Materials Chemistry and Biomolecular Materials at Ames Laboratory

Macroscopic Growth of Metal-Rich Solid-State Phases

Program Scope: A first goal is to design, discover, grow, and characterize novel materials with exotic and/or interesting physical properties. A second goal is to stimulate the international scientific community by sharing our high-quality samples in collaborative studies. Emphasis is placed on quasicrystalline and large-unit-cell crystalline materials. The size and quality of our samples allows the measurement of intrinsic material properties, circumventing the (oft-critical) relationship between growth quality and properties that can lead to spurious results.

Major Program Achievements: We have been the only research group to develop synthesis routes leading to large (up to 2.5 cm³) single grains of these binary phases, specifically the Cd–Yb icosahedral phase (Cd₈₄Yb₁₆), its hexagonal approximant (Cd₅₁Yb₁₄) and the cubic approximant (Cd₈₆Yb₁₄). Thus, the research group was able to study the correlations between local and long-range order in the quasicrystal phase and its corresponding approximant phase.High resolution transmission electron microcopy (HRTEM) and image simulation techniques through focal images revealed a high degree of structural perfection and the remarkable similarity between the local atomic structure of the QC and its approximant phase. This program also made single crystals of icosahedral phase (Cd₁₇Ca₃) and cubic approximant phase (Cd₆Ca). and the migration of pure Cd to form islands and fine whisker was investigated the role of preferential oxidation of Yb or Ca was found to be crucial for enhancing the mobility of Cd atoms across the surface. The characterization by HRTEM on these compounds is ongoing. In addition, this group is the first one to grow centimeter-sized Zn-Sc single grain approximant phase which are sufficient for neutron scattering studies. According to the prediction by M. Mihalkovic (2004) of aperiodic compounds in Mg-Ru-B, we have developed processing techniques to grow single crystals of Mg-Ru-B. Characterizations by powder XRD and single crystal diffraction showed that these single crystals do not correspond to the two known approximant phases. Further structure determination is ongoing. Evaluation of candidate low melting pure metal liquids for fluxes for the single crystal growth Ti-based quasicrystals was initiated. While an appropriate solution has yet to be found we have found and are characterizing several new ternary Ti-Zr based compounds.

Program Impact: Our efforts continue to have a significant impact on the understanding on the structure of quasicrystals and quasicrystalline surfaces and of this program has been tremendous. We continue to share high quality single crystals for collaborative research. Over 30 labs throughout the world have used the high quality quasicrystals samples synthesized at Ames Laboratory, thus allowing the field to advance at a pace faster than otherwise possible. Through such collaborations, for example, our samples have led to consensus on the fundamental surface structure of icosahedral quasicrystals.

