Nanomaterials,Nanostructures and Nano devicesM
Hierarchical assembly of nano-scale building blocks
It is generally accepted that by improving control over the synthesis and assembly of nanoparticle building blocks it will be possible to produce materials with tailored and predictable properties. Furthermore, by incorporating hierarchical control into the assembly (through type, size and spatial distribution of the NPs) it will be possible to improve materials properties and performance and develop new functionalities
During the last few decades, an outstanding library of elemental, multinary, and multicompound nanoparticle building blocks with extremely precise controlled properties have become available. To take full advantage of the huge potential of these materials in their wide range of applications, equally precise assembly strategies and technologies need to be developed. The goal of this symposium is bring together groups developing nanoparticle assemblies, modelling the particle assembly mechanisms, and assessing the influence of order on the emergent functional properties of the assemblies for a variety of applications, to discuss the latest developments in the field and to inspire new ideas and start new collaborations in these areas. We will address current concerns/challenges in; (i) the formation of nanoparticles with sufficient control over size and monodispersity; (ii) solution based particle assembly techniques; (iii) scaling of these processes; (iv) the selection of assembly processes to provide control over emergent properties in single- and multi-component assemblies, and ; (v) the potential of computation to guide these developments.
Hot topics to be covered by the symposium
- Mechanisms and strategies for the preparation of nanoparticle clusters and 1D, 2D and 3D nanoparticle assemblies.
- Modelling of nanoparticle self- and directed-assembly
- In-situ characterization of nanoparticle assembling
- characterization of nanoparticle assemblies
- Modelling optical and transport properties of nanoparticles assemblies
- Use and integration of nanoparticle assemblies in biomedical, energy conversion and storage, optoelectronic, photonic, and other relevant applications
- Scale-up of nanoparticle synthesis and assembly processes
Tentative list of invited speakers
- Yadong Yin, University of California at Riverside, USA
- Y. Charles Cao, University of Florida, USA
- Bartosz A. Grzybowski, Northwestern University, USA
- Christopher B. Murray, IBM T. J. Watson Research Center, USA
- Elena Shevchenko, Argonne National Laboratory, USA
- Rafal Klajn, Weizmann Institute of Science, Israel
- Willem K. Kegel, Utrecht University, The Netherlands
- Luis Liz Marzan, CIC biomaGUNE, Spain
- Alexander Eychmüller, Technische Universitat Dresden, Germany
- Teresa Pellegrino, Italian Institute of Technology, Italy
Tentative list of scientific committee members
- Andrey Rogach, City University of Hong Kong
- Nicholas Kotov, University of Michigan, USA
- Claire Wilhelm, University Paris Diderot, France
- Jordi Arbiol, ICMAB, Spain
- Peter Reiss, CEA, France
- Kevin Ryan, Limerick University, Ireland
- Hong Liu, Shandong University, China
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Authors : Karolina Milowska1,2, Jenny Merlin1,2, Dermot Brougham,3 Jacek Stolarczyk1,2
Affiliations : 1.Photonics and Optoelectronics Group, Ludwig-Maximilians-Universität München, Amalienstr. 54,80799 Munich (Germany); 2.Nanosystems Initiative Munich (NIM), Schellingstr. 4, 80799 Munich (Germany) 3. School of Chemical Sciences Dublin City University, Dublin 9, Ireland
Resume : We present a model of assembly of nanoparticles into size-controlled nanoparticle clusters. In the process, the steric repulsion of the nanoparticles is gradually reduced by competitive stabilizer desorption arising from the presence of a tertiary silica phase.[1,2] The kinetics of assembly is analysed using Smoluchowski aggregation equation and Fuchs stability ratio dependent on nanoparticle-nanoparticle colloidal interactions. We show that by including a rigorous treatment of van der Waals, steric (osmotic and elastic) and magnetic interactions the experimental evolution of the size distribution obtained by dynamic light scattering can be correctly reproduced. The model can be extended to other systems based on polymer-decorated gold nanoparticles and includes the formation of multicomponent clusters (e.g. gold and iron oxide). We also show that the model of nanoparticle interactions can be of great use to predict the magnetic and colloidal properties of the resulting clusters as well as to design novel multifunctional nanoparticle clusters. 1.J. K. Stolarczyk et al, Angew. Chem. Int. Ed. 2009,48,175. 2.C.J. Meledandri et al, ACS Nano 2011,5,1747 3.K.Milowska et al, in preparation 4. J.K.Stolarczyk et al, to be submitted
Authors : Pai Liu, Shalini Singh, Ning Liu, Kevin M. Ryan
Affiliations : Materials and Surface Science Institute and Department of Chemical and Environmental Sciences, University of Limerick, Limerick, Ireland
Resume : The colloidal cadmium chalcogenides nanorods are under particular attention because of their tunable and directional emission spectra, high damage threshold and low energy formation processes, which lead to their perspective application in photovoltaic and optoelectronic devices. However, fully harnessing the enhancement from assembly requires complete orientational and positional order of the nanorods across an entire substrate. Herein, we describe electric field assisted perpendicularly aligned film of CdSexS1-x nanorods via a solution based method. This study involves the synthesis of semiconductor nanorods via a hot injection route and the subsequent deposition of nanorods suspension under a uniform DC field. We demonstrate this method can be applied to various types of semiconductor nanorods forming a highly orientated film and fabricating into practical devices. The numeric studies are extensively investigated on different types of rods to interpret the mechanism behind the alignment. It is also illustrated that the low production cost, and ability to assemble on any conductive substrate make this method a highly attractive alternative to epitaxially grown materials.
