ADVANCES AND APPLICATIONS IN CARBON RELATED

NANOMATERIALS: FROM PURE TO DOPED

STRUCTURES INCLUDING HETEROATOM LAYERS

OrganizersR. Arenal (LMA - INA, chairman)

C. P. Ewels (Nantes U.)D. Golberg (MANA - NIMS - U. Tsukuba)

V. Meunier (Rensselaer Polytechnic Institute)A. Rubio (U. País Vasco - Fritz Haber Institut - Max Plank Gesellschaft, cochair)

2015, Dec 07 -- Dec 11

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Tuesday, December 08

Chair Session: A. KRASHENINNIKOV (Aalto University, Finland)

08:30h Remarks / announcements

08:45h Optical properties of atomically thin semiconductors layers and heterostructures

Invited speaker - Tony F. HEINZ (Stanford University, USA)

09:20h Theoretical Probing Of Excitonic Effects In Transition Dichalcogenides Monolayers: A True Numerical Experience

GERBER, Iann, LPCNO INSA-Toulouse

09:40h luminescence at defects in h-bn: excitons at stacking faults and single photon emitters

TARARAN, Anna, Paris-Sud Orsay Univ.

10:00h Hydrogen-Assisted, Highly Efficient Synthesis Of Boron Nitride Nanotubes

KIM, Keun Su, National Research Council Canada

10:20h Spectroscopic fingerprints of tailored 1D and 2D nanocarbons

Invited speaker - Thomas PICHLER (University of Vienna, Austria)

10:55h Coffee break

Chair Session: HEINZ, Tony (Stanford univ., USA)

11:20h Extended Spiropyran-SWNTs conjugated complexes: A new class of photochromic materials

Invited speaker - Antonio SETARO (Free University Berlin, Ger.)

11:55h Electron conduction and trapping in single-walled carbon nanotubes sorted by gel chromatography

ANSÓN-CASAOS, Alejandro: Inst. de Carboquímica, ICB-CSIC

12:15h Carbon/MoS2 Composite Structures: Synthesis, Electonic Properties And Application

KOROTEEV, Victor: NIIC SB RAS

12:35h Liquid adhesion and capillary actions at the nanoscopic level: Direct observations ofinteractions between water and single WS2 nanotubes

TENNE, Reshef: Weizmann Inst. Sc., Israel

12:55h Free time (lunch is not included)

Chair Session: O.A. WILLIAMS (Cardiff University, UK)

18:30h Diamond spin quantum sensors

Invited speaker - Joerg WRACHTRUP (Stuttgart University, Ger.)

19:05h Synthesis And Luminescent Properties Of Single-Crystal Diamond Pyramids

OBRAZTSOVA, Ekaterina: Semyakin&Ovchinnikov I. Bioorg. Chem.

19:25h Nanodiamond / silicon carbide nanocomposites for membranes applicationsoral contribution

ALAUZUN, Johan: Universite Montpellier

19:45h Poster session

Cocktail during the poster session

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Wednesday, December 09

Chair Session: K. SUENAGA (AIST, Japan)

08:30h Remarks / announcements

08:45h Native And Irradiation-Induced Defects In Two-Dimensional Inorganic Materials

Invited speaker - Arkady KRASHENINNIKOV (Aalto University, Fin.)

09:20h Electrical transport measured in sp1-hybridized chains of carbon atoms

BANHART, Florian: University of Strasbourg, IPCMS

09:40h Formation Mechanism of Nanostructured WS2 in the Confinement of an Ordered Mesoporous Carbon Prepared by a One Pot Synthesis

PARMENTIER, Julien: Inst. de Science Matériaux de Mulhouse

10:00h In-situ Growing of Carbon Nanotubes Encapsulated within Boron Nitride Nanotubes via Electron Irradiation

ARENAL, Raul: Universidad de Zaragoza

10:20h Misfit layered nanotubes as a new class of low dimensional materials

Invited speaker - Leela PANCHAKARLA (Weizmann Inst. Sc., Is.)

10:55h Coffee break

Chair Session: W. MASER (ICB, CSIC, Spain)

11:20h Azafullerene-Based Hybrids For Managing Charge-Transfer Processes

Invited speaker - Nikos Tagmatarchis (Nat. Hellenic Res. F., Gr.)

11:55h Photoelectrochemical properties of tio2-carbon nanomaterial composite electrodes

HERNÁNDEZ FERRER, Javier: Instituto de Carboquímica-CSIC

12:15h Covalent Functionalization of Boron Nitride Nanotubes via Reduction Chemistry

SHIN, Homin: National Research Council Canada

12:35h Doped Carbon Nanostructures for Cold Field Emission: Structural and Analytical studies

WANG, Rongrong: CEMES-CNRS and Universidad de Zaragoza

12:55h Free time (lunch is not included)

Chair Session: R. TENNE (Weizmann Inst. Sc., Israel)

18:30h Thin Films of Heteronanohybrids of Carbon Nanotubes and Acceptor Molecules for Conducting Transparent Electrodes

Invited speaker - Elena OBRAZTSOVA (Prokhorov Gen. Phys. I., Rus.)

19:05h Organic Synthesis of Carbon Heterostructures

BERGER, Reinhard Franz Josef: TU Dresden

19:25h Evidences For The Unexpected Filling Of Double-Wall Carbon Nanotubes With IodineNanocrystals

NIE, Chunyang: CEMES-CNRS

19:45h Poster session

Cocktail during the poster session

Thursday, December 10

Chair Session: R. ARENAL (Universidad de Zaragoza, Spain)

08:30h Remarks / announcements

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08:45h Atomic-scale observations of growth, oxidation, de-fect formation and phase transition in low-dimensional materials

Invited speaker - Kazu SUENAGA (AIST, Japan)

09:20h Manipulating individual atoms with an electron beam

SUSI, Toma: University of Vienna

09:40h Nanostructures in two-dimensional materials sculpted with electrons and applications

MLACK, Jerome: University of Pennsylvania

10:00h Spectromicroscopy investigation of fluorine and nitrogen doped carbon nanomaterials

SCARDAMAGLIA, MATTIA: University of Mons

10:20h Some Recent Advances In Stem Spectroscopies For Exploring Graphene And Layered Bn Structural And Electronic Properties

Invited speaker - Odile STEPHAN (Paris-Sud Orsay Univ., Fr.)

10:55h Coffee break

Chair Session: E. OBRAZTSOVA (Prokhorov Gen. Phys. Inst., Russia)

11:20h Graphene Oxide Papers And Films As Electrode Materials

Invited speaker - Wolfgang MASER (ICB, CSIC, Spain)

11:55h IrOx Nanostructured Hybrids with Graphene / Graphene Oxide / Carbon Nanotubes Electrodes for Neural Stimulation and Repair

CASAÑ PASTOR, Nieves: ICMAB-CSIC

12:15h Performance evaluation of doped carbon nanotube/polysulfone nanofiltration membranes

NXUMALO, Edward: University of South Africa

12:35h Promises Of Graphene Oxide Frameworks For Water Desalination Applications

NICOLAI, Adrien: Université de Bourgogne Franche-Comté

12:55h Free time (lunch is not included)

Chair Session: T. PICHLER (University of Vienna, Austria)

18:30h Production and Applications of Diamond Films and Particles

Invited speaker - Oliver A. WILLIAMS (Cardiff University, UK)

19:05h Interaction of tritium and chlorine 36 with defects in graphite: insights from theory

LECHNER, Christoph: EDF R&D

19:25h Assembling Graphene Oxide – Multiwalled Carbon Nanotube Layered Hybrids For Energy Applications

NUÑEZ, J. David: Instituto de Carboquímica (ICB-CSIC)

19:45:20:05h Synthesis of Heteroatom-Doped Carbon Foams for Hydrogen Energy Technologies

STEPHEN Lyth (Kyushu University)

20:45h Conference banquet (included)

Friday, December 11

08:30h Departure to Barcelona

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Index

INVITED TALKS............................................................................................................................................... 7

ATOMIC-SCALE OBSERVATION OF GROWTH, OXIDATION, DEFECT FORMATION AND PHASE TRANSTION IN LOW-DIMENSIONAL MATERIALS.........................................................................................8

AZAFULLERENE-BASED HYBRIDS FOR MANAGING CHARGE-TRANSFER PROCESSES.......................9

DIAMOND SPIN QUANTUM SENSORS........................................................................................................10

EXTENDED SPIROPYRAN-SWNTS CONJUGATED COMPLEXES: A NEW CLASS OF PHOTOCHROMIC MATERIALS.................................................................................................................................................... 11

GRAPHENE OXIDE PAPERS AND FILMS AS ELECTRODE MATERIALS...................................................12

MISFIT LAYERED NANOTUBES AS A NEW CLASS OF LOW DIMENSIONAL MATERIALS.......................13

NATIVE AND IRRADIATION-INDUCED DEFECTS IN TWO-DIMENSIONAL INORGANIC MATERIALS......14

OPTICAL PROPERTIES OF ATOMICALLY THIN SEMICONDUCTORS LAYERS AND HETEROSTRUCTURES................................................................................................................................ 15

PRODUCTION AND APPLICATIONS OF DIAMOND FILMS AND PARTICLES.............................................16

SOME RECENT ADVANCES IN STEM SPECTROSCOPIES FOR EXPLORING GRAPHENE AND LAYERED BN STRUCTURAL AND ELECTRONIC PROPERTIES................................................................17

SPECTROSCOPIC FINGERPRINTS OF TAILORED 1D AND 2D NANOCARBONS....................................18

THIN FILMS OF HETERONANOHYBRIDS OF CARBON NANOTUBES AND ACCEPTOR MOLECULES FOR CONDUCTING TRANSPARENT ELECTRODES...................................................................................19

CONTRIBUTED TALKS................................................................................................................................. 20

ASSEMBLING GRAPHENE OXIDE – MULTIWALLED CARBON NANOTUBE LAYERED HYBRIDS FOR ENERGY APPLICATIONS.............................................................................................................................. 21

CARBON/MoS2 COMPOSITE STRUCTURES: SYNTHESIS, ELECTONIC PROPERTIES AND APPLICATION................................................................................................................................................ 22

COVALENT FUNCTIONALIZATION OF BORON NITRIDE NANOTUBES VIA REDUCTION CHEMISTRY..23

DOPED CARBON NANOSTRUCTURES FOR COLD FIELD EMISSION: STRUCTURAL AND ANALYTICAL STUDIES........................................................................................................................................................ 24

ELECTRICAL TRANSPORT MEASURED IN sp1-HYBRIDIZED CHAINS OF CARBON ATOMS.................25

ELECTRON CONDUCTION AND TRAPPING IN SINGLE-WALLED CARBON NANOTUBES SORTED BY GEL CHROMATOGRAPHY............................................................................................................................ 26

EVIDENCES FOR THE UNEXPECTED FILLING OF DOUBLE-WALL CARBON NANOTUBES WITH IODINE NANOCRYSTALS.............................................................................................................................. 27

FORMATION MECHANISM OF NANOSTRUCTURED WS2 IN THE CONFINEMENT OF ORDERED MESOPOROUS CARBON PREPARED BY A ONE POT SYNTHESIS..........................................................28

HYDROGEN-ASSISTED, HIGHLY EFFICIENT SYNTHESIS OF BORON NITRIDE NANOTUBES..............29

INTERACTION OF TRITIUM AND CHLORINE 36 WITH DEFECTS IN GRAPHITE: INSIGHTS FROM THEORY......................................................................................................................................................... 30

IN-SITU GROWING OF CARBON NANOTUBES ENCAPSULATED WITHIN BORON NITRIDE NANOTUBES VIA ELECTRON IRRADIATION...............................................................................................31

IROX NANOSTRUCTURED HYBRIDS WITH GRAPHENE / GRAPHENE OXIDE / CARBON NANOTUBES ELECTRODES FOR NEURAL STIMULATION AND REPAIR........................................................................32

LIQUID ADHESION AND CAPILLARY ACTIONS AT THE NANOSCOPIC LEVEL: DIRECT OBSERVATIONS OF INTERACTIONS BETWEEN WATER AND SINGLE WS2 NANOTUBES.................................................33

LUMINESCENCE AT DEFECTS IN H-BN: EXCITONS AT STACKING FAULTS AND SINGLE PHOTON EMITTERS...................................................................................................................................................... 34

MANIPULATING INDIVIDUAL ATOMS WITH AN ELECTRON BEAM............................................................35

NANOSTRUCTURES IN TWO-DIMENSIONAL MATERIALS SCULPTED WITH ELECTRONS AND APPLICATIONS.............................................................................................................................................. 36

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NANODIAMOND / SILICON CARBIDE NANOCOMPOSITES FOR MEMBRANES APPLICATIONS............37

ORGANIC SYNTHESIS OF CARBON HETEROSTRUCTURES...................................................................38

PERFORMANCE EVALUATION OF DOPED CARBON NANOTUBE/POLYSULFONE NANOFILTRATION MEMBRANES................................................................................................................................................. 39

PHOTOELECTROCHEMICAL PROPERTIES OF TIO2-CARBON NANOMATERIAL COMPOSITE ELECTRODES............................................................................................................................................... 40

PROMISES OF GRAPHENE OXIDE FRAMEWORKS FOR WATER DESALINATION APPLICATIONS.......41

SPECTROMICROSCOPY INVESTIGATION OF FLUORINE AND NITROGEN DOPED CARBON NANOMATERIALS......................................................................................................................................... 42

SYNTHESIS AND LUMINESCENT PROPERTIES OF SINGLE-CRYSTAL DIAMOND PYRAMIDS..............44

SYNTHESIS OF HETEROATOM-DOPED CARBON FOAMS FOR HYDROGEN ENERGY TECHNOLOGIES........................................................................................................................................................................ 45

THEORETICAL PROBING OF EXCITONIC EFFECTS IN TRANSITION DICHALCOGENIDES MONOLAYERS: A TRUE NUMERICAL EXPERIENCE..................................................................................46

POSTERS....................................................................................................................................................... 47

ATOMIC STRUCTURAL AND CHEMICAL INVESTIGATIONS OF MISFIT LAYERED NANOTUBES............48

CHANGES OF CARBON STRUCTURE IN MANGANESE DIOXIDE/GRAPHENE HYBRID MATERIAL SYNTHESIZED BY DIRECT REDOX REACTION..........................................................................................49

ELECTROCHEMICAL CAPACITIVE BEHAVIOUR OF CARBON BASED /SPINEL FERRITES NANOCOMPOSITES...................................................................................................................................... 50

ELECTROMAGNETIC PROPERTIES OF POLYMER BASED COMPOSITES WITH VAROUS CARBON INCLUSIONS.................................................................................................................................................. 51

ENERGY STORAGE APPLICATION OF NICKEL HYDROXIDES OR OXIDES /CARBON SOURCE NANOHYBRIDS............................................................................................................................................. 52

HIERARCHICALLY STRUCTURED COPPER-COBALT NANOPARTICLE/CNF/ACF CATALYST FOR ETHANOL CONVERSION.............................................................................................................................. 53

INDIUM-ZINC NANO OXIDE THIN FILM TRANSISTOR FABRICATED BY UV ASSISTED SPIN CASTING 54

IN-SITU MWNTS / NiCo HYDROXIDE BASED NANO-HYBRIDS FOR SUPERCAPACITORS.....................55

NANO TIOX/TIO2 BASED RESISTIVE SWITCHING MEMORY WITH RAPID THERMAL ANNEALING.......56

NANOHYBRID ELECTROACTIVE MATERIALS BASED ON IRON OXIDE NANOSTRUCTURES AND CARBON SOURCE FOR ENERGY STORAGE.............................................................................................57

NITROGEN-DOPED GRAPHENE-BASED ELECTRODE MATERIALS FOR ELECTRIC DOUBLE LAYER CAPACITORS................................................................................................................................................. 58

REDUCED GRAPHENE OXIDE: SYNTHESIS, DISPERSION AND THIN FILM ELECTRODES FOR ORGANIC PHOTOVOLTAICS........................................................................................................................59

SPATIALLY-CONFINED HYBRIDIZATION OF NANOSIZED NIFE HYDROXIDES INTO NITROGEN-DOPED GRAPHENE FRAMEWORKS TOWARDS SUPERIOR OXYGEN EVOLUTION REACTIVITY......................60

STICKY RICE GRAPHENE: CARBONIZATION OF TERNARY SLURRY AND APPLICATION AS SUPERIORBIFUNCTIONAL OXYGEN ELECTROCATALYST..........................................................................................61

SURFACE PLASMON RESONANCE IN SEMICONDUCTING WS2 NANOTUBES AND MOS2 NANOPARTICLES.......................................................................................................................................... 62

THE IMPACT OF SOFT BAKE TEMPERATURE IN NANO OXIDE TFT WITH HIGH MOBILITY...................63

THE SORPTION OF AZO DYE ONTO FUNCTIONALIZED CNTS AND A NATUREL RESIDUE (OLIVE STONES)........................................................................................................................................................ 64

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INVITED TALKS

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ATOMIC-SCALE OBSERVATION OF GROWTH, OXIDATION, DEFECT FORMATION AND PHASETRANSTION IN LOW-DIMENSIONAL MATERIALS

Kazu SuenagaAIST Tsukuba 305-8565 Japan

Operating TEM/STEM at lower acceleration voltage is important to enhance the image/EELS contrast as wellas to minimize the knock-on damage and therefore is bene-ficial when one aims to image any light elementmatters and/or beam sensitive objects. In order to compensate the poor spatial resolution due to the lowacceleration voltage, Sawada et al. designed a new type of Cs corrector with triple dodecapole elements (theDELTA system) to reduce the six-fold astigmatism under a JST triple C project [1].

In this presentation, I summarize our recent progress of low-voltage TEM/STEM within the scheme of triple Cproject. The current status of our monochromator and aber-ration corrector developments will be shown. Theexamples of in situ microsco-py/spectroscopy at atomic scale such as the graphene growth [2], oxidation [3],defect formation and phase transition in dichalcogenides [4,5] will be also presented.

[1] H. Sawada et al., Phys. Rev. Lett., 114 (2015) 166102[2] Z. Liu et al., Nature Communications, 5:4055 (2014)[3] L. Tizei et al., Phys. Rev. Lett., 114 (2015) 197602[4] YC Lin et al., Nature Nanotechnology, 9 (2014) pp. 436-442[5] YC Lin et al., Nature Communications, 6:6736 (2015)[6] This work is partially supported by a JST research acceleration programme.

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Figure 1: In situ observation of oxidationreaction. Eu atomic chain will get oxidizedwithin nanotube when react with oxygen.

See Tizei et al., Phys. Rev. Lett., (2015) [3]

AZAFULLERENE-BASED HYBRIDS FOR MANAGING CHARGE-TRANSFER PROCESSES

Nikos Tagmatarchis, Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation48 Vassileos Constantinou Avenue, Athens 11635, Hellas

T: + 30 210 7273835, tagmatar@eie.gr

Fullerene-based donor – acceptor hybrid materials, in which a photo- and/or electro-active unit is attached tothe fullerene sphere, comprise a topic of intense research. The substitution of a carbon with a nitrogen atomonto the skeleton of the most abundant fullerene molecule leads to azafullerene dimer (C59N)2, due todifference in valence between carbon and nitrogen, possessing better electron accepting properties ascompared with the parent C60.

