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    Segregated Network Polymer Composites with High Electrical Conductivity and Well Mechanical Properties based on PVC, P(VDFTFE), UHMWPE, and rGO
    (Washington, DC : ACS Publications, 2020) Shiyanova, Kseniya A.; Gudkov, Maksim V.; Gorenberg, Arkady Ya; Rabchinskii, Maxim K.; Smirnov, Dmitry A.; Shapetina, Maria A.; Gurinovich, Tatiana D.; Goncharuk, Galina P.; Kirilenko, Demid A.; Bazhenov, Sergey L.; Melnikov, Valery P.
    The formation of a segregated network structure (wittingly uneven distribution of a filler) is one of the most promising strategies for the fabrication of electrically conductive polymer composites at present. However, the simultaneous achievement of high values of electrical conductivity with the retention of well mechanical properties within this approach remains a great challenge. Here, by means of X-ray photoelectron spectra (XPS), near-edge X-ray absorption fine structure (NEXAFS) spectra, scanning electron microscopy (SEM), dielectric spectroscopy, and compression engineering stress-strain curve analysis, we have studied the effect of a segregated network structure on the electrical conductivity and mechanical properties of a set of polymer composites. The composites were prepared by applying graphene oxide (GO) with ultralarge basal plane size (up to 150 μm) onto the surface of polymer powder particles, namely, poly(vinyl chloride) (PVC), poly(vinylidene fluoride-co-tetrafluoroethylene) (P(VDF-TFE)), and ultrahigh-molecular-weight poly(ethylene) (UHMWPE) with the subsequent GO reduction and composite hot pressing. A strong dependence of the segregated network polymer composites' physical properties on the polymer matrix was demonstrated. Particularly, 12 orders of magnitude rise of the polymers' electrical conductivity up to 0.7 S/m was found upon the incorporation of the reduced GO (rGO). A 17% increase in the P(VDF-TFE) elastic modulus filled by 1 wt % of rGO was observed. Fracture strength of PVC/rGO at 0.5 wt % content of the filler was demonstrated to decrease by fourfold. At the same time, the change in strength was not significant for P(VDF-TFE) and UHMWPE composites in comparison with pure polymers. Our results show a promise to accelerate the development of new composites for energy applications, such as metal-free supercapacitor plates and current collectors of lithium-ion batteries, bipolar plates of proton-exchange membrane fuel cells, antistatic elements of various electronic devices, etc. © 2020 American Chemical Society.
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    Charge carrier density, mobility, and Seebeck coefficient of melt-grown bulk ZnGa2O4 single crystals
    (New York, NY : American Inst. of Physics, 2020) Boy, Johannes; Handwerg, Martin; Mitdank, Rüdiger; Galazka, Zbigniew; Fischer, Saskia F.
    The temperature dependence of the charge carrier density, mobility, and Seebeck coefficient of melt-grown, bulk ZnGa2O4 single crystals was measured between 10 K and 310 K. The electrical conductivity at room temperature is about σ = 286 S/cm due to a high electron concentration of n = 3.26 × 1019 cm−3 caused by unintentional doping. The mobility at room temperature is μ = 55 cm2/V s, whereas the scattering on ionized impurities limits the mobility to μ = 62 cm2/Vs for temperatures lower than 180 K. The Seebeck coefficient relative to aluminum at room temperature is SZnGa2O4−Al = (−125 ± 2) μV/K and shows a temperature dependence as expected for degenerate semiconductors. At low temperatures, around 60 K, we observed the maximum Seebeck coefficient due to the phonon drag effect. © 2020 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
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    Ultrathin two-dimensional conjugated metal– organic framework single-crystalline nanosheets enabled by surfactant-assisted synthesis
    (Cambridge : RSC, 2020) Wang, Zhonghao; Wang, Gang; Qi, Haoyuan; Wang, Mao; Wang, Mingchao; Park, SangWook; Wang, Huaping; Yu, Minghao; Kaiser, Ute; Fery, Andreas; Zhou, Shengqiang; Dong, Renhao; Feng, Xinliang
    Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have recently emerged for potential applications in (opto-)electronics, chemiresistive sensing, and energy storage and conversion, due to their excellent electrical conductivity, abundant active sites, and intrinsic porous structures. However, developing ultrathin 2D c-MOF nanosheets (NSs) for facile solution processing and integration into devices remains a great challenge, mostly due to unscalable synthesis, low yield, limited lateral size and low crystallinity. Here, we report a surfactant-assisted solution synthesis toward ultrathin 2D c-MOF NSs, including HHB-Cu (HHB = hexahydroxybenzene), HHB-Ni and HHTP-Cu (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene). For the first time, we achieve single-crystalline HHB-Cu(Ni) NSs featured with a thickness of 4-5 nm (∼8-10 layers) and a lateral size of 0.25-0.65 μm2, as well as single-crystalline HHTP-Cu NSs with a thickness of ∼5.1 ± 2.6 nm (∼10 layers) and a lateral size of 0.002-0.02 μm2. Benefiting from the ultrathin feature, the synthetic NSs allow fast ion diffusion and high utilization of active sites. As a proof of concept, when serving as a cathode material for Li-ion storage, HHB-Cu NSs deliver a remarkable rate capability (charge within 3 min) and long-term cycling stability (90% capacity retention after 1000 cycles), superior to the corresponding bulk materials and other reported MOF cathodes. This journal is © The Royal Society of Chemistry.