Authors : Suraj Naskar, Nadja C. Bigall
Affiliations : Leibniz Universit?t Hannover Institute of Physical Chemistry and Electrochemistry Callinstr. 3A D-30167 Hannover, Germany
Resume : Growth of noble metal domains on various semiconductor counterparts provides the opportunity to manipulate both the properties of metal and the semiconductor in the single segment. A general synthesis procedure to grow site-selective noble metal domains, namely Au, Pd and Pt, has been achieved on quasi 2D five monolayer thick CdSe nanoplatelets (NPLs). Optimization of the reaction parameters and of the type of metal precursor enables us to grow metal domains only at the corners and the shorter side edges (for Au and Pd), and all around the edges of the NPLs (for Pt). Different morphologies obtained for the different noble metals e.g. quasi spherical (for Au and Pt) and quasi rectangular (for Pd) are characterized both by bright field and dark field transmission electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy and also by UV-Vis absorption and PL emission spectroscopy. All the nanoheteroplatelets show efficient charge carrier separation at the metal-semiconductor interface and are therefore suitable for applications in e.g. photocatalysis, which is examplarily shown for the degradation of methylene blue upon visible light irradiation. Furthermore, the assembly of these nanoheteroplatelets to form 3D networks under specific conditions is presented. S. Naskar, A. Schlosser, J. F. Miethe, F. Steinbach, A. Feldhoff, N. C. Bigall (2015): Site-Selective Noble Metal Growth on CdSe Nanoplatelets, Chemistry of Materials DOI: 10.1021/acs.chemmater.5b01110
Session II : Willem Kegel
Authors : Florian Guignard, Marco Lattuada
Affiliations : Adolphe Merkle Institute, University of Fribourg, Chemin des Verdiers 4, 1700 Fribourg, Switzerland
Resume : The vast majority of the existing work on self-assembly of nanoparticles focused on spherical isotropic nanoparticles, which are easy to prepare for a broad range of materials. However, spherical isotropic particles do not offer many opportunities in terms of the variety of structures that can be prepared by self-assembly. In this work we present a more complex type of particles, namely Janus dumbbells, and discuss their self-assembly features. These particles can be synthesized in a broad range of sizes and aspect ratio, in addition to bearing asymmetric functionalized, with silane groups exclusively located on one hemisphere of the dumbbells. These particles have been functionalized in a broad variety of manners [1,2]. The hydrolysis and condensation of a silane precursor covered one lobe of the particles with a thin layer of silica. Upon removal of the polymeric template, silica nanobowls bearing a well-defined opening in their shell were prepared. Calcination of the template at 550 °C led to purely hydrophilic silica nanobowls, while the dissolution of the template in THF gave birth to Janus nanobowls having a thin polymer layer on their inner side, with a different reactivity of the inside and outside surfaces . Magnetic anisotropic nanoparticles were prepared by starting with magnetic beads as seed particles. The asymmetric dumbbells, with different aspect ratios, were self-assembled in the presence of an external magnetic field, in order to explore the effect of their aspect ratio on the formation of chains. By creating dipolar dumbbells, we prepared Janus nanomotors by selectively attaching citrate-coated platinum nanocrystals on one hemisphere.
Authors : K. Z. Milowska , Habeeb M. M. Abubaker , Markus Doblinger , J. Rodriguez Fernandez , J. K. Stolarczyk 
Affiliations : Department of Physics and Center of Nanoscience, Ludwig-Maximilians University Munich, Amalienstr. 54, 80799 Munich, Germany Department of Chemistry, Ludwig-Maximilians-University Munich, Butenandtstrasse 5-13 (E), 81377 Munich, Germany
Resume : The hierarchically-ordered nanoparticle assemblies attract a lot of research activity because of wide range of potential applications. The assemblies of ultra-small gold nanoparticles (usNP, nanoclusters) due to distinctive quantum confinement and geometric effects are of particular interest. Here, we present results of extensive and systematic studies of periodically assembled (1D, 2D & 3D) ligand-protected Au usNP. Our theoretical studies are based on the ab initio calculations in the framework of the density functional theory (DFT) including van der Waals interactions on one hand and colloidal stability theory (CST) on the other hand. Eight different Au usNP (Aum, m=11,13,16,19,38,55,79,144) protected with different lengths of thiolate ligands (-S(CH2)nCH3, n=0,..,7) are considered. We focus on interactions between usNP which are a subject of hot debate and crucial for the design of functional devices. We compare DFT and CST approaches and show that ligand interactions are of more importance for obtaining stable assemblies of Au ultra-small nanoparticles rather than van der Waals interactions between their cores. Moreover, we found that fcc is energetically most preferable type of arrangement. There theoretical predictions are compared with experimental observations (HRTEM, SAXS) obtained for synthesized supracrystals of Au144(SC6H13)60 nanoclusters.
