamond (B-NCD) overgrowth in a microwave plasma reactor. After overgrowth with B-NCD the SiO2 spheres were etched away with HF giving rise to diamond foam consisted of B-NCD shells accumulated on the substrate. This process has the advantage that the thickness of diamond foam can increase infinitely by repeating the growth and etching processes. Structural and electrochemical characterizations show that the diamond foam electrodes show a surface enlargement of around 40 while keeping good chemical stability as well as a diamond related structural properties.

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 (MV0) was used as a model system. The adsorption of MV0 was examined on hydrogen- and oxygen-terminated surfaces. On the hydrogenated nanoelectrode surface, a sharp anodic stripping peak was observed upon oxidation of MV0, revealing strong adsorption of MV0. In contrast, a sigmoidal voltammogram was recorded with an oxygenated electrode surface, indicating there was no MV0 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 MV0 with diamond NEAs. The results suggest that the adsorption of MV0 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.

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.

In this report, the fabrication of all-nanocrystalline diamond (NCD) nanoelectrode arrays (NEAs) by e-beam lithography as well as of all-diamond nanoelectrode ensembles (NEEs) using nanosphere lithography is presented. In this way, nanostructuring techniques are combined with the excellent properties of diamond that are desirable for electrochemical sensor devices. Arrays and ensembles of recessed disk electrodes with radii ranging from 150 to 250 nm and a spacing of 10 μm have been fabricated. Electrochemical impedance spectroscopy as well as cyclic voltammetry was conducted to characterize arrays and ensembles with respect to different diffusion regimes. One outstanding advantage of diamond as an electrode material is the stability of specific surface terminations influencing the electron transfer kinetics. On changing the termination from hydrogen- to oxygen-terminated diamond electrode surface, we observe a dependence of the electron transfer rate constant on the charge of the analyte molecule. Ru(NH(3))(6)(+2/+3) shows faster electron transfer on oxygen than on hydrogen-terminated surfaces, while the anion IrCl(6)(-2/-3) exhibits faster electron transfer on hydrogen-terminated surfaces correlating with the surface dipole layer. This effect cannot be observed on macroscopic planar diamond electrodes and emphasizes the sensitivity of the all-diamond NEAs and NEEs. Thus, the NEAs and NEEs in combination with the efficiency and suitability of the selective electrochemical surface termination offer a new versatile system for electrochemical sensing.

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.

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.

The electron transfer process and the peroxidase activity of native and denatured cytochrome c were investigated on OH-terminated diamond nano-textured surfaces. The nano-textured surfaces with geometrical properties of typical protein dimensions were fabricated by a top-down technology, where diamond nanoparticles are used as etching masks. The cyclic voltammogram of native cytochrome c shows an adsorption-controlled, reversible electron transfer process of the heme redox center, which was not detected for denatured cytochrome c. Native cytochrome c denatures in the presence of hydrogen peroxide. Higher peroxidase activity was found on the denatured cytochrome c than on native cytochrome c. The apparent Michaelis–Menten constants K m for denatured cytochrome c and the native cytochrome c were determined to be 0.08 and 0.23 mM, respectively.

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.

All-diamond ultra-microelectrode arrays (UMEAs) were fabricated using standard photolithography processes. The array consists of typically 45 ultra-microelectrodes with a diameter of 10 mu m and with a center-to-center spacing of 60 mu m. The quasi-reference and counter electrodes are made from conductive diamond and integrated on a 5 x 5 mm(2) chip. The arrays with different surface terminations were characterized using cyclic voltammetry and the redox couple of Fe(CN)(6)(3-/4-) as probes. A peak-shaped voltammogram was detected on electrochemically hydrogen-terminated surface if scanned with a slow scan rate (e.g. 20 mV/s), resulting in a higher ratio of the Faradaic current (signal) to capacitive charging current (background current). A sensitive and reproducible detection of hydrogen peroxide was achieved by using the UMEA. The net-charge for the oxidation of hydrogen peroxide at 0.4 V (vs. C) is linear with the concentration of hydrogen peroxide in the range of 6.5-650 mu M. The detection limit is 2.0 mu M, which is 100 times better than that obtained on the macro-sized boron-doped diamond electrode. (C) 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

In atomic force microscopy (AFM), sharp and wear-resistant tips are a critical issue. Regarding scanning electrochemical microscopy (SECM), electrodes are required to be mechanically and chemically stable. Diamond is the perfect candidate for both AFM probes as well as for electrode materials if doped, due to diamond's unrivaled mechanical, chemical, and electrochemical properties. In this study, standard AFM tips were overgrown with typically 300 nm thick nanocrystalline diamond (NCD) layers and modified to obtain ultra sharp diamond nanowire-based AFM probes and probes that were used for combined AFM-SECM measurements based on integrated boron-doped conductive diamond electrodes. Analysis of the resonance properties of the diamond overgrown AFM cantilevers showed increasing resonance frequencies with increasing diamond coating thicknesses (i.e., from 160 to 260 kHz). The measured data were compared to performed simulations and show excellent correlation. A strong enhancement of the quality factor upon overgrowth was also observed (120 to 710). AFM tips with integrated diamond nanowires are shown to have apex radii as small as 5 nm and where fabricated by selectively etching diamond in a plasma etching process using self-organized metal nanomasks. These scanning tips showed superior imaging performance as compared to standard Si-tips or commercially available diamond-coated tips. The high imaging resolution and low tip wear are demonstrated using tapping and contact mode AFM measurements by imaging ultra hard substrates and DNA. Furthermore, AFM probes were coated with conductive boron-doped and insulating diamond layers to achieve bifunctional AFM-SECM probes. For this, focused ion beam (FIB) technology was used to expose the boron-doped diamond as a recessed electrode near the apex of the scanning tip. Such a modified probe was used to perform proof-of-concept AFM-SECM measurements. The results show that high-quality diamond probes can be fabricated, which are suitable for probing, manipulating, sculpting, and sensing at single digit nanoscale.

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.

The adsorption and conformational state of the electron transfer protein cytochrome c (cyt c) on flat, boron doped polycrystalline diamond electrodes was investigated using electrochemical techniques and atomic force microscopy (AFM). An electrochemical reduction wave from the adsorbed protein was identified as oxygen reduction, which is catalysed by the deformed heme redox centre of cyt c. We show that this catalytic activity only occurs after partial denaturation of cyt c. Therefore the reduction peak was used for characterization of the conformational state of adsorbed cyt c. AFM characterizations with molecular resolution show different conformational states of cyt c on diamond surfaces ranging from native to denaturated. Both applied techniques indicate that hydrophobic hydrogenated diamond tends to denaturate cyt c upon adsorption, while wet chemically oxidized diamond surfaces can provide extensive but non-denaturating cyt c adsorption. The conformation and orientation of cyt c on wet chemically oxidized diamond is beneficial for the electron transfer between the protein redox centre and the diamond electrode even in the presence of oxygen. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim