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Introduction to Nanoscience

LECTURE 10 Nanomaterials, Surface and Structure II
G.L. Hornyak Copyright: CRC Press 2009

Agenda

• Crystal Systems • Packing Fraction and Densities

Copyright: CRC Press 2009

CRYSTAL SYSTEMS Copyright: CRC Press 2009 .

Cubic Systems Bravais Lattice Systems .

FCC (Bottom Left) and HCP (Bottom Right) Tetragonal Hole (Left). Octahedral Hole (Right) Copyright: CRC Press 2009 .

Gauss: π 3 2 = 0.F.74 Copyright: CRC Press 2009 .HCP and FCC A A B A B C The highest density of packing of spheres follows the rule of C.

a macroscopic crystal. Coordination number (CN or Z) is the number of nearest neighbors an atom has within the unit cell. Coordination and Packing Fraction The Unit Cell is an irreducible representation of the crystal structure of a pure material.γ. eventually. It is defined by a set of parameters called “lattice parameters”. Lattice parameters include: cell dimensions a. Copyright: CRC Press 2009 . Packing fraction f is the fraction of space occupied by atoms in the unit cell compared to the whole volume of the cell.b.c and crystallographic angles α.β.The Unit Cell. Adding unit cells together result in. There are 14 Bravais lattices.

γ). Factors affecting lattice structure and constants: • Crystal type (affects bond length) • Atom size • Temperature and pressure • Chemical composition • Particle size? Copyright: CRC Press 2009 .c) and the angles between them (α.β.b.Lattice Constants Lattice constants (or parameters) are characteristics of the unit cell that define its volume (a.

Freeman & Co. New York (1990) .97 6 0. P.E. Langford.96 4 0. Bond length varies with CN: Coordination Number Relative Radius 12 1. W.Coordination Number Coordination number is: – Large for metals (typically 8 – 12) – Intermediate for ionic compounds (typically 6) – Low for molecular solids (covalent.00 8 0.H. Inorganic Chemistry. Shriver. Atkins and C. metals are the most dense → covalent solids the least.88 This should serve as an indication of things to come! Source: D.. 4) Therefore.H.W.

Copyright: CRC Press 2009 . Nano Phenomenon #38 Lattice constants are influenced by particle size— unsaturated coordination of surface atoms causes distortions in the lattice. Unit cells are at the small frontier of the nanometer.Nano Phenomenon #37 It takes only a couple unit cells to make a nanometer.

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Copyright: CRC Press 2009 .Cubic Systems • Metal atom bonds = non-directional. Only polonium is sc. “Hard sphere models” adequately illustrate the packing. • Cubic systems are the simplest to visualize a = b = c and α = β = γ • There are three basic kinds: – Simple (or primitive) cubic (sc) – Body-centered cubic (bcc) – Face-centered (or closest-packed) cubic (fcc) • Many metals are configured as bcc and fcc (others as hcp). Metals (and ionic compounds) are polymorphic (due to T & P).

Copyright: CRC Press 2009 .Atomic Radius and Lattice Constants SC r dbody BCC FCC dface ao = 2r dbody = ao√3 = 4r dface = ao√2 = 4r Atoms are touching along these vectors.

04631 nm3 fcc However.34% Vfcc 0. it metamorphs into the fcc structure. At higher temperatures (> 913°C).Example 10.02347) ΔV = = x100 = −1. € Copyright: CRC Press 2009 . Vbcc = a 3 bcc = (0.2863 nm) = 0.02347 nm3 3 3 Vfcc = a 3 = (0.1 Q: Allotropic transformations: At lower temperatures.3591 nm. iron has a bcc structure (< 911°C).04695 Iron contracts upon heating.2863 nm and afcc = 0.3591 nm) = 0. a bcc cell has 2 atoms while an fcc has 4 per unit cell: € Vfcc − 2 ⋅ Vbcc 0. What is the change in volume of a bcc iron transition to fcc iron at temperature given that abcc = 0.04631− 2 ⋅ (0.

The Al remains as an fcc lattice. The multilayers have a common [111] growth direction.High resolution TEM of Ti and Al multilayers grown by E-beam deposition. The TiH is hcp but transforms to an an fcc atomic arrangement. National Institute of Standards and Testing (NIST) (2008). . Source: Metallurgy Division of the Materials Science and Engineering Laboratory (MSEL).

633a (ideally) Many metals crystallize as hcp structures.Hexagonal Close Packed Systems A B co CN = 12 Polytype: ABABABAB… a=b≠c α = β = 90° γ= 120° ao = 2r c = 1. A ao = 2r Copyright: CRC Press 2009 .