The current contribution deals with the development of a synthetic route that gives access to a C59N-basedcarboxylic acid derivative as key material for diverse C59N-based dyads with organic electron donors. In thiscontext, the preparation of C59N-based dyads consisting of azafullerene C59N as acceptor with diverseorganic electron donors in charge-transfer processes will be presented. Furthermore, the first organic-inorganic C59N-Au nanohybrid via ligand exchange of pre-stabilized gold nanoparticles with dithiolane-modified azafullerene will be also discussed. Diverse analytical techniques were applied to fully characterizeall new C59N-based materials, while the redox and photophysical properties were probed withelectrochemistry and photoluminescence assays.

Partial financial support under the European Union, Horizon 2020 Framework Programme for Research andInnovation, Marie Sklodowska-Curie Innovative Training Networks, EC Grant Agreement No 642742, project“Enabling Excellence”, is acknowledged.

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DIAMOND SPIN QUANTUM SENSORS

Jörg Wrachtrup, P. Neumann, S. Yang, A. Finkler3rd Institute of Physics, Stuttgart University, Germany

The precision of measurements is ultimately limited by quantum mechanics. However, achieving the quantum limit in practical measurement application like sensing proves to be a significant challenge. Traditional sensing techniques often become subject to increasing levels of environmental noise especially inintegrated designs or when the sensor size approaches small length scales. However, recently developed quantum control techniques originally targeting quantum information processing and communications show strategies to control quantum states even in noisy environment. Furthermore, specifically designed quantum states can enhance sensing precision when control is obtained. The talk shall describe nanoscale sensing of electric, magnetic fields, temperature etc. utilizing spin quantum sensors. Applications in such diverse areas like solid-state physics or cellular biology shall be discussed.

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EXTENDED SPIROPYRAN-SWNTS CONJUGATED COMPLEXES: A NEW CLASS OF PHOTOCHROMICMATERIALS.

Antonio Setaro, Mareen Gläske, Stephanie Reich, Physics Department of the Freie Universität BerlinArnimallee 14, 14195 Berlin (Germany)

T: +49 (0)30 83856156, setaro@physik.fu-berlin.deM. Adeli, R. Haag, Chemistry Department of the Freie Universität Berlin

Takustr. 3, 14195 Berlin (Germany)

Here we report about a nondestructive, controlled synthesis of covalently functionalized single walled carbonnanotubes. The covalent decoration of the tubes’ sidewall, even at high density of functional groups, doesnot disrupt their extended sigma network and preserves their unique quantum optoelectronic properties. Ourscheme provides a strong platform to immobilize desired functional species on the nanotubes sidewall. By conjugating the photochromic molecular switching spiropyran/merocyanine moiety to the tubes, we createnovel heterostructures exhibiting phenomenology not observable in standard functionalization approaches.Changes in the physical and chemical properties of the two isomeric configuration of the photochrome resultin different interactions with the tubes. In this way, we are able to to quench the emission of our complexesby exposing them to radiation of the proper wavelength.

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Figure 4 – PLE chart of spiropyran-SWNTs complexes (left panel). The emission yield of the complexes is reduced by converting the photochrome into the merocyanine form (right panel).

Spiropyran

Merocyanine

GRAPHENE OXIDE PAPERS AND FILMS AS ELECTRODE MATERIALS

Wolfgang K. Maser, Instituto de Carboquímica (ICB-CSIC)C/Miguel Luesma Castán 4, Zaragoza, Spain

T: +34 976 73 39 77, wmaser@icb.csic.esAna M. Benito, Instituto de Carboquímica (ICB-CSIC), Spain

Graphene oxide is a highly versatile nanoscale building block for the development of novel high performancematerials with tailored properties. Ease of synthesis, tailoring of functionality, and providing favorableprocessing conditions towards their macroscopic assembly in the form of films and papers arises increasedinterest for technological applications ranging from organic solar cells and touch screens towardselectrochemical energy storage and (bio) sensing applications. The importance of effective synthesis strategies and processing routes to profit at maximum from theproperties of graphene oxide in the form of papers and films will be described. Their efficient use aselectrode materials for significantly improved sensing of ions, living microorganisms and organic analytes ishighlighted [1-6].

[1] C. Vallés, J.D. Núñez, A.M. Benito, W.K. Maser, Carbon 50 (2011), 835[2] R. Hernández, J. Riu, J. Boback, C. Vallés, P. Jiménez, A.M. Benito, W.K. Maser, F. Xavier Rius, J. Phys. Chem. C 116 (2012) 22570[3] R. Hernández, C. Vallés, A.M. Benito, F.x. Rius, J. Rius, Biosens. Bioelectr. 54 (2014) 553[4] S. Azzouzi, L. Rotariu, A.M. Benito, W.K. Maser, M. Ben Ali, C. Balas, Biosens. Bioelectr. 69 (2015), 280[5] A.M. Benito, J.D. Núnez, W.K. Maser, in prep (2015)[6] J.D. Núñez, A.M. Benito, J. Aragón, R. González, R. Arenal, W.K. Maser, Carbon 79 (2014) 590

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MISFIT LAYERED NANOTUBES AS A NEW CLASS OF LOW DIMENSIONAL MATERIALS

Leela S Panchakarla and Reshef TenneDepartment of Materials and Interfaces, Weizmann Institute of Science, Rehovot, 76100 Israel

Tel:+972-8-9342598; e-mail: panchakarla@weizmann.ac.il

Nanotubes are attracting increasing interest as exciting one-dimensional nanomaterials since the synthesisof carbon and inorganic nanotubes.[1,2] A large number of materials have demonstrated the capability toform stabile nanotubular morphologies so far.[3-5] Misfit layered compounds (MLC) can be considered asincommensurate composite structures formed by alternative stacking of two different molecular layers withthe general formula [(MX)1+x]m[TX2]n, where M = Sn, Pb, Bi, Sb and rare earths, T = Sn, Nb, Ta, Ti, V, Cr, andother elements, and X = S, Se, Te.[6] The misfit stress between the layers is generated by the difference inlattice parameters of the MX and TX2 in at least one of the directions, thus leading to the bending of thestructure. Furthermore, the minimization of the high energy dangling bonds at the layer edges provides thedriving force to form seam-less hollow structures. This talk will present the recent progress in the synthesis ofmisfit layer nanotubes in our lab and the large variety of misfit layer compounds able to create nanotubes [7].This talk will further focus on the structure, formation mechanism and some of the physical properties ofthese unique low-dimensional materials.

[1] Iijima, S. Nature 1991, 354, 56−58.[2] Tenne, R.; Margulis, L.; Genut, M.; Hodes, G. Nature 1992, 360, 444−446.[3] Tenne, R. Nat. Nanotechnol. 2006, 1, 103−111.[4] Rao, C. N. R.; Govindaraj, A. Nanotubes and Nanowires; RSC Publishing: Cambridge, UK, 2005.[5] Tenne, R.; Front. Phys. 2014, 9, 370-377.[6] Wiegers, G. A. Prog. Solid St. Chem. 1996, 24, 1−139.[7] Panchakarla, L. S.; Radovsky, G.; Houben, L.; Popovitz-Biro, R.; Dunin-Borkowski, R. E.; Tenne, R. J. Phys. Chem. Lett. 2014, 5, 3724−3736

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Figure 1 formation mechanism of misfit nanotubes and nanoscrolls from misfit layered compounds

NATIVE AND IRRADIATION-INDUCED DEFECTS IN TWO-DIMENSIONAL INORGANIC MATERIALS

Arkady Krasheninnikov1,2 1Institute of Ion Beam Physics and Materials Research, Helmholtz Zentrum Dresden-Rossendorf, Germany

2 Department of Applied Physics, Aalto University, Finland Tel: +358504333260; e-mail: arkady.krasheninnikov@aalto.fi

Two-dimensional (2D) materials such as graphene, hexagonal boron nitride, transition metal dichalcogenides(TMDs) and silica bilayers have recently received lots of attention due to their unique properties andnumerous potential applications. All these materials have defects, which naturally affect their characteristics.Moreover, defects and impurities can deliberately be introduced by irradiation or chemical treatment to tailorthe properties of these systems. In my talk, I will present the results of our first-principles theoretical studies[1-7] of defects in 2D systems, compare them to the experimental transmission electron microscopy data,and discuss how defect and impurities can be used to engineer the electronic structure of 2D materials.Specifically, we showed that vacancies produced by the electron beam agglomerate and form line structures,which can be used for engineering material properties [2]. In some chalcogen-deficient TMDs, rotationaldefects appear under electron beam [4], which eventually give rise to formations of new grains inside thematerial. We further demonstrated that TMDs can be doped by filling the vacancies with impurity atoms orintroducing impurities during the growth stage [1,3]. We also studied the atomic scale morphology of non-stoichiometric 2D TMDe MoSe 2−x and showed that a Se-deficit in single layers of MoSe2 grown by molecularbeam epitaxy gives rise to a dense network of mirror-twin-boundaries (MTBs) decorating the 2D-grains [5].Using density functional theory calculations, we further demonstrated that MTBs are thermodynamicallystable structures in Se-deficient sheets. These line defects host localized states close to the valence bandminimum thus giving rise to enhanced conductance along straight MTBs. I will also touch upon oursimulations of defect production under ion [8,9] and electron [1] irradiation. For the former, the Ehrenfestdynamics and time-dependent density functional theory was shown to be an accurate approach beyond theadiobatic approximation to calculate electronic stopping power in graphene [9]. The latter (specifically theknock-on damage) can quantitatively be described [1] by density-functional theory-based moleculardynamics and McKinley-Feshbach formalism. I will also touch upon Stone-Wales transformations ingraphene and silica bilayers [10], 2D materials with the hexagonal symmetry, and address the equivalenttransformations in 2D materials with the trigonal symmetry, such as BN or TMDs [4]. I will present thetheoretical data on defect evolution, migration and agglomeration and compare the theoretical results to theavailable experimental data.

[1] H-P. Komsa, J. Kotakoski, S. Kurasch, O. Lehtinen, U. Kaiser, and A. V. Krasheninnikov, Phys. Rev. Lett. 109, 035503 (2012).[2] H.-P. Komsa, S. Kurasch, O. Lehtinen, U. Kaiser, and A. V. Krasheninnikov, Phys. Rev. B 88, 035301 (2013).[3] Y.-C. Lin, D.O. Dumcenco, H.-P. Komsa, Y. Niimi, A.V. Krasheninnikov, Y.-S. Huang, and K. Suenaga, Advanced Materials 26, 2857 (2014).[4] Y.-C. Lin, T. Björkman, H.-P. Komsa, P.-Y. Teng, C.-H. Yeh, F.-S. Huang, K.-H. Lin, J. Jadczak, Y.-S. Huang, P. Chiu, A.V. Krasheninnikov, and K. Suenaga, Nature Comm. 6 (2015) 6736[5] O. Lehtinen, H.-P. Komsa, A. Pulkin, M.B. Whitwick, M.-W. Chen, O.V. Yazyev, A. Kis, U. Kaiser, and A.V. Krasheninnikov, ACS Nano 9 (2015) 3274.[6] H.-P. Komsa, and A. V. Krasheninnikov, Phys. Rev. B 91 (2015) 125304.[7] H.-P. Komsa, N. Berseneva, A. V. Krasheninnikov and R.M. Nieminen, Phys. Rev. X 4 (2014) 031044.[8] S. Standop, O.J. Lehtinen, C. Herbig, G. Lewes-Malandrakis, F. Craes, J. Kotakoski, T. Michely, A. V. Krasheninnikov, and C. Busse, Nano Letters 13, 1948 (2013).[9] A. Ojanperä, A. V. Krasheninnikov, and M. Puska, Phys. Rev. B 89, 035120 (2014). [10] T. Björkman, S. Kurasch, O. Lehtinen, J. Kotakoski, O.Yazyev, A. Srivastava, V. Skakalova, J. Smet, U. Kaiser, and A.V. Krasheninnikov, Scientific Reports 3, 3482 (2013).

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OPTICAL PROPERTIES OF ATOMICALLY THIN SEMICONDUCTORS LAYERSAND HETEROSTRUCTURES

Tony F. Heinz, Departments of Applied Physics and Photon Science348 Via Pueblo Mall, Stanford, CA 94305, USA

T: +1-650-723-1810, Email: tony.heinz@stanford.edu

In this paper we discuss recent advances in our understanding of the optical properties of monolayers of thetransition metal dichalcogenide (TMDC) materials, including MoS2, MoSe2, MoTe2, WS2, WSe2. Thesematerials share several unusual characteristics, including a transition from an indirect-gap material in thebulk to a direct-gap, emissive material at monolayer thickness. They also exhibit selectivity to excitation ofthe degenerate K or K’ valley under circularly polarized radiation.In our discussion we will highlight progress in understanding two types of interactions in these materials: themany-body interactions between charge carriers in one layer and interactions between carriers that arisewhen two monolayer sheets of materials stacked on one another to form a bilayer.The many-body electronic interactions in monolayer TMDC crystals play a central role in defining their opticalproperties. Here we will stress recent spectroscopic studies in which we have identified the progression ofexcited exciton states in precise absorption measurements. This study directly reveals exciton bindingenergies of several hundred meV. A strongly non-hydrogenic disposition of levels is also observed. Thestrength of Coulomb interactions is also manifest in high-order excitonic states, including the three-body trion(or charged excitons) and the recently observed four-body biexcitons. Also of not is the possibility ofmodifying the many-body interactions through carrier doping or through the presence of high densities ofexcitation. Another unusual type of interaction associated with these materials concerns the electronic states andtransitions expected in stacks of TMDC monolayers. We will present results of studies of the opticalresponse of vertical heterostructures composed of two monolayers the same material (but with an adjustabletwist angle) and bilayers of two different crystals. In the latter case, we have identified spectroscopicsignatures for rapid charge separation associated with the staggered band structure.

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PRODUCTION AND APPLICATIONS OF DIAMOND FILMS AND PARTICLES

Oliver Williams, School of Physics and Astronomy, Cardiff UniversityQueens Buildings, The Parade, Cardiff CF24 3AA.

T: +44 29 2087 4978, williamso@cf.ac.uk

Diamond exhibits many extreme properties that make it attractive for a diverse array of applications such asheat spreading, optical/laser windows, tribology / abrasives, radiation detection, electrochemical electrodes,Micro-Electro-Mechanical Systems (MEMS) and single photon sources for biomarkers / quantum informationprocessing. The production of diamond falls into roughly two categories, those of mimicking nature (HighPressure, High Temperature synthesis - HPHT) and cheating nature (Chemical Vapour Deposition – CVD).HPHT is predominately used for cutting tools and abrasive applications and is by far the largest market byvolume. CVD can produce larger areas of diamond and has the added advantage of integration with othermaterials.

Unfortunately, the growth of diamond on foreign substrate results in polycrystalline material, with grain sizeevolving with thickness. Thin films are nanocrystalline with electron mobility and thermal conductivity limitedby grain boundary scattering. However, many properties of nanocrystalline films are identical or at leastcomparable to bulk diamond, such as Young’s Modulus, Coefficient of Friction and wear resistance. Electricalconductivity in nanodiamond films can be controlled from insulating (>1012 Ωcm) through semiconducting topseudo-metallic and even superconducting at low temperatures. Nanodiamond films have applications asdiverse as a Micro-Electro-Mechanical Systems (MEMS), SQUIDs, SAW, heat spreaders, bio-sensors andelectro-chemical electrodes.

Nanodiamond particles are fundamental low dimensional diamonds with extreme surface to volume fractions,as high as 400m2/g. This surface to volume fraction has a profound effect on the properties of these particles,with 20% of the carbon atoms residing at the surface. The reactivity of these particles differs substantially forbulk diamond and considerable effort is required to disperse them from their aggregated commercial source.Their applications are as diverse as the seeds for diamond film growth through drug delivery to single photonsources. This talk will demonstrate nanocrystalline diamond films with Young’s Modulus values up to 1100 GPa,control of conductivity via boron doping over 12 orders of magnitude as well as superconductivity at lowtemperatures. Micro Electro- Mechanical Systems (MEMS) and Surface Acoustic Wave devices fabricatedfrom NCD will demonstrated with resonant frequencies as high as 30 GHz and FQ products greater than 1013

Hz. The production of diamond nanoparticles with single photon sources such as the SiV will be detailed. Anew approach using superconducting diamond for NEMS and SQUIDS will be proposed.

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SOME RECENT ADVANCES IN STEM SPECTROSCOPIES FOR EXPLORING GRAPHENE ANDLAYERED BN STRUCTURAL AND ELECTRONIC PROPERTIES

Odile StéphanLaboratoire de Physique des Solides, bâtiment 510, Université Paris-Sud, 91405 Orsay, France

Some recent results on spatially-resolved Electron-Energy-Loss Spectroscopy (EELS) andcathodoluminesence will be presented on graphene and layered-BN.Electron Confinement effect in graphene nanoribbons will be discussed by relying on very subtle shifts asobserved in EELS experiments on the absorption edge of carbon [1].In the case of a highly sensitive material, strategies for limiting the electron dose while optimizing the signaldetection have to be employed. The results of EELS experiments performed at low voltage (60 keV) andliquid nitrogen temperature on graphene oxide (GO) will be discussed in the light of a revisited atomic modelfor GO and reduced GO [2]High detection efficiency is a pre-requisitite when aiming at detecting single atom spectroscopic signals.Examples will be given for the identification of heteroatom bonding in carbon nanotubes [3].Finally novel experiments relying on a combination of cathodoluminescence measurements (using a home-made setup for collecting the light emitted by the sample under electron illumination) with TEM structuralinvestigations will be detailed to discuss the link between the crystal structure of (h-BN), its defects and itsoptical properties [4].

[1] I. Palacio et al, Nano Lett., 2015, 15 (1), pp 182–189; DOI: 10.1021/nl503352v[2] A. Tararan et al, unpublished[3] R. Arenal et al, Nano Lett., 2014, 14 (10), pp 5509–5516; DOI: 10.1021/nl501645g[4] R. Bourrellier et al, ACS Photonics, 2014, 1 (9), pp 857–862; DOI: 10.1021/ph500141j

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SPECTROSCOPIC FINGERPRINTS OF TAILORED 1D AND 2D NANOCARBONS

Thomas PichlerFaculty of Physics, University of Vienna, Boltzmanngasse 5 1090 Vienna

Contact e-mail: thomas.pichler@univie.ac.at

In this contribution I will present recent progress on unraveling the influence of charge transfer, local strainand hybridization on the electronic transport properties of single walled carbon nanotubes and graphene withspecial emphasis on the influence of basic correlation effects on the two particle excitation and the nature ofthe metallic ground state. In order to tailor their properties I will compare different functionalization routes anduse resonance Raman, photoemission and x-ray absorption spectroscopy as probes. I will first brieflydiscuss recent results on charged and strained 2D graphene layers in graphite intercalation compounds andsubstitutionally doped graphene as well as intercalated and substituted 1D SWCNT. Then I will present a gassensing model based on external functionalisation shows how reactive gases like nitric oxides arepredominantly physisorbed on ultrapure SWCNT. I will also highlight the pathway how this interaction can betailored by advanced filling reactions with metallocenes and metalacetylacetonates towards roomtemperature selectivity and sensitivity. As a last example I will review how such encapsulation inside SWCNTcan be used for confined nanochemical reactions to stabilize new hybrid systems with novel electronic andoptical properties. Work supported by FWF and the EU.

