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Crystal

y Structure

Eui Tae Kim


Eui-Tae

Department of Materials Science & Engineering


Chungnam National University
Crystal structure determination

ƒ What holds atoms together? Æ Valence electrons of the atoms


ƒ What is the special arrangement of these atoms Æ Crystal structure
ƒ Why diamond structure?
C 6 1s2 2s2 2p2
Si 14 1s2 2s2 2p6 3s2 3p2 1/4,3/4,3/4

Ge 32 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p2


3/4,1/4,3/4
Ga 31 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p1
As 33 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p3
3/4,1/4,1/4
1/4,1/4,1/4
Æ Valence electrons contribute to bonding, electrical
transport, optical properties, etc. 0,0,0

For Si, Ge, etc.


¾ Free atom Æ s2p2 Æ will be cubic
¾ Solid Æ sp3 (in along <111>) Æ diamond structure
4 sp3 hybrid orbitals
Æ Tetrahedral bond
Slide 2
Crystal structure determination

ƒ Atomic orbitals
s u100 ~ exp(-zr/ao)
p u210 ~ exp(-zr/2ao)·cosθ
d u32±1 ~ exp(-zr/3ao)·sinθcosθ (l=2, m=-2, -1, 0, 1, 2 Æ 5 d orbitals)

s orbital y p orbital y
[px, py, pz] +
- + ex) Ni Æ 3d84s2
x x Æ FCC
-
Ni y Ni
d orbital d orbital z
[dxy, dyz, dzx] y [dz^2, dx^2-y^2]
+
- + Ni
- - x
x x
+ - + Ni Ni

Slide 3
Periodic Table for structure information

He He

Li Be B C N O F Ne

Na Mg Al Si P S Cl Ar

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra Ac

BCC HCP FCC Dia. At Room temp.

Slide 4
Characteristics of Cubic Lattices

Simple BCC FCC

Volume, conventional cell a3 a3 a3


Lattice points per cell 1 2 4
Volume, primitive cell a3 1/2a3 1/4a3
Lattice points per unit volume 1/a3 2/a3 4/a3
Number of nearest neighbors 6 8 12
Nearest-neighbor distance a 0.866a 0.707a
Number of second neighbors 12 6 6
Second neighbor distance 21/2a a a
Packing fraction 1/6π 1/8π√3 1/6π√2
=0.524 =0.680 =0.740

Slide 5
Crystal Structure

Making Close Packed Structures

Cubic Close Packed


(CCP) Structure:

Hexagonal Close Packed


(HCP) Structure

Slide 6
Crystal Structure

FCC (111) and HCP (0001) planes Æ close packed planes.


Stacking of FCC along the [111] Æ ABCABC…
Stacking of HCP along the [0001] Æ ABABAB… Slide 7
Crystal Structure

CsCl (different surroundings)


Different atoms !!!

Simple cubic

Cs+: 000, Cl-: ½ ½ ½.

NaCl
(different surroundings)
Different atoms !!!

FCC
4Na+: 000, ½ ½ 0, ½ 0 ½, and 0 ½ ½.
-
4 Cl : ½ ½ ½, 0 0 ½, 0 ½ 0, and ½ 0 0.
4 Na+: 000 + face-centered translations.
4 Cl-: ½ ½ ½ + face-centered translations.
Only consider the same surroundings to determine a lattice Slide 8
Crystal Structure

Comparison of CsCl and NaCl planes

Slide 9
Crystal Structure

Diamond and Zinc Blende

000 + face-centered translations.


¼ ¼ ¼ + face-centered translations.
Slide 10
Solid Solutions: Substitutional vs.
Interstitial

Substitutional: Mo in Cr
Mo

Cr

interstitial: C in α-Fe

Fe

Slide 11
Octahedral and Tetrahedral Sites

Slide 12
Octahedral and Tetrahedral Sites in
Close Packed Structure

Tetrahedral holes Octahedral holes

3 Pointing up (at sides)


1 Pointing down (at center) Slide 13
Octahedral sites in FCC

Shared with 4

# of sites/unit cell = 1 + 12x1/4 = 4

Slide 14
Tetrahedral sites in FCC

This account for 4

This account for another 4

# of sites/unit cell = 4x2 = 8

# of “Tetra” = 2 x # of “Octa” Slide 15


Octahedral sites in HCP

# of sites/unit cell = 6 (or 6/3 = 2)

Slide 16
Tetrahedral sites in HCP

This account for 6

Interior position
Shared position

This account for


another 6
# of sites/unit cell (2 + 12x1/3 = 6)
= 12/3 = 4

# of sites/unit cell = 12 or (12/3 =4)


# of “Tetra” = 2 x # of “Octa” Slide 17
Another type of site: Cubic Site

Cubic sites are not present is close packed structures.


The cubic site has a larger interstitial volume than “octa” and “tetra”.

Slide 18
All Octahedral Sites Occupied

NaCl (FCC) NiAs (HCP)

CCP Na+ with Cl- in all Octahedral sites HCP As with Ni in all Octahedral sites
Lattice: fcc Lattice: Hexagonal - P
Motif: Na at (0,0,0); Cl at (1/2,0,0) Motif: 2Ni at (0,0,0) & (0,0,1/2) 2As at
4NaCl in unit cell (2/3,1/3,1/4) & (1/3,2/3,3/4)
2NiAs in unit cell

Slide 19
All Tetrahedral Sites Occupied

CaF2 (FCC) ? (HCP)

Not known

CCP Ca2+ with F- in all Tetrahedral holes


Lattice: fcc
Motif: Ca2+ at (0,0,0);
2F- at (1/4,1/4,1/4) & (3/4,3/4,3/4)
4CaF2 in unit cell

Slide 20
Half Tetrahedral Sites Occupied

ZnS, Zinc Blende (FCC) ZnS, Wurtzite (HCP)

HCP S2- with Zn2+ in half Tetrahedral


CCP S2- with Zn2+ in half Tetrahedral holes Lattice: Hexagonal - P
holes Lattice: fcc Motif: 2S at (0,0,0) & (2/3,1/3,1/2);
Motif: S at (0,0,0); Zn at (1/4,1/4,1/4) 2Zn at (2/3,1/3,1/8) & (0,0,5/8)
4ZnS in unit cell 2ZnS in unit cell

Slide 21
Cubic Site Occupied

CsCl (SC)

SC Cs+ with cubic holes


Lattice: simple cubic
Motif: Cl- at (0,0,0); Cs+ at (1/2,1/2,1/2)
1CsCl in unit cell

Slide 22

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