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- Backes, Claudia, et al.
(författare)
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Production and processing of graphene and related materials
- 2020
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Ingår i: 2D Materials. - : IOP Publishing. - 2053-1583. ; 7:2
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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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- Kaufmann, Tobias, et al.
(författare)
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Common brain disorders are associated with heritable patterns of apparent aging of the brain
- 2019
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Ingår i: Nature Neuroscience. - : Nature Publishing Group. - 1097-6256 .- 1546-1726. ; 22:10, s. 1617-
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Tidskriftsartikel (refereegranskat)abstract
- Common risk factors for psychiatric and other brain disorders are likely to converge on biological pathways influencing the development and maintenance of brain structure and function across life. Using structural MRI data from 45,615 individuals aged 3-96 years, we demonstrate distinct patterns of apparent brain aging in several brain disorders and reveal genetic pleiotropy between apparent brain aging in healthy individuals and common brain disorders.
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- Belova, Valentina, et al.
(författare)
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Evidence for Anisotropic Electronic Coupling of Charge Transfer States in Weakly Interacting Organic Semiconductor Mixtures
- 2017
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 139:25, s. 8474-8486
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Tidskriftsartikel (refereegranskat)abstract
- We present a comprehensive investigation of the charge-transfer (CT) effect in weakly interacting organic semiconductor mixtures. The donor-acceptor pair diindenoperylene (DIP) and N,N′-bis(2-ethylhexyl)-1,7-dicyanoperylene-3,4/9,10-bis(dicarboxyimide) (PDIR-CN2) has been chosen as a model system. A wide range of experimental methods was used in order to characterize the structural, optical, electronic, and device properties of the intermolecular interactions. By detailed analysis, we demonstrate that the partial CT in this weakly interacting mixture does not have a strong effect on the ground state and does not generate a hybrid orbital. We also find a strong CT transition in light absorption as well as in photo- and electroluminescence. By using different layer sequences and compositions, we are able to distinguish electronic coupling in-plane vs out-of-plane and, thus, characterize the anisotropy of the CT state. Finally, we discuss the impact of CT exciton generation on charge-carrier transport and on the efficiency of photovoltaic devices.
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- Beyer, Franziska, et al.
(författare)
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Deep levels in tungsten doped n-type 3C-SiC
- 2011
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Ingår i: Applied Physics Letters. - : American Institute of Physics. - 0003-6951 .- 1077-3118. ; 98:15, s. 152104-
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Tidskriftsartikel (refereegranskat)abstract
- Tungsten was incorporated in SiC and W related defects were investigated using deep level transient spectroscopy. In agreement with literature, two levels related to W were detected in 4H-SiC, whereas only the deeper level was observed in 6H-SiC. The predicted energy level for W in 3C-SiC was observed (E-C-0.47 eV). Tungsten serves as a common reference level in SiC. The detected intrinsic levels align as well: E1 (E-C-0.57 eV) in 3C-SiC is proposed to have the same origin, likely V-C, as EH6/7 in 4H-SiC and E7 in 6H-SiC, respectively.
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5. |
- Beyer, Paul, et al.
(författare)
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Fermi level pinned molecular donor/acceptor junctions : Reduction of induced carrier density by interfacial charge transfer complexes
- 2020
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Ingår i: Journal of Materials Chemistry C. - : Royal Society of Chemistry (RSC). - 2050-7534 .- 2050-7526. ; 8:43, s. 15199-15207
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Tidskriftsartikel (refereegranskat)abstract
- Increased hole density in an electron donor-type organic semiconductor can be achieved by deposition of a strong acceptor-type molecular layer on top, and has been shown to enable adjusting the carrier density in organic field effect transistors (OFETs). This interfacial charge transfer is due to simultaneous Fermi level (EF) pinning of the donor's highest occupied level and the acceptor's lowest unoccupied level. Here, we investigate the electrical properties of such an EF-pinned junction formed by diindenoperylene (DIP, as donor) and hexafluoro-tetracyano-naphthoquinodimethane (F6, as acceptor) in OFETs, as well as its electronic properties by photoelectron spectroscopy and electrostatic modelling. We find that, in addition to the EF-pinning induced integer charge transfer across the interface, DIP and F6 form charge transfer complexes (CPXs) at their junction. The molecularly thin CPX interlayer acts as insulator and significantly reduces the density of carriers induced on either side of the junction, compared to a scenario without such an interlayer. CPX formation is thus unfavourable for the effectiveness of controlling carrier density at molecular donor/acceptor junctions by EF-pinning. This journal is
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- Gällström, Andreas, et al.
(författare)
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Electronic Configuration of Tungsten in 4H-, 6H-, and 15R-SiC
- 2012
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Ingår i: Materials Science Forum Vols 717 - 720. - : Trans Tech Publications Inc.. - 9783037854198 ; , s. 211-216
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Konferensbidrag (refereegranskat)abstract
- A commonly observed unidentified photoluminescence center in SiC is UD-1. In this report, the UD-1 center is identified to be tungsten related. The identification is based on (i) a W-doping study, the confirmation of W in the samples was made using deep level transient spectroscopy (DLTS), (ii) the optical activation energy of the absorption of UD-1 in weakly n-type samples corresponds to the activation energy of the deep tungsten center observed using DLTS. The tungsten-related optical centers are reported in 4H-, 6H-, and 15R-SiC. Further, a crystal field model for a tungsten atom occupying a Si-site is suggested. This crystal field model is in agreement with the experimental data available: polarization, temperature dependence and magnetic field splitting.
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- Gällström, Andreas, 1978-, et al.
(författare)
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Influence of Cooling Rate after High Temperature Annealing on Deep Levels in High-Purity Semi-Insulating 4H-SiC
- 2007
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Ingår i: Materials Science Forum, vol. 556-557. - : Trans Tech Publications. ; , s. 371-
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Konferensbidrag (refereegranskat)abstract
- The influence of different cooling rates on deep levels in 4H-SiC after high temperature annealing has been investigated. The samples were heated from room temperature to 2300°C, followed by a 20 minutes anneal at this temperature. Different subsequent cooling sequences down to 1100°C were used. The samples have been investigated using photoluminescence (PL) and IV characteristics. The PL intensities of the silicon vacancy (VSi) and UD-2, were found to increase with a faster cooling rate.
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- Gällström, Andreas, et al.
(författare)
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Optical identification and electronic configuration of tungsten in 4H-and 6H-SiC
- 2012
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Ingår i: Physica. B, Condensed matter. - : Elsevier. - 0921-4526 .- 1873-2135. ; 407:10, s. 1462-1466
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Tidskriftsartikel (refereegranskat)abstract
- Several optically observed deep level defects in SiC are still unidentified and little is published on their behavior. One of the commonly observed deep level defects in semi-insulating SiC is UD-1. less thanbrgreater than less thanbrgreater thanThis report suggests that UD-1 is Tungsten related, based on a doping study and previously reported deep level transient spectroscopy data, as well as photo-induced absorption measurements. The electronic levels involved in the optical transitions of UD-1 are also deduced. The transitions observed in the photoluminescence of UD-1 are from a Gamma(C3v)(4), to two different final states, which transform according to Gamma(C3v)(5)circle plus Gamma(C3v)(6) and Gamma(C3v)(4), respectively.
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