Authors : Rumi Tamato1, Jiaji Cheng1, Emilie Pouget1, Sophie Lecomte1 , Philippe Barois2, Ashod Aradian2, Virgine Ponsinet2,Reiko Oda1, Marie-Hélène Delville3*
Affiliations : 1 CBMN, Allée Geoffroy Saint Hilaire, Bât B14, 33600 Pessac 2 CRPP, CNRS UPR 8641, Universite of Bordeaux 115 avenue du docteur Schweitzer F-33608 Pessac Cedex FRANCE 3 ICMCB, CNRS UPR 9048, Universite of Bordeaux 87 Avenue du Dr Schweitzer F-33608 Pessac Cedex FRANCE
Resume : In the field of emerging nanoscale materials with switchable properties chiral structures like helices or twisted ribbons are of great interest because of their intrinsic optical and mechanical properties. In this contribution, we present a study about the properties of SiO2 and SiO2@Au helical nanosprings synthesized by an original and simple technique from organic nanotubes through inorganic transcription. Beside their potential applications in NEMS, ranging from physical sensing and signal processing to ultra-low power radio frequency signal generation, thanks to their striking features these 1D nano-objects can also exhibit interesting photonic properties. The originality of the synthesis method consists in the possibility to obtain 3D organized nanostructures with specific morphology and properties based on 1D objects. Hybrid nano-helices are synthesized using amphiphilic organic chiral self-assemblies forming very well defined helix or ribbons structures and exploits them as templates for inorganic nanomaterial formation1. Their bio-inspired mineralization creates silica nano-helices with very well controlled morphologies usable in functional nanodevices. In this case they were used to prepare a large variety of gold nanoparticledecorated helical surperstructures.We can control both handedness and structural metrics by controlling the sizes of the GNPs building blocks varying from 3.5 nm-6 nm as well as reach an overall coverage of the silica (for SERS applications),2 and the silica nanohelices or twisted ribbons. The resulting objects exhibit well-defined chiral arrangement of the GNPs following the chirality of the silica helices through electrostatic intereactions. A clear surface plasmon resonnance was observed in UV visible range. These nanohybrid systems are under study for photonic applications such as chiral metamaterials and optical sensors based on the 3D network of GNPs. Project funded by ANR SIMI8 programm 2010-2014: NANOSPRINGS and Labex Amadeus 1. (a) Delclos, T.; Aime, C.; Pouget, E.; Brizard, A.; Huc, I.; Delville, M.-H.; Oda, R., Individualized silica nanohelices and nanotubes: Tuning inorganic nanostructures using lipidic self-assemblies. Nano Letters 2008, 8 (7), 1929-1935; (b) Okazaki, Y.; Cheng, J.; Dedovets, D.; Kemper, G.; Delville, M.-H.; Durrieu, M.-C.; Ihara, H.; Takafuji, M.; Pouget, E.; Oda, R., Chiral Colloids: Homogeneous Suspension of Individualized SiO2 Helical and Twisted Nanoribbons. ACS Nano 2014, 8 (7), 6863-6872. 2. Tamoto, R.; Lecomte, S.; Si, S.; Moldovan, S.; Ersen, O.; Delville, M.-H.; Oda, R., Gold Nanoparticle Deposition on Silica Nanohelices: A New Controllable 3D Substrate in Aqueous Suspension for Optical Sensing. J. Phys. Chem. C 2012, 116, 23143-23152.
Session IV : Alexander Govorov
Authors : Amelie Heuer-Jungemann (a), Pascal H. Harimech (a), Johanna Midelet (a), Afaf H. El-sagheer (b), Tom Brown (b), Antonios G. Kanaras (a, c).
Affiliations : (a) Physics and Astronomy, University of Southampton, Southampton, SO171BJ, United Kingdom (b) Department of Chemistry, University of Oxford Chemistry Research Laboratory, Oxford OX1 3TA, United Kingdom (c) Institute for Life Sciences, University of Southampton, Southampton, So171BJ, United Kingdom
Resume : The ability to control the bottom-up self-assembly process of nanoparticles is of continuous research interest. The ultimate aim is to master the fabrication of long range structures with hybrid properties deriving from a specific combination of their individual building blocks. In order to achieve this great degree of programmability, it is important to develop a set of tools that allow manipulating the way that particles assemble to each other. In this presentation, I will discuss the current relevant developments in my group using DNA, light, peptides and polymers to master the assembly of nanoparticles. I will particularly focus on gold nanoparticles but then I will expand my discussion on other types of nanoparticles including upconversion and magnetic nanoparticles. (1) Relevant Reference: (1)Heuer-Jungemann, A.; Kirkwood, R.;El-Sagheer, A.; Brown, T.; Kanaras, A. G. Nanoscale 2013, 5 (16), 7209-7212
Authors : Hongkang Wang and Andrey L. Rogach
Affiliations : Department of Physics and Materials Science & Centre for Functional Photonics City University of Hong Kong
Resume : Tin dioxide (SnO2) is an important n-type wide-bandgap semiconductor with applications in transparent conductive films, gas sensors, lithium ion batteries, and solar cells . For many of these applications, complex three-dimensional hierarchical structures assembled from well-defined low-dimensional nanosized building blocks are of a special importance. We outline synthetic strategies of hierarchical SnO2 nanostructures in terms of the dimension and the facet control, creation of porous and hollow structures, as well as modification of their optical properties by doping with other elements [2-6]. We further review recent progress in our design of composite nanostructured Sn−Ti−O ternary systems [7-9], which are promising materials for lithium ion batteries .
Authors : Eoin Fox1, Fadwa El Haddassi1, Jose Hierrezuelo1, Jacek Stolarczyk2 and Dermot Brougham1*
Affiliations : 1School of Chemical Sciences, Dublin City University, Glasnevin, Dublin 9, Ireland. 2 Photonics and Optoelectronics Group, Department of Physics and Center for NanoScience (CeNS), Ludwig-Maximilians-Universit?t Munich, Amalienstrasse 54, 80799 Munich, Germany
Resume : Robust, cheap and scaleable routes to monodisperse multi-component nanoparticle assemblies are required for a wide range of biological and materials applications. Here we describe recent advances in a novel process, competitive stabilizer desorption (CSD), [1,2] for preparing monodisperse assemblies from a range of starting nanoparticle types and combinations. With CSD the relative monodispersity of the assemblies improves, as compared to the starting particles, and assemblies can be prepared over a broad size range. A detailed kinetics study will be presented that reveals the mechanism and identifies initial conditions for controlled assembly. CSD uses cheap materials, is reproducible, robust and scaleable, and uniquely the particle and cluster size can be selected independently, as can the final surface chemistry, allowing detailed evaluation of the contribution of each of these component to the emergent properties. The potential of magnetic nanoparticle assemblies prepared by CSD for MRI-guided drug delivery applications will be described. 1) C. J. Meledandri, J. K. Stolarczyk, D. F. Brougham, ACS Nano 2011, 5, 1747-1755. 2) J. K. Stolarczyk, D. F. Brougham, Angew. Chem. Int. Ed. 2009, 48, 175-178.
Authors : Priyanka Dey,[1,2] Kristofer J. Thurecht, Idriss Blakey, Peter M. Fredericks and Jessica Rodríguez-Fernández[1,2]
Affiliations : Department of Physics and CeNS, Ludwig-Maximilians-Universität München, Munich, Germany. Nanosystems Initiative Munich (NIM), Munich, Germany. Australian Institute of Bioengineering and Nanotechnology and Centre for Advanced Imaging, University of Queensland, St. Lucia, Australia. School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology, Brisbane, Australia.
