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1.
  • Backes, Claudia, et al. (författare)
  • Production and processing of graphene and related materials
  • 2020
  • Ingår i: 2D Materials. - : IOP Publishing. - 2053-1583. ; 7:2
  • Tidskriftsartikel (refereegranskat)abstract
    • We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV-VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resource-consuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown. Section VIII discusses advances in GRM functionalization. A broad range of organic molecules can be anchored to the sp(2) basal plane by reductive functionalization. Negatively charged graphene can be prepared in liquid phase (e.g. via intercalation chemistry or electrochemically) and can react with electrophiles. This can be achieved both in dispersion or on substrate. The functional groups of GO can be further derivatized. Graphene can also be noncovalently functionalized, in particular with polycyclic aromatic hydrocarbons that assemble on the sp(2) carbon network by pi-pi stacking. In the liquid phase, this can enhance the colloidal stability of SLG/FLG. Approaches to achieve noncovalent on-substrate functionalization are also discussed, which can chemically dope graphene. Research efforts to derivatize CNMs are also summarized, as well as novel routes to selectively address defect sites. In dispersion, edges are the most dominant defects and can be covalently modified. This enhances colloidal stability without modifying the graphene basal plane. Basal plane point defects can also be modified, passivated and healed in ultra-high vacuum. The decoration of graphene with metal nanoparticles (NPs) has also received considerable attention, as it allows to exploit synergistic effects between NPs and graphene. Decoration can be either achieved chemically or in the gas phase. All LMs,
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2.
  • Dillner, Lars, 1968, et al. (författare)
  • Frequency Multiplier Measurements on Heterostructure Barrier Varactors on a Copper Substrate
  • 2000
  • Ingår i: IEEE Electron Device Letters. - : Institute of Electrical and Electronics Engineers (IEEE). - 0741-3106 .- 1558-0563. ; 21:5, s. 206-208
  • Tidskriftsartikel (refereegranskat)abstract
    • We have fabricated heterostructure barrier varactors (HBV) on a copper substrate, which offers reduced spreading resistance, and improved thermal conductivity compared to an InP substrate. The devices are fabricated without degrading the electrical characteristics. The three-barrier HBV material grown by MOVPE has a leakage current of only 0.1 mu A/ mu m/sup 2/ at 19 V. The maximum capacitance is 0.54 fF/ mu m/sup 2/. In a frequency tripler experiment a maximum output power of 7.1 mW was generated at 221 GHz with a flange-to-flange efficiency of 7.9%.
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4.
  • Dillner, Lars, 1968, et al. (författare)
  • High Efficiency HBV Multipliers for Millimetre Wave Generation
  • 2000
  • Ingår i: the XIII International Conference on Microwaves, Radar and Wireless Communications. - 8390666235 ; 3, s. 47-54
  • Konferensbidrag (refereegranskat)abstract
    • We describe the heterostructure barrier varactor (HBV) diode and its application in frequency multipliers. Different material systems and HBV models are described. In a frequency tripler experiment a maximum output power of 7.1 mW was generated at 221 GHz with a flange-to-flange efficiency of 7.9%.
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5.
  • Habibpour, Omid, 1979, et al. (författare)
  • Graphene FET Gigabit On-Off Keying Demodulator at 96 GHz
  • 2016
  • Ingår i: IEEE Electron Device Letters. - 0741-3106 .- 1558-0563. ; 37:3, s. 333-336
  • Tidskriftsartikel (refereegranskat)abstract
    • We demonstrate the demodulation of a multi-Gb/s ON-OFF keying (OOK) signal on a 96 GHz carrier by utilizing a 250-nm graphene field-effect transistor as a zero bias power detector. From the eye diagram, we can conclude that the devices can demodulate the OOK signals up to 4 Gb/s.
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6.
  • Habibpour, Omid, 1979, et al. (författare)
  • Wafer scale millimeter-wave integrated circuits based on epitaxial graphene in high data rate communication
  • 2017
  • Ingår i: Scientific Reports. - : Springer Science and Business Media LLC. - 2045-2322 .- 2045-2322. ; 7, s. 41828-
  • Tidskriftsartikel (refereegranskat)abstract
    • In recent years, the demand for high data rate wireless communications has increased dramatically, which requires larger bandwidth to sustain multi-user accessibility and quality of services. This can be achieved at millimeter wave frequencies. Graphene is a promising material for the development of millimeter-wave electronics because of its outstanding electron transport properties. Up to now, due to the lack of high quality material and process technology, the operating frequency of demonstrated circuits has been far below the potential of graphene. Here, we present monolithic integrated circuits based on epitaxial graphene operating at unprecedented high frequencies (80-100 GHz). The demonstrated circuits are capable of encoding/decoding of multi-gigabit-per-second information into/from the amplitude or phase of the carrier signal. The developed fabrication process is scalable to large wafer sizes.
