Various scales. atomic scale. nanoscale. mesoscale m m m

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1 Various scales atomic scale nanoscale mesoscale m 10-9 m 10-6 m 10-3 m

2 Analogy between atomic crystals and supracrystals: Atoms are replaced by (uncompressible) nanocrystals (much heavier!) and tomic bonds are replaced by coating agent ( loose springs). * Fe particles synthetized in magneto bacteria and in vitro * Crystalline structures retained with crystals of either atoms or nanocrystals * Growth of atoms in nanocrystals and nanocrystals in supracrystals * Orientational growth processes is retained with crystals of atoms or nanocrystals * Self-Assembly of particles * Negative crystals * Quasi-crystals * Vicinal surfaces * Self-Assembly of small and large particles at various scales * Crystal growth at the air-solvent interface under saturated atmosphere * Breathing modes * Coherent Longitudinal Acoustic Phonons Analogy between atomic crystals produced in nature and in vitro Fe 3 O 4 particles Analogy between nature and film of nanocrystals: Cracks Marangoni process at various scales

3 Fe particles synthetized in magneto bacteria and in vitro Crystalline structure of Fe 3 O 4 microparticles in in the magnetostatic bacteria Synthesis of Fe 3 O 4 nanocrystals [011] [001] [112] [114] - [111] truncated octahedron E.Alphandry, Y.Ding, A.T.Ngo, Z.LWang, F.F.Wu and M.P.Pileni. ACS Nano, 2009, 3, , J. Park, K. An, Y. Hwang, J-G Park, H-J. Noh, J-Y Kim, J-H Park, N-M Hwang and T. Hyeon Nature Material, 2004, 3, ,

4 Crystalline structures retained with crystals of either atoms or nanocrystals Single domain Nanocrystal Supracrystals Bulk Fluorite 5 µm 5cm Polycrystal Nanocrystal Supracrystals Bulk Casserite 500 nm M.P. Pileni J. Phys. Chem. C, 2007,111, , N. Goubet and M. P. Pileni. J. Phys. Chem. Lett, 2011,. 2,

5 Growth of atoms in nanocrystals and nanocrystals in supracrystals {111} Truncature on the {111} surface {111} Tetrahedron Troncated decahedron Expected mechanism with association of two truncated decahedron with 3 nucleation sites Surface reconstruction and formation of nanodisks Truncated tetrahedral of Ag atomic crystal 5 µ Truncated m tetrahedral of Au Nanocrystals Nanodisks of Au Nanocrystals 1 c Mineral truncated m of Au atomic crystals Association of truncated decahedron of Au nanocrystals C. N. Goubet and M. P. Pileni. J. Phys. Chem. Lett., 2011, 2, Mineral association of truncated decahedron atomic crystals

6 Orientational growth processes is retained with crystals of atoms or nanocrystals {111} {110} Additional (110) planes {100} Copper atomic single domain elongated rods Au supracrystal rods [110] 100 nm 20 nm I. Lisiecki, A. Filankembo, H. Sack-Kongehl, K. Weiss, M.P. Pileni and J. Urban Phys. Rev. B, 2000, 61, Mineralrods 500 nm 100 nm Copper atomic nanocubes spectific growth of {111} facets {111} {100} Mineral Grenat Mineral Fluorine {100} 28 nm M.P.Pileni Adv. Funct.Mat., 2005,15, 1277.

7 Analogy between atomic crystals and supracrystals: Self-Assembly of particles Five billions years ago in the early solar system Nozawa, J.; Tsukamoto, K.; van Enckevort, W.; Nakamura, T.; Kimura, Y.; Miura, H.; Satoh, H.; Nagashima, K.; Konoto, M. J. Am. Chem. Soc. 2011, 133, Au supracrystals of nanocrystals differing by size Cigar like ferrite nanocrystals 1 mm 1 m m N.Goubet., H. Portalès.,C.Yang., I. Arfaoui.,P.A. Albouy, A. Mermet. And M.P.. Pileni J. Am, Chem.Soc., 2012, 134, T. Ngo and M.P.Pileni J.Applied Physics 2002,92, 4649, Colloids and Surfaces A: Physicochem. Eng. Aspects, 2003,

8 Analogy between atomic crystals and supracrystals: Negative crystals Negative mineral crystals Negative supracrystals of Au nanocrystals µm {100} 1 {111} bcc {100} {111} {111} fcc nm {111} {100} N. Goubet and M-P. Pileni Nano Res.,2014, 7,

