Disruptive technologies are usually characterised by universal, versatile applications, which change many aspects of our life simultaneously, penetrating every corner of our existence. In order to become disruptive, a new technology needs to offer not incremental, but dramatic, orders of magnitude improvements. Moreover, the more universal the technology, the better chances it has for broad base success. Significant progress has been made in taking graphene and related materials from a state of raw potential to a point where they can revolutionize multiple industries. When it comes to electrochemical applications, Raman spectroscopy is an ideal non-destructive technique to study degradation in graphite anodes, as it is sensitive to doping, strain, defects, and interlayer coupling. I will discuss how in-situ Raman spectroscopy can unravel the signatures of Li-ion induced doping, intercalation staging and degradation upon cycling.
Anionic and cationic lipids are key molecules involved in many cellular processes; their distribution in biomembranes is highly asymmetric, and their concentration is well-controlled. Graphene solution-gated field-effect transistors (SGFETs) exhibit high sensitivity toward the presence of surface charges. Here, we establish conditions that allow the observation of the formation of charged lipid layers on solution-gated field-effect transistors in real time. We quantify the electrostatic screening of electrolyte ions and derive a model that explains the influence of charged lipids on the ion sensitivity of graphene SGFETs. The electrostatic model is validated using structural information from X-ray reflectometry measurements, which show that the lipid monolayer forms on graphene. We demonstrate that SGFETs can be used to detect cationic lipids by self-exchange of lipids. Furthermore, SGFETs allow measuring the kinetics of layer formation induced by vesicle fusion or spreading from a reservoir. Because of the high transconductance and low noise of the electrical readout, we can observe characteristic conductance spikes that we attribute to bouncing-off events of lipid aggregates from the SGFET surface, suggesting a great potential of graphene SGFETs to measure the on-off kinetics of small aggregates interacting with supported layers.
Supercapacitors are called to play a prominent role in the newly emerging markets of electric vehicles, flexible displays and sensors, and wearable electronics. In order to compete with current battery technology, supercapacitors have to be designed with highly conductive current collectors exhibiting high surface area per unit volume and uniformly coated with pseudocapacitive materials, which is crucial to boost the energy density while maintaining a high power density. Here, we present a versatile technique to prepare thickness-controlled thin-film micro graphene foams (μGFs) with pores in the lower micrometer range grown by chemical vapor deposition which can be used as highly conductive current collectors in flexible supercapacitors. To fabricate the μGF, we use porous metallic catalytic substrates consisting of nickel/copper alloy synthesized on nickel foil by electrodeposition in an electrolytic solution. Changing the duration of the electrodeposition allows the control of the thickness of the metal foam, and thus of the μGF, ranging from a few micrometers to the millimeter scale. The resulting μGF with a thickness and pores in the micrometer regime exhibits high structural quality which leads to a very low intrinsic resistance of the devices. Transferred onto flexible substrates, we demonstrate a uniform coating of the μGFs with manganese oxide, a pseudocapacitively active material. Considering the porous structure and the thickness of the μGFs, square wave potential pulses are used to ensure uniform coverage by the oxide material boosting the volumetric and areal capacitance to 14 F cm-3 and 0.16 F cm-2. The μGF with a thickness and pores in the micrometer regime in combination with a coating technique tuned to the porosity of the μGF is of great relevance for the development of supercapacitors based on state-of-the-art graphene foams.
The direct conversion of sunlight into chemical energy via photosynthesis is a unique capability of plants and some bacterial species. Aimed at mimicking this energy conversion process, the combination of inorganic substrates and organic photoactive proteins into an artificial biohybrid system is of a great interest for artificial biophotovoltaic applications. It also allows to better understand charge transfer processes involved in the photosynthetic chain. In this work, single layer graphene (SLG) and multilayer graphene (MLG) electrodes are used as a platform for the immobilization of reaction centers (RCs) from purple bacteria Rhodobacter sphaeroides, a protein complex responsible for the generation of photo-excited charges. Electrochemical experiments with graphene electrodes and redox molecules reveal fundamental differences in the charge transfer processes for SLG and MLG films. We demonstrate that both graphene-based materials enable the immobilization of RCs without loss of functionality, attested by a photocurrent generation under illumination with IR-light at a wavelength of 870 nm. Furthermore, we report on the dependence of the generated photocurrent on the applied bias voltage, as well as on the presence of charge mediators in the surrounding electrolyte. This work demonstrates that SLG and MLG are a suitable platform for RC immobilization and subsequent photocurrent generation, suggesting a promising potential for graphene-based materials in bio-photovoltaics.