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    Liquid sensing: Smart polymer/CNT composites
    (Amsterdam [u.a.] : Elsevier, 2011) Villmow, T.; Pegel, S.; John, A.; Rentenberger, R.; Pötschke, P.
    Today polymer/carbon nanotube (CNT) composites can be found in sports equipment, cars, and electronic devices. The growth of old and new markets in this area has been stimulated by our increased understanding of relevant production and processing methods, as well as the considerable price reduction of industrial CNT grades. In particular, CNT based electrically conductive polymer composites (CPCs) offer a range of opportunities because of their unique property profile; they demonstrate low specific gravity in combination with relatively good mechanical properties and processability. The electrical conductivity of polymer/CNT composites results from a continuous filler network that can be affected by various external stimuli, such as temperature shifts, mechanical deformations, and the presence of gases and vapors or solvents. Accordingly, CNT based CPCs represent promising candidates for the design of smart components capable of integrated monitoring. In this article we focus on their use as leakage detectors for organic solvents.
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    Towards uniform electrochemical porosification of bulk HVPE-grown GaN
    (Pennington, NJ : Electrochemical Society Inc., 2019) Monaico, E.; Moise, C.; Mihai, G.; Ursaki, V.V.; Leistner, K.; Tiginyanu, I.M.; Enachescu, M.; Nielsch, K.
    In this paper, we report on results of a systematic study of porous morphologies obtained using anodization of HVPE-grown crystalline GaN wafers in HNO3, HCl, and NaCl solutions. The anodization-induced nanostructuring is found to proceed in different ways on N-and Ga-faces of polar GaN substrates. Complex pyramidal structures are disclosed and shown to be composed of regions with the degree of porosity modulated along the pyramid surface. Depending on the electrolyte and applied anodization voltage, formation of arrays of pores or nanowires has been evidenced near the N-face of the wafer. By adjusting the anodization voltage, we demonstrate that both current-line oriented pores and crystallographic pores are generated. In contrast to this, porosification of the Ga-face proceeds from some imperfections on the surface and develops in depth up to 50 μm, producing porous matrices with pores oriented perpendicularly to the wafer surface, the thickness of the pore walls being controlled by the applied voltage. The observed peculiarities are explained by different values of the electrical conductivity of the material near the two wafer surfaces.