Contact Information:
Thomas Lograsso

Selected Publications

Y. Q. Wu, M. J. Kramer and T. A. Lograsso, "Local Order in Single Grain Cd-Yb Icosahedral Phase", Quasicrystals 2003--Preparation, Properties and Applications, Eds.: E. Belin-Ferré, M. Feuerbacher, Y. Ishii, D. Sordelet, MRS Symposium Proceedings, 805, LL7.4 (2004).
V. Fournée, A.R. Ross, T.A. Lograsso and P.A. Thiel, "Orientation Relationship Between Metallic Thin Films and Quasicrystalline Substrates", Quasicrystals 2003--Preparation, Properties and Applications, Eds.: E. Belin-Ferré, M. Feuerbacher, Y. Ishii, D. Sordelet, MRS Symposium Proceedings, 805, LL8.3 (2004).
G. Krauss, S. Deloudi, A. Steiner, W. Steurer, A. R. Ross and T. A. Lograsso, " The Stability of Icosahedral Cd-Yb" Quasicrystals 2003--Preparation, Properties and Applications, Eds.: E. Belin-Ferré, M. Feuerbacher, Y. Ishii, D. Sordelet, MRS Symposium Proceedings, 805, LL1.8 (2004).
H. R. Sharma, M. Shimoda, J. Barrow, A. R. Ross, T. A. Lograsso, P. A. Thiel and A. P. Tsai, "Morphology of Sn Films Grown on the Fivefold Surface of Icosahedral Al63Cu23Fe13 Investigated by Scanning Tunneling Microscopy", Quasicrystals 2003--Preparation, Properties and Applications, Eds.: E. Belin-Ferré, M. Feuerbacher, Y. Ishii, D. Sordelet, MRS Symposium Proceedings, 805, LL 7.11.1 (2004).
F. Yu, M. Bischoff, A. R. Ross, T. A. Lograsso, H. van Kempen and T. Janssen, " SEM and AFM Studies of 5-fold Surface of Icosahedral AlPdMn ", J . of Noncrystalline Solids, 334-335, 495 (2004).
J. Ledieu, J. T. Hoeft, D. E. Reid, J. A. Smerdon, R. D. Diehl, T. A. Lograsso, A. R. Ross and R. McGrath, " Pseudomorphic Growth of a Single Element Quasiperiodic Ultrathin Film on a Quasicrystal Substrate ", Phys. Rev. Lett., 92, 135507 (2004).	Reprint
S. Francoual, K. Shibata, M. de Boissieu, A. Q. R. Baron, S. Tsutsui, R. Currat, H. Takakura, A. P. Tsai, T. A. Lograsso and A. R. Ross, " Experimental Study of the Dynamics of the Icosahedral CdYb Phase and Its 1/1 Periodic Approximant ", Ferroelectrics, 305, 235 (2004).
C. A. Swenson, T. A. Lograsso, N. E. Anderson, Jr. and A. R. Ross, "Bridgman-grown i -Al68.9 Pd21.6 Mn9.5 Quasicrystal, Comparison of alpha , Cp, beta and gama with those for Flux-grown Samples", Phys. Rev. B, 70, 094201(2004).	Reprint
H. R. Sharma, V. Fourn é e, M. Shimoda, A. R. Ross, T. A. Lograsso, A. P. Tsai and A. Yamamoto, "Structure of the Fivefold Surface of the Icosahedral Al-Cu-Fe Quasicrystal: Experimental Evidence of Bulk Truncations at Larger Inter-layer Spacings", Phys Rev Lett., 93, 165502 (2004).	Reprint
J. Schreuer, W. Steurer, T .A. Lograsso and D. Wu, "Elastic Properties of Icosahedral i - Cd 84Yb16 and Its Hexagonal Approximant h - Cd51Yb14 ", Phil. Mag. Lett., 84, 643 (2004).
H. R. Sharma, M. Shimoda, V. Fournée, A. R. Ross, T. A. Lograsso and A. P. Tsai, " First Steps in the Growth of Cu Thin Films on the Fivefold Surface of the Icosahedral Al-Cu-Fe Quasicrystal", Appl. Surface Science , 241, 256 (2005).	Reprint
B. Unal, T. A. Lograsso, A. Ross, C. J. Jenks and P. A. Thiel, "Terrace Selection during Equilibration at an Icosahedral Quasicrystal Surface", Phys. Rev. B, 71 , 165411 (2005).	Reprint
J. Ledieu, E. J. Cox, R. McGrath, N. V. Richardson, Q. Chen, V. Fournee, T. A. Lograsso, A. R. Ross, K. J. Caspersen, B. Unal, J. W. Evans and P. A. Thiel, "Step Structure on the Five-Fold Al-Pd-Mn Quasicrystal Surface, and on Related Surfaces", Surface Science, 583, 4 (2005).	Reprint
T. C. Q. Noakes, P. Bailey, C. F. McConville, C. R. Parkinson, M. Draxler, J. Smerdon, J. Ledieu, R. McGrath, A. R. Ross and T. A. Lograsso, " Compositional and Structural Changes in i -AlPdMn Quasicrystals Induced by Sputtering and Annealing: A Medium Energy Ion Scattering Study", Surface Science, 583, 139 (2005).	Reprint
