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2015 Spring

Advanced Materials Synthesis, Processing and Characterization


ANIM 2: Advances and Enhanced Functionalities of Anion-controlled New Inorganic Materials

Anion-controlled functional materials present a wide range of applications due to their basic functionalities. This second edition ANIM 2 aims to cover a large domain from the synthesis to the understanding of the fundamental properties of novel devices based on enhanced properties offered by such inorganic mixed-anions materials. Based on the success of the first edition (E-MRS symposium T, spring 2013), this symposium will focus on the solid state chemistry and physics of such materials with interdisciplinary research and industrial applications, not yet widely known, but with vast application prospects.




The present E-MRS symposium aims creating a European forum for the different types of researchers necessary for this field (physicists – experimentalists and theoreticians, materials scientists, solid state chemists, analytical scientists and device design engineers). The symposium will facilitate interdisciplinary discussions between these differing “core groups”, thereby stimulating collaboration and thus it will strengthen the European and Worldwide activities in this expanding field.

The symposium’s main topics cover the following aspects:

  1. Theoretical fundamentals: theoretical concepts for novel physics expected to be derived from new functions and properties of coordinate covalent-bonding engineered ceramic material systems, epitaxial and polycrystalline thin films, glasses, single crystals, quantum size effects in nanoparticles and nanosized powders.
  2. Advances in synthesis that have enabled the development of N-containing materials using less toxic methods.
  3. Surveying the anion-substituted materials landscape: combined experimental and theoretical prediction investigations of various classes of materials systems, searches for new perovskite and related materials with a view to expand and optimize their functionalities and electronic properties (e.g. ferroelectric, ferromagnetic, semiconductive, thermoelectric, electroresistive, magnetoresistive, conductive transparent high temperature stable electrodes, solid state electrolytes, ionic conductors, photocatalytic, luminescent materials, nonlinear optical materials, dipole glasses, quasi-2-dimensional electron gases (Q2-DEG) in insulating hetero-interfaces).
  4. Overviewing of anion-substituted inorganic materials in device development activities: state-of the-art characterization and electronic properties improvement based on heterostructures, interface phenomena, electrode interactions and various device prototypes demonstrations.


Hot topics to be covered by the symposium:


  1. Innovative synthesis routes for Anion-substituted New Inorganic Materials (ANIM) oxynitrides, oxyfluorides, oxyhydrides and other mixed anion materials (powders, nanomaterials, bulk ceramics, glasses, thin films and single crystals).
  2. Structural features and anion order of ANIM.
  3. ANIM-based (photo)catalyst materials.
  4. Optical properties: luminescence, nonlinear optical properties of ANIM materials.
  5. Feromagnetic, paramagnetic; paraelectric, high-K gate, ferroelectric, multifferoic properties of ANIM materials. ANIM-type semiconducting and highly conducting electrode materials.
  6. ANIM-based energy materials for production and storage of energy: solid electrolytes, fuel cell materials electrode materials, supercapacitor materials, battery materials, hydrogen storage materials, ionic conductor and thermoelectric materials.
  7. Theory, simulations and combinatorial approaches for design of new anion-controlled materials and prediction of their functionalities.
  8. Technical challenges in the analytical and functional properties characterization of ANIM materials


List of invited speakers:


  • Alain Demourgues, ICMCB, Bordeaux, France
  • Amparo Fuertes, ICMAB, Barcelona, Spain
  • Shiv Halasyanami, University of Houston, Houston, USA
  • Mike Hayward, University of Oxford, UK
  • Hiroshi Kageyama, Kyoto University, Japan
  • Ivoyl P. Koutsaroff, Murata Manufacturing Co., Ltd., Shiga, Japan
  • Philip Lightfoot, University of St Andrews, UK
  • Ru-Shi Liu, NTU, Taiwan
  • Ram Seshadri, University of California, Santa Barbara, USA
  • Anke Weidenkaff, University of Stuttgart, Germany


List of invited speakers:


  • Duncan Gregory, University of Glasgow, UK
  • Takashi Hisatomi, The University of Tokyo, Japan
  • Stéphane Jobic, IMN, Nantes, France
  • Laurent Le Gendre, IETR, St Brieuc, France
  • Thomas Lippert, Paul Scherrer Institut (PSI), Würenlingen, Switzerland
  • Emma McCabe University of Kent, Canterbury, UK
  • Yuji Masubuchi, Hokkaido University, Sapporo, Japan
  • Alain Tressaud, ICMCB, Bordeaux, France




High quality manuscripts will be published in a special issue of Solid State Sciences (Elsevier)


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Authors : V. Chornii(1), S. Nedilko(1), M. Slobodyanik(1), M. Miroshnichenko(1,2), K. Terebilenko(1), V. Boyko(3), O. Gomenyuk(4), V. Sheludko (4)
Affiliations : (1) Taras Shevchenko National University of Kyiv, 01601, Kyiv, Ukraine; (2) University of Angers, 49000 Angers, France; (3) National University of Life and Environmental Sciences of Ukraine, 03041 Kyiv, Ukraine; (4) Oleksandr Dovzhenko Hlukhiv National Pedagogical University, 41400, Glukhiv, Ukraine

Resume : Zirconia has good optical, electrical, mechanical and thermal properties as one that belong to oxide materials family. From practical viewpoint the ZrO2 crystals are interesting for elaboration of luminophores, biocompatible fluorescence markers, oxygen sensors etc. Obviously, intensive luminescence of ZrO2 is highly desirable for the mentioned applications. Doping with RE ions improves characteristics of zirconia however high concentration of dopants cannot be reached for good quality crystals. At the same time anion substitution also can improve optical and other properties of materials. In this work, a set of solid solutions based on ZrO2 with europium and fluorine are investigated by luminescence spectroscopy. The ZrO2:F and ZrO2:F,Eu samples have been synthesized by solid state technique. The XRD patterns have shown the presence of monoclinic and cubic phases in all samples. The increase of fluorine content enriches in cubic phase. The SEM images indicate the spherical morphology of samples with the size of grains 50-200 nm. Undoped ZrO2:F reveals complex PL band in the 380 - 600 nm spectral range at low temperature (T = 4.2 K) and under excitation in UV region. Samples of the ZrO2:F,Eu reveal both host and rare-earth ion emission. Increasing of the Eu luminescence intensity was observed with increasing of fluorine content. The luminescence properties are discussed in a light of electronic band structure calculations performed for ZrO2:F and ZrO2:F,Eu crystals.

Authors : Maria Batuk 1, Artem Abakumov 1,2, Joke Hadermann 1
Affiliations : 1 Electron Microscopy for Materials Research (EMAT), University of Antwerp, Antwerp, Belgium, 2 Department of Inorganic Chemistry, Moscow State University, Moscow, Russia

Resume : Combining electrical and magnetic properties is highly desired in the field of multiferroics. For example, attempts were made to add magnetic dn cations to ferroelectric Aurivillius phases, which unfortunately gives spin glasses. We have investigated an alternative parent compound hematophanite, a combination of perovskite slabs and halide layers, and have succesfully made a homologous series An+1BnO3n-1Cl based on it. We characterized the compounds using NPD and atomic resolution TEM. All compounds are G-type antiferromagnetic, and their Neel temperature is independent of the thickness of the perovskite blocks. An interesting feature is their layered order at the B cation positions. This is extremely rare in perovskites when not coupled with simultaneous order of the oxygen atoms and vacancies. There is also Ti in square pyramidal coordination, which exists in only very few compounds. Following our observation of PbBiO2 defects in higher members of the series, we also designed and succesfully synthesized single phases of a second new homologous series [PbBiO2]An+1BnO3n-1Cl2 that combines An+1BnO3n-1 perovskite and -PbO type [A2O2] blocks and halide layers. While the hematophanite has one magnetic slab per unit cell, the second series has two, in a body centered arrangement that cancels exchange interactions. The two new homologous series leave a lot of room for experimenting with further adaptations. A.A. is grateful to RSF for financial support (grant 14-13-00680)

Authors : S. Jacq, L. Le Gendre, C. Le Paven, R. Benzerga, F. Tessier, F. Cheviré, A. Sharaiha
Affiliations : S. Jacq; L. Le Gendre; C. Le Paven; R. Benzerga; A. Sharaiha : Institut d’Electronique et de Télécommunications de Rennes (IETR), Equipe Matériaux Fonctionnels, IUT Saint-Brieuc, Université de Rennes 1, 22000 Saint Brieuc, France. F. Tessier; F. Cheviré : Institut des Sciences Chimiques de Rennes (ISCR), Equipe Verres et Céramiques, Université de Rennes 1, 35000 Rennes, France.