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THIN FILMS OF HETERONANOHYBRIDS OF CARBON NANOTUBES AND ACCEPTOR MOLECULESFOR CONDUCTING TRANSPARENT ELECTRODES

Elena D. Obraztsova, A.M. Prokhorov General Physics Institute, RAS38 Vavilov street, Moscow, Russia

T: +7 499 503 8206, e-mail:elobr@mail.ruAlexander A. Tonkikh, A.M. Prokhorov General Physics Institute, RAS

Viktor I. Tsebro, P.N. Lebedev Physicsl Institute, RASEkaterina A. Obraztsova, A.M. Prokhorov General Physics Institute, RAS

Pavel V. Fedotov, A.M. Prokhorov General Physics Institute, RASA.G. Nasibulin, Department of Applied Physics, Aalto University, Espoo, FinlandE.I. Kauppinen, Department of Applied Physics, Aalto University, Espoo, Finland

A.L. Chuvilin, CIC NanoGune Consolide, San Sebastian, Spain

Materials with a high optical transparency and a low electrical resistance are necessary for formation ofconductive electrodes for optoelectronics and solar cells. Today the most popular material used in this field isindium tin oxide (ITO). In this work we propose and investigate a new material being able to replace ITO.This is a thin (thinner than 100 nm) film of single-wall carbon nanotubes (SWNTs) filled with differentacceptor molecules (iodine, CuCl). We have realized a gas-phase filling of aerosol-grown SWNTs and haverevealed (by HRTEM (Fig.1)) the formation inside nanotubes of one-dimensional crystals. The opticalspectroscopy has shown a Fermi level shift into a valence band and a complete metallization of thenanotubes [1]. To confirm this suggestion we have measured the electrical resistance of filled SWNT filmsand registered a big drop of electrical resistance (of one order of magnitude). The best values were 50Ohm/square at 90% transparency. The temperature dependence of resistance (R(T)) demonstrated twocontributions – from inter-tube interactions and from filled nanotubes by themselves. For the strongeracceptor (CuCl instead of iodine [2]) the minimum value of R(T) shifted toward low temperatures (Fig.2).

Fig.1. HRTEM image of SWNTs filled with CuCl. Fig.2. Illustration of R(T) minimum shift toward low temperatures for SWNTs filled

with stronger acceptor.

The work was supported by RSF project 15-12-30041, E.A.O. thanks project RFBR-15-32-20941, P.V.F.thanks grant SP-170.2015.3 of Ministry of Education and Science of Russian Federation.

[1] A.A. Tonkikh, V.I. Tsebro, E.A. Obraztsova, et al. “Metallization of single-wall carbon nanotube thin filmsinduced by gas phase iodination”, Carbon 94 (2015) 768.[2] P.V. Fedotov, A.A. Tonkikh, E.A. Obraztsova, et al. “Optical properties of single-walled carbon nanotubesfilled with CuCl by gas-phase technique”, Physica Status Solidi B 251 (2014) 2466.

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CONTRIBUTEDTALKS

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ASSEMBLING GRAPHENE OXIDE – MULTIWALLED CARBON NANOTUBE LAYERED HYBRIDS FORENERGY APPLICATIONS

J. David Núñez, Instituto de Carboquímica ICB-CSICc/ Miguel Luesma Castan 4, Zaragoza, Spain

T: +34 600876749, dnunez@icb.csic.es; davidnunezg@gmail.comAna M Benito, Instituto de Carboquímica ICB-CSIC

Pascale Launois, Université Paris-Sud CNRSStéphan Rouzière, Université Paris-Sud CNRS

Raúl Arenal, Instituto de Nanociencia de Aragón UNIZARP. M. Ajayan, Rice University

Wolfgang K. Maser, Instituto de Carboquímica ICB-CSIC

GO is a highly defective chemically modified form of graphene with many different types of oxygen functionalgroups (oFG) on its basal plane and its edges. The presence of oFG in GO make it a nonconductivehydrophilic material, which favor processing from dispersions, combination with other materials, andassembling in macroscopic forms, such as supported films or freestanding membranes (paper-likematerials). The drawback of lack of conductivity can be overcome by applying different types of reductiontreatments to obtain RGO with improved conductivity [1]. Accordingly, a variety of macroscopicallyassembled graphene-based materials with tailored conducting properties can be used for applications suchas electrochemical electrodes for sensors and energy storage [2]. Herein, we evaluate different processing routes towards the fabrication of self-assembly GO-MWCNT hybridfreestanding membranes (GOBucky) for electrochemical electrodes [3,4]. We study how the assemblingmethod affect the structural uniformity, the electrical conductivity, and the thermal stability of the GOBucky.Additionally, we analyze the evolution of intercalated water and oFG within the GOBucky papers duringchemical-thermal reduction treatments and its implication for the carbon sp2 structure and the chemicalcomposition of GO. In agreement with the structural characterization, the cycle-voltammetry results showthat the electrochemical capacity of GOBucky not only depends on the optimum GO/CNT ratio but also onthe assembling procedure and the thermal post-treatment (Figure 1). Our work provides important insightsfor the fabrication of nanostructured carbon-based hybrid electrodes for promising energy storageapplications.

[1] Dreyer, D. R.; Park, S.; Bielawski, C. W.; Ruoff, R. S., The chemistry of graphene oxide. ChemicalSociety Reviews 2010, 39 (1), 228-240.[2] Simon, P.; Gogotsi, Y., Capacitive Energy Storage in Nanostructured Carbon–Electrolyte Systems. [3] Accounts of Chemical Research 2013, 46 (5), 1094-1103.[4] David Núñez, J. et al, Processing of graphene oxide – carbon nanotubes hybrid electrodes for energystorage applications. In preparation[5] David Núñez, PhD Thesis, Univ. Zaragoza, 2015Acknowledgements: Spanish MINECO and EU Regional Developm. Fund (ENE2013-48816-C5-5-R),Government of Aragon and the EU Social Fund (DGA-ESF-T66). CSIC for PhD grant (JAE-PRE_09_01155CSIC)

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Figure 1. CV curves of 220 ºC heated samplesGOBucky1-15%, GOBucky1-10%, and GOpaperin (1 M) H2SO4 at 10 mV/s.

CARBON/MoS2 COMPOSITE STRUCTURES: SYNTHESIS, ELECTONIC PROPERTIES ANDAPPLICATION

Victor O. Koroteev, Nikolaev institute of inorganic chemistry SB RASLavrentiev ave. 3, 630090, Novosibirsk, Russia

+7-(383)-330-5352, koroteev@niic.nsc.ruDmitri A. Bulushev, Boreskov institute of catalysis SB RAS, Novosibirsk, Russia

Andrey Chivilin, CIC NanoGUNE, Donostia – San-Sebastian, SpainLyubov G. Bulusheva, Nikolaev institute of inorganic chemistry SB RAS, Novosibirsk, RussiaAlexander V. Okotrub, Nikolaev institute of inorganic chemistry SB RAS, Novosibirsk, Russia

Low dimensional materials, such as nanotubes and graphene are attracting attention of materialscientists over the last years. Further development and enhancement of the unique properties of lowdimensional materials can be done, combining them into the composites. Combination of carbonnanomaterials, possessing high electrical conductivity and high specific surface, with semiconductingnanoparticles allows creating a new class of low-dimensional hybrid materials with unique electronicstructure, optical and chemical properties. Molybdenum disulfide is layered indirect band gap semiconductor,which is actively studied after graphene discovery. Hexagonal lattice structure of carbon nanomaterials andmolybdenum sulfide MoS2 allow jointing these compounds in a hybrid, producing different kinds ofmolybdenum sulfide nanoparticles and layers on graphitic surface.

We are using two different methods for materials preparation. High temperature method is based onMoS3 decomposition and results in formation of molybdenum disulfide nanoparticles with different size on

graphitic surface, depending on annealing temperature.The other method is based on hydrothermal reactionbetween sulfur and molybdenum precursors. As theresult, we can obtain molybdenum disulfide layerscovering surface of carbon nanotubes or thermallyexpanded graphite. Using the same hydrothermalmethod, we can prepare composite structures with flower-like MoS2 on aligned carbon nanotubes arrays (figure 1).

The composites obtained were studied usingRaman spectroscopy, optical spectroscopy, x-rayphotoelectron spectroscopy, scanning and transmissionelectron microscopy. Raman investigation allows MoS2

nanoparticles size determination. While opticalspectroscopy and XPS reveal some electronic structurefeatures.

It shown that structure of obtained MoS2 andinteraction between the components strongly depends ondeposition conditions and carbon substrate.

Li-intercalation study shows that materialsobtained was tested as anodes for lithium-ion batterieswith specific capacity of 800 mAh/g, which is at least two

times more than conventional carbon-based anodes.Obtained materials were tested as catalysts for hydrogen production in formic acid decomposition

reaction. Catalytic activity and Li-intercalation performance strongly depends on particle size. Correlationallows one to suggest that this reaction occurs on the Mo-edge atoms exposed mainly by the MoS 2 clusters.Optimization of the synthetic procedure aiming to a MoS2/graphene catalyst containing solely 1-nm-sizedclusters may lead to highly active catalysts for different important reactions taking place on MoS2 edge sites,such as hydrogen evolution reaction or hydroprocessing of petroleum fractions.

This work is done with the financial support of the Russian Foundation for Basic Research (Grant No. 14-03-31633). This publication has also emanated from research conducted with the financial support of ScienceFoundation Ireland (under Grant No. 06/CP/E007). Collaboration between partner institutions is partlysupported by Grant No. FP7-PEOPLE-2011-IRSES N295180 (MagNon-Mag).

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Figure 1 – MoS2 particles on aligned carbonnanotube array.

COVALENT FUNCTIONALIZATION OF BORON NITRIDE NANOTUBES VIA REDUCTION CHEMISTRY

Homin Shin, Security and Disruptive Technologies Portfolio, National Research Council Canada100 Sussex Drive, Ottawa, ON K1A 0R6, CanadaT: 1-613-990-0741, Homin.Shin@nrc-cnrc.gc.ca

Jingwen Guan, Security and Disruptive Technologies Portfolio, National Research Council CanadaMarek Z. Zgierski, Security and Disruptive Technologies Portfolio, National Research Council Canada

Keun Su Kim, Security and Disruptive Technologies Portfolio, National Research Council CanadaChristopher Kingston, Security and Disruptive Technologies Portfolio, National Research Council Canada

Benoit Simard, Security and Disruptive Technologies Portfolio, National Research Council Canada

Boron nitride nanotubes (BNNTs) exhibit a range of properties that hold great potential for many fields ofscience and technology;1 however, they have inherently low chemical reactivity, making functionalization forspecific applications difficult. Here we propose that covalent functionalization of BNNTs via reductionchemistry could be a highly promising and viable strategy.2 Through density functional theory (DFT)calculations of the electron affinity of BNNTs and their binding energies with various radicals, we reveal thattheir chemical reactivity can be significantly enhanced via reducing the nanotubes (i.e., negatively charging).For example, a 5.5 fold enhancement in reactivity of reduced BNNTs towards NH2 radicals was predictedrelative to their neutral counterparts. The localization characteristics of the BNNT π electron system lead theexcess electrons to fill the empty p orbitals of boron sites, which promote covalent bond formation with anunpaired electron from a radical molecule. In support of our theoretical findings, we also experimentallyinvestigated the covalent alkylation of BNNTs via reduction chemistry using 1-bromohexane. Thethermogravimetric measurements showed a considerable weight loss (12~14 %) only for samples alkylatedusing reduced BNNTs, suggesting their significantly improved reactivity over neutral BNNTs. This finding willprovide an insight in developing an effective route to chemical functionalization of BNNTs.

[1] D. Golberg, Y. Bando, Y. Huang, T. Terao, M Mitome, C. Tang and C. Zhi, ACS Nano, 2010, 4, 2979-2993.[2] H. Shin, J. Guan, M. Z. Zgierski, K. S. Kim, C. T. Kingston and B. Simard, ACS Nano, 2015 (justaccepted, DOI: 10.1021/acsnano.5b06523).

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DOPED CARBON NANOSTRUCTURES FOR COLD FIELD EMISSION: STRUCTURAL ANDANALYTICAL STUDIES

Rongrong WANG, CEMES - CNRS, University of Toulouse - France, and LMA-INA U. Zaragoza - Spain29 Rue Jean Marvig, Toulouse, France

T: +33647890856, rongrong.wang@cemes.frRaul Arenal, LMA-INA U. Zaragoza and Fundacion ARAID, Zaragoza - Spain

Aurélien Masseboeuf, David Neumeyer, Marc Monthioux, CEMES - CNRS, University of Toulouse - FranceAlejandro Lopez-Bezanilla, Materials Science Div., Argonne National Lab. Illinois, USA

Electron sources based on cold field emitters provide outstanding performances in terms of spatial andenergy resolutions for electron microscopes (EM) [1]. In such cases, electrons are emitted, at roomtemperature, when a strong electrostatic field is applied to the emitter/tip. Up to date, tungsten tips havebeen employed as electron sources, due to their high melting point, low work function and small apex radius.Recently, a new kind of carbon nanocones, offering better performances than tungsten tips, have beensuccessfully synthesized [1-3]. This work is devoted to ameliorate the emission performances of carbonnanostructures by nitrogen and/or boron incorporations and to the evaluation of these doped carbon nano-objects by different characterization techniques [4,5]. Thus, in this contribution, we will present our recentresults related to doping of carbon nanotubes. High resolution TEM (HRTEM) imaging, spatially-resolvedelectron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS) studies have beendeveloped on these NTs, see Fig.1.

Figure 1 - Structural study (a) and (b) at different magnification and compositional study (c) and (d).

This work was supported by the project ANR LASCAR (ANR-13-BS04-0007), the project ESTEEM2 (Integrated Infrastructure Initiative - I3, Grant Agreement 312483), the Spanish MINECO (FIS2013-46159-C3-3-P), and international associated laboratory TALEM (CNRS - U. of Zaragoza). TEM studies were developed in the Advanced Microscopy Laboratory (LMA) of Institute of Nanoscience of Aragon (INA) - U. of Zaragoza (Spain).

[1] Houdellier, F.; Houdellier, F.; Masseboeuf, A.; Monthioux, M. & Hÿtch, M. J., Carbon 50 (2012), p. 2037-2044.[2] Jacobsen, R. L.; Monthioux, M.; Nature 385 (1997), p. 211-212.[3] de Knoop L.; Houdellier F.; Gatel C.; Masseboeuf A.; Monthioux M.; Hÿtch M., Micron 63 (2014), p. 2-8.[4]Ayala, P.; Arenal, R.; Loiseau, A.; Rubio, A.; Pichler, T. ; Rev. Modern Physics 82 (2010), p. 1843 – 1885.[5] Wang, R.; Lopez-Bezanilla, A. ; Masseboeuf, A. ; Monthioux, M, ; Arenal, R., submitted (2015).

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ELECTRICAL TRANSPORT MEASURED IN sp1-HYBRIDIZED CHAINS OF CARBON ATOMS

Florian Banhart, IPCMS, Université de Strasbourg, 23 rue du Loess, 67034 Strasbourg, FranceT: +33-388-107103, Email: florian.banhart@ipcms.unistra.frAlessandro La Torre, IPCMS, CNRS, Strasbourg, France

Ovidiu Cretu, MANA, National Institute of Materials Science, Tsukuba, JapanAndrés Botello-Mendez, Institute of Condensed Matter, Université catholique de Louvain, Belgium

Jean-Christophe Charlier, Institute of Condensed Matter, Université catholique de Louvain, Belgium

Carbon in the sp1 hybridization is able to form atomic chains. Despite many efforts, it has always beenimpossible to synthesize carbon chains in appreciable quantities and so to study their propertiesexperimentally. It has been predicted that carbon chains are unusual conductors that may occur either asmetallic cumulene with double bonds or as semiconducting polyyne with alternating single and triple bonds.Now, it became possible to generate carbon chains in in-situ experiments in an electron microscope. Ascanning tunnelling microscopy setup integrated into the specimen holder of a transmission electronmicroscope allowed to establish contacts to graphenic material and, by controlled retraction of theelectrodes, to unravel chains of carbon atoms. At the same time, the electrical properties could be measured.Contacting the chains with metals or graphitic carbon allowed to measure their electrical properties [1, 2]. Byrecording current-voltage curves of individual carbon chains, both cumulene and polyyne were identified. Itwas found experimentally and by quantum conductance calculations that transport through narrow resonantstates makes the conductivity much lower than predicted in previous theoretical work. When the 1D systemis under strain, the chains exhibit a semiconducting behavior, corresponding to polyyne. Conversely, whenthe chain is unstrained, an ohmic behavior, corresponding to cumulene, is observed [3]. This confirms arecent theoretical prediction, namely that the Peierls distortion, which would stabilize polyyne, is suppressedby zero-point vibrations in an unstrained chain so that cumulene is the stable configuration. In the presenceof strain, however, polyyne is favoured by the Peierls instability. Thus, a metal-insulator transition can beinduced by adjusting the strain. Furthermore it is shown that these atomic chains can act as rectifying diodeswhen they are in a non-symmetric contact configuration.

[1] O. Cretu, A. R. Botello-Mendez, I. Janowska, C. Pham-Huu, J.-C. Charlier, F. Banhart, Nano Lett. 13, 3487 (2013).[2] A. La Torre, F. Ben Romdhane, W. Baaziz, I. Janowska, C. Pham-Huu, S. Begin-Colin, G. Pourroy, F. Banhart, Carbon 77, 906 (2014).[3] A. La Torre, A. Botello-Mendez, W. Baaziz, J.-C. Charlier, F. Banhart, Nature Comm. 6, 6636 (2015).

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ELECTRON CONDUCTION AND TRAPPING IN SINGLE-WALLED CARBON NANOTUBES SORTED BYGEL CHROMATOGRAPHY

Alejandro Ansón-Casaos, Instituto de Carboquímica, ICB-CSICMiguel Luesma Castán 4, 50018 Zaragoza, Spain

T: 34 976 733977, alanson@icb.csic.esCristina Rubio-Muñoz, Instituto de Carboquímica, ICB-CSIC

Javier Hernández-Ferrer, Instituto de Carboquímica, ICB-CSICM. Teresa Martínez, Instituto de Carboquímica, ICB-CSIC

Ana M. Benito, Instituto de Carboquímica, ICB-CSICWolfgang K. Maser, Instituto de Carboquímica, ICB-CSIC

Different methods are currently utilized for the synthesis of single-walled carbon nanotubes (SWCNTs), including arc-discharge, laser ablation, chemical vapor deposition (CVD), and aerosol synthesis. In all the cases, important advances have been done, allowing the preparation of materials with increasing purities. However, the selectivity towards a few different conformational species is limited to certain CVD methods, and it is not complete. Therefore, post-synthesis sorting, linked to rigorous purification protocols, has to be applied for the obtention of singular samples. Among the SWCNT sorting methods, gel chromatography has recently gained an impulse owing to the discovery of the high efficiency of certain sepharose gels. Many sorting conditions have been already tested by modifying the temperature, pH, surfactant concentration, pressure, volume, and elution sequence.