Resume : Plasmonic metal nanoparticles (NPs) display localized surface plasmon resonances (LSPRs) that can be tuned by controlling their shape and size, but also by forming nano-assemblies. Ordered nano-assemblies contribute to enhanced plasmonic properties, including coupled LSPR modes, plasmonic heating and surface enhanced Raman scattering (SERS). Hence, they find applications in photothermal therapy, catalysis, SERS chemical sensors, SERS bio-diagnostic agents and many more. Motivated by this, here we have developed colloidal gold nano-assemblies with controlled morphology, number of NPs per assembly (aggregation number) and interparticle distance. Our strategy involves the utilization of molecular linkers in a colloidal self-assembly approach. Following this, we investigated the role of structurally different tailor-made molecular ligands in the formation of stable colloidal gold nano-assemblies. Depending on the type of ligand employed i.e., organic molecule, linear polymer or branched polymers, we observed the formation of various 1D, 2D and 3D gold nano-assembly morphologies. A good control over the aggregation number and morphologies was achieved. These included dimers, nanochains, nanobranches, nanoplates, core-satellite as well as 3D globular structures. They were characterized by UV-Vis, DLS, AFM and cryo-TEM at various tilt angles. We also observed a strong dependence of the LSPR coupling and SERS signal enhancement on the nano-assembly morphology and its aggregation number. Such customized gold nano-assemblies further demonstrated potential for applications as SERS sensors. 1. Daniel, M. et. al., Chem. Rev. 2004, 104, 293−346. 2. Ko, H. et. al., Small, 2008, 4(10), 15761599. 3. Dey, P. et. al., Langmuir, 2013, 29 (2), 525533.
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Authors : Jan Paczesny, Robert Hołyst
Affiliations : Institute of Physical Chemistry Polish Academy of Sciences Kasprzaka 44/52 01-224 Warsaw, Poland
Resume : We search for the rules which connect the functionality of the self-assembled nanostructures and the design building blocks of which it is composed. We study subtle parameters of the molecular design, i.e. stiffness, amphiphilic balance and geometrical packing. We find that the tendency for self-assembly of ligand molecules can be transferred to other species, i.e. nanoparticles. The proper design of capping ligands or addition of judiciously chosen molecules result in control over 2D self-assembly of nanoparticles. The advances in manipulation of nanoparticles allowed us to prepare novel surface enhance Raman spectroscopy (SERS) platform according to true bottom-up approach. Three consecutive steps were utilized. First, gold nanoparticles were deposited on a solid substrates. Afterwards such substrates were used for the chemical vapor deposition process of gallium nitride nanowires growth. On such scaffolding a third step of material fabrication was performed, i.e. deposition of gold microflowers. The final morphology was controlled at each step to tailor the properties for the desired purposes. The recorded SERS enhancement factor was around 107 for p mercaptobeznoic acid. SERS spectra were reproducible both across a single sample and between different platforms. The material proved to be very mechanically stable. Our platforms were suitable for biological and biomedical applications. We demonstrated the label free detection of DNA.
Authors : Boris N. Feigelson, James A. Wollmershauser, Kedar Manandhar
Affiliations : Boris N. Feigelson US Naval Research Laboratory; James A. Wollmershauser US Naval Research Laboratory; Kedar Manandhar ASEE Postdoctoral Fellow residing at U.S. Naval Research Laboratory
Resume : With designed bulk nanostructures, one could potentially combine properties that are mutually exclusive in a single bulk material, and, as a result, dramatically improve the desired performance. However, a major research challenge and roadblock is how to produce 3D nanostructured materials consistently with the required phases arranged in designated spatial order that are at the same time fully dense without porosity and detrimental phases. Known state-of-the-art techniques for producing bulk nanostructures cannot simultaneously meet all these requirements. As a result, the inherent properties of such bulk monolithic nanostructured materials are greatly unknown and unexplored. We developed an Enhanced High Pressure Sintering (EHPS) approach to consolidate oxide, metal, and semiconductor nanoparticles into 3-dimensional nanostructured materials. EHPS incorporates stringent environmental control and utilizes high pressures to break agglomerates while simultaneously exploiting the increased pristine surface potential of nanoparticles for surface-energy-driven densification without microstructural changes. Using this approach, monolithic nanocrystalline transparent ceramics with grain size bellow 30 nm are demonstrated. Such ceramics exhibit a 30% increase in hardness over a corresponding order of magnitude reduction in grain size and suggest that Hall-Petch type (strengthening via grain size reduction) relations exist in ceramics at least down to 30nm.
Authors : K. Brassat, Ch. Brodehl, J.K.N. Lindner
Affiliations : Dept. of Physics, University of Paderborn, Germany; Center for Optoelectronics and Photonics Paderborn CeOPP, Paderborn, Germany
Resume : During the last decades the synthesis, modification and functionalization of nanoparticles has been intensively studied. In order to fully exploit their properties, it is essential to control the nanoparticles position, allowing to connect the nanoobjects to the macro-world. For a sufficient statistics it is desirable to contact many nanoparticles in parallel. To this end we have developed a template-assisted self-assembly technique which allows us to create inside microfluidic channels millimeter long rows of nanogap electrodes attached to macroscopic contacts. Dielectrophoresis is used to trap particles in the inhomogeneous electric field formed between the electrodes. For single particle trapping the electrodes gap size needs to be tuned to the particle dimensions. For this polystyrene-spheres from colloidal suspensions are arranged in a linear chain in trenches on Si-surfaces by means of convective self-assembly. The spheres act as shadow masks in a subsequent metal deposition step. Opposing pairs of sharp metallic nanotips remain after sphere removal, with tip distances adjustable from several hundred nm to less than 30 nm. We demonstrate that an applied voltage leads to strong field enhancements at the tips. The field gradients between tips are exploited to arrange fluorescent core-shell SiO2 nanoparticles in the channel. Fluorescence microscopy and scanning electron microscopy are used to study the dielectrophoretic arrangement.