Example 10.633⋅ (2 ⋅ 0.633a.866 = 0.04634nm ) ⋅ (6.633⋅ (2rhcp ) ⋅ 0.04634 nm3 3 € ρ Mg (# Atoms per unit cell) ⋅ M = Vhcp ⋅ N A Mg = 2 ⋅ 24. What is the theoretical density of Mg (r = 0.866 = 0.160 nm)? f hcp f hcp = (# Atoms ⋅ unit cell) ⋅ V = Vhcp = 4 3 3 πrhcp hcp 8 3 Atom (2) ⋅ 2 hcp 3 πrhcp 3 € € (2r ) ⋅ (1.74g ⋅ cm  cm  Copyright: CRC Press 2009 . c = 1.2 Q: Packing fraction of hcp: Calculate f for a hexagonal close packed structure where a = 2r.633⋅ (2rMg ) ⋅ sin60° = 1.31g ⋅ mol−1 ( ) ⋅ mol-1 (0.022x10 3 23 ) 10 7 nm 3 −3 ⋅  = 1.160 nm) ⋅ 0.74 Density of Mg: Vhcp− Mg = 1. Vhcp = a2c(sin60°).633⋅ 2r ) ⋅ sin 60° 3 1.

are directional.g. There are two kinds of tetragonal lattices: simple and body-centered.ZnS) is similar to diamond cubic with Zn2+ filling one-half the tetrahedral holes. Si. Ge. Diamond cubic (dc) is a special version of an fcc crystal in which one-half of the tetrahedral holes are filled with additional atoms.Tetragonal Systems Metal bonds are non-directional resulting in simple crystal structures. However. Sn and diamond are configured in the dc crystal types. Tetragonal systems are like cubic systems with one axis extended (a = b ≠ c and α = β = γ = 90°). Covalent bonds. covalent and metal compounds are more complex. Bodycentered tetragonal bct is an extended bcc system. ionic. for example. Copyright: CRC Press 2009 . Zinc Blende (e.

dbody = ao√3 = 8r There are 8 atoms per dc cell: dbody # Atoms ⋅ VAtom f = and 8r = ao 3 Vdtc f = € 3 4 # Atoms ⋅ 3 πrSi a 3 o = 3 4 8 ⋅ 3 πrSi (8r Si 3 ) 3 = 0. Visualization is not easy for this cell. The white circles represent voids. dc structures are therefore quite open.Example 10. Copyright: CRC Press 2009 .34 € ao The packing fraction is much lower than for any of the metals.3 Q: Determine the packing fraction f for a dc cell.

3253 nm) ⋅ (0.Example 10.52a Copyright: CRC Press 2009 .687 Atoms touch along the body diagonal where: a a € and c = 1.3253 nm.1626 nm.189) ⋅ (0.1626 nm) 2 3 c € (0.4956 nm and r = 0.4956 nm) d Body = a 2 + a 2 + c2 = 4r = 0. # Atoms → are like bcc = 2 r  4 πr 3  x ⋅ VIn f = = 2⋅ 3 2   ac  VCell   = 2 ⋅ (4.4 Q: Calculate the packing fraction for Indium— a metal that crystallizes in a tetragonal body-centered bct configuration: a = 0. c = 0.

01 g ⋅ cm 3 Vfcc ⋅ N A (0. its density should increase. € bcc Iron (α-Fe): ρα −Fe = # Atoms ⋅ M Fe Vbcc ⋅ N A The accepted density of iron is 7.022x1023  cm  4 ⋅ 55. # atoms = 2 and 4 respectively. γ-Fe? Atomic mass In = 114.818 g·mol-1. € fcc Iron (γ-Fe): 10 7 nm 3 3 = ⋅  = 7.27 g ⋅ cm a 2c ⋅ 6.5 # Atoms ⋅ M In ρ In = VUnitCell ⋅ N A 3 2 ⋅ 114.31 g·cm-3.90 g ⋅ cm 3 0.818 g ⋅ mol−1 10 7 nm  3 = ⋅  = 7. Copyright: CRC Press 2009  10 7 nm 3 # Atoms ⋅ M In 3 = = ⋅  = 8.Q: What is the theoretical density of indium? of α-.874 g·cm-3.3591) ⋅ 6. Indium: Example 10.022x1023  cm  ( 2 ⋅ 55.845 g ⋅ mol−1 ( ) € .022x1023  cm  ( ) The accepted density of indium is 7.845 g ⋅ mol−1 ( ) ργ −Fe Since iron contracts upon heating. a and c are as before.2863) ⋅ 6.

Although this section was fairly descriptive and fundamental to materials science. Copyright: CRC Press 2009 . it is essential to the understanding of what is to come later on in the course. Unit cells exist at the frontier of the nanoscale 38. Lattice parameters are influenced by size. More Nano Phenomena 37.Summary Once again we are dealing with a concept or characteristic that exists at the frontier boundary of the nanoscale.