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7.
  • Ingvarson, Mattias, 1974, et al. (författare)
  • Design of Material Structures for Heterostructure Barrier Varactors
  • 2001
  • Ingår i: 19th Nordic Semiconductor Meeting. ; , s. 68-
  • Konferensbidrag (refereegranskat)abstract
    • The Heterostructure Barrier Varactor (HBV), first proposed by Kollberg et al. [1], has a symmetric C-V and an anti-symmetric I-V characteristic. Therefore it will only produce odd harmonics of the input frequency when used in mm- and submm-wave frequency multipliers, which greatly simplifies the multiplier design. The high-bandgap barriers prevent electron transport through the structure so that the depletion region of the modulation layers is controlled by the applied bias, thus modulating the capacitance of the device. By varying the number of barriers and the thickness and doping of the modulation layers, it is possible to tailor the HBV diode for various applications, e.g. power-handling capability and frequency of operation.We present four different InGaAs/InAlAs HBV materials on InP fabricated by MOVPE. Two are designed for high-power, mm-wave applications and the other two are optimised for high efficiency up to submm-wave frequencies. In order to handle high power levels, materials 1816 and 1817 have six barriers and a relatively low doping concentration which results in a high break-down voltage. The measured break-down voltage for 1817 of approximately 52 Volts for a current density of 0,1µA/µm2 is, to the best of our knowledge, the highest value reported for HBVs. Materials 1819 and 1820 have higher doping concentrations and shorter modulation layers to reduce losses and the effect of current saturation, see Table 1. Design methods and predicted RF-performance will be presented.
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8.
  • Liu, Xianjie, et al. (författare)
  • Tunable Interface Properties between Pentacene and Graphene on the SIC Substrate
  • 2013
  • Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society. - 1932-7447 .- 1932-7455. ; 117:8, s. 3969-3975
  • Tidskriftsartikel (refereegranskat)abstract
    • Understanding energy-level alignment and molecular growth characteristics of an organic semiconductor on the graphene surface is crucial for graphene-related device performance. Here we demonstrate that tunable interface properties and molecular orientation can be achieved by modifying graphene films on a SiC substrate with monolayer copper-hexadecafluorophthalocyanine (F16CuPc) molecules. On clean graphene, pentacene molecules form a tilted configuration even at very low coverage (one or two monolayers) rather than flat-lying as on the graphite surface. Pentacene molecules prefer to grow with a (022) plane parallel to the clean graphene surface. With increasing coverage, X-ray adsorption data indicate there is no obvious change of molecular stacking orientation. The corresponding hole injection barrier is about 0.7 eV. On the modified graphene where thin (one or two monolayers) F16CuPc molecules are flat-lying on graphene, an almost perfect up-standing molecular stacking of pentacene film was formed on the modified surface. A low hole injection barrier of 0.3 eV was observed. Furthermore, the interface of dirty graphene upon pentacene was also discussed.
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9.
  • Lupina, Grzegorz, et al. (författare)
  • Residual Metallic Contamination of Transferred Chemical Vapor Deposited Graphene
  • 2015
  • Ingår i: ACS Nano. - : American Chemical Society (ACS). - 1936-0851 .- 1936-086X. ; 9:5, s. 4776-4785
  • Tidskriftsartikel (refereegranskat)abstract
    • Integration of graphene with Si microelectronics is very appealing by offering a potentially broad range of new functionalities. New materials to be integrated with the Si platform must conform to stringent purity standards. Here, we investigate graphene layers grown on copper foils by chemical vapor deposition and transferred to silicon wafers by wet etching and electrochemical delamination methods with respect to residual submonolayer metallic contaminations. Regardless of the transfer method and associated cleaning scheme, time-of-flight secondary ion mass spectrometry and total reflection X-ray fluorescence measurements indicate that the graphene sheets are contaminated with residual metals (copper, iron) with a concentration exceeding 10(13) atoms/cm(2). These metal impurities appear to be partially mobile upon thermal treatment, as shown by depth profiling and reduction of the minority charge carrier diffusion length in the silicon substrate. As residual metallic impurities can significantly alter electronic and electrochemical properties of graphene and can severely impede the process of integration with silicon microelectronics, these results reveal that further progress in synthesis, handling, and cleaning of graphene is required to advance electronic and optoelectronic applications.
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