Authors : B. Kalska-Szostko*, U.Wykowska*, D. Satuła#
Affiliations : * Institute of Chemistry, University of Bialystok, Hurtowa 1, 15-399 Białystok, Poland #Department of Physics, University of Bialystok, Ciolkowskiego 1L, 15-245 Białystok, Poland
Resume : Cooperation of few functionally different spices in one heterostructure in general is not prohibited. However, the conditions for its merging should be find out in any case. Magnetic nanoparticles, carbon nanostructure and/or biologically active particles is possible to link by bond activation between immobilized proteins and surface of the nanostructures . Not only magnetic or noble metals nanoparticles are key players used in nanotechnology but also carbon structures in nanosize (nanodiamonds, fullerenes, nanotubes) have shown widespread interest due to their unique specification. Each of these structures shows extraordinary magnetic, electrical, mechanical and optical properties. Therefore by linking more than two different items combination of the characteristic features can be obtained. Similarly to magnetic nanoparticles surface of the carbon structures should be chemically modified by attachment of various (needed) functional groups. This opens possibility for creation of hierarchical structures such as composites or hybrid nanostructures. Fabrication of heterostructures causes that carbon nanomaterials brings to medicine possibility of electronic science . In this study, nanocomposites from different kind of nanoparticles were fabricated, and compared. In the first step, various magnetic nanoparticles were synthesized and both with carbon nanostructures were functionalized at the surface to amine or carboxyl groups. Finally either particles were used as a building blocks for composites fabrication and with vitamin-biotin immobilization. The resulting nanocomposites were tested by infra-red spectroscopy, Transmission Electron Microscope, X-ray diffraction, Mössbauer spectroscopy.  K.Woo, J.Hong, J.P.Ahn., Journal of Magnetism and Magnetic Materials 293 (2005) 177-181  Z.Markovic, V.Trajkovic, Biomaterials 29 (2008) 3561-3573
Session VIII : Alexander Bittner
Authors : Massimo Morbidelli
Affiliations : Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Z?rich, CH-8093 Z?rich, Switzerland
Resume : Emulsion polymerization is a well developed technology which allows producing polymer colloids or nanoparticle with highly controlled size and polydispersity, in a variety of different chemical composition and with well controlled morphology. Typically, after the polymerization reactors latexes are coagulated into powders again using consolidated processes. Recent results in the theory of colloidal systems indicated the possibility to exploit these aggregation and breakage events under controlled conditions to produce macrostructures which are other ways not realizable. For example one can mix dispersions of different composition and realize composites with a well controlled dispersion of one phase into the other. By controlling the gelation process one can create inside such composites percolating phases which allow transporting at the macroscopic scale properties exhibited by colloids only at the nanoscale. Examples of different structured materials of interest in various application fields are discussed. These include the production of controlled porous materials in the form of micro-particles or monoliths, which can be used as adsorbents for large (bio) molecules or as thermal insulators. Other areas of interest include drug delivery and enhanced oil recovery.
Authors : M. Ibáñez1,2, O. Drobozhan,3 G. Nedelcu, 1,2 A. Cabot3,4, M. Kovalenko1,2
Affiliations : 1 Institute of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zürich, CH-8093, Switzerland 2 Empa - Swiss Federal Laboratories for Materials Science and Technology, Dübendorf, CH-8600, Switzerland 3Catalonia Institute for Energy Research IREC, 08930 Sant Adrià de Besòs, Barcelona, Spain 4 Institució Catalana de Recerca i Estudis Avançats ICREA, 08010 Barcelona, Spain
Resume : In the last decade the field of thermoelectrics had seen many advances, originating largely from the engineering of suitable nanostructured materials. So far the dominating strategies for producing bulk thermoelectric nanomaterials are grinding and precipitation of secondary phases in metastable solid solutions. Both approaches have limited control over the distribution of phases at the nanoscale and/or lack compositional versatility. Another powerful strategy can be devised from the bottom-up assembly and consolidation of colloidal nanoparticles (NPs) into bulk-like materials. Such approach is virtually unlimited in terms of compositional variety and dimensionality of constitutents. Efficient and predictable electronic doping remains a key challenge for maximizing carrier density (deliberately for holes or electrons). At nanoscale, conventional substitutional atomic doping can be supplemented with the mesoscale doping - carrier donation between individual NPs. Here we demonstrate that through the engineering of nanocomposites by simple co-assembly of various NP building blocks the charge carrier concentration can be enhanced via mutual doping, while preserving low thermal conductivities and high Seebeck coefficients, thereby increasing the overall thermoelectric figure of merit.
Authors : S. Ortega (1), D. Cadavid (1), Y. Liu (1), M. Ibáñez (2,3), A. Cabot (1,4)
Affiliations : 1 Catalonia Institute for Energy Research IREC, 08930 Sant Adrià de Besòs, Barcelona, Spain 2 Institute of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zürich, CH-8093, Switzerland 3 Empa - Swiss Federal Laboratories for Materials Science and Technology, Dübendorf, CH-8600, Switzerland 4 Institució Catalana de Recerca i Estudis Avançats ICREA, 08010 Barcelona, Spain
Resume : The design and engineering of nanomaterials by the bottom-up assembly of solution-processed nanocrystal building blocks opens up countless opportunities to produce metamaterials with controlled functional properties. Furthermore, solution-based thin film deposition methods are particularly interesting as they promise lower manufacturing costs, and open the door to new routes for the design of flexible solid-state thermoelectric devices  that can play a big role on remote power or personal devices, i.e. wearables. In this work, we detail the preparation of bulk thermoelectric nanocomposites from the bottom-up assembly of solution-processed nanocrystals. Taking advantage of the versatility [2,3] of this technique, we engineer nanocomposites by simple assembly of precisely designed nanocrystal building blocks. We will prove that this methodology provides the necessary level of compositional and morphological control to produce high performance thermoelectric materials. In addition, we have step forward into the preparation of a flexible thermoelectric device based on the solution-processed material developed. References:  Z. Lu, M. Layani, X. Zhao, L. P. Tan, T. Sun, S. Fan, Q. Yan, S. Magdassi, H. H. Hng, Fabrication of flexible thermoelectric thin film devices by inkjet printing, Small, 10 (17), 3551-3554 (2014).  D. Cadavid, M. Ibáñez, S. Gorsse, A. M. López, J. R. Morante, A. Cabot, Bottom-up processing of thermoelectric nanocomposites from colloidal nanocrystal building blocks: the case of Ag2Te-PbTe, J. Nanopart. Res., 14, 1328 (2012).  M. Ibáñez, R. Zamani, S. Gorsse, J. Fan, S. Ortega, D. Cadavid, J. R. Morante, J. Arbiol, and A. Cabot, Core-Shell Nanoparticles As Building Blocks for the Bottom-Up Production of Functional Nanocomposites: PbTe_PbS Thermoelectric properties, ACS Nano, 7 (3), 2573-2586 (2013).