In this communication, HiPco SWCNTs are dispersed in a sodium dodecyl sulfate (SDS) surfactant and separated into several fractions by a gel chromatography method utilizing Sephacryl S-200 gel. The separation is performed at ambient conditions using concentrations of SDS or sodium deoxycholate between0.5-1.5 w/v % for the sequencial elution of the retentate. The possibility of up-scaling the separation method is considered by a 5-fold increase in the volume of the chromatographic column. The sorted SWCNT fractions are first analyzed by optical absorption spectroscopy.

For the study of the electron conduction properties, the SWCNT dispersions are air-sprayed onto glass substrates, forming transparent thin films. The residual surfactant is removed by immersion of the suported films in water. Two parallel silver electrodes are painted on the SWCNT films, and the resistance between them is measured at variable temperature.

For the study of the electron trapping properties, small amounts of the SWCNT dispersions are added to a TiO2 dispersion in ethanol and air-sprayed onto fluorinated tin oxide (FTO)/glass substrates. The resulting films are washed by immersion in water, annealed at 450ºC, and analyzed by photoelectrochemical methods. The illumination of TiO2 with a solar simulator produces a current towards the electrode, which is interferred due to the presence of SWCNTs. The potential of the trapping states is determined by cyclic voltammetry.

The aim of this study is to acquire information about electron transport properties in sorted SWCNTs, and its relationship with the optical spectrum features.

AcknowledgementsThis work has been funded by the Spanish Ministry MINECO and the European Regional Development Fundunder the project ENE2013-48816-C5-5-R, and the Government of Aragon and the European Social Fund(DGA-ESF-T66 Grupo Consolidado).

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EVIDENCES FOR THE UNEXPECTED FILLING OF DOUBLE-WALL CARBON NANOTUBES WITHIODINE NANOCRYSTALS

Chunyang Nie, CEMES, UPR8011 CNRS - CIRIMAT, UMR5085 CNRS - Université Toulouse III, Toulouse,France, T: +33 (0)5 62 25 78 86, nie@chimie.ups-tlse.fr

Thierry Michel, L2C, UMR5221 CNRS – Université Montpellier, FranceMatthieu Paillet, L2C, UMR5221 CNRS – Université de Montpellier, France

Anne Marie Gilbert, CIRIMAT, UMR5085 CNRS – Université Toulouse III, FranceBrigitte Soula, CIRIMAT, UMR5085 CNRS – Université Toulouse III, France

Lucien Datas, Centre de Microscopies Raymond Castaing – Université Toulouse III, FranceEmmanuel Flahaut, CIRIMAT, UMR5085 CNRS – Université Toulouse III, France

Marc Monthioux, CEMES, UPR8011 CNRS – Université Toulouse III, France

Attempts to fill carbon nanotubes with iodine have started as early as in 1998 [1], aiming to modify theelectronic structure of the resulting hybrid materials. Since then, it has involved either single-wall, or double-wall, or multi-wall carbon nanotubes [2,3], previously opened or not, using either the sublimation, or thesolvent phase, or the molten phase filling procedure [4]. Actual modification of the electronic behavior hasbeen achieved, demonstrating some interaction between the doping phase – iodine – and the carbonnanotubes. However, in spite of the variety of conditions already used in the literature, the iodine phase hasbeen found either under a molecular form or as polyiodine chains, wherever it is found filling the carbonnanotube hollow core [2] or filling the voids left between the nanotubes when bundled [3,5]. Hence, whateverthe synthesis conditions, obtaining iodine nanocrystals filling the host nanotube hollow core has been rarelyachieved to date.

We report the synthesis and characterization of an iodine/carbon nanotube hybrid material whichwas obtained an unexpected way. Indeed, we first performed a series of synthesis experiments aiming to findthe conditions for the successful filling of double-wall carbon nanotubes (DWCNTs) with Ni nano-magnets,starting with soaking double-wall carbon nanotubes (DWCNTs) in molten nickel iodide, and then reducing theresulting material in a hydrogen flow at 300-500°C. While we found no evidence for having producedNi@DWCNT materials, we found evidences for the formation, at some point in the course of the process, ofNiI2@DWCNT and then I@DWCNTs. Furthermore, the encapsulated iodine was not found under the usualform of helical polyiodine chains, but as genuine nanocrystals, for which examples are scarce in the literature[2]. Meanwhile Ni nanoparticles were found outside the DWCNTs, hence decorating the DWCNT bundles.Interestingly, the behavior is not the same when filling with FeI2 and CoI2, instead of NiI2.

The characterization of the various filled DWCNT materials were made by aberration-corrected highresolution transmission electron microscopy, high-angle annular dark field imaging, electron energy lossspectroscopy, and multi-wavelength Raman spectroscopy. Formation mechanisms are discussed. Furtherwork is in progress, aiming at modelling the crystal structure and measuring the transport properties ofindividual, iodine-crystal-filled DWCNTs.

(a) STEM-HAADF image of rod-like iodine nanocrystalsencapsulated in DWCNTs, fromthe material after reduction at500°C. (b) is an EELS spectrumacquired with a local nanoprobeon a filled DWCNT similar tothat shown in (a). The spectrumshows the presence of theiodine edge (at ~630 eV), andthe quasi absence of the Niedge (at ~855 eV).

[1] Grigorian L., Williams K.A., Fang S., Sumanasekera G.U., Loper A.L., Dickey E.C., Pennycook S.J., Eklund P.C., Phys. Rev. Lett. 80(1998) 5560

[2 Guan L., Suenaga K., Shi Z., Gu Z., Iijima S., NanoLett. 7 (2007) 1532[3] Michel T., Alvarez L., Sauvajol J.L., Almairac R., Aznar R., Mathon O., Bantignies J.L., Flahaut E.,J. Phys.

Chem. Sol., 67 (2006), 1190.[4] Monthioux M., Flahaut E., Cleuziou J.P., J. Mater. Res. 21 (2006) 2774[5] Cambedouzou J., Sauvajol J.L., Rahmani A., Flahaut E., Peigney A., Laurent C., Phys. Rev. B 69 (2004),

235422.

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FORMATION MECHANISM OF NANOSTRUCTURED WS2 IN THE CONFINEMENT OF ORDEREDMESOPOROUS CARBON PREPARED BY A ONE POT SYNTHESIS

Parmentier J.*, Kiener J.* #, Girleanu M.#, Ersen O. #

*: Institut de Science des Matériaux de Mulhouse (IS2M), France. #: Institut de Physique et de Chimie des Matériaux de Strasbourg (IPCMS), France

Transition metal sulfides, like MoS2 and WS2, are layered inorganic materials (2H-WS2) that can adoptfullerene-like and nanotubes nanostructures. These structures, termed also inorganic fullerenes (IF), havebeen extensively studied for different applications including solid lubrication, hydrogen storage, lithiumbatteries and hydrodesulfurization catalysis. We have developped a one pot synthesis based on the soft templating process that yied orderedmesoporous carbon structure embedding up to four different WS2 nanostructures depending on sulfidationtemperature in pure H2S : tungsten nanocluster, 2H-WS2 nanoparticles, IF-WS2 nanocages (Figure 1) and IF-WS2 nanotubes. Extensive TEM studies led us to propose a new growth mechanism of these IF structures(nanocages and nanotubes) beside the classic sulfidation mechanism described by Feldman et al. 1. It isproposed that the simultenous occurrence of well dispersed W precursor within the carbon wall(nanoclusters) associated with the carboneous reductive atmosphere and the cylindrical mesopore shapepromote these particular WS2 IF structures.

Figure 5: TEM micrograph of IF-WS2 nanocages embedded in an ordered mesoporous carbon matrix.

[1] Feldman, Y.; Frey, G. L.; Homyonfer, M.; Lyakhovitskaya, V.; Margulis, L.; Cohen, H.; Hodes, G.;Hutchison, J. L.; Tenne, R. J. Am. Chem. Soc. 1996, 118 (23), 5362.

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HYDROGEN-ASSISTED, HIGHLY EFFICIENT SYNTHESIS OF BORON NITRIDE NANOTUBES

Keun Su Kim, Security and Disruptive Technologies Portfolio, National Research Council Canada100 Sussex Drive, Ottawa, ON K1A 0R6, CanadaT: 1-613-998-5365, KeunSu.Kim@nrc-cnrc.gc.ca

Christopher Kingston, Security and Disruptive Technologies Portfolio, National Research Council CanadaMark Plunkett, Security and Disruptive Technologies Portfolio, National Research Council CanadaBenoit Simard, Security and Disruptive Technologies Portfolio, National Research Council Canada

Boron nitride nanotubes (BNNTs) are isoelectronic analogues of carbon nanotubes (CNTs) and exhibit arange of properties that are as compelling as those of CNTs.1,2 Despite having been first synthesized in1995,3 progress in science and technology of BNNTs is still hampered by their very low production volume.Here we report the high-yield production of small-diameter (avg. 5 nm) BNNTs from 100 % h-BN powderusing an induction thermal plasma. This new method, called a hydrogen-assisted BNNT synthesis (HABSmethod) makes use of hydrogen, which dramatically increases yield of small-diameter BNNT (i.e., 20-30 g/h)even at atmospheric pressure.4,5 To understand the catalytic role of hydrogen, we investigate the hydrogen-mediated plasma chemistry by examining reaction by-products and gas-phase intermediate species in thehot plasma zone using optical emission spectroscopy (OES). This study suggests that molecular hydrogeninhibits the formation of N2 from N radicals and promotes the creation of B-N-H intermediate species, whichprovide faster chemical pathways to the reformation of an h-BN-like phase in comparison to nitridation fromN2. The detailed mechanism of BNNT formation will be presented. The high selectivity of our plasma processtowards small-diameter BNNT will be also discussed considering the effects of the rapid quenching ofreaction stream (~105 K/s) via both TEM analysis and computational fluid dynamics (CFD) simulations.

[1] R. Arenal, X. Blase and A. Loiseau, Adv. Phys., 2010, 59, 101-179. [2] D. Golberg, Y. Bando, Y. Huang, T. Terao, M Mitome, C. Tang and C. Zhi, ACS Nano, 2010, 4, 2979-2993.[3] N. G. Chopra, R. J. Luyken, K. Cherrey, V. H. Crespi1, M. L. Cohen, S. G. Louie and A. Zettl, Science,1995, 269, 966-967.[4] K. S. Kim, C. T. Kingston, A. Hrdina, M. B. Jakubinek, J. Guan, M. Plunkett and B. Simard, ACS Nano,2014, 8, 6211-6220.[5] A. Fathalizadeh, T. Pham, W. Mickelson and A. Zettl, Nano Lett., 2014, 14, 4881.

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INTERACTION OF TRITIUM AND CHLORINE 36 WITH DEFECTS IN GRAPHITE: INSIGHTS FROMTHEORY

Christoph Lechner, EDF R&D - Department Materials and Mechanics of Components (MMC)EDF Lab Les Renardières, Avenue des Renardières, F-77818 Moret-sur-Loing Cedex, France

+33160576508, christoph.lechner@edf.fr

Philippe Baranek, EDF R&D - Department Materials and Mechanics of Components (MMC)Holger Vach, CNRS-LPICM, Ecole Polytechnique, F-91128 Palaiseau Cedex, France

In the upcoming years, nine nuclear power plants of the type UNGG (Uranium Naturel Graphite Gaz) willhave to be dismantled in France. In this type of power plant, nuclear graphite was used as a neutronmoderator and deflector and was activated during operation. The dismantlement will lead to 23000 tons ofirradiated graphite waste, which will have to be managed. The graphite is classified as nuclear wastecontaining radionuclides with low activity and long half-life. Amongst them, chlorine 36 has one of the longesthalf-lives (about 300000 years) and is partially responsible for the activity of the graphite waste in the longterm. With a half-life of only 12 years, tritium is rather short lived, but contributes significantly to the initialactivity of the waste. The high interest in its behavior in nuclear graphite is due to its potential risk of beingreleased, while the graphite waste is prepared and transported to the site for permanent disposal. Previousexperimental studies suggest that both, chlorine 36 and tritium, are mainly fixed at different traps in graphite,which are defective structures, such as dislocation loops, surfaces, or grain boundaries. Since the onlysignificant diffusion mechanism of these radionuclides is release, it is important to understand, where thesetraps are located and under which conditions the trapped species are released.

A computational study of the interaction of tritium and chlorine 36 with defects in graphite has been achievedto develop models for the previously mentioned traps at the density functional theory (DFT) level by using thePBE functional with Grimme's D3 dispersion correction within the code CRYSTAL. The physisorption andchemisorption of atomic and molecular hydrogen or chlorine on graphite surfaces, (001), (100), and (110),with or without mono- and divacancies, have been investigated. The stabilities of the formed complexes areinterpreted in terms of the formation energy. To obtain insight into the nature of the bonding (covalent,charge transfer, van der Waals) a population analysis of the systems has been performed. While the bondingof hydrogen is mostly covalent for chemisorption and van der Waals for physisorption, the behavior ofchlorine is much more complex. Depending on the defect site, both, dominantly covalent and dominantlycharge transfer bonding, is observed. For the atomic species, the importance of using spin resolvedcalculations is presented, as their physisorption often leaves the single electron residing on the adsorbateand using a spin averaged description leads to underestimated formation energies. One of the mostimportant tools to analyze irradiated graphite for experimentalists is Raman spectroscopy. It suffers,however, from the lack of resolution and difficulties to separate the contributions caused by irradiationdamages and the insertion of radionuclides. Thus, the vibrational spectra for selected structures have beeninvestigated, in order to evaluate, if the commonly known defect bands can be reproduced.

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IN-SITU GROWING OF CARBON NANOTUBES ENCAPSULATED WITHIN BORON NITRIDENANOTUBES VIA ELECTRON IRRADIATION

R. Arenal, Instituto Nanociencia Aragon & ARAID FundationC/ Mariano Esquillor, Zaragoza, Spain

Tel:+34-976-76-2985, Email: arenal@unizar.esAlejandro Lopez-Bezanilla, Materials Science Div., Argonne National Lab. Illinois, USA

In the last 15 years several studies have demonstrated the capability of electron-irradiation for modifying thebehavior of carbon-based and related nanomaterials under extreme conditions and radiation [1]. Here wereport the synthesis and growth of crystalline carbon nanotubes (NTs) inside a larger diameter boron nitride(BN) NT via in-situ electron irradiation in a TEM [2]. Electron beam irradiation and HRTEM studies wereperformed using an imaging-side aberration-corrected FEI Titan-Cube microscope working at 80 kV,equipped with a Cs corrector. Complementary spatially-resolved EELS-STEM measurements were alsocarried out using a FEI Titan Low-Base microscope, working at 80 kV, which is equipped with a Cs probecorrector. In both cases, particular attention was devoted to avoid contamination during acquisition. Single-walled (SW) BNNT were produced by laser vaporization technique [3]. Some of these BNNT can be partiallyfilled by amorphous carbon [3]. Furthermore, density functional theory (DFT) simulations were conducted fordetermining the structural stability and electronic properties of the hybrid system. In summary, we demonstrate the feasibility of growing pure and crystalline carbon nanotubes within boronnitride nanotubes with electron irradiation as the driven force. The formation of single-walled CNTencapsulated within single- and multi- BNNT as a pathway to construct a BNC heterostructures wasinvestigated. The resulting CNT remains stable and encapsulated within the outer BN tube which provides aprotective shell against environment perturbations, suggesting an alternative method for the fabrication ofBNC-based electronic devices.

[1] F. Banhart, World Scientific, Singapore (2008).[2] R. Arenal and A. Lopez-Bezanilla, ACS Nano 8, 8419-8425 (2014). [3] R. Arenal, O. Stephan, J.L. Cochon, and A. Loiseau, JACS 129, 16183 (2007).[4] The research leading to these results has received funding from the European Union Seventh

Framework Program under Grant Agreement 312483 - ESTEEM2 (Integrated Infrastructure Initiative – I3)and under Grant Agreement 604391 Graphene Flagship. R.A. also acknowledges funding from the SpanishMinisterio de Economia y Competitividad (FIS2013-46159-C3-3-P).

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Figure 4 – (a)-(f) Six-frame HRTEM image sequence displaying the formation process of a crystalline CNT fromamorphous C encapsulated in a BNNT under electron beam irradiation (high doses for short periods of time, seeFig. 1 (c)) in a TEM. (g) EEL spectra recorded in 2 different areas (marked in the HAADF-STEM image showedbelow), displaying B-K, C-K and N-K edges. Scale bars in Fig. 1 (a) and (g) are 2 nm.

IROX NANOSTRUCTURED HYBRIDS WITH GRAPHENE / GRAPHENE OXIDE / CARBON NANOTUBESELECTRODES FOR NEURAL STIMULATION AND REPAIR

N. Casañ-Pastor, E. PérezInstitut Ciència de Materials de Barcelona (ICMAB-CSIC), Campus UAB, E-08193, Bellaterra, Barcelona

(Spain) * nieves@icmab.es.

M. P. Lichtenstein, C. Suñol Institut d’Investigacions Biomèdiques de Barcelona (IIBB-CSIC); Institut d’Investigacions Biomèdiques

August Pi i Sunyer (IDIBAPS). 08036 Barcelona (Spain). # CIBER Epidemiología y Salud Pública(CIBERESP)

R. Fernandez-Pacheco, R. ArenalLaboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon (LMA-INA), Universidad de

Zaragoza, 50018 Zaragoza (Spain)

Biocompatibility in inert form is not enough when using electrodes in biological systems. Their action, whenan electric field is applied, must assume not only a capacitive behavior but also prevent radical ion formation.In that sense, intercalation materials with mixed valence chemistries and good conductivities are beingdeveloped based on conducting polymers, IrOx, and lately carbon nano phases. This work shows thesignificant increase in charge capacities achieved when graphene oxide, pristine graphene and carbonnanotubes are nanostructured with IrOx, which is the best material for neurons. These studies also show thatsuch effect, obtained under optimal compatibility conditions, provides neuronal stimulation and in vitro repair. HRTEM and EDS analyses developed on a STEM and in a SEM show the fundamental nanostructure ofthese hybrids materials. IrOx adheres to graphene platelets and when is deposited, it forms a flaky pastry(stacked-like material) with alternating IrOx and graphene. This later result explains the 10 fold increase incapacity and also the high stability which is not observed if graphite is used. The true chemistry is based onIrOx redox changes. In fact, the chemical identity of IrOx is this one of a hydrated oxohydroxide intercalatingprotons as well as Na+ and K+ ions. Thus, when acting as electrode, is the material itself the one undergoingthe ion-electron exchange needed in any electrochemical process, and therefore offers a mechanism thatprevents radical formation, protecting the neural system. Coatings are easily obtained by electrodeposition,driven by the easiness of electrodeposition of IrOx, while dynamic processes favor adhesion to any platinumpreformed electrode, or any platinized surface like medical silicone coated with Pt, etc.