Resume : This contribution presents the synthesis of perovskite compounds as oxide and oxynitride thin films. The (Sr0.99La0.01)2(Ta0.99Ti0.01)2O7 oxide composition has been chosen to achieve a ferroelectric Curie temperature close to 300 K. Its nitridation results in the (Sr0.99La0.01)(Ta0.99Ti0.01)O2N oxynitride composition. Depositions are made by RF magnetron sputtering, with both O2 and N2 in the reactive part of the plasma. The deposition discharge content is studied by optical emission spectroscopy and is correlated with both the deposition rate and the films structure. Dielectric properties are also measured to evaluate the potential for integrating these materials into agile and/or miniaturized antennas. Without dinitrogen in the discharge, oxide thin films are epitaxially grown on single-crystalline MgO (001) substrate, with a band-gap value close to 4.5 eV in good accordance with literature values reported for Sr2Ta2O7. Introducing dinitrogen into the plasma leads to a decrease in the films crystalline quality and the oxynitride contribution becomes predominant. The film deposited under a dinitrogen/argon mixture (i.e. without dioxygen) exhibits a pure oxynitride structure with a strong (00l) preferred orientation and a band-gap of 2.45 eV, close to the SrTaO2N bulk value. Further results on plasma, structure and dielectric characterizations will be discussed in the final contribution.

Authors : Olesia Karakulina1, Artem Abakumov1, Vasily Sumanov2, Oleg Drozhzhin3, Joke Hadermann1
Affiliations : 1 Electron Microscopy for Materials Research (EMAT), University of Antwerp, Antwerp, Belgium, 2 Department of Inorganic Chemistry, Moscow State University, Moscow, Russia 3 Department of Electrochemistry, Moscow State University, Moscow, Russia

Resume : Electron diffraction tomography (EDT) based on taking electron diffraction patterns of crystals out of zone axis is used for the ab initio structure determination of a single nm-sized crystals, potentially allowing detection of the light elements, such as Li. Due to low electron dose this technique is appropriate for the study of Li- or Na-based battery materials which are inaccessible with other electron microscopy techniques. Furthermore, only a small amount of sample is needed for such experiment, which is an important advantage for studying charged cathodes. The structure solution of LiFePO4 was performed from EDT data using PETS software (Palatinus, 2011) demonstrating a quality comparable to that for powder X-ray diffraction. By the use of difference Fourier maps the position of the Li atoms was determined. The refinement revealed the atomic coordinates were in a good agreement with the literature data and the values of the bond valence sums correspond to nominal cation and anion valences. Ex-situ experiments were performed on pristine and charged (4.3V) LiFe0.5Mn0.5PO4. The presence of Li atoms in the latter was not revealed, which is consistent with the full delithiation process. A clear difference in the unit cell parameters between the pristine and charged samples has been detected. These examples demonstrate that EDT is a reliable method of structure determination for cathode materials from submicron-sized crystallites.

Authors : Baptiste Polteau a), Franck Tessier a), François Cheviré a), Stéphane Jobic b), Laurent Cario b), Fabrice Odobel c)
Affiliations : a) Institut des Sciences Chimiques de Rennes, Université de Rennes 1, France; b) Institut des Matériaux Jean Rouxel, Université de Nantes, France; c) CEISAM, Université de Nantes, France