Authors : A.Zitouni, S.Bentata, B.Bouadjemi, T.Lantri, W. Benstaali, Z.Aziz, S.Cherid
Affiliations : aLaboratory of Technology and of Solids Properties, Faculty of Sciences and Technology, BP227 Abdelhamid Ibn Badis University, 27000 Mostaganem, Algeria
Resume : we investigate the structural, electronic and magnetic properties of the diluted magnetic semiconductors (DMSs) CdCoTe and CdMnTe in the zinc blende phase with 25% of Co and Mn. The calculations are performed by the recent ab initio full potential augmented plane waves (FP_L/APW) method within the spin polarized density-functional theory (DFT) and the generalized gradient approximation GGA. Structural properties are determined from the total energy calculations and we found that these compounds are stable in the ferromagnetic phase. We discuss the electronic structures, total and partial densities of states and total magnetic moments. The calculated densities of states presented in this study identify the half-metallic of CdCoTe and CdMnTe.
Authors : D. Drude, K. Brassat, Ch. Brodehl, J.K.N. Lindner
Affiliations : Dept. of Physics, University of Paderborn, Paderborn, Germany; Center for Optoelectronics and Photonics Paderborn CeOPP, Paderborn, Germany
Resume : Nanosphere lithography is an established technique for the formation of ordered nanoparticles on large areas at low cost. Hexagonally self-arranged mono- or bilayers of colloidal nanospheres act as a shadow mask for subsequent site-controlled surface modifications such as material deposition, leaving a periodic array of nanoparticles. The hexagonal order as well as defects of the sphere mask are directly transferred to the nanoparticle pattern. We use the doctor blade technique based on a convective self-assembly process to form hexagonal monolayers of polystyrene beads from an aqueous suspension on silicon surfaces. The particles arrange themselves at the triple-phase boundary between suspension, solid substrate and surrounding gas phase. This process depends on several experimental parameters such as the relative humidity, substrate temperature, particle concentration, particle size distribution and blade velocity. We investigate the influence of these parameters on the formation of typical defects in the monolayer such as voids, quadratic arrangements, grain boundaries and other inhomogeneities. Optical and scanning electron microscope images are analyzed by a new algorithm based on Delaunay triangulation and defect densities are calculated. We show, that the densities of different defect types correlate directly with the experimental parameters. This allows to minimize selected defect densities by adjusting experimental conditions during the self-assembly process.
Authors : C. Spaas, R. Dok, O. Deschaume, C. Bartic, P. Hoet, F. Van den Heuvel, J.P. Locquet, S. Nuyts, C. Van Haesendonck
Affiliations : KU Leuven, Department of Physics and Astronomy KU Leuven, Department of Oncology KU Leuven, Department of Public Health and Primary Care, Environment and Health University of Oxford, CRUK/MRC Institute for Radiation Oncology and Biology
Resume : With as main prospective the localized eradication of malignant cells, the radiosensitization of gold nanoparticles is most effective in close proximity to the cellular DNA. However, the preservation of colloidal stability and the implementation of specific cell targeting requires a supplementary organic coating grafted on the gold nanoparticle surface. The latter consisting of functionalizing polymers and antibodies, necessary for the internalization to the nucleus, attenuates the irradiation dose enhancement caused by the GNPs. The influence of the nanoparticle capping layer thickness, build up with PEG polymers of MW 1 to 20 kDa, on the radiosensitizing effect of GNPs is demonstrated by evaluation of the relaxation pattern of supercoiled DNA. Image analysis of gel electrophoresis and subsequent quantification conclude that on average 58% of the radiosensitizing efficiency is lost when the radial dimensions of the functionalizing layer are increased from 4.1 to 15.3 nm. An experimental supplement is thereby provided for biophysical simulations and demonstrates the influence of an important parameter in the development of nanomaterials for targeted therapies in cancer radiotherapy. Alongside the PEG functionalization, supplementary antibodies are then introduced to create cell specific interactions. Maximal affinity and stability of the nanocomplex is created and proposed for further experimental research on the radiosensitization performances of gold nanoparticles.