Establishing a reliable communication interface between the brain and electronic devices is of paramount importance for exploiting the full potential of neural prostheses. Current microelectrode technologies for recording electrical activity, however, evidence important shortcomings, e.g. challenging high density integration. Solution-gated field-effect transistors (SGFETs), on the other hand, could overcome these shortcomings if a suitable transistor material were available. Graphene is particularly attractive due to its biocompatibility, chemical stability, flexibility, low intrinsic electronic noise and high charge carrier mobilities. Here, we report on the use of an array of flexible graphene SGFETs for recording spontaneous slow waves, as well as visually evoked and also pre-epileptic activity in vivo in rats. The flexible array of graphene SGFETs allows mapping brain electrical activity with excellent signal-to-noise ratio (SNR), suggesting that this technology could lay the foundation for a future generation of in vivo recording implants.
Three-dimensional ( 3D) graphene-based structures combine the unique physical properties of graphene with the opportunity to get high electrochemically available surface area per unit of geometric surface area. Several preparation techniques have been reported to fabricate 3D graphene-based macroscopic structures for energy storage applications such as supercapacitors. Although reaserch has been focused so far on achieving either high specific capacitance or high volumetric capacitance, much less attention has been dedicated to obtain high specific and high volumetric capacitance simultaneously. Here, we present a facile technique to fabricate graphene foams ( GF) of high crystal quality with tunable pore size grown by chemical vapor deposition. We exploited porous sacrificial templates prepared by sintering nickel and copper metal powders. Tuning the particle size of the metal powders and the growth temperature allow fine control of the resulting pore size of the 3D graphene-based structures smaller than 1 mu m. The as-produced 3D graphene structures provide a high volumetric electric double layer capacitance ( 165 mF cm(-3)). High specific capacitance ( 100 Fg(-1)) is obtained by lowering the number of layers down to single layer graphene. Furthermore, the small pore size increases the stability of these GFs in contrast to the ones that have been grown so far on commercial metal foams. Electrodes based on the as-prepared GFs can be a boost for the development of supercapacitors, where both low volume and mass are required.
1 Walter Schottky Institut und Physik-Department, Technische Universität München, Am Coulombwall 4, 85748 Garching, Germany 2 Institut D' Investigacions Biomèdiques August Pi i Sunyer (IDIBAPS), Barcelona 08036, Spain 3 Instituto de Microelectronica de Barcelona (IMB-CNM), CSIC, Campus UAB, 08913 Bellaterra, Barcelona, Spain 4 Centro de Investigacion Biomédica en Red, Biomateriales y Nanomedicina (CIBER-BBN), Spain 5 ESIEE-Paris, ESYCOM, University Paris EST, Cité Descartes BP99, Noisy-Le-Grand 93160, France 6 Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, 08193 Barcelona, Spain 7 ICREA, Institució Catalana de Recerca i Estudis Avançats, 08070 Barcelona, Spain
Different deposition parameters, for the growth of (111)-oriented single crystalline diamond samples were varied, such as temperature, methane concentration, methane/oxygen ratio and chamber pressure. It was shown that good quality material can be deposited at low methane concentrations with oxygen addition at high temperatures. Therefore, a growth temperature of 850°C is used along with a pressure of 200mbar, a CH4/O2 ratio of 3 and a methane concentration of 0.3% in order to prevent the incorporation of silicon in the single crystal diamond. Diamond layers with a thickness of 100nm and 300μm show RMS roughness values of around 0.26nm and 200nm, respectively.