Resume : Over the last decade, p-type semiconductors (SC) have known a renewed interest. Indeed these materials may have potential applications for light-emitting diodes, transistors, solar cells, etc. Since the achievement of the first Dye Sensitized Solar Cells by Grätzel [1] in 1991 a new generation of solar cells has been developed [2] where the n-type SC is replaced by a p-type one. This leads to the photo-injection of holes instead of electrons in the circuit. To date nickel oxide (NiO) is the reference p-type semiconductor. However yields are still far from those of DSSC-n and many studies aim to replace NiO by other systems such as CuAlO2, CuGaO2, CuCrO2 or NiCo2O4 nanoparticles. Following our recent synthesis of N doped ZnO with stabilization of p-type charge carriers [3], we focus now on the preparation of N doped NiO nanoparticles to improve the p-type conductivity of NiO. We will study here the chemical reactivity of a nickel oxohydroxo precursor under air and ammonia that conducts to nanostructured Ni-poor NiO. References: 1. B. O'Regan, M. Grätzel, Nature 353, 737-740 (1991). 2. F. Odobel, L. Le Pleux, Y. Pellegrin, E. Blart, Acc. Chem. Res., 43, 1063−1071, (2010). 3. B. Chavillon, L. Cario, A. Renaud, F. Tessier, F. Cheviré, M. Boujtita, Y. Pellegrin, E. Blart, A. Smeigh, L. Hammarström, F. Odobel, S. Jobic, J. Am. Chem. Soc. 134, 464-470 (2012).

Authors : Arnaud Valour a), François Cheviré a), Franck Tessier a), Fabien Grasset b), Stéphane Jobic c), Laurent Cario c), Eric Faulques c), Tengfei Jiang c)
Affiliations : a) Institut des Sciences Chimiques de Rennes (UMR CNRS 6226) – Université de Rennes 1 – Rennes, France b) Laboratory for Innovative Key Materials and Structures – National Institute of Material Science (UMI 3629 CNRS/Saint Gobain) – Tsukuba, Japon c) Institut des Matériaux Jean Rouxel (UMR CNRS 6502) – Université de Nantes – Nantes, France

Resume : Zinc oxide is a material of great interest exhibiting pigmental, photocatalytic, piezoelectric, antibacterial, or varistor properties that have already been developed in many different fields of industry. Still novel applications emerge in various domains but they often require the preliminary stabilization of a p-type ZnO counterpart to the natural n-type ZnO to be stimulated. In optoelectronics for instance, the high optical transparency of ZnO thin films coupled with their high electrical conductivity and their strong room temperature luminescence could indeed open up the door to revolutionary technologies as transparent electrodes in solar cells and flat panel displays, light emitting diodes, lasers, etc. We have previously reported the stabilization of p-type nitrogen doped Zn1 xO nanoparticles (ZnO:N) obtained through the decomposition of zinc peroxide (ZnO2) at low temperature under ammonia flow [1]. Our objective is now to extend these results to the realization of p-type ZnO thin films by colloidal route in order to achieve n-ZnO/p-ZnO:N homojonctions which would led to various applications in optoelectronics. The aim of the present work is to prepare nitrogen doped Zn1-xO thin film by thermal decomposition of ZnO2 films obtained by chemical conversion of ZnO colloidal thin films. [1] B. Chavillon, L. Cario, A. Renaud, F. Tessier, F. Cheviré, M. Boujtita, Y. Pellegrin, E. Blart, A. Smeigh, L. Hammarström, F. Odobel, S. Jobic, J. Amer. Chem. Soc. 134, 464-470 (2012)

Authors : M. Bouzidi*, Z. Benzarti, I. Halidou, S. Soltani, Z. Chine, B. El Jani
Affiliations : Université de Monastir, Faculté des Sciences Unité de recherche sur les Hétéro-Epitaxies et Applications (URHEA), 5000 Monastir, Tunisia.

Resume : Electrical and optical properties of several GaN films with a thickness range varying from 0.1 to 5µm grown on silicon nitride (SiN)-treated c-plane sapphire substrates by atmospheric pressure metalorganic vapor phase epitaxy (MOVPE) are investigated. The samples were characterized by room temperature Van der Pauw–Hall electrical transport, low temperature (13 K) photoluminescence (PL) and photoreflectance (PR) measurements. In contrast to the PL where only heavy-hole free excitons (FXA) transition show strong response, light-hole (FXB) and crystal field splitting hole (FXB) free exciton transitions can be well resolved in the PR spectra. Combining PR spectra and Hall effect measurements a strong correlation between electron concentration and excitons linewidth is observed. We show that the linewidth of FXA, FXB and FXC transition have not the same sensitivity to the carrier concentration. Keywords: (SiN)-treated sapphire, MOCVD, photoluminescence, Photoreflectance, Free exciton.