Authors : B. Kalska-Szostko*, U.Wykowska*, B. Piotrowska*, D. Satuła#
Affiliations : * Institute of Chemistry, University of Bialystok, Hurtowa 1, 15-399 Białystok, Poland #Department of Physics, University of Bialystok, Ciolkowskiego 1L, 15-245 Białystok, Poland
Resume : Today, preparation of 0D well-defined nanoparticles which represents inert structure divided on core and shell have obtained extensive interest among scientist. The reason of such popularity of low dimensional structures is that the core-shell nanoparticles have many interesting optical, magnetic, electrical, and mechanical properties which can be combined in one species  in contrast to single element particles. In presented paper, core-shell ferrite nanoparticles, with various composition of the core were prepared. Presented nanoparticles, has a core obtained from a mixture of Fe3+, Fe2+ and Men+ ions (where Me = Co2+, Co3+, Mn2+, Mn3+ or Ni2+), in such way, to preserve crystalline structure of magnetite. Then the magnetite shell layer was added, to obtain core-shell structure. Seeds of nanoparticles were fabricated from the proper metal acetylacetonate salts in diphenyl ether, oleic acid and oleyl amine environment. Characterization of the nanoparticles was done by Transmission Electron Microscopy, X-ray diffraction, Infrared spectroscopy, and Mössbauer spectroscopy.  Y. Zhu, H. Da, X. Yang, Y. Hu, Colloids and Surfaces A: Physicochem. Eng. Aspects 231 (2003) 123-129
Authors : Cezary Czosnek 1a*, Mariusz Drygaś 1a, Jerzy F. Janik 1a, Mirosław M. Bućko 1b, Zbigniew Olejniczak 2
Affiliations : 1 AGH University of Science and Technology, aFaculty of Energy and Fuels, b Faculty of Materials Science and Ceramics; al. Mickiewicza 30, 30-059 Krakow, Poland 2 Institute of Nuclear Physics, Polish Academy of Sciences, ul. Radzikowskiego 152, 31-342 Krakow, Poland *firstname.lastname@example.org
Resume : Silicon carbide SiC has many advantageous properties including the high thermal, mechanical, and chemical stabilities, relatively low density, and semiconducting properties. In this regard, the high thermal conductivity makes this material a valuable catalyst support for exothermic reactions, for instance, in reacting carbon monoxide and hydrogen towards methane. Herein, presented is a study on the effect of temperature of the first aerosol-assisted stage on silicon carbide crystallization during the second stage temperature treatment of the bulk raw powder. Nanocrystalline SiC was prepared from aerosolized hexamethyldisiloxane at 1200 and 1400 C followed by a second stage pyrolysis under argon at 1650 C. Additionally, the sample obtained in the first aerosol-assisted stage at 1400 C was thermally treated in bulk at the same temperature for 1 hour under argon. The as-prepared products were characterized by powder XRD, SEM, solid state 29Si MAS NMR, and FT-IR spectroscopy. The data clearly confirmed the impact of the temperature treatment on the kind of polytype(s) and average crystallite size of the resulting nano-SiC. Acknowledgment. This work was supported by AGH University of Science and Technology Grant No. 22.214.171.124.
Authors : Szilárd Pothorszky, Dániel Zámbó, András Deák
Affiliations : Institute for Technical Physics and Materials Science, HAS Centre for Energy Research, P.O. Box 49, H-1525 Budapest, Hungary
Resume : Assembly of plasmonic nanoparticles rely on colloidal interactions including eletrostatic-, van der Waals, molecular dipole, and many other different forces.1 The collective properties of assembled particles depend on size, shape and their relative orientation. By using gold nanorods (AuNRs) its intrinsic shape-anisotropy gives the opportunity for anisotropic assembly, which can be exploited in a number of important applications,, like surface-enhanced Raman scattering (SERS)2 or nanoparticle networks3. Here, we report a novel strategy to assemble gold nanoparticles (AuNPs) in an orientation-controlled way based on colloidal interactions. By means of regio-selective surface modification of AuNRs we succesfully achieved a robust system in which only the tips of the nanorods are preferable for spherical particles independently from their concentration. The assembly of the rod and spherical nanoparticles was carried out in the bulk and followed by means of VIS spectroscopy. The assembled structures were investigated by SEM. The approach of site-selective surface modification is based on taking advantage of the slightly anisotropic coverage of AuNRs by the CTAB bilayer. The nanorod tips were functionalized with a well defined amount of charged thiol molecules without stripping the side face. In a second step the sides of the NRs were covered by mPEG-SH which acts as a stabilizer against NR aggregation and inhibitor for side-adsorption of spherical nanoparticles, hence the spherical nanoparticles adsorb mainly at the tips of the NRs. As the size of the spherical particles increases, the side adsorption gets more preferred, independently of the site selective surface modification of the NRs. ACKNOWLEDGEMENTS This work received funding from the European Unions Seventh Framework Programme for research, technological development and demonstration under Grant N° 310250. The project was supported by the Hungarian Scientific Research Fund OTKA-PD-105173 and K-112114. A.D. acknowledges the support of the János Bolyai Research Fellowship from the Hungarian Academy of Sciences. SZ.P. and D.Z. acknowledges the support of the Pro Progressio Foundation and József Varga Foundation. REFERENCES 1. Bishop, K. J.; Wilmer, C. E.; Soh, S.; Grzybowski, B. A. Nanoscale Forces and Their Uses in Self-Assembly. Small 2009, 5, 16001630. 2. Zhong, L. et al. Rational design and SERS properties of side-by-side, end-to-end and end-to-side assemblies of Au nanorods. Journal of Materials Chemistry 21, 14448 (2011). 3. Sanchot, A. et al. Plasmonic Nanoparticle Networks for Light and Heat Concentration. ACS Nano 6, 34343440 (2012).
Authors : F. Mohamed, M. Corva, E. Vesselli, M. Peressi
Affiliations : University of Trieste, Department of Physics, Trieste (Italy)
Resume : For most practical applications, metal nanoparticles (NPs) need to be supported on a substrate that can act as a deposition template for the growth of regular arrays and is relevant in preventing sintering at high temperatures, a process that would deactivate the catalytic devices. The Moire pattern due to the small lattice mismatch between graphene and Ir(111) could be an efficient template for an ordered array of metal NPs. With the help of ab-initio calculations we compare the behaviour of different metals, with the aim of finding those more suitabile for an ordered growth. The role of a possible seed is also discussed.