9 Quasi-crystals Natural quasicrystal with decagonal symmetry Quasi supracrystals of nanocrystals (binary system Co/Ag) A B 20 μm 100 nm C D Quasicrystal, (Al 7 1Ni 24 Fe 5, in the Khatyrka meteorite, 20 nm 2 L. Bindi, N. Yao, Ch. Lin, L. S. Hollister, C. L. Andronicos, V. V. Distler, M. P. Eddy, A. Kostin, V Kryachko, G J. MacPherson, William M. Steinhardt, Marina Yudovskay & Paul J. Steinhardt. Scientific reports, 2015, 5 : 9111 Quasi-supracrystal, (Co/Ag nanocrystals) Z.Yang, J. Wei, P. Bonville and M. P. Pileni J.Am.Chem.Soc, 2015, 137, Similar structure with Ag/Ag nanocrystals J. Wei, N. Schaeffer and M. P Pileni J. Am. Chem. Soc., 2015,137,

10 Vicinal surfaces Atomic vicinal surfaces 100 nm 100 nm Au Supracrystals vicinal surfaces 100 nm 100 nm 5 µm 5 µm N. Goubet, J.Yang, P.A.Albouy and M.P.Pileni Nano. Lett., 2014, 14,

11 Self-Assembly of small and large particles at various scales Self-Assembly of small and large silicon microparticles having two different sizes J. V. Sanders, M. J. Murray, ordered arrangements of spheres of two different sizes in opal. Nature, 1978, M. J. Murray, J. V. Sanders, Close-packed structures of spheres of two different sizes II. The packing densities of likely arrangements. Philosophical Magazine A, 1980, 42, Self-Assembly of small and large metal nanocrystals having two different sizes NaZn 13 (100) AlB 2 (110) Z. Yang, J. Wei, P. Bonville, M.P. Pileni Adv. Funct.Mater., 2015, 25, J.Wei, N.Schaeffer and M.P.Pileni Chem. Mater., 2016, 28,

12 Crystal growth at the air-solvent interface under saturated atmosphere Cave pools in central Texas (U.S.A) Crystals growth at the air-water interface Saturated Toluene atmosphere Film of Au nanocrystals SEM image of the film supracrystal Au colloidal solution 1 cm 200 nm N.Goubet., H. Portalès.,C.Yang., I. Arfaoui.,P.A. Albouy, A. Mermet. And M.P.. Pileni J. Am, Chem.Soc., 2012, 134,

13 Isolated nanocrystals Ag Nanocrystals :Breathing modes l exc =488nm Quadrupolar mode I nc (n) µ I D (n)f(n) Fundame ntal radial mode First harmonic Atoms in a nanocrystal breath coherently Nanocrystals self assembled in small 3D supracrystals or forming a disordered film Disordered film I (s) sc (n) µ I 2 nc (n) I nc 2 I cc supracrystals Nanocrystals in supracrystal breath coherently A. Courty, A. Mermet, P.A. Albouy, E. Duval and M.P. Pileni Nature materials, 2005, 4,

14 Longitudinal Acoustic Phonons Cobalt Supracrystals polystirene PMMA Fuse silica Atoms are replaced by (uncompressible) cobalt nanospheres (much heavier! Atomic bonds are replaced by carbon chains ( loose springs). I. Lisiecki, D. Polli, C. Yan, G. Soavi, E. Duval, G. Cerullo and M.P. Pileni Nano Letters, 2013, 13,

15 Cracks Film of 10nm Ferrite nanocrystals Desert 10 mm A T.Ngo, J. Richardi,, and M. P. Pileni Nanoletters, 2008, 8, J.Phys.Chem.B.,, 2008, 112, Yellowstone National Park (USA) Road on a sand dune in the Nil valley 0.5 cm

16 Marangoni process at various scales 350 nm P g Pince anticapillaire Grille de microscpoe T T T+DT T-DT T 0 M. Maillard, L. Motte, A.T. Ngo, and M.P. Pileni J. Phys. Chem.,2000, 104, 11871,, M. Maillard, L. Motte and M.P. Pileni Advanced Mater.,2001, 13, 200), M.P.Pileni J. Phys. Chem.,2001, 105, 3358