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    Two-dimensional electron gas of the In2O3 surface: Enhanced thermopower, electrical transport properties, and reduction by adsorbates or compensating acceptor doping
    (Woodbury, NY : Inst., 2020) Papadogianni, Alexandra; Rombach, Julius; Berthold, Theresa; Polyakov, Vladimir; Krischok, Stefan; Himmerlich, Marcel; Bierwagen, Oliver
    In2O3 is an n-type transparent semiconducting oxide possessing a surface electron accumulation layer (SEAL) like several other relevant semiconductors, such as InAs, InN, SnO2, and ZnO. Even though the SEAL is within the core of the application of In2O3 in conductometric gas sensors, a consistent set of transport properties of this two-dimensional electron gas (2DEG) is missing in the present literature. To this end, we investigate high-quality single-crystalline as well as textured doped and undoped In2O3(111) films grown by plasma-assisted molecular beam epitaxy to extract transport properties of the SEAL by means of Hall effect measurements at room temperature while controlling the oxygen adsorbate coverage via illumination. The resulting sheet electron concentration and mobility of the SEAL are ≈1.5×1013cm−2 and ≈150cm2/Vs, respectively, both of which are strongly reduced by oxygen-related surface adsorbates from the ambient air. Our transport measurements further demonstrate a systematic reduction of the SEAL by doping In2O3 with the deep compensating bulk acceptors Ni or Mg. This finding is supported by x-ray photoelectron spectroscopy (XPS) measurements of the surface band bending and SEAL electron emission. Quantitative analyses of these XPS results using self-consistent, coupled Schrödinger-Poisson calculations indicate the simultaneous formation of compensating bulk donor defects (likely oxygen vacancies), which almost completely compensate the bulk acceptors. Finally, an enhancement of the thermopower by reduced dimensionality is demonstrated in In2O3: Seebeck coefficient measurements of the surface 2DEG with partially reduced sheet electron concentrations between 3×1012 and 7×1012cm−2 (corresponding average volume electron concentration between 1×1019 and 2.3×1019cm−3) indicate a value enhanced by ≈80% compared to that of bulk Sn-doped In2O3 with comparable volume electron concentration.
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    Chirality flip of Weyl nodes and its manifestation in strained MoTe2
    (College Park, MD : APS, 2021) Könye, Viktor; Bouhon, Adrien; Fulga, Ion Cosma; Slager, Robert-Jan; van den Brink, Jeroen; Facio, Jorge I.
    Due to their topological charge, or chirality, the Weyl cones present in topological semimetals are considered robust against arbitrary perturbations. One well-understood exception to this robustness is the pairwise creation or annihilation of Weyl cones, which involves the overlap of two oppositely charged nodes in energy and momentum. Here we show that their topological charge can in fact change sign, in a process that involves the merging of not two, but three Weyl nodes. This is facilitated by the presence of rotation and time-reversal symmetries, which constrain the relative positions of Weyl cones in momentum space. We analyze the chirality flip process, showing that transport properties distinguish it from the conventional, double Weyl merging. Moreover, we predict that the chirality flip occurs in MoTe$_2$, where experimentally accessible strain leads to the merging of three Weyl cones close to the Fermi level. Our work sets the stage to further investigate and observe such chirality flipping processes in different topological materials.
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    Comparison of novel semi-airborne electromagnetic data with multi-scale geophysical, petrophysical and geological data from Schleiz, Germany
    (Amsterdam [u.a.] : Elsevier Science, 2020) Steuer, Annika; Smirnova, Maria; Becken, Michael; Schiffler, Markus; Günther, Thomas; Rochlitz, Raphael; Yogeshwar, Pritam; Mörbe, Wiebke; Siemon, Bernhard; Costabel, Stephan; Preugschat, Benedikt; Ibs-von Seht, Malte; Zampa, Luigi Sante; Müller, Franz
    In the framework of the Deep Electromagnetic Sounding for Mineral EXploration (DESMEX) project, we carried out multiple geophysical surveys from regional to local scales in a former mining area in the state of Thuringia, Germany. We prove the applicability of newly developed semi-airborne electromagnetic (EM) systems for mineral exploration by cross-validating inversion results with those of established airborne and ground-based investigation techniques. In addition, supporting petrophysical and geological information to our geophysical measurements allowed the synthesis of all datasets over multiple scales. An initial regional-scale reconnaissance survey was performed with BGR's standard helicopter-borne geophysical system deployed with frequency-domain electromagnetic (HEM), magnetic and radiometric sensors. In addition to geological considerations, the HEM results served as base-line information for the selection of an optimal location for the intermediate-scale semi-airborne EM experiments. The semi-airborne surveys utilized long grounded transmitters and two independent airborne