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Session IX : Beatriz Hernandez-Juarez
Authors : Maryna I. Bodnarchuk, Sergii Yakunin, Maksym. V. Kovalenko
Affiliations : ETH Zürich, Department of Chemistry and Applied Biosciences, CH-8093, Zurich, Switzerland and Empa-Swiss Federal Laboratories for Materials Science and Technology, CH-8600, Dübendorf, Switzerland
Resume : Colloidal metallic and semiconductor nanocrystals (NCs), functionalized with inorganic capping ligands such as metal chalcogenide complexes (MCCs), have recently emerged as versatile optoelectronic materials for applications in photovoltaics, photodetectors, thermoelectrics, and field-effect transistors. As-prepared MCC-capped NCs are highly charged and dispersible only in polar solvents, and lack the ability to spontaneously form long-range ordered NC superlattices. Here we present a simple and general methodology, based on host-guest coordination of MCC-capped NCs with macrocyclic ethers (crown ethers and cryptands), enabling the solubilization of inorganic-capped NCs in solvents of any polarity and improving the ability to form NC superlattices. The corona of organic molecules can also serve as a convenient knob for the fine adjustment of charge transport in films of NCs, as demonstrated here for the photoconductive properties of PbS NCs. In particular, high infrared photon detectivities of 3.3·10e11 Jones with a fast response (3 dB cut-off at 3 kHz) at 1200 nm were obtained for a photoconductor based on PbS/K3AsS4/decyl-18-crown-6 films. At the same time, films of crown-free PbS/K3AsS4 NCs are too conductive to observe efficient photocurrent generation, while initial oleate-capped PbS NCs are fully insulating.
Session X : Maksym Kovalenko
Authors : Bartosz A. Grzybowski, FRSC
Affiliations : UNIST and IBS Center for Soft and Living Matter
Resume : Nanoscopic objects stabilized with charged organics exhibit properties fundamentally different from either molecular or macromoleculer ions, and can combine ionic-like properties with electronic and ionic conductivity and/or photoexcitability. By careful control of electrostatic interactions, nanoions of various shapes and material compositions can be assembled into functional nanomaterials including 3D supracrystals, layered crystals, or extended films. Depending on the properties of the charged organics, these nanomaterials can act as chemical amplifiers, photoconductors, diodes, transistors, or even full-fledged electronic circuits containing no semiconductors. This last set of constructs can integrate on the nanoparticles electronic function with chemical sensing.
Authors : Michaela Meyns (1), Pablo Guardia (2), Gihan Joshua (1), Andreu Cabot (1,3)
Affiliations : (1) Catalonia Energy Research Institute (IREC), 08930 Barcelona, Spain; (2) Centre Tecnol?gic de la Qu?mica de Catalunya, 43007 Tarragona, Spain; (3) Instituci? Catalana de Recerca i Estudis Avancats (ICREA), 08010 Barcelona, Spain.
Resume : Self-assembly of nanoparticles has led to a fascinating variety of accessible well-defined super structures. Of particular interest is the assembly of binary nanoparticle arrays with complementary or synergistic properties. The electrostatic assembly of oppositely charged nanoparticles offers the possibility of a high degree of control and increased variety of accessible superstructures such as diamond-like Au-Ag supercrystals compared to van-der-Waals driven processes [Kalsin et al. Science 2006, 312, 420]. There is number of strategies to achieve sufficient charging of nanoparticles, from atomic to polymeric ligands, from aqueous synthesis to ligand exchange. A critical point in the assembly process is the colloidal stability of the charged particles. Different strategies for charging nanoparticles and their implications on colloidal stability and for the later assembly will be discussed with an emphasis on post-synthetic ligand exchange and binary semiconductor-metal systems.
Session XI : Ajay Singh
Authors : Maria Acebrón, Héctor Rodríguez-Rodríguez, J. Ricardo Arias-González and Beatriz H. Juárez
Affiliations : Universidad Autónoma de Madrid, Spain
Resume : SiO2 encapsulation of alloyed CdSeZnS nanocrystals (NCs) shows differences in terms of optical properties and luminescence quantum yield, depending on the surface composition, size, and ligand content. In this work, emphasis has been placed on the fine control required to obtain luminescent SiO2 encapsulated NCs by studying the role of oleic acid (OA), stearic acid (SA), and dodecanethiol (DDT) ligands on the alloyed NCs. While the use of anchored DDT molecules is essential to preserve the optical properties, intercalated OA and SA play a critical role for SiO2 nucleation, as stated by 1H NMR (including DOSY and NOESY) spectroscopy. (1). Furthermore, optical trapping (2,3) of these encapsulated NCs allows for their individual manipulation and acquisition of their optical properties and evolution in solution. Surface effects generated by the laser beams composing the optical tweezer and the surrounding medium will be discussed. These results emphasize the importance of surface chemistry in semiconducting NCs.
Authors : Alessandro Lauria, Irene Villa, Andreas Braendle, Mauro Fasoli, Walter Caseri, Anna Vedda, Markus Niederberger
Affiliations : Laboratory for Multifunctional Materials, Department of Materials, ETH Zürich, Vladimir-Prelog-Weg 5, 8093 Zürich, Switzerland Department of Materials Science, University of Milano-Bicocca, Via R. Cozzi 55, 20125 Milano, Italy
Resume : The employment of nanoparticles in optical applications is an ideal strategy for minimizing the light scattering associated with the discrete form of the material. The control over structure and emission maxima is crucial in order to tailor materials for the final application. Hafnium dioxide is a wide band-gap semiconductor with outstanding thermal stability, remarkable chemical inertness, high density, and UV-visible transparency. We report a strategy for the production of nearly spherical HfO2 nano-dots obtained by nonaqueous sol-gel where the multifunctional role of rare earth doping is evidenced. On one hand, rare earth dopant ions activate the visible luminescence of the nanocrystals. On the other hand the incorporation of trivalent ions is shown to be suitable for the room temperature stabilization of the cubic polymorph of HfO2, with potentially great benefits in the realization of new polycrystalline optical ceramics for scintillator applications with reduced birefringence. We incorporated the colloids into trasparent hosts such as polymers and oxides, obtaining luminescent composites where the processability of the host and the outstanding photostability of inorganic nano-phosphors are merged together. These systems might be suitable for new low-cost/solution-processed radiation detectors and scintillators, and for luminescent solar concentrators expressly designed for the photoconversion in harsh conditions of high energy radiation, from the UV to the X-rays rang
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