Graphene solution-gated field-effect transistors (SGFETs) are a promising platform for the recording of cell action potentials due to the intrinsic high signal amplification of graphene transistors. In addition, graphene technology fulfills important key requirements for in-vivo applications, such as biocompability, mechanical flexibility, as well as ease of high density integration. In this paper we demonstrate the fabrication of flexible arrays of graphene SGFETs on polyimide, a biocompatible polymeric substrate. We investigate the transistor’s transconductance and intrinsic electronic noise which are key parameters for the device sensitivity, confirming that the obtained values are comparable to those of rigid graphene SGFETs. Furthermore, we show that the devices do not degrade during repeated bending and the transconductance, governed by the electronic properties of graphene, is unaffected by bending. After cell culture, we demonstrate the recording of cell action potentials from cardiomyocyte-like cells with a high signal-to-noise ratio that is higher or comparable to competing state of the art technologies. Our results highlight the great capabilities of flexible graphene SGFETs in bioelectronics, providing a solid foundation for in-vivo experiments and, eventually, for graphene-based neuroprosthetics.
For future on-chip communication schemes, it is essential to integrate nanoscale materials with an ultrafast optoelectronic functionality into high-frequency circuits. The atomically thin graphene has been widely demonstrated to be suitable for photovoltaic and optoelectronic devices because of its broadband optical absorption and its high electron mobility. Moreover, the ultrafast relaxation of photogenerated charge carriers has been verified in graphene. Here, we show that dual-gated graphene junctions can be functional parts of THz-circuits. As the underlying optoelectronic process, we exploit ultrafast photo-thermoelectric currents. We describe an immediate photo-thermoelectric current of the unbiased device following a femtosecond laser excitation. For a picosecond time-scale after the optical excitation, an additional photo-thermoelectric contribution shows up, which exhibits the fingerprint of a spatially inverted temperature profile. The latter can be understood by the different time-constants and thermal coupling mechanisms of the electron and phonon baths within graphene to the substrate and the metal contacts. The interplay of the processes gives rise to ultrafast electromagnetic transients in high-frequency circuits, and it is equally important for a fundamental understanding of graphene-based ultrafast photodetectors and switches.
The interface between graphene and aqueous electrolytes is of high importance for applications of graphene in the field of biosensors and bioelectronics. The graphene/electrolyte interface is governed by the low density of states of graphene that limits the capacitance near the Dirac point in graphene and the sheet resistance. While several reports have focused on studying the capacitance of graphene as a function of the gate voltage, the frequency response of graphene electrodes and electrolyte-gated transistors has not been discussed so far. Here, we report on the impedance characterization of single layer graphene electrodes and transistors, showing that due to the relatively high sheet resistance of graphene, the frequency response is governed by the distribution of resistive and capacitive circuit elements along the graphene/electrolyte interface. Based on an analytical solution for the impedance of the distributed circuit elements, we model the graphene/electrolyte interface both for the electrode and the transistor configurations. Using this model, we can extract the relevant material and device parameters such as the voltage-dependent intrinsic sheet and series resistances as well as the interfacial capacitance. The model also provides information about the frequency threshold of electrolyte-gated graphene transistors, above which the device exhibits a non-resistive response, offering an important insight into the suitable frequency range of operation of electrolyte-gated graphene devices.
Resumen del trabajo presentado al 2nd International Workshop Graphene Industry – Challenges & Opportunities, celebrado en Barcelona (Espana) el 13 de diciembre de 2016.-- et al.
Chemical vapor deposition in a hot wall reactor is the most common technique for the production of large area single layer graphene. However, growth in this type of reactors is time consuming and the results are limited by the surface quality of the widely used catalytic metal foils as growth substrates. In this work we demonstrate the use of millimeter-thick Cu and Pt substrates for graphene growth via inductive magnetic heating, which allows for fast temperature ramps during heat up and cooling. Based on a detailed growth study, a two-step growth process resulting in continuous monolayer graphene films of high crystal quality with grain size of larger than 90 pm is established. An electrochemical transfer process is used to separate the graphene film from the metallic substrate, yielding excellent results in terms of defect density, doping and residual contamination. Back-gated graphene field-effect transistors fabricated on Si/SiO2 structures exhibit a high reproducibility with a peak mobility higher than 4000 cm(2)/Vs. The combination of the highly time efficient graphene growth and electrochemical transfer together with the reusability of the growth substrates and the possibility of applying novel surface pretreatments pave the way for the use of high quality substrates in industrial applications. (C) 2014 Elsevier B.V. All rights reserved.