Authors : Franck Tessier, Erwan Ray, François Cheviré, Vincent Lecocq
Affiliations : Institut des Sciences Chimiques de Rennes (UMR CNRS 6226), équipe Verres et Céramiques, Université de Rennes 1, F-35042 Rennes cedex, France; 1 Institut Français du Pétrole - Energies Nouvelles (IFPEN), F-69360 Solaize, France

Resume : Phosphates, especially aluminophosphate oxynitrides (AlPOxNy), are known to present attractive properties for basic catalysis. The nitrogen (N3-) / oxygen (O2-) substitution has been reported within X-rays amorphous metallophosphates (Al-P-O, Ga-P-O, Al-Ga-P-O, Zr-P-O, In-P-O, Ti-P-O) by thermal reaction under ammonia flow. The resulting metallophosphate oxynitride powders maintain the high specific surface area of the precursor making them interesting catalysts, and moreover, the incorporation of nitrogen in the anionic network is an effective way to modify the surface acid-base properties. In collaboration with the Institut Français du Pétrole-Energies Nouvelles (IFPEN), we study the interest of such phases, as heterogeneous catalysts, in the transesterification reaction of vegetable oils.

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Oxynitride materials 2 : Shinichi Kikkawa
Authors : Anke Weidenkaff and Marc Widenmeyer
Affiliations : Materials Chemistry, Institute for Materials Science, University of Stuttgart, Heisenbergstr. 3, DE-70569 Stuttgart; Germany

Resume : Perovskite-type oxynitrides are among the most prospective candidates for future highly efficient solar thermoelectric1 and photocatalytic2, 3 converters as well as for memristor3, luminescent4 and dielectric applications5. Semiconductors based on perovskite-type oxynitrides show substantial potential for solar energy conversion processes, due to their suitable band structure and strongly correlated electronic systems. They can capture a large portion of the solar spectrum, be catalytically highly active due to their regenerative properties and can store light as luminescent pigments. The broad application of these materials in future energy technologies requires the development of new active, stable, low cost and sustainable compositions and structures. Improved materials are being developed and tested in respective applications following theoretical predictions and concepts. Advanced analytical tools are applied to unravel the structure-property relationships providing a rational materials design. The lecture will provide a summary on the field of advanced perovskite-type oxynitride synthesis, processing and characterisation methods gaining importance for future energy applications. References 1. Sagarna,L., Rushchanskii, K. Z. , Maegli,A., Yoon, S. Populoh,S., Shkabko,A., Pokrant, S. LeZaic, M., Waser,R. and Weidenkaff, A., Structure and thermoelectric properties of EuTi(O,N)3 , J. Appl. Phys. 114, (2013) 033701. 2. Maegli, A. E., Hisatomi, T., Otal, E. H., Yoon, S.

Authors : Stefan G. Ebbinghaus, Florian Oehler
Affiliations : Martin Luther University Halle-Wittenberg Institute of Chemistry Kurt-Mothes-Str. 2 06120 Halle/Saale Germany

Resume : Perovskite oxynitrides ABO3-xNx containing transition elements with d0 configuration often are intensively colored, giving rise to a number of potential applications e.g. as pigments or photocatalysts. In addition, unusual electric and dielectric properties have been observed for such oxynitrides. We report on soft-chemistry synthesis techniques resulting in nano-sized oxynitrides of very high crystallinity and with large specific surface areas. Structure and optical properties of the samples have been examined using XRD, TEM, SEM and UV-Vis spectroscopy. The photocatalytic activities in different test reactions like the solution-based decomposition of organic dyes and the gas-phase oxidation of small organic molecule have been investigated and the effects of co-catalysts have been systematically studied. As a second topic, we describe facile approaches to obtain dense oxynitride ceramics and we report on their (di-) electric properties.