H. R. Sharma, M. Shimoda, V. Fournée, A. R. Ross, T. A. Lograsso and A. P. Tsai, "RHEED and STM Studies of the Pseudo-Tenfold Surface of the x '-Al77.5Pd19Mn3.5 Approximant Crystal", Phys. Rev B., 71, 224201 (2005).	Reprint
M. J. Kramer, D. J. Sordelet and T. A. Lograsso, " Solid and Liquid Thermal Expansion and Structural Observations in the Quasicrystalline Cd84Yb16 Compound ", Phil Mag. Lett., 85, 151 (2005).
J. Ledieu, J. T. Hoeft, D. E. Reid, J. A. Smerdon, R. D. Diehl, N. Ferralis, T. A. Lograsso, A. R. Ross, and R. McGrath, " Copper Adsorption on the Fivefold Al70Pd21Mn9 Quasicrystal Surface", Phys. Rev. B, 72, 035420 (2005).	Reprint
H. R. Sharma, M. Shimoda, A. R. Ross, T. A. Lograsso, and A. P. Tsai, " Real-Space Observation of Quasicrystalline Sn Monolayer Formed on the Fivefold Surface of Icosahedral Al-Cu-Fe Quasicrystal" Phys. Rev. B., 72, 045428 (2005).	Reprint
V. Fournée, H. R. Sharma, M. Shimoda, A. P. Tsai, B. Unal, A. R. Ross, T. A. Lograsso and P. A. Thiel, "Quantum Size Effects in Metal Thin Films Grown on Quasicrystalline Substrates", Phys. Rev Lett., 95, 155504 (2005).	Reprint
J. Ledieu, P. Unsworth, T. A. Lograsso, A. R. Ross, and R. McGrath , " Ordering of Si Atoms on the Five-fold Al-Pd-Mn Quasicrystal Surface ", Phys. Rev. B, 73, 012204 (2006).	Reprint
J. T. Hoeft, J. Ledieu, S. Haq, T. A. Lograsso, A. R. Ross and R. McGrath, "Adsorption of Benzene on the Five-fold Surface of the i -Al70Pd21Mn9 Quasicrystal", Phil. Mag, 86, 869 (2006).
J. A. Smerdon, J. Ledieu, J. T. Hoeft, D. E. Reid, L. H. Wearing, R. D. Diehl, T. A. Lograsso, A. R. Ross and R. McGrath, "Adsorption of Cobalt on the Five-Fold Surface of AlPdMn and the Ten-Fold Surface of AlNiCo", Phil. Mag, 86, 841 (2006).
H. R. Sharma, M. Shimoda, A. R. Ross, T. A. Lograsso and A.P. Tsai, " Observation of Terrace Dependent Morphology of Thin Sn Film Deposited on the Fivefold Surface of the Icosahedral Al-Cu-Fe Quasicrystal ", Phil. Mag., 86 , 807 (2006).
D. Wu, O. Ugurlu, L. S. Chumbley, M. J. Kramer and T. A. Lograsso, " Synthesis and Charact erization of Hexagonal Cd51Yb14 Single Crystals", Phil. Mag., 86 , 381 (2006).
G. Krauss , W. Steurer, A. R. Ross and T. A. Lograsso, "Stability of Icosahedral Cd-Yb at Low Temperature", Phil. Mag., 86 , 505 (2006).
B. Unal, T. A. Lograsso, A. R. Ross, C. J. Jenks, and P. A. Thiel, " Voids and Pits on Sputter-Annealed Fivefold Terraces of Icosahedral Al-Pd-Mn Quasicrystals", Phil. Mag., 86 , 819 (2006).
R. Bastasz, J. A. Whaley, T. A. Lograsso and C. J. Jenks, " Hydrogen Interactions with Quasicrystalline Al-Pd-Mn Surfaces ", Phil. Mag., 86 , 855 (2006).
T. C. Q. Noakes, P. Bailey, M. Draxler, C. F. McConville, A. R. Ross, T. A. Lograsso, L. Leung, J. A. Smerdon and R McGrath, "Film Growth arising from the Deposition of Au onto an i -Al-Pd-Mn Quasicrystal: A Medium Energy Ion Scattering Study", J. Phys.: Condens. Matter , 18 , 5017 (2006).
J. A. Smerdon, J. Ledieu, R. McGrath, T. C. Q. Noakes, P. Bailey, M. Draxler, C. F. McConville, T. A. Lograsso, and A. R. Ross, " Characterization of Aperiodic and Periodic Thin Cu Films Formed on the Five-fold Surface of i -Al70Pd21Mn9 using Medium-energy Ion Scattering Spectroscopy", Phys. Rev B, 74, 035429 (2006).	Reprint
L. Leung, J. Ledieu, P. Unsworth, T.A. Lograsso , A.R. Ross and R. McGrath, " Ordering of Si atoms on the Ten-fold Surface of the Decagonal Al72Ni11Co17 Quasicrystal", Surface Science, 600, 4752 (2006).	Reprint

Materials Chemistry and
Biomolecular Materials Program

Ames Laboratory
Iowa State University
142 Spedding Hall
Ames, IA 50011 USA

Phone: 1.515.294.7568
FAX: 1.515.294.4709