receiver instruments: induction coil magnetometers and SQUID sensors. Due to the limited investigation depth of the HEM method, local-scale electrical resistivity tomography (ERT) and long-offset transient electromagnetic (LOTEM) measurements were carried out on a reference profile, enabling the validation of inversion results at greater depths. The comparison of all inversion results provided a consistent overall resistivity distribution. It further confirmed that both semi-airborne receiver instruments achieve the bandwidth and sensitivity required for the investigation of the resistivity structure down to 1 km depth and therewith the detection of deeply seated earth resources. A 3D geological model, lithological and geophysical borehole logs as well as petrophysical investigations were integrated to interpret of the geophysical results. Distinct highly-conductive anomalies with resistivities of less than 10 Om were identified as alum shales over all scales. Apart from that, the petrophysical investigations exhibited that correlating geophysical and geological information using only one single parameter, such as the electrical resistivity, is hardly possible. Therefore, we developed a first approach based on clustering methods and self-organizing maps (SOMs) that allowed us to assign geological units at the surface to a given combination of geophysical and petrophysical parameters, obtained on different scales. © 2020 The Authors
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    Electrically conductive and piezoresistive polymer nanocomposites using multiwalled carbon nanotubes in a flexible copolyester: Spectroscopic, morphological, mechanical and electrical properties
    (Amsterdam [u.a.] : Elsevier, 2022) Dhakal, Kedar Nath; Khanal, Santosh; Krause, Beate; Lach, Ralf; Grellmann, Wolfgang; Le, Hai Hong; Das, Amit; Wießner, Sven; Heinrich, Gert; Pionteck, Jürgen; Adhikari, Rameshwar
    Nanocomposites of multiwalled carbon nanotubes (MWCNTs) with poly(butylene adipate-co-terephthalate) (PBAT), a flexible aromatic–aliphatic copolyester, were prepared by melt mixing followed by compression moulding to investigate their spectroscopic, morphological, mechanical and electrical properties. A comparison of the Fourier transform infrared (FTIR) spectra of the neat polymer matrix and the composites showed no difference, implying a physical mixing of the matrix and the filler. A morphological investigation revealed the formation of a continuous and interconnected MWCNT network embedded in the polymer matrix with partial agglomeration. Increasing Martens hardness and indentation modulus and decreasing maximum indentation depth with increasing filler concentration demonstrated the reinforcement of the polymer by the MWCNTs. A volume resistivity of 4.6 × 105 Ω cm of the materials was achieved by the incorporation of only 1 wt.-% of the MWCNTs, which confirmed a quite low percolation threshold (below 1 wt.-%) of the nanocomposites. The electrical volume resistivity of the flexible nanocomposites was achieved up to 1.6 × 102 Ω cm, depending on the filler content. The elongation at the break of the nanocomposites at 374% and the maximum relative resistance changes (ΔR/R0) of 20 and 200 at 0.9 and 7.5% strains, respectively, were recorded in the nanocomposites (3 wt.-% MWCNTs) within the estimated volume resistivity range. A cyclic strain experiment shows the most stable and reproducible ΔR/R0 values in the 2%–5% strain range. The electrical conductivity and piezoresistivity of the investigated nanocomposites in correlation with the mechanical properties and observed morphology make them applicable for low-strain deformation-sensing.
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    Semimetal to semiconductor transition in Bi/TiO2 core/shell nanowires
    (Cambridge : Royal Society of Chemistry, 2021) Kockert, M.; Mitdank, R.; Moon, H.; Kim, J.; Mogilatenko, A.; Moosavi, S.H.; Kroener, M.; Woias, P.; Lee, W.; Fischer, S.F.
    We demonstrate the full thermoelectric and structural characterization of individual bismuth-based (Bi-based) core/shell nanowires. The influence of strain on the temperature dependence of the electrical conductivity, the absolute Seebeck coefficient and the thermal conductivity of bismuth/titanium dioxide (Bi/TiO2) nanowires with different diameters is investigated and compared to bismuth (Bi) and bismuth/tellurium (Bi/Te) nanowires and bismuth bulk. Scattering at surfaces, crystal defects and interfaces between the core and the shell reduces the electrical conductivity to less than 5% and the thermal conductivity to less than 25% to 50% of the bulk value at room temperature. On behalf of a compressive strain, Bi/TiO2 core/shell nanowires show a decreasing electrical conductivity with decreasing temperature opposed to that of Bi and Bi/Te nanowires. We find that the compressive strain induced by the TiO2 shell can lead to a band opening of bismuth increasing the absolute Seebeck coefficient by 10% to 30% compared to bulk at room temperature. In the semiconducting state, the activation energy is determined to |41.3 ± 0.2| meV. We show that if the strain exceeds the elastic limit the semimetallic state is recovered due to the lattice relaxation.