2015 International year of light and light-based technologies (2) : J. Paul Attfield
Authors : Ru-Shi Liu (a), Shu-Fen Hu (b)
Affiliations : (a) Department of Chemistry, National Taiwan University, Taipei, Taiwan (b) Department of Physics, National Taiwan Normal University, Taipei, Taiwan

Resume : We successfully control luminescence of phosphors such as M2Si5N8:Eu (M = Ca, Sr, Ba) and Ca12Al14O32F2:Eu with anion- and lattice strain- controlled effects. we show that size-mismatch between host (cations and anions) and dopant cations tunes photoluminescence shifts systematically in M1.95Eu0.05Si5−xAlxN8−xOx lattices, leading to a red shift when the M = Ba and Sr host cations are larger than the Eu2+ dopant, but a blue shift when the M = Ca host is smaller. A local anion clustering mechanism in which Eu2+ gains excess nitride coordination in the M = Ba and Sr structures, but excess oxide in the Ca analogues, is proposed for these mismatch effects. Furthermore, the Ca12Al14‑zSizO32+zF2−z:Eu revealed a crystal chemistry approach to reduce Eu ions from 3+ to 2+ in the lattice which replacing Al3+−F− by the appreciate dopant Si4+−O2− is adopted to enlarge the activator site that enables Eu3+ to be reduced. Photoluminescence results indicated that as-synthesized phosphors display an intense blue emission peaking at 440 nm that was produced by 4f−5d transition of Eu2+, along with the intrinsic emission of Eu3+ under UV excitation. According to these results, we demonstrate that optical and other properties that are sensitive to local coordination environments.

Authors : Tanguy Pussacq 1, Houria Kabbour 1, Herv? Vezin 2, Silviu Colis 3, C?dric Tassel 4, Hiroshi Kageyama 4, Olivier Mentr? 1
Affiliations : 1 UCCS, University of Lille Nord de France , France; 2 LASIR, University of Lille Nord de France, France; 3 IPCMS, University of Strasbourg, France 4 Department of Energy and Hydrocarbon Chemistry, Kyoto University, Japan

Resume : In oxides, the less common topochemical modification concerns hydride (H-) replacing oxide anions, leading to oxyhydride compounds. It recently leads to BaTi(O,H)3 [1] using CaH2 reactants. However the competition between the incorporation of hydride and reduction is important and depends on the target compounds (see the transformation of SrFeO3 into SrFeO2 using NaH, LiH or also CaH2 [2]). We have recently used similar routes for elaboration of the Ln2Ti2(O, H)7 (Ln = La, Nd, Pr) oxohydrides which may conserve ferroelectric properties of the parent Ln dititanates. Their layered structure is formed by infinite blocks (4 octahedra thick) of strongly distorted TiO6 octahedras, likely for H- accommodation. Besides the color change which denote a reduction of Ti4 into mixed Ti3 /4 valence responsible for magnetic modifications, proofs for incorporation of H- were given by spectroscopic evidences including pulsed EPR and magnetic measurements. Neutron diffraction data are in progress and will allow to determine precisely the O/H ratio and its dependence on the Ln nature. [1] Y. Kobayashi et al. Nat. Mater. 11, 507, 2012 [2] C. Tassel et al, J. Am. Chem. Soc., 130, 3764, 2008


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Symposium organizers
Franck TESSIERInstitut des Sciences Chimiques de Rennes (UMR CNRS 6226) - Université de Rennes 1

Campus de Beaulieu 35042 Rennes cedex France

+33 2 23 23 62 56
Paul AttfieldCentre for Science at Extreme Conditions - University of Edinburg

Edinburgh EH9 3JZ UK

+44 131 651 7229
+44 131 651 7049
Kenneth PoeppelmeierNorthwestern University

2145 Sheridan Road Evanston, IL 60208-3133 USA

+1 (847) 491 3505
+1 (847) 491 7713
Shinichi KikkawaHokkaido University - Graduate School of Engineering

N13 W8, Kita-ku Sapporo 060-8628 Japan

+81 (0)11 706 6739
+81 (0)11 706 6739