Figure 1. SEM and macroscopic images of IrOx coatings, spongy structure of IrOx and adhesion of IrOx to graphene exfoliated electrochemically and to CNT

[1] The synthesis of graphene sheets with controlled thickness and order using surfactant-assisted electrochemical processes .M. Alanyologlu,..N. Casañ-Pastor. Carbon, 50, 2012 , 142; [2] Iridium Oxohydroxide, a Significant Member in the Family of Iridium Oxides. A. M. Cruz,..and N. Casañ-Pastor*;J. Phys. Chem. C , 116 , 2012, 5155–5168. [3] J. Moral-Vico, et al. N. Casañ-Pastor. Nanocomposites of iridium oxide and conducting polymers as electroactive phases in biological media. Acta Biomaterialia, 10 (2014) 2177–2186. [4] Nina M. Carretero et al. Nieves Casañ-Pastor*, IrOx-Carbon Nanotubes Hybrid:A Nanostructured Materialfor Electrodes with Increased Charge Capacity in Neural systems. Acta Biomaterialia, 10, 2014, 4548-4558[5 ] N. M. Carretero, M. P. Lichtenstein, E. Pérez, S. Sandoval, G. Tobias, C. Suñol , N. Casan-Pastor* Enhanced Charge Capacity in Iridium Oxide-Graphene Oxide Hybrids. Electrochimica Acta , 157, 2015, 369-377. [6] E. Pérez, et al N. Casan-Pastor*. Coatings of Nanostructured Pristine Graphene-IrOx Hybrids for Neural Electrodes: Layered Stacking and the role of non-oxygenated Graphene. Materials Science & Engineering C, 55, 2015, 218-226.

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LIQUID ADHESION AND CAPILLARY ACTIONS AT THE NANOSCOPIC LEVEL: DIRECT OBSERVATIONS OF INTERACTIONS BETWEEN WATER

AND SINGLE WS2 NANOTUBES

Ohad Goldbart1, Ifat Kaplan-Ashiri2, Andrey Enyashin3, Sidney R. Cohen2, Reshef Tenne1, H. DanielWagner1.

1. Department of Materials and Interfaces, Weizmann Institute, Rehovot 76100, Israel2. Chemical Research Support, Weizmann Institute of Science, Rehovot 76100, Israel

3. Institute of Solid State Chemistry, 620990 Ekaterinburg, Russia

The use of different nanostructures as fillers in polymer composite materials attracts an ever-growinginterest. While the impact of nanoparticles on composite properties is well studied, the relations betweenindividual filler nanoparticles and the host matrix are yet to be fully understood. The elucidation of theseinteractions on the bulk composite properties requires the study of the wetting, adhesion to the matrix,surface energy, morphology etc. of a single nanoparticle.

It was reported that the addition of these inorganic nanoparticles leads to improved mechanicalproperties [1], thermal stability [2] and electrical properties [3] of the polymer composites. Although thosenanoparticles alter the properties of the composite, the nature of the nanotube-matrix interactions is stillvague. The goal of our study is to investigate the interactions of single WS2 nanotubes with different matricesand liquids.

In this work, a new technique to measure the interactions of individual nanotubes with differentliquids and polymers is presented. This technique is based on pullouts of nanotubes from water films andother liquids using environmental scanning electron microscope (ESEM) and atomic force microscope (AFM)[4] systems. Using these techniques the effect of WS2 nanotube morphology and structure on the interactionstrength between different liquids and the nanotubes are assessed. From these experiments, as well as fromtheoretical simulations, it follows that the morphology of the WS2 nanotube has a significant effect on theinteraction of the NT and the surrounding media.

The interaction energy/cross-section area of the nanotubes falls-off dramatically with the diameter ofthe nanotubes (30-70 nm) and then levels-off. These differences are currently attributed to the capillaryinteraction of the small hollow core nanotubes and the water molecules. MD simulations show that the highlyconfined space results in large interaction energy between the water molecules and the inner core of thenanotubes. This interaction leads to imbibition of the water molecules into the nanotube’s hollow core. Theseeffects and the impact of the nanotubes surface chemistry on the interaction energy are presented anddiscussed.

[1] Zohar, E., Baruch, S., Shneider, M., Dodiuk, H., Kenig, S., Tenne, R., Wagner, H.D., The effect of WS2

nanotubes on the properties of epoxy-based nanocomposites, J. Adhes. Sci. Technol. 25, 1603-1617 (2011).[2] Naffakh, M., Martin, Z., Fanegas, N., Marco, C., Gomez, M., Jiménez, I., Influence of inorganic fullerene ‐like WS2 nanoparticles on the thermal behavior of isotactic polypropylene, J. Polym. Sci., Part B: Polym.Phys. 45, 2309-2321 (2007).[3] Voldman, A., Zbaida, D., Cohen, H., Leitus, G., Tenne, R., A Nanocomposite of Polyaniline/InorganicNanotubes, Macromol. Chem. Phys. 214, 2007-2015 (2013).[4] Barber, A.H., Cohen, S.R., Wagner, H.D., Static and dynamic wetting measurements of single carbonnanotubes, Phys. Rev. Lett. 92, 186103 (2004).

33

LUMINESCENCE AT DEFECTS IN H-BN: EXCITONS AT STACKING FAULTS AND SINGLE PHOTONEMITTERS

A. Tararan, Laboratoire de Physique des Solides, Univ. Paris Sud, CNRS UMR 8502, 91405 Orsay, FranceT: +33 0169155371, anna.tararan@u-psud.fr

R. Bourrellier, Laboratoire de Physique des Solides, Univ. Paris Sud, CNRS UMR 8502, 91405 Orsay,France

S. Meuret, Laboratoire de Physique des Solides, Univ. Paris Sud, CNRS UMR 8502, 91405 Orsay, FranceL.H.G. Tizei, Laboratoire de Physique des Solides, Univ. Paris Sud, CNRS UMR 8502, 91405 Orsay, France

T. Taniguchi, Advanced Nanomaterials Laboratory, National Institute for Materials Science, 1-1 Namiki,Tsukuba, Ibaraki 305-0044, Japan

M. Kociak, Laboratoire de Physique des Solides, Univ. Paris Sud, CNRS UMR 8502, 91405 Orsay, FranceO. Stéphan, Laboratoire de Physique des Solides, Univ. Paris Sud, CNRS UMR 8502, 91405 Orsay, FranceA. Zobelli, Laboratoire de Physique des Solides, Univ. Paris Sud, CNRS UMR 8502, 91405 Orsay, France

Hexagonal Boron Nitride (h-BN) has been attracting large interest in the field of far UV light emitting devices.Pure h-BN monocrystals emission spectrum is characterized by a unique intense free excitonic peak at 5.8eV, while more common crystals present a far more complex emission spectrum with additional featuresusually attributed to structural defects. The exact nature of emitting centers is still under discussion.In this work we address this question using an experimental and theoretical approach that combinesnanometric resolved cathodoluminescence, high resolution transmission electron microscopy and state ofthe art theoretical spectroscopy methods. Cathodoluminescence maps show that emission spectra arestrongly inhomogeneous within individual few layer flakes. We demonstrated that additional excitons occur atstructural deformations, such as faceted plane folds, that lead to local changes of the h-BN layers stackingorder [1]. Furthermore sharp emissions within the band gap present a high spatial localization, typically less than 100nm, and thus they can be related to individual point defects. When addressed individually through a highlyfocused electron probe they might exhibit a single photon emitter quantum character. We confirmed thishypothesis by experiments combining our cathodoluminescence system with an Hanbury Brown and Twiss(HBT) interferometer [2]. Finally, coupling cathodoluminescence and Electron Energy Loss Spectroscopy canprovide insights into the chemical nature of the emission centers.

[1] R. Bourrellier et al., ACS Photonics 1, 857–862 (2014).[2] A. Tararan et al., in preparation.

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FFigure 1 – Dark Field image and CL filtered image of an h-BN flake. CL spectrum and HBTautocorrelation function of the selected region.

MANIPULATING INDIVIDUAL ATOMS WITH AN ELECTRON BEAM

Toma Susi, University of Vienna, Faculty of PhysicsBoltzmanngasse 5, A-1090 Vienna, Austria

T: +43 664 527 3054, toma.susi@univie.ac.at

Demie Kepaptsoglou, SuperSTEM Laboratory, STFC Daresbury Campus, United KingdomQuentin Ramasse, SuperSTEM Laboratory, STFC Daresbury Campus, United Kingdom

Jani Kotakoski, University of Vienna, Faculty of Physics, Austria

Single-layer graphene is arguably the ideal material for atomic resolution electron microscopy. However,even in the so-called ’gentle’ conditions used for atom-by-atom investigations, beam effects rarely can beneglected. From another perspective, this may be seen as an advantage.

We observed that 60 keV electrons can cause 3-foldcoordinated silicon dopants found in the graphenelattice to jump by one site at a time [1] (Figure 1).However, it is very unlikely for a a low-voltageelectron beam to perturb dopants heavier than carbonvia elastic knock-on [2]. Indeed, our first principlesmolecular dynamics simulations instead show that aC atom next to the out-of-plane Si can be partiallyejected from the lattice, but due to their attractiveinteraction immediately recaptured. Crucially,relaxation of the Si into the position vacated by theejected C leads to the Si-C bond inversion (Figure 2),allowing controlled movement. Further progresstowards creating multi-atom structures is hindered bythe lack of sufficiently clean and Si-rich samples,which we propose can be addressed by ionimplantation.

More recently, we have observed a similar effect forin-plane boron dopants [3], but with significantlyhigher doses. The low likelihood of these eventsnecessitates further improvements in their modeling.For this reason, we have been further refining theexisting method [4] to account for lattice vibrationsduring the electron impact. Finally, we will show that alarge angle momentum transfer is required to explainthe recently observed jumping of a pyridinic nitrogendopant between the two equivalent sides of agraphene single vacancy [5].

[1] T. Susi et al., Phys. Rev. Lett. 113 (2014) 115501. doi:10.1103/PhysRevLett.113.115501[2] T. Susi et al. ACS Nano 6 (2012) 883. doi: 10.1021/nn303944f[3] T. Susi, D. Kapaptsoglou, Q. Ramasse, J. Kotakoski, in preparation.[4] J.C. Meyer et al., Phys. Rev. Lett. 108, 196102 (2012). doi:10.1103/PhysRevLett.108.196102.[5] T.Susi, Y.-C. Lin, J. Kotakoski, K. Suenaga, in preparation.

35

Figure 1 – a) STEM HAADF image of 3-coordinatedSi atom (bright contrast) in the graphene lattice. b-c)After irradiating the area with 60 keV electrons, theSi is observed to jump from one lattice site to thenext with no damage. d-e) DFT structure model.

Figure 2 – DFT/MD simulation of a 140 fs trajectoryafter the C neighbor to the Si is given an initial

kinetic energy of 15 eV perpendicular to the sheet.Since this is below the knock-on threshold, the

attractive interaction with the Si pulls it back into thelattice, but onto the other side of the Si.

NANOSTRUCTURES IN TWO-DIMENSIONAL MATERIALS SCULPTED WITH ELECTRONS ANDAPPLICATIONS

Jerome MLACK, University of Pennsylvaniajmlack@sas.upenn.edu

Understanding, shaping and manipulating matter at atomic scale remains one of the major contemporarychallenges in science and technology. In this respect, electron beams constitute the power tools to shapematerials with atomic resolution inside a transmission electron microscope (TEM). I will describe experimentswhere we push the limits of device size to atomic scale, and expand their function and precision, whileaddressing fundamental questions about structure and properties at nanometer and atomic scales.Experiments are performed in situ or ex situ TEM. In situ TEM experiments include the study of electronsflow in nanowires in novel two-dimensional materials including graphene, molybdenum disulfide andphosphorene, as a function of their structure as they are nanosculpted down to zero width. We reveal theelectrical current scaling with size and atomic structure and develop methods to realize pristine and highlyconducting sub-10-nm-wide wires. Ex situ TEM include the ultrafast, all-electronic detection and analysis ofbiomolecules or nanoparticles by threading them through tiny holes – or nanopores – in thin membranes,including efforts towards mapping a human genome under 10 minutes. As particles are driven throughnanoholes in solution, they block the current flow resulting in current reductions from which particle’s physicaland chemical properties are inferred, where are are improving the temporal and spatial resolution andsensitivity. I will also describe alternative uses of nanoholes such as electrically controllable chemicalnanoreactors, and explore the use of nanoholes created in two-dimensional nanowires to highly localize andprobe molecules.

From left to right: illustrations of graphene nanoribbon sculpting with the electron beam; passage of a DNAmolecule through a ~ 1nm-thick silicon nanopore; nanohole drilling through graphene nanoribbon transistor;one-atom-large hole in a MoS2 sheet.

References: Drndic, Nature Nanotechnology 9, 743, 2014; Puster et al., ACS Nano 9 (6), 6555, 2015; Qi et

al., ACS Nano, 9(4), 3510, 2015; Balan et al., Nano Letters 14 (12), 7215, 2015; Venta et al., Nano Letters

14 (9), 5358, 2014; Qi et al., Nano Letters 14 (8), 4238, 2014; Venta et al., ACS Nano, 7 (5), 4629, 2013;

Venta et al., Nano Letters 13 (2), 423, 2013; Puster et al, ACS Nano, 7 (12), 11283, 2013; Rosenstein et al.,

Nature Methods, 9 (5), 487, 2012;Merchant et al., Nano Letters 10 (8), 2915, 2010; Wanunu et al. Nature

Nanotechnology, 5, 807, 2010.

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NANODIAMOND / SILICON CARBIDE NANOCOMPOSITES FOR MEMBRANES APPLICATIONS

Johan Alauzun, Institut Charles Gerhardt Montpellier (CMOS), UMR 5253, Université de Montpellier, PlaceEugène Bataillon, 34095 Montpellier Cedex 5, France

T: +33 4 67 14 38 02, E-mail: johan.alauzun@umontpellier.fr

Anthony Ballestero, IEM, UMR 5635 Université de Montpellier, Place Eugène Bataillon, 34095 Montpellier Cedex 5, France.

Philippe Miele IEM, UMR 5635 Université de Montpellier, Place Eugène Bataillon, 34095 Montpellier Cedex 5, France.

Samuel Bernard IEM, UMR 5635 Université de Montpellier, Place Eugène Bataillon, 34095 Montpellier Cedex 5, France

Preceramic polymers have been proposed in the late seventy’s as non-oxide silicon based ceramicprecursors generally called PDCs for “Polymer Derived Ceramics”.Compared to traditional synthesis ways, the PDCs route can offer many advantages in terms ofcompositions, structures and textures of ceramics. Furthermore, the synthesis and cross-linking of thepreceramic polymers offer the possibility to modify some characteristics of these compounds such as theirsolubility, viscosity and fusibility allowing the elaboration of shaped ceramics in a way not known byconventional routes.Due to its intrinsic properties (thermal, chemical and mechanical resistance, semi-conductor behavior,...),silicon carbide (SiC) and their derivatives with nitrogen (silicon carbonitride, SiCN) can be considered as oneof the best materials for the next generation of ceramic based membranes, in particular in the hydrogenproduction processes (from CO2, CH4 or through the water gas shift reaction for example).By investigating the PDCs route, a hydrophobic and amorphous SiC material suitable for hydrogenseparation process exhibiting good permeability/selectivity ratio, high thermal mechanical and chemicalresistance coupled with a good stability under wet atmosphere up to 500°C can be proposed.However, the disadvantage of the preceramic polymers is their volume shrinkage which occurs during thepyrolysis to convert the polymer into ceramic. Indeed, preceramic polymers lose weight (evolution ofgaseous by-products), whereas their density increases during their transformation into ceramics bothinducing volume shrinkage. Residual stresses caused by the volume shrinkage lead to the formation ofdefects, cracks or even delamination of the coatings.

Within this context, the solution considered to limit the volume shrinkage was addition of fillers in the polymerto form nanocomposites.

The talk will be dedicated to the description of ND@SiC nanocomposites by the PDCs route, its application to membrane elaboration, the characterization of the membranes and their application to gas separation.

37

ORGANIC SYNTHESIS OF CARBON HETEROSTRUCTURES

Reinhard lyu, Dresden University of TechnologyDepartment of Chemistry and Food Chemistry

Chair for Molecular Functional Materialsphone : +49 351 463-42424

fax: +49 351 463-43268e-mail: reinhard.berger@mailbox.tu- dresden.de

Graphene has attracted tremendous interest within the materials science community because of itsexceptional electronic and optic properties. Moreover, doping of graphene with heteroatoms has further ledto new materials suitable for catalysis and energy storage applications. For Example, nitrogen dopedgraphene as a metal free catalyst material has proven to be a promising candidate for the oxygen reductionreaction (ORR) at the cathode in fuel cells.We are currently working on the synthesis of different heteroatom doped nanographenes. For this, we applytechniques of solution or surface assisted organic synthesis to gain polyphenylene precursors which uponring-closure produce the desired graphene materials. In contrast to a top-down method for example thetreatment of graphene or graphene oxide with nitrogen sources like ammonia or the pyrolysis of nitrogenenriched precursors, the heteroatoms are at designated positions in graphene and the edge structure thuscan be designed by the synthesis of the monomers. It shall further be highlighted that nanographenes withnitrogen in a zig-zag periphery are accessible as well. This structure is a formal azomethine ylide and hasbeen embedded in a polyaromatic framework for the first time. In summary, it is possible to extend theestablished method of bottom-up synthesis to a new class of nitrogen containing nanographenes andgraphene nanoribbons.1-4

[1] J. Cai, C. A. Pignedoli, L. Talirz, P. Ruffieux, H. Söde, L. Liang, V. Meunier, R. Berger, R. Li, X. Feng, K. Müllen and R. Fasel, Nature Nanotechnology, 2014, 9, 896-900.

[2] Y. Zhang, Y. Zhang, G. Li, J. Lu, X. Lin, S. Du, R. Berger, X. Feng, K. Müllen and H.-J. Gao, Applied Physics Letters, 2014, 105, -.

[3] R. Berger, A. Giannakopoulos, P. Ravat, M. Wagner, D. Beljonne, X. Feng and K. Müllen, Angewandte Chemie International Edition, 2014, 53, 10520-10524.

[4] R. Berger, M. Wagner, X. Feng and K. Müllen, Chemical Science, 2015, 6, 436-441.

38

PERFORMANCE EVALUATION OF DOPED CARBON NANOTUBE/POLYSULFONE NANOFILTRATIONMEMBRANES

Edward Nxumalo, University of South AfricaCnr Christiaan de Wet & Pioneer Avenue, 1710, Johannesburg, South Africa

T: +27 11 670 9498, E: nxumaen@unisa.ac.zaKholiswa Yokwana, University of South AfricaSabelo Mhlanga, University of South AfricaBhekie Mamba, University of South Africa

This work describes the fabrication and performance evaluation of doped carbon nanotubes(CNTs)/polysulfone (PSf) membranes. PSf blend membranes were prepared via modified phase inversionmethod using nitrogen doped CNTs (N-CNTs) as functional additives. Results reveal that the morphologicalparameters and flux performance of the membranes have a significant inter-relationship with the surface andstructural properties of the doped CNTs added on the PSf backbone. The PSf composite membranesmodified with N-CNTs are more hydrophilic, and have significantly improved properties: water uptake,surface charge and permeation. Scanning electron microscopy studies demonstrated that the addition of thedoped CNTs resulted in the formation of ‘finger-like’ structures subsequently leading to increased membraneporosities and pore sizes. In addition, atomic force microscopy analysis revealed that the addition of N-CNTsleads to a reduced surface roughness, suggesting a good dispersion of the N-CNTs in the matrix. Theaddition of doped CNTs to the membrane resulted in an increase in salt rejection (with increase in theamount of N-CNTs) for (NaCl) [from 29.1 to 33.5% and from 88.0 to 95.0% (MgSO4)] also accompanied by adecrease in water flux from 84.7 to 51.3 L/m2h, respectively. Thus, the presence of N in the CNTs impartedon the transport mechanism of the parent membranes resulting in enhanced flow rates and better selectivity.This increase could be due to a combination of steric limitations from the carboxylic functional groups(present in their surfaces leading to electrostatic repulsions between functional groups present in themembranes and also the humic acid molecules).

[1] E. Celik, H. Park, H. Choi, H. Choi, Water Res. 2011, 45, 274.[2] K.Yokwana, N. Gumbi, F. Adams, S. Mhlanga, E. Nxumalo, B. Mamba, J. Appl. Poly. Sci. 2015, 132 21.

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PHOTOELECTROCHEMICAL PROPERTIES OF TIO2-CARBON NANOMATERIAL COMPOSITEELECTRODES

Javier Hernández-Ferrer, Instituto de Carboquímica-CSICc/Miguel Luesma Castán 4, 50018 Zaragoza, Spain

T: +34976733977, jhernandez@icb.csic.esAlejandro Ansón-Casaos, Instituto de Carboquímica-CSIC

Olga Sanahuja, Instituto de Carboquímica-CSICSandra Víctor, Instituto de Carboquímica-CSIC

Mª Teresa Martínez, Instituto de Carboquímica-CSICAna Benito, Instituto de Carboquímica-CSIC

Wolfgang Maser, Instituto de Carboquímica-CSIC

Different carbon nanomaterials exhibit different electronic properties due to their different structure.Graphene oxide (GO), reduced graphene oxide (rGO), which have a 2D structure, Ultracentrifuged singlewalled carbon nanotubes (Ucf-SWCNTs), with 1D structure, and electrochemically synthesized graphenequantum dots (ECGQDs), with 0D discretization of electronic levels, are photoelectrochemically tested incombination with TiO2 (Degussa P25) as possible components of solar cells.

The effect of the different carbon nanomaterials on photocurrent is shown in figure 1. A modification of theelectronic properties of the materials is observed. ECGQDs modify the electronic levels of the material thusimproving photocurrent and inhibiting electron-hole recombination, graphene-like materials also improvephotocurrent with no change in electronic levels of TiO2, while UcfSWCNTs cause a significant degree inphotooxidation currents due to the formation of trap states.

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I/mA

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Figure 2 – Arial 10 pt Italics

PROMISES OF GRAPHENE OXIDE FRAMEWORKS FOR WATER DESALINATION APPLICATIONS

Adrien Nicolaï, Department of Physics, Applied Physics and Astronomy. Rensselaer Polytechnic Institute.Troy, NY USA and Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS-Univ. Bourgogne

Franche-Comté, Dijon, FRANCE.

Vincent Meunier, Department of Physics, Applied Physics and Astronomy. Rensselaer Polytechnic Institute.Troy, NY USA.

Bobby G. Sumpter, Center for Nanophase Materials Sience and Computer Science. Oak Ridge NationalLaboratory. Oak Ridge, TN USA.

“Water, water, everywhere, nor any drop to drink” wrote Samuel Taylor Coleridge in his poem The Rime ofthe Ancient Mariners in 1798. Today's scientific advances in water desalination strive to alter the second partof the sentence into “and every drop to drink.” by transforming seawater into fresh water. However,successfully gaining adequate access to clean water remains a technological challenge. This requiresconsiderably more efficient water treatment technologies than are currently available. Today, the well-established reverse osmosis (RO) technology represents more than 40% of the total desalination capacity,due to its economical and technical capability to desalt seawater on a large scale. The RO process involvesthe use of a semipermeable membrane: under the influence of external pressure, a larger fraction of waterpasses through the membrane than the dissolved salts or organic molecules. Although this technique is themost efficient to date, it suffers from low desalination capacity and high capital costs, thereby limiting itslarge-scale deployment in most developing markets. Clearly, membranes with higher flux, higher selectivity,improved stability, and resistance to chlorine and fouling are needed. The design of novel materials whichcan reduce the energy consumption of the RO process by showing high water permeability coupled with highsalt rejection capacity is crucial.

Graphene Oxide Frameworks (GOFs) are a class of nanoporous materials consisting of layers of grapheneoxide sheets covalently interconnected by linear boronic acid linkers L. Since their synthesis in 2011, severalexperimental studies have been performed to investigate the chemical tunability of such materials and it hasbeen shown that, for a given L and a proper linker concentration n, one can tune a large set of geometricalparameters of GOF-L-n materials, such as the pore size, the pore volume or the accessible surface area forexample.

The possibility of employing GOF materials as membrane for seawater desalination is studied using classicalMolecular Dynamics (MD) simulations. First, we use quantum mechanical calculations to develop a set offorce-field parameters due to the lack of parameters for linear boronic acid compounds. Second, MDsimulations of water molecules inside bulk GOF-n materials reveals significant variations of their diffusionproperties depending on n. Finally, the desalination performances across GOF membranes are estimated asa function of n, their thickness h and applied pressure ∆P. This reveals that first, the water permeability ofthese materials is several orders of magnitude higher than conventional RO membranes and, second, highwater permeabilities can be coupled with a 100% efficiency of salt rejection by choosing the correct (n,h)pair, which means that GOF membranes may have a significant role to play for water desalinationapplications.

[1] A. Nicolaï, P. Zhu, B. G. Sumpter & V. Meunier. 2013. J. Chem. Theory. Comput.,9, 4890-4900. [2] A. Nicolaï, B. G. Sumpter & V. Meunier. 2014. Phys. Chem. Chem. Phys., 16, 8646-8654.

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SPECTROMICROSCOPY INVESTIGATION OF FLUORINE AND NITROGEN DOPED CARBONNANOMATERIALS

Mattia Scardamaglia, ChIPS - University of Mons, Place du Parc 20, 7000 Mons, BelgiumT: +32 65554963, mattia.scardamaglia@umons.ac.be

Claudia Struzzi, ChIPS - University of MonsRony Snyder, ChIPS - University of Mons & Materia Nova Research Center

Carla Bittencourt, ChIPS - University of Mons

The grafting of functional groups in a controllable way has been proposed as a strategy for graphene andcarbon nanotubes band gap engineering. In this framework nitrogen and fluorine doping of graphene-basedcarbon nanostructures gained a lot of interest from both technological and fundamental point of view.To date a controllable doping strategy is still lacking. Among the methods used to incorporate different atomsin the hexagonal carbon lattice, post-synthesis plasma-based functionalization and ion implantation methodshave the advantage to be solvent-free, time efficient and flexible.Within this context, we discuss nitrogen and fluorine incorporation in different carbon nanostructures: verticalaligned carbon nanotubes [1,2,3], suspended graphene [4] and graphene supported on copper foils [5].Ultraviolet and x-ray photoemission spectroscopy and spectromicroscopy measurements were performed todetermine the effect of the incorporation of the heteroatom in the hexagonal carbon lattice. The effect ofthermal heating will be discussed: a surface rearrangement takes place, thus allowing the identification of themost thermal stable species. The thermal treatment, allowed to identify the different contributions to chargecarrier doping of nitrogen species in N-graphene on copper foil by studying the Dirac cone shift. We identifiedgraphitic nitrogen as being responsible for n-doping when the counterbalancing action of pyridinic is reducedupon thermal heating (Figure 1). We will discuss the role of the supporting substrate, the dependence of the chemical composition on theplasma parameters used and the nonequivalent response of monolayer and bilayer graphene to fluorinationtreatments. The changes in orbital hybridization, the doping induced by the grafting, the moiré pattern thatdrives the functionalization and the opening of a bandgap are some of the results achieved in fluorinatedgraphene.

42

[1] M Scardamaglia et al. Carbon 77, 319-328 (2014).[2] M Scardamaglia, C Struzzi et al. Carbon 83, 118-127 (2015).[3] C Struzzi, M Scardamaglia et al. submitted (2015)[4] M Scardamaglia et al. Carbon 73, 371-381 (2014).[5] M Scardamaglia, C Struzzi et al., submitted (2015).

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Figure 3 – ARPES spectra of graphene Dirac cone, the evolution of electronic band structure for pristine graphene, after nitrogen plasma exposure and after thermal heating to 500°C; the total amount of nitrogen is constant (8 at.%) for step two and three while the graphitic/pyridinic ratio changed due to the thermal heating.

SYNTHESIS AND LUMINESCENT PROPERTIES OF SINGLE-CRYSTAL DIAMOND PYRAMIDS

Ekaterina A. Obraztsova1,2,3, Feruza T. Tuyakova4,5, Evgeny V. Korostylev6, Dmitry V. Klinov1,7, Kirill A.Prusakov7, Andrey A. Alekseev8, Rinat R. Ismagilov8, Alexander N. Obraztsov4, 8

1M.M. Shemyakin, Institute of Bioorganic Chemistry, Russian Academy of SciencesYu.A. Ovchinnikov, Institute of Bioorganic Chemistry, Russian Academy of Sciences

2A.M. Prokhorov General Physics Institute, Russian Academy of Sciences, Russia3 National University of Science and Technology “MISIS”, Russia

4 Department of Physics and Mathematics, University of Eastern Finland, Finland5 Moscow State Institute of Radio Engineering, Electronics and Automation, Moscow, Russia

6Moscow Institute of Physics and Technology, Dolgoprudny, Russia7Research Institute for Physico-Chemical Medicine, Moscow, Russia

8M.V. Lomonosov Moscow State University, Department of Physics, Moscow, Russia

e.a.obraztsova@gmail.com

In this work we report on synthesis of single-crystal diamond pyramids with controllable luminescentproperties. In our previous works we have demonstrated that individual diamond crystallites with lengths upto 150 µm and transverse dimensions up to about 10 µm can be obtained by selective oxidation ofpolycrystalline films produced by chemical vapor deposition (CVD) from hydrogen-methane gas mixtureactivated by a direct current (DC) discharge. In this work diamond films and crystallites were obtained alsowith addition of gaseous nitrogen during CVD growth.The samples of the needle-like diamonds of these two types (obtained with and without nitrogen addition)were studied to obtain photoluminescence (PL) and cathodoluminescence (CL) spectra and spatialdistribution of the luminescence intensity at various wavelengths. Spectral characteristics of PL and CLindicate presence of luminescence centers related to nitrogen and silicon in diamond structure. Whiledetected space distribution of the luminescence intensity is assumed to be connected with structuralperformance of the crystallites, its dependence on excitation by photons and electrons is assumed to beevidence of charge state variation of corresponding luminescent centers. The diamond pyramids have beeneffectively used as probes for atomic force microscopy. We suppose that these diamond crystallites withcontrollable luminescence can be used in other scanning probe microscopy techniques.

This work was supported by the Russian Science Foundation (Grant 14-12-00511). EAO, DVK and KAP arealso grateful for financial support from Russian Federation President program for young scientist supportgrant МК-6201.2014.2 and Russian Science foundation grant 14-14-01001. SEM equipment of MIPT Centersof Collective Usage was used in the work with financial support from the Ministry of Education and Scienceof the Russian Federation (Grant No. RFMEFI59414X0009).

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SYNTHESIS OF HETEROATOM-DOPED CARBON FOAMS FOR HYDROGEN ENERGYTECHNOLOGIES

S. M. Lyth,1,5,6 B. V. Cunning,1 T. Bayer,1 A. Mufundirwa,1,2 J. Liu,7 S. Yu,1 K. Sasaki1,2,3,4

1. I2CNER; 2. Department of Mechanical Engineering; 3. NEXT-FC; 4. International Research Center forHydrogen Energy, Kyushu University; 5. Leeds University; 6. Sheffield University; 7. Shanghai University ofElectric Power

Graphene-like carbon foam can be prepared at multi-gram scale by the decomposition of sodium ethoxide.We produce such materials with surface area >2500 m2/g (Fig. 1a,b). In its undoped form, it has potentialapplications in hydrogen storage. We report excess H2 uptake of 2.6 wt% via physisorption at 77K.Additionally the material is an ideal catalyst support; we record high electrochemical surface area andimpressive fuel cell performance after Pt-decoration (Fig. 1c). Due to the bottom-up nature, heteroatom doping can be performed by varying the starting molecule. Bydecomposing “amino-ethoxides”, few-layer nitrogen-doped graphene-like foam can be produced. This is aneffective electrocatalyst in acid media, giving insight into the oxygen reduction reaction in metal-freesystems. In alkaline media, the activity is comparable to Pt, and negligible degradation is seen over 60,000potential cycles, far out-performing Pt in this respect (Fig 1d). Finally, by decomposing “fluoroethoxides” hollow fluorinated carbon nanospheres are produced (Fig 1e).These have superhydrophobic properties (Fig 1f) and can be printed or sprayed onto arbitrary substrates.These nanoparticles are being applied in gas diffusion layers in electrolysers in order to improve the watersupporting force and simplify water management. In summary, heteroatom doping is an extremely important method of engineering the properties of carbon.By having precise control over the properties, we can make improvements in the performance of newenergy-related technologies.

1. Hydrogen Adsorption on Graphene Foam Synthesized by Combustion of Sodium Ethoxide, S. M. Lyth etal, Int. J. of Hydrogen Energy 39 (1), 376-380 (2014)2. Defective Nitrogen-Doped Graphene Foam: A Metal-Free Electrocatalyst for the Oxygen ReductionReaction in Acid, J. Liu et al, J. Electrochem. Soc. 161 (4), F544-F550 (2014)3. Defective Graphene Foam: A Platinum Catalyst Support for PEMFCs, J. Liu et al., J. Electrochem. Soc.,161 (9), F838-F844 (2014)4. Pt-decorated N-doped graphene foam electrocatalysts, J. Liu, et al., Fuel Cells 14, 728 (2014)5. Solvothermal Synthesis of Nitrogen-Containing Graphene for Electrochemical Oxygen Reduction, S. M.Lyth, et al, eJ. Surf. Sci. & Nanotech., 10, 29-32 (2012) 6. Solvothermal Synthesis of Superhydrophobic Carbon Nanoparticles from Fluorinated Alcohol, S. M. Lythet al, Submitted (2015)

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THEORETICAL PROBING OF EXCITONIC EFFECTS IN TRANSITION DICHALCOGENIDESMONOLAYERS: A TRUE NUMERICAL EXPERIENCE

I. C. Gerber1, G. Wang1, B. Urbaszek1, T. Amand1, X. Marie1

1Uinversité de Toulouse, INSA-CNRS-UPS, LPCNO, 135 Av. de Rangueil, 31077 Toulouse, FranceEmail:igerber@insa-toulouse.fr, web site: http://www.lpcno.insa-toulouse.fr

Monolayers of transition metal dichalcogenides (TMDC) such as WSe2 and MoS2 are a new class of two-dimensional (2D) materials with fabulous properties for opto-electronics, non-linear optics or for exploringelectron k-valley physics. Crystal inversion symmetry breaking plus a strong spin-orbit interaction lead to anextraordinary coupling of carrier spin and k-space valley physics. Indeed, when electrons and holes aresimultaneously present, they form excitons since the Coulomb interaction is enhanced by a strong quantumconfinement, with large effective masses and a reduced dielectric screening in these ideal 2D systems. Inthis talk, we will discuss some theoretical studies of the electronic and optical properties of such systemsfrom a theoretical point of view, and more particularly the challenges, formally and numerically speaking, theyrepresent [1]. We will compare theoretical results beyond the standard density functional theory withexperimental data, to account for many-body effects, which are prominent in such ideal systems. Morespecifically we will deal with WSe2 [2], MoSe2 [3] ML cases by presenting quasi-particle band structure andsimulated absorption spectra obtained at the GW+BSE level, the current edge methodology.

[1] I. Gerber, in preparation [2] G. Wang, X. Marie, I. Gerber, T. Amand, D. Lagarde, L. Bouet, M. Vidal, A. Balocchi, and B. Urbaszek,Phys. Rev. Lett. 114 (2015) 097403.[3] G. Wang, X. Marie, I. Gerber, T. Amand and B. Urbaszek, submitted to 2D materials (arXiv:1504.06333).

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47

ATOMIC STRUCTURAL AND CHEMICAL INVESTIGATIONS OF MISFIT LAYERED NANOTUBES

Luc Lajauniea, Leela S Panchakarlab, Gal Radovskyb, Reshef Tenneb and Raul Arenala,c

a Laboratorio de Microscopías Avanzadas, Instituto de Nanociencia de Aragón, Universidad de Zaragoza,50018 Zaragoza, Spain

e-mail: lajaunie@unizar.esb Department of Materials and Interfaces, Weizmann Institute of Science, Rehovot, 76100 Israel

c ARAID Foundation, 50018 Zaragoza, Spain.

Misfit layered compounds can be considered as inter-grown materials with a general formula [(MX)1+x]m[TX2]n,where M is rare earths, Pb, Sb, etc; T is Ti, V, Cr, Nb, etc. and X is S, Se. They constitute an heterostructureformed by the stacking of TX2 dichalcogenides layers with MX layers.1 In 2011, nanotubes based on the SnS-SnS2 system were synthetized for the first time2. Later, the syntheses were generalized to many othersystems. However, making these structures in the nano-size is rather challenging. Most of the misfitnanotubes reported in the earlier reports have wall thickness of more than a few dozen of nanometers. Inorder to improve the synthesis conditions, detailed structural and chemical analyses at the nanoscale arehighly needed.

In this work, few layers thick nanotubes based on the TbS-CrS2 system are reported. Their detailedstructure and chemical composition are elucidated by different TEM techniques including high-resolutionscanning TEM (HR-STEM) and spatially-resolved EELS (SR-EELS). Surprisingly, structural modulation andcomposition variation along the thin nanotubes axis were observed.3 In light of this new structural andchemical information, a growth mechanism for these nanotubes is proposed. Comparison with lanthanum-based misfit nanotubes and oxide nanotubes of the SrCoO family will also be discussed.

Figure 1: HR-STEM ADF micrograph of a wavy TbS-CrS2 NT. The inset shows theTb/Cr ratio obtained from SR-EELS elemental quantification performed on the area

delimited by the red square

[1] J. Rouxel, A. Meerschaut, and G. Wiegers, J. Alloys Compd. 229, 144 (1995)[2] G. Radovsky, R. Popovitz-Biro, M. Staiger, K. Gartsman, C. Thomsen, T. Lorenz, G. Seifert, and R. Tenne, Angew. Chem. Int. Ed. 50, 12316 (2011).[3] L.S. Panchakarla, L. Lajaunie, R. Tenne, R. Arenal. J. Phys. Chem. C (2015), In Press.

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CHANGES OF CARBON STRUCTURE IN MANGANESE DIOXIDE/GRAPHENE HYBRID MATERIALSYNTHESIZED BY DIRECT REDOX REACTION

Suk Woo Lee, Yonsei UniversityShinchon-dong, Seodaemun-gu, Seoul, Korea

T: 82-2-365-7745, steyn@yonsei.ac.krMyeong-Seong Kim, Yonsei University

Jun-Hui Jeong, Yonsei UniversityKwang-Bum Kim, Yonsei University

Structural changes of the carbon in a MnO2/reduced graphene oxide (RGO) hybrid materials prepared by thedirect redox reaction between carbon and permanganate ions (MnO4

-) were explored to reach betterunderstanding for the effects of carbon corrosion on carbon loss and its bonding nature during the hybridsynthesis. We have demonstrated the changes in the RGO structure that occur during synthesis ofMnO2/RGO hybrids by the direct redox deposition of MnO2 onto RGO. Our results demonstrate that theredox reaction between MnO4

- ions and RGO gives rise not only to quantitative carbon loss but also tochanges in the electronic structure of the carbon remaining after the redox deposition of MnO2. The directredox deposition of MnO2 onto RGO, which is a carbon-destructive approach, leads to a substantial carbonloss from the initial RGO structure, as evidenced in our EA results. In addition, C K-edge NEXAFS resultssuggest that there is an oxidized carbon environment at the interface within the hybrids that results in alocalized electronic structure of the RGO remaining in the R- MnO2/RGO hybrid after the carbon loss duringredox deposition of MnO2. Therefore, disruption of the sp2 carbon bonding of the RGO and strong Mn-O-Ccovalent bonding interactions between the MnO2 and RGO in the R- MnO2/RGO hybrids may have adetrimental effect on the electrical properties of the hybrids. Electrochemical measurements of theMnO2/reduced graphene oxide hybrid using a Cavity Micro Electrode revealed unfavorable electrochemicalproperties mainly due to the poor electrical conductivity of the hybrid. This study provides a useful guide for arational approach to synthesizing metal/RGO or metal oxide/RGO hybrid materials.

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ELECTROCHEMICAL CAPACITIVE BEHAVIOUR OF CARBON BASED /SPINEL FERRITESNANOCOMPOSITES

Aïcha Harat, LEREC Laboratory, Physics Department, Badji Mokhtar-Annaba University,BP.12, Annaba 23000, Algeria

T: (213) 38875399, Email: harat_aicha@yahoo.fr / aicha.harat@univ-annaba.dzOuanassa Guellati, Hiba Kennaz and Mohamed Guerioune, LEREC Laboratory,

Physics Department, Badji Mokhtar-Annaba University, BP.12, Annaba 23000, AlgeriaDamilola. Y. Momodu, Julien K. Dangbegnon and Ncholu Manyala,

Department of Physics, Institute of Applied Materials, SARChI Chair in Carbon Technology and Materials,University of Pretoria, Pretoria 0028, South Africa

Spinel ferrites (MFe2O4) and their related nanocomposites have shown their potential application both in Li-ion battery and supercapacitors [1-3]. In this context, we investigate nanohybrid materials based on carbon nanotubes (MWCNTs) and/or activated carbon (AC) with Co-ferrite and Ni-ferrite magnetic nanoparticles (MNPs) as electrodes in supercapacitors. In a first step, MNPs ferrites have been synthesized by combustionand hydrothermal methods. The structural and morphological characterizations of the as-prepared materials were investigated using XRD, FESEM, HRTEM, BET and Raman spectroscopy. In the second step, these MFe2O4 MNPs where used to prepare MWNTs and/or AC– MFe2O4 nanohybrids on Ni-foam electrode. The electrochemical performances were measured using three electrode configuration by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and chronopotentiometry (CP).

[1] V.S. Kumbhar, A.D. Jagadale, N.M. Shinde, C.D. Lokhande, Appl. Surf. Sci. 259, 39 (2012).[2] P. He, K. Yang, W. Wang, F. Dong, L. Du, and Y. Deng; Russian Journal of electrochemistry 49, 359 (2013).[3] Y. X. Zhang, X. D. Hao, Z. P. Diao, J. Li, Y. M. Guan, Materials Letters 123, 229 (2014).

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ELECTROMAGNETIC PROPERTIES OF POLYMER BASED COMPOSITES WITH VAROUS CARBONINCLUSIONS

Mikhail Kanygin, Nikolaev institute of inorganic chemistry SB RAS, 3 Acad. Lavrentiev ave., Novosibirsk, RussiaT: +7 (383) 330-53-52, mkanygin@gmail.com

Olga Sedelnikova, Nikolaev institute of inorganic chemistry SB RASNatalie Arutunian, Prokhorov General Physics Institute RASVitaliy Kubarev, Budker Institute of Nuclear Physics SB RAS

Gennady Mikheev, Institute of Mechanics UB RASLyubov Bulusheva, Nikolaev institute of inorganic chemistry SB RASAlexander Okotrub, Nikolaev institute of inorganic chemistry SB RAS

Composite materials based on dielectric polymer matrix with conductive inclusions are promising materialsfor electromagnetic shielding. Of particular interest are materials with predetermined arrangement ofconductive nanoparticles, which provide special electromagnetic response in a certain frequency range. Inthis context, carbon nanomaterials like nanotubes and graphene have attracted special attention dueextremely high shielding efficiency of composites at different frequency ranges including gigahertz andterahertz regions even at low content of the filler in composite. Electromagnetic characteristics of compositeare governed by many factors, such as polymer base, geometry, length, defectiveness, concentration anddistribution of filler in the matrix. Variation any of these parameters could drastically change property ofcomposite material. Possibility to alignment carbon inclusions in the certain direction are quite promising forthe fabrication of novel optical elements. Here we demonstrate some effects of interaction electromagnetic radiation with nanotubes and graphenebased composites. Composite materials with various carbon filler were synthesized. Effect of fabrication onthe structure of obtained carbon filler/polymer composite are discussed. Potential of forge-rolling techniquefor production of homogenous composites with onion-like carbon and nanodiamonds usage as a filler weredemonstrated. Anisotropic composite materials with carbon nanotubes were prepared by multiple forge-rolling technique and by stretching method. Graphene based composites were produced by forge-rollingtechnique. The electromagnetic response from obtained composite was measured in the THz, IR, visible andlow-frequency regions. Nanotube contained composite demonstrate anisotropic transmission of THz, IR andvisible radiation depend on the method of their production. The angular distribution of energy transmission atthe low frequency THz region was measured at the Novosibirsk Free Electron Laser. The quite highanisotropy of transmitted energy of THz radiation about 0.97 was found. In the frameworks of Gaussiandistribution of CNT in the samples the average misalignment of nanotubes were calculated. Comparing ofobtained experimental data with polarized Raman spectroscopy allows to reveal the effect of nanotubesbending in the samples. Additionally, the anisotropic reflection of IR radiation by CNT based composites wererecorded.

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ENERGY STORAGE APPLICATION OF NICKEL HYDROXIDES OR OXIDES /CARBON SOURCENANOHYBRIDS

S. Kettaf 1, O.Guellati1,2, A. Harat1, D. Momodu3, J. Dangbegnon3, N. Manyala3 and M. Guerioune1

(1) LEREC Laboratory, Physic Department, Badji-Mokhtar University of Annaba, BP. 12, 23000, Algeria(2) Mohamed Chérif Messaadia University of Souk-Ahars, BP. 1553, 41000, Algeria

(3) Department of Physics, Institute of Applied Materials, SARChI Chair in Carbon Technology and Materials,University of Pretoria, Pretoria 0028, South Africa.

(*) guellati23@yahoo.fr

Supercapacitors are nowadays a prominent domain of research for energy storage devices as they havehigh power density, long cycling life and short charging time [1-2]. A number of inorganic materials have beenapplied as electrode materials in electrochemical supercapacitor [3,4] and among them nickel oxide andhydroxide materials which have excellent and unique properties. In this report, we have successfully synthesized nickel oxides (NiO) and hydroxides (Ni-OH) nanoparticles bysimple and low cost hydrothermal method. Structural and morphology characteristics of the obtainedproducts were analyzed using X-Rays Diffraction (XRD), FESEM, HRTEM microscopy and Ramanspectroscopy in order to investigate quantitatively and qualitatively experimental parameters effect.Working electrodes prepared with Ni(OH)2 and NiO nanoparticles as well as their nanocomposites withdifferent carbon source were performed using nickel foam as current collector for electrochemicalmeasurements and storage energy application.

Key words: Nickel hydroxide, Nickel oxide, Hydrothermal method, electrochemical performance, energystorage.

[1] Kuperman A, Aharon I: Battery–ultracapacitor hybrids for pulsed current loads: a review. RenewableSustainable Energy Rev. 2011, 15:981–992[2]Simon P, Gogotsi Y: Materials for electrochemical capacitors. Nat Mater. 2008, 7:845–854. [3]Karlsson J, Roos A: Angle-resolved optical characterization of an electrochromic device. Sol Energy. 2000,68:493–497.[4] Miller EL, Rocheleau RE: Electrochemical behavior of reactively sputtered iron‐doped nickel oxide. JElectrochem Soc. 1997, 144:3072–3077.

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HIERARCHICALLY STRUCTURED COPPER-COBALT NANOPARTICLE/CNF/ACF CATALYST FORETHANOL CONVERSION

Ekaterina Ponomareva, Lomonosov Moscow University of Fine Chemical TechnologyVernadskogo pr., 86, Moscow, Russia

T: 007-916-542-82-78, katerinaii@inbox.ruIrina Krasnikova, Boreskov Institute of Catalysis, Novosibirsk, Russia

Ilya Mishakov, Boreskov Institute of Catalysis, Novosibirsk, Russia

In last years a grown interest was displayed in the hierarchical structured composites based on CNF- orCNT-modified carbon fibers. The main area of their application is design of reinforced polymer composites[1]. Nevertheless, they can be used as adsorbents [2] or supports for metal catalysts [3]. In this workpossibility of application of hierarchical structured catalyst (Cu-Co/CNF/ACF) for ethanol conversion processhas been shown.Activated carbon cloth (ACF AW1103, KoTHmex, Taiwan) was used as a macroscopic host structure for thecatalyst prepared. For comparison Cu/ACF, Co/ACF and Cu-Co/ACF systems were tested as well. Metalloading in every sample was 5 wt.%. For bimetallic samples the mass ratio was Cu:Co=1:1. The catalystspreparation steps include wetness impregnation of initial fibers with the aqueous solution of copper andcobalt nitrates, calcination in an argon flow for 30 min at 350 °C to convert nitrates to oxides and reduction ofoxides in a flow of hydrogen. Carbon nanofibers (CNF) were synthesized by CCVD technique at 600 °C withethylene used as a carbon source. CNF yield of around 6% was obtained within 2 min. The catalysts werecharacterized by SEM (fig.1) and XRD. The ethanol conversion experiments were carried out using a conventional quartz flow reactor withintemperature interval 200-400 °C at atmosphere pressure. 0,5 ml of a catalyst sample was used in every test.Liquid flow rate of ethanol was 32 h-1. Received products were analyzed by gas chromatography.

XRD spectra of Cu/ACF catalyst showed that the sample contained Cu2O, while bicomponent catalysts havecopper and cobalt in their pure metallic phase. Ethanol conversion test showed that Co/ACF catalyst was not active in the process at temperature below300 °C (fig. 2). In the presence of Cu/ACF ethanol dehydrogenated into acetaldehyde within the wholetemperature range studied. Acetaldehyde and hydrogen also were predominant products under the Cocontaining catalysts. However, many by-products were observed when the temperature was above 275 °C:C4 – compounds, CO and CH4, produced by sequential acetaldehyde conversion reactions; ethylene andCO2 revealed occurrence of ethanol dehydration and vapor conversion reactions respectively. Nevertheless,it should be noted that activity of the hierarchical structured catalyst, which contains 2,5 wt.% of copper, wasas high as that in the presence of 5 Cu/ACF till cobalt starts taking part into the ethanol conversion reactions.

[1] Qian H., Greenhalgh E., Shaffer M., Bismarck A. // J. Mater. Chem., 2010, 20, 4751-4762.[2] Singh S., Singh A., Bais V., Prakash B., Verma N. // Mater. Sci. Eng, 2014, 38, 46–54[3] Holmen A., Venvik H., Mystad R., Zhu J., Chen D. // Catal. Today, 2013, 216, 150-157.

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Figure 1. SEM images of Cu-Co/ACF (left) and Cu-Co/CNF/ACF(right) catalysts

Figure 2. Activity of the catalysts in ethanol conversion process

INDIUM-ZINC NANO OXIDE THIN FILM TRANSISTOR FABRICATED BY UV ASSISTED SPIN CASTING

Won-You Kim, Ju-Song Eom, Shan Fei and Sung-Jin Kim*College of Electrical and Computer Engineering, Chungbuk National University, Cheongju, South Korea

* e-mail of Corresponding Author : cugatech@gmail.com

A much attention of nano oxide semiconductor such as indium zinc nano oxide (IZO) is spotlighted as awide bandgap, high light transmission. That is possible to use as a new material to the back-plane of thedevice characteristics due to the transparent display having a high mobility.

This presentation showed the performance variation of IZO TFT fabricated by UV assisted spin castingtechnique. IZO TFT was produced in top-contact bottom-gate structure; heavily doped n-type silicon waferwas used as the substrate. An indium-zinc oxide TFT produced was measured using a semiconductoranalyzer of the Agilent 4156C to measure the electrical characteristics of the device according to the UVirradiation time in air. The element spin-casting while UV is irradiating for 90 seconds measured the bestresult that is mobility 3.06cm2/vs, threshold voltage 2.97 V, on/off ratio 3.33 x 10^7, and subthreshold swing0.36V/dec.

KeywordsOxide TFT, Spin casting, UV irradiation, IZO

AcknowledgementThis research was supported by the MSIP(Ministry of Science, ICT and Future Planning), Korea, under theITRC(Information Technology Research Center) support program (IITP-2015-R0992-15-1008) supervised bythe IITP(Institute for Information & communications Technology Promotion). This work was also supported bythe Human Resources Development of the Korea Institute of Energy Technology Evaluation and Planning(KETEP) grant funded by the Korea government Ministry of Trade, industry & Energy (No.20144030200450).

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IN-SITU MWNTS / NiCo HYDROXIDE BASED NANO-HYBRIDS FOR SUPERCAPACITORS

Ouanassa Guellati 1,2,4*, Aicha Harat 1, Damilola Momodu 3, Julien Dangbegnon 3, Ncholu Manyala 3,Dominique Begin 4, Izabella Janowska 4, Cuong Pham-Huu 4 and Mohamed Guerioune 1

(1) LEREC Laboratory, Physic Department, Badji Mokhtar University of Annaba, BP. 12, Annaba 23000, Algeria

(2) Mohamed Chérif Messaadia University, BP. 1553, Souk-Ahras 41000, Algeria(3) Department of Physics, Institute of Applied Materials, SARChI Chair in Carbon Technology and Materials,

University of Pretoria, Pretoria 0028, South Africa.(4) ICPEES Institute, ECPM - CNRS, UdS, 25 rue Becquerel, 67087 Strasbourg, France.

(*)guellati23@yahoo.fr

Nanohybrid materials based on nanoporous carbon materials such as MWNTs and Ni-Co based metalhydroxides have attracted much attention as a promising heterostucture for mostly energy storage and sen-sing application.

In this investigation, we focalize on the in-situ synthesis of MWNTs and Ni(OH)2/Co(OH)2 hydroxideswith hydrothermal method in hybrid nano-heterostructures to be used on nickel foam as working electrode forsupercapacitors. The morphologic and the structural selectivity of the as-prepared materials wereinvestigated using XRD, FESEM, HRTEM, BET and Raman spectroscopy. Moreover, the electrochemicalperformances were measured using three electrode configurations by cyclic voltammetry (CV),electrochemical impedance spectroscopy (EIS) and chronopotentiometry (CP).

Keywords: Nanohybrid materials, MWNTs, ferrite nanostructures, NiCo hydroxides, supercapacitors,electrochemical double layer capacitors EDLC, pseudocapacitance.

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NANO TIOX/TIO2 BASED RESISTIVE SWITCHING MEMORY WITH RAPID THERMAL ANNEALING

Ju-Song Eom, Won-you Kim, Shan Fei and Sung-Jin Kim*

Chungbuk National University, Gaesin-dong, Heungdeok-gu Cheongju, Chungbuk 361-763, South Korea*E-mail address (corresponding author): cugatech@gmail.com

ReRAM (Resistive Random Access Memory) is a highly promising candidate for next generation non-volatilememory because it has simple MIM(Metal-Insulator-Metal) structure and low power consumption, highspeed, nondestructive write/read operation and low-power consumption compared to Si-based nonvolatilememory.

In this presentation, we report on resistive switching behaviour in a memristor device composed of a bilayernano TiOx/TiO2 fabricated with atomic layer deposition based on key process parameters, such as the rapidthermal annealing temperature. The oxygen-deficient TiOx active layer annealed at 600°C acted as a trap forelectrons and contributed to the resistive switching. The proposed ultra-thin memristor exhibited nonvolatilememory characteristics, such as write-erase-read operation and repeatable hysteresis loops in I-V curves.

AcknowledgementThis research was supported by the MSIP(Ministry of Science, ICT and Future Planning), Korea, under theITRC(Information Technology Research Center) support program (IITP-2015-R0992-15-1008) supervised bythe IITP(Institute for Information & communications Technology Promotion). This work was also supported bythe Human Resources Development of the Korea Institute of Energy Technology Evaluation and Planning(KETEP) grant funded by the Korea government Ministry of Trade, industry & Energy (No.20144030200450).

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NANOHYBRID ELECTROACTIVE MATERIALS BASED ON IRON OXIDE NANOSTRUCTURES ANDCARBON SOURCE FOR ENERGY STORAGE

M. Boufas 1, O. Guellati 1,2*, A. Harat 1, D. Momodu 3, J. Dangbegnon 3, N. Manyala 3 and M. Guerioune1

(1) LEREC Laboratory, Physic Department, Badji-Mokhtar University of Annaba, BP. 12, 23000, Algeria(2) Mohamed Chérif Messaadia University of Souk-Ahras, BP. 1553, 41000, Algeria

(3) Department of Physics, Institute of Applied Materials, SARChI Chair in Carbon Technology and Materials,University of Pretoria, Pretoria 0028, South Africa.

(*)guellati23@yahoo.fr

Electrochemical supercapacitors and ultracapacitors [1] have attracted considerable attention inenergy storage due to their characteristics [2].

Our aim in this investigation is to prepare a nanohybrid electroactive materials based on both ironoxide (FexOy) nanostructure obtained by hydrothermal method at different conditions and carbon source ascarbon nanotubes and activated carbon with two different specific area. The quantitatively and qualitativelyanalysis of these nanohybrid materials were carried out using X-Rays Diffraction (XRD), RamanSpectroscopy, FESEM and HRTEM microscopy.

The electrochemical performance of these nanohybrids was determined with Cyclic Voltametry andelectrochemical impedance spectroscopy (EIS) using “FexOy/Carbon” deposited electroactive materials onnickel foams. We study the effect of carbon source porosity and nature on the capacitance performance in 6M KOH electrolyte.

Key words: Nanohybrids, electroactive materials, iron oxide nanostructures, electrochemical properties,supercapacitors, energy storage

[1] P. Lorkit, M. Panapoy, B. Ksapabutr, Energy Procedia 56 (2014) 466 - 473[2] Y. Li, L. Kang, G. Bai, P. Li, J. Deng; X. Liu, Y. Yang, F. Gao, W. Liang, Electrochimica Acta 134 (2014) 67-75.

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NITROGEN-DOPED GRAPHENE-BASED ELECTRODE MATERIALS FOR ELECTRIC DOUBLE LAYERCAPACITORS

Hee-Chang Youn, Yonsei UniversityShinchon-dong, Seodaemun-gu, Seoul, KoreaT: 82-2-365-7745, ppopssong@yonsei.ac.kr

Kwang-Bum Kim, Yonsei University

Graphene has garnered tremendous research attention in the fields of sensors, energy storage, and energyconversion devices owing to the unique physical and chemical properties associated with its single-atomic-layered sp2 carbon network.[1] In particular, considerable research in the field of energy storage devices hasfocused on graphene as an electrode material for EDLCs because of its beneficial characteristics: superiorhigh surface area and electrical conductivity.[2, 3] However, most of graphene-based electrode materialsreported in the literature showed relatively low specific capacitance compared to the theoretical value (ca.550 F/g) of a single layer graphene supported by an intrinsic EDL capacitance of 21 μF/cm and a specificsurface area of 2650 m2/g.[2, 4] As an electrode material for EDLCs, reduced graphene oxide (denoted asRGO) prepared by exfoliation and reduction of graphene oxide is extensively investigated due to itsadvantages of bulk-scale productivity and versatility in chemical functionalization.[5] However, oxidationtreatment of graphite involved in the preparation of graphite oxide (denoted as GO) induces a variety ofdefects and oxygen functional groups, which break up the π-conjugated electronic structure of graphene andthereby degrade the electrical conductivity. The thermal/chemical reduction processes employed to reduceGO to RGO cannot completely restore this π-conjugated structure. Furthermore, the RGO sheet tends toagglomerate due to strong π-π interaction between them during the reduction process, and thereby loses thespecific surface area. Therefore, key issues in preparing RGO as an electrode material for EDLCs are anefficient exfoliation for high specific surface area and an extended recovery of the π-conjugated structure ofRGO for high electrical conductivity.The heteroatom doping is another consideration for improving the electrochemical properties by manipulatinglocal electronic structure of the RGO and hence increase in the EDL capacitance and electronic conductivity.[6] Since the quantum capacitance of RGO is thought to be in series with its EDL capacitance, the specificcapacitance of RGO, which is the equivalent capacitance for the two capacitances in series, is expected toincrease with an increase of the quantum capacitance. A nanoscale EDL is between a carbonaceous activematerial and an electrolytic solution and contribute to the specific capacitance of RGO, therefore, care shouldbe taken not to decrease the specific surface area of RGO during heteroatom doping.[7]In this study, a nitrogen-doped RGO (denoted as N-RGO) with high specific surface area, electricalconductivity and low oxygen contents was synthesized using a time-efficient and scalable process composedof microwave irradiation and heat-treatment under NH3 gas. The near-edge X-ray absorption fine structure(NEXAFS) spectroscopy was employed to investigate the sequential recovery of the π-conjugated structurewith removal of oxygen functional groups as well as the chemical bonding environments of incorporatednitrogen atoms in N-RGO. More detailed on the synthetic procedure, morphology, electrochemical andstructural properties of encapsulated selenium in graphene micro-ball hybrid materials will be discussed atthe meeting..

[1] K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grigorieva, A. A.Firsov. Science, 306 (2004) 666[2] M. D. Stoller, S. Park, Y. Zhu, J. An, R. S. Ruoff. Nano Letters., 8 (2008) 3498[3] X. Huang, Z. Zeng, Z. Fan, J. Liu, H. Zhang. Advanced Materials, 24 (2012) 5979[4] J. Xia, F. Chen, J. Li, N. Tao. Nature Nanotechnology, 4 (2009) 505[5] M. Choucair, P. Thordarson, J. A. Stride. Nature Nanotechnology 4 (2009) 30[6] L. L. Zhang, X. Zhao, H. Ji, M. D. Stoller, L. Lai, S. Murali, S. McDonnell, B. Cleveger, R. M. Wallace, R.S. Ruoff. Energy & Environmental Science, 5 (2012) 9618.[7] Y. Qiu, X. Zhang, S. Yang. Physical Chemistry Chemical Physics, 13 (2011) 12554

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REDUCED GRAPHENE OXIDE: SYNTHESIS, DISPERSION AND THIN FILM ELECTRODES FORORGANIC PHOTOVOLTAICS

Sandra Víctor-Román, Instituto de Carboquímica ICB-CSICC/Miguel Luesma Castán 4, E-50018 Zaragoza, Spain

T: +34 976 73 39 77, svictor@icb.csic.esOlga Sanahuja, Instituto de Carboquímica

Yegraf Reyna, Institut Catalá de Nanociència y Nanotecnologia ICN-CSICAlba Mingorance, Institut Catalá de Nanociència y Nanotecnologia ICN-CSIC

Mónica Lira Cantú, Institut Catalá de Nanociència y Nanotecnologia ICN-CSICAna M. Benito, Instituto de Carboquímica ICB-CSIC

Wolfgang K. Maser, Instituto de Carobquímica ICB-CSIC

Graphene oxide, with its ease of synthesis and possibilities for functionalization, reduction, tailoringelectronic properties coupled to favorable thin film processing strategies, has attracted increased interest inthe field organic photovoltaics. It has been used as transparent electrode layer1,2, active layer3, electron4 andhole5 transporter layer, and interfacial layer6, contributing to enhanced performance or organic solar cells.Operational functionality critically depends on the parent graphene oxide, the applied reduction processesand functionalization strategies, dispersions, and thin film processing techniques.Here we present a first study on the preparation of graphene oxide with different degrees of reduction, theelaboration of corresponding dispersions and their processing into the films for obtaining solar cells.Reflux processing using a broad set of reducing agents was employed. Thin films were prepared usingautomatic spray and spin coating techniques. Dispersion, thin films and solar cell were characterized by UV-Vis spectroscopy, zeta potential, optical microscopy, and conductivity.

[1] Z.Y. Yin, S.Y. Sun, T. Salim, S.X. Wu, X.A. Huang, Q.Y. He, Y.M. Lam, H.Zhang, ACS Nano 4 (2010) 5263[2] Z. Yin, S. Wu, x. Zhou, X. Huang, Z. Zhang, F. Boey, H. Zhang, Small 6 (2010), 307[3] Z. Liu, Q. Liu, Y. Huang, Y. Ma, S. Yin, X. Zhang, W. Sun, Y. Chen, Adv. Mater 20, (2008) 3924[4] D.H. Wang, J.K. Kim, J.H. Seo, I. Park, B.H. Hong, J.H. Park, A.J. Heeger, Agew. Chem. Int. Ed. 52 (2013) 2874[5] J. Kim, V.C. Tung, J. Huang, Adv. Energy Mater. 1 (2011) 1052[6] V.C. Tung, J. Kim, L.J. Cote, J.X. Huang, JACS 133 (2011) 9262

Acknowledgement: Funding by Spanish Ministry MINECO and European Regional Development Fund (Project ENE2013-48816-C5-5-R, and PhD Grant BES-2014-068727), and the Government of Aragon and the European Social Fund (ProjectDGA-ESF-T66).

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Figure 4 – Solar cell with inverted configuration andgraphene oxide with different degrees of reduction

SPATIALLY-CONFINED HYBRIDIZATION OF NANOSIZED NIFE HYDROXIDES INTO NITROGEN-DOPED GRAPHENE FRAMEWORKS TOWARDS SUPERIOR OXYGEN EVOLUTION REACTIVITY

Cheng Tang, Han-Sen Wang, Hao-Fan Wang, Qiang Zhang*, Gui-Li Tian, Jing-Qi Nie, & Fei WeiBeijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical

Engineering, Tsinghua University, Beijing 100084, PR China. E-mail: zhang-qiang@mails.tsinghua.edu.cn (Q. Zhang)

Oxygen evolution reaction (OER) catalysis constitutes the bottleneck of water splitting for a sustainablehydrogen economy, and more importantly, is coupled with various renewable energy systems such as solarcells, metal-air batteries, and fuel cells. Emerged as a family of outstanding alternatives, transition metaloxides and their derivatives (Ni, Co, Fe, Mn, et al.) have attracted great attention recently, which iscontributed from their remarkable catalytic activity, high stability, earth-abundant and environmental benigncharacters. In this work, a novel composite based on NiFe LDH and graphene was scrupulously designed and facilelyfabricated herein towards high-performance oxygen evolution electrocatalysis. As illustrated in Figure 1a,nitrogen-doped graphene framework (NGF) is employed as a mesoporous substrate for the in-situ growthand decoration of nanosized NiFe LDH (nNiFe LDH). The nitrogen dopant and topology-induced defects ofgraphene contributed to the adsorption and anchor of metal cations and then the in-plane mesopores servedas nano-reactors for spatially-confined nucleation and growth of nNiFe LDH (Figure 1b). Attributed from theunique structure features and synergetic effect, nNiFe LDH/NGF was demonstrated as a high-performanceOER catalyst (Figure 1c), with a remarkably low Tafel slope (~45 mV dec-1), a substantially decreasedoverpotential (~337 mV required for 10 mA cm-2) and enhanced durability. The topology-assisted design andfabrication strategy opens up new avenues and sheds light on a novel branch of advanced nano-architectured materials, thereby facilitating the wise hybridization of excellent components towards specificapplications.

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Figure 5 – Morphology and oxygen revolution electrocatalysis performance of as-fabricated catalysts. a) Schematic of the spatially-confined hybrids. b) Cross-sectional TEM image of a sheet of hybrid catalysts. c) LSVcurves of different samples in 0.1 M KOH electrolyte. Scan rate was 5 mV s-1. The loading was about 0.25 mg cm-2 for all samples.

STICKY RICE GRAPHENE: CARBONIZATION OF TERNARY SLURRY AND APPLICATION ASSUPERIOR BIFUNCTIONAL OXYGEN ELECTROCATALYST

Cheng Tang, Hao-Fan Wang, Bo-Quan Li, Qiang Zhang*, Fei WeiBeijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical

Engineering, Tsinghua University, Beijing 100084, PR China. E-mail: zhang-qiang@mails.tsinghua.edu.cn (Q. Zhang)

Oxygen electrochemistry, including oxygen reduction reaction (ORR) and oxygen evolution reaction (OER),constitutes the bottleneck of next-generation energy storage technologies such as rechargeable metal-airbatteries and regenerative fuel cells. However, these heterogeneous multi-electron process significantlysuffer from a sluggish kinetic and a high overpotential, which calls for high-performance catalysts forcommercial applications and has stimulated intense research interest. Up to date, the precious metal oxidessuch as Pt and IrO2 are identified as the most active catalysts, but only satisfy either ORR or OER,respectively. Additionally, their practical use is prohibited by the low abundance, high cost, and poordurability. Therefore, it is of great concern and emergence to develop highly active and also low-costbifunctional catalysts for both ORR and OER towards practical applications.Heteroatom-doped carbon materials are considered and investigated as the most promising low-costbifunctional oxygen electrocatalysts. The charge delocalization induced by heteroatom incorporation resultsin the non-electroneutrality of catalysts and more active sites for oxygen and intermediate adsorption,thereby facilitating the ORR and OER. Herein, a novel porous nitrogen-doped graphene was facilelyfabricated and demonstrated to exhibit excellent bifunctional activity. Sticky rice/melamine/MgO ternary slurrywas obtained via a one-pot process by mixing the carbon source/nitrogen source/catalytic templateuniformly. After high-temperature carbonization and purification, nitrogen-doped graphene material with ahigh surface area of 1100 m2 g-1, a large pore volume of 2.7 cm3 g-1, and 7.6 at.% nitrogen functionalities wasproduced. The potential gap between the OER potential (required for 10 mA cm -2) and the ORR half-wavepotential is less than 1.0 V, which is comparable to the highly active novel metals and among the best non-metal materials. This work sheds light on the utilization of biomass for advanced and low-cost energymaterials for sustainable next-generation batteries.

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SURFACE PLASMON RESONANCE IN SEMICONDUCTING WS2 NANOTUBES AND MOS2

NANOPARTICLES

L. Yadgarov, B. Visic, R. Rosentsveig, Ron Tenne, R. Levi, A. Polyakov, T. Dolgova, E.A. Goodilin, D. Oronand R. Tenne

Weizmann Institute of Science, Rehovot, IsraelMoscow State University, Moscow, Russia

Localized surface plasmon resonance (LSPR) was discovered in semiconducting WS2/MoS2 nanoparticlesand nanotubes1. The total extinction measurements showed that, in addition to the excitonic and indirectbandgap transition, there is an additional transition at 650-800 nm. This spectral peak has not been reportedpreviously for WS2/MoS2 nanoparticles and nanotubes. Comparison of the total extinction and decoupledabsorption spectrum indicates that this peak largely originates from scattering. Furthermore, the dependenceof this peak on nanoparticle size, shape, surface charge and solvent refractive index, suggest that thistransition arises from a plasmon resonance. In addition to the newly observed LSPR phenomena, it was found that WS 2 nanotubes exhibit strong exciton-plasmon coupling. The interaction between exciton and plasmon is often studied in the limits of weak andstrong coupling. The Förster energy transfer between a donor and acceptor2 is one of the examples for weakcoupling. For those systems the transfer rate from donor to acceptor is smaller than the relaxation rate ofacceptor, thus the back energy transfer to the donor is negligible. The system moves toward the strongcoupling regime once the energy interaction becomes larger and the back transfer to the donor becomespossible3. Under strong coupling regime it is impossible to distinguish between donor and acceptor. Theexcitation becomes delocalized, and the pair must be regarded as one system. Strong exciton-plasmoncoupling is usually studied in hybrid plasmonic nanostructures, where one material carries the exciton andanother one carries the plasmon. Thus, the discovery of that fundamental electromagnetic phenomenonstrong (exciton-plasmon coupling) in individual WS2 nanotube is of the particular interest.

[1] L. Yadgarov, et al.;ACS nano 2014, 8 (4), 3575-3583.; [2] Förster, T.,Ann. Phys. 1948, 437 (1‐2), 55-75.; [3] Novotny, L., Am. J. Phys 2010, 78 (11), 1199-1202.

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THE IMPACT OF SOFT BAKE TEMPERATURE IN NANO OXIDE TFT WITH HIGH MOBILITY

Shan Fei, Won-You Kim, Ju-Song Eom and Sung-Jin KimCollege of Electrical and Computer Engineering, Chungbuk National University, Cheongju, South Korea

KEYWORDS: Oxide transistor, Spin casting, soft baking, IZO

The nano IZO(Indium Zinc Oxide) semiconductor has attracted public attention as a new material formanufacturing transparent Oxide TFT backplane element because it possess the features of wide band gap,excellent light permeability and high mobility. On the basis of soft baking and hard baking, the annealingprocess has been studied separately during the IZO Oxide TFT manufacturing process. Also, the recognitionof IZO TFT performance evaluation has very important impact according to selecting the temperatureparameters and the annealing processes of different model components.Thermal Oxide or Silicon Dioxide (SiO2) is the insulating layer commonly used in semiconductors. So 100nmSiO2 insulator film was formed by thermal oxidation method in our study. The key here is that the indium-zincoxide TFT were made by different soft bake temperature（90 ℃, 120 ℃, 150 ℃, 200 ℃）.The indium-zinc Oxide TFT was measured using a semiconductor analyzer of the Agilent 4156C to measurethe electrical characteristics of the device according to different soft bake temperature. Both of the indium-zinc Oxide TFT with different soft bake temperature have a remarkable performance, though with 120 ℃ softbake on the indium-zinc Oxide TFT's clearly superior. The best result of 120 ℃ soft bake on the indium-zincOxide TFT that is mobility 7.4 cm2/vs, threshold voltage 1.1 V, on/off ratio 2.5 x 108, and subthreshold swing0.42V/dec.

AcknowledgementThis research was supported by the MSIP(Ministry of Science, ICT and Future Planning), Korea, under theITRC(Information Technology Research Center) support program (IITP-2015-R0992-15-1008) supervised bythe IITP(Institute for Information & communications Technology Promotion). This work was also supported bythe Human Resources Development of the Korea Institute of Energy Technology Evaluation and Planning(KETEP) grant funded by the Korea government Ministry of Trade, industry & Energy (No.20144030200450).

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THE SORPTION OF AZO DYE ONTO FUNCTIONALIZED CNTS AND A NATUREL RESIDUE (OLIVESTONES)

A. Nait Merzoug: Laboratoire des Science et Techniques de l’eau et d’environnement, UniversitéMohamed Cherif Messadia de Souk Ahras, BP1553, 41000-Souk-Ahras, ALGERIE.

T: 00 213 7 76 08 24 67, Email address: abenlala@yahoo.frO. Guellati: Laboratoire d’Etude et de Recherche des Etats Condensés (LEREC), Département de Physique,

Université Badji-Mokhtar de Annaba, BP. 12, Annaba 23000, ALGERIA.

A. Benjaballah: Université Mohamed Cherif Messadia de Souk Ahras, BP1553, 41000-Souk-AhrasALGERIE

H. Merazig: Unité de recherche de chimie de l’environnement et moléculaire structurale UniversitéConstantine 1.

D. Bégin: Laboratoire des Matériaux, Surfaces et Procédés pour la Catalyse (LMSPC), ECPM -CNRS, UdS, 25 Rue Becquerel, 67087 Strasbourg, FRANCE.

M. Guerioune: Laboratoire d’Etude et de Recherche des Etats Condensés (LEREC), Départementde Physique, Université Badji-Mokhtar de Annaba, BP. 12, Annaba 23000, ALGERIA.

C. Pham-Huu: Laboratoire des Matériaux, Surfaces et Procédés pour la Catalyse (LMSPC), ECPM- CNRS, UdS, 25 Rue Becquerel, 67087 Strasbourg, FRANCE.

Industrial growth and technological advancement have led globally to the introduction of pollutants of diversenature into water bodies. Such pollutants include dyes, heavy metals and organic contaminants. Theirpresence in industrial effluents or drinking water is a public health problem, due to their absorption andpossible accumulation in living organisms. Water pollution regulations require dye industries to reducesubstantially the amount of color in their effluents. Adsorption, as a wastewater treatment process, exploitsthe ability of some solids to concentrate certain substances from solution onto their surface. The aim of this study is to compare the adsorption of an azo-dye Tartrazine (Sin 102) in aqueous solutionusing functionalized carbon nanotubes and an Algerian naturel residue (olive stones) transformed toactivated carbon. The characterization of both adsorbents was performed by IR spectroscopy, X ray diffraction (XRD) andBET. The study incorporates also the effect of different parameters such us: pH, initial dye concentration,adsorbent weight, contact time and temperature on the adsorption kinetic on the nanostructured support andthe activated carbon from the naturel residue. Consequently, we have found that the kinetic behavior of removal process for this pollutant is better withusing functionalized carbon nanotubes than with the activated carbon. Acidic pH was found the favourdisperse dyes removal.

Key words: Multi-walled carbon nanotubes, Adsorption, Kinetics, Azo dyes, Tartrazine.

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