MSE 5043 Lecture 2 8/21/13

Review of vector algebra 7 Crystal systems 14 Bravais lattices Planes and directions Symmetry
Mirror planes Rotational symmetry Inversion symmetry

Number density of atoms on a plane (2-D) Number density of atoms along a direction (1-D)

Crystal systems
Easy to see how cubic structures are built by stacking planes of atoms, i.e., the hard sphere model. What if the basic building blocks of the crystal are not spheres? Need a systematic way to describe more complicated unit cells. Definitions: crystalline - long range periodic order amorphous - no long range order (glass, liquid, or gas) crystal structure - The manner in which atoms or ions are arrayed in space. Given by unit cell geometry and the positions within the unit cell. crystal system - a systematic variation of the unit cell geometry (i.e., side lengths and angles)
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Filling Space
Options in 2-D
Note: the unit cell is made up of two sets of parallel lines.

a=b, g=90o
a b g b

ab, g=90o
a g b

a=b, g 90o g=120o a g b

a b, g 90o

a
g

Could fill an entire 2-D plane by repeating any of these Which has the most symmetry? 3

Need a 3-D unit cell

Use 3 sets of parallel planes. Overlap of two planes is a line, three planes is a point. What parameters are necessary to describe this set of planes? Need distance between the planes and angle between the planes. What vectors should we use to describe the set of points defined by the intersection of three planes?
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plane set 2

plane set 1

The general 3-D unit cell

We can vary the spacing between planes (a, b, c) as well as the angles (a, b, g) How many combinations can we have? (1)cubic: a=b=c, a=b=g=90o (2)tetragonal: a=bc, a=b=g=90o (3)orthorhombic: a bc, a=b=g=90o (4)rhombohedral: a = b=c, a=b=g 90o (5)hexagonal: a = bc, a=b=90o, g=120o (6)monoclinic: a bc, a=b =90o, g 90o (7)triclinic: a bc, a b g 90o
b

c a b a g

The Space Lattice and Unit Cells

Atoms, arranged in repetitive 3-Dimensional pattern, in long range order (LRO) give rise to crystal structure. Properties of solids depends upon crystal structure and bonding force. An imaginary network of lines, with atoms at intersection of lines, representing the arrangement of atoms is called space lattice. Space Lattice

Unit cell is that block of atoms which repeats itself to form space lattice.
Materials arranged in short range order are called Unit Cell amorphous materials
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Crystal Systems and Bravais Lattice

Only seven different types of unit cells are necessary to create all point lattices. According to Bravais (1811-1863) fourteen standard unit cells can describe all possible lattice networks. The four basic types of unit cells are Simple Body Centered Face Centered Base Centered

Types of Unit Cells

Cubic Unit Cell
a=b=c

= = = 900

Simple

Body Centered

Face centered Tetragonal

a =b c

= = = 900

Simple

Body Centered

8 After W.G. Moffatt, G.W. Pearsall, & J. Wulff, The Structure and Properties of Materials, vol. I: Structure, Wiley, 1964, p.47.)

Types of Unit Cells (Cont..)

Orthorhombic
a b c

= = = 900

Simple

Base Centered

Body Centered Face Centered Rhombohedral

a =b = c

= = 900

Simple
9 After W.G. Moffatt, G.W. Pearsall, & J. Wulff, The Structure and Properties of Materials, vol. I: Structure, Wiley, 1964, p.47.)

Types of Unit Cells (Cont..)

Hexagonal
a= b c

= = 90o, = 120o

Simple

Monoclinic
a b c

= = 900

Base Centered Triclinic

a b c

Simple

900

Simple
10 After W.G. Moffatt, G.W. Pearsall, & J. Wulff, The Structure and Properties of Materials, vol. I: Structure, Wiley, 1964, p.47.)

Cubic
a=b=c a=b=g=90o TOP b a g c a SIDE

FRONT b c a

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Tetragonal
a=bc a=b=g=90o b TOP g c a b SIDE

FRONT b
c a

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Orthorhombic
ab c a=b=g=90o b a

TOP a c b

SIDE

FRONT b c a

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Monoclinic
ab c a=b= 90o ;g90o b g a c b TOP a SIDE

FRONT b c a

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Directions and planes

vector: a set of coordinates that defines a point in space.
z p w y u v x

p =ui+vj+wk i, j, k are unit vectors in Cartesian coordinate system Based on the coordinate system, we can uniquely define any vector p by specifying the values for u, v, and w.

z p x y

p =ua+vb+wc a, b, c are unit cell vectors

Based on the coordinate system, we can uniquely define any vector p by specifying the values for u, v, and w.

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Lattice Directions
c [111] [121] b

Pick a convenient origin multiply or divide by a scalar to reduce to the smallest set of integers possible express direction as [uvw] (note: no commas)
[110]

[101]

negative sign shown as a bar over the number equivalent directions exist; the spacing of points along those directions is identical (e.g., in cubic systems the body diagonals are equivalent so -- --- -- - [111], [111], [111],[111],[111],[111],[111],[111]

[101]

-c

[121] a

---

--[111]

[110]

--

4 are unique lines we can now define a family of lines as <111>

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Directions in Cubic Unit Cells

In cubic crystals, Direction Indices are vector components of directions resolved along each axes, resolved to smallest integers. Direction indices are position coordinates of unit cell where the direction vector emerges from cell surface, converted to integers.

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Procedure to Find Direction Indices

Produce the direction vector till it emerges from surface of cubic cell Determine the coordinates of point of emergence and origin Subtract coordinates of point of Emergence by that of origin x z
(1,1/2,1)

(1,1/2,1) - (0,0,0) = (1,1/2,1) y 2 x (1,1/2,1) = (2,1,2)

(0,0,0)

The direction indices are [212] Convert them to smallest possible integer by multiplying by an integer.

NO Are all are integers? YES Are any of the direction vectors negative?
YES Represent the indices in a square bracket without comas with a over negative index (Eg: [121])
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NO
Represent the indices in a square bracket without comas (Eg: [212] )
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Direction Indices - Example

Determine direction indices of the given vector. Origin coordinates are (3/4 , 0 , 1/4). Emergence coordinates are (1/4, 1/2, 1/2).

Subtracting origin coordinates from emergence coordinates, (1/4, 1/2, 1/2) - (3/4 , 0 , 1/4) = (-1/2, 1/2, 1/4) Multiply by 4 to convert all fractions to integers 4 x (-1/2, 1/2, 1/4) = (-2, 2, 1) Therefore, the direction indices are [ 2 2 1 ]

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Miller Indices
Miller Indices are are used to refer to specific lattice planes of atoms. They are reciprocals of the fractional intercepts (with fractions cleared) that the plane makes with the crystallographic x,y and z axes of three nonparallel edges of the cubic unit cell.

Miller Indices =(111)

y x
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Miller Indices - Procedure

Choose a plane that does not pass through origin

Determine the x,y and z intercepts of the plane

Find the reciprocals of the intercepts Fractions? Place a bar over the Negative indices

Clear fractions by multiplying by an integer to determine smallest set of whole numbers

Enclose in parenthesis (hkl)where h,k,l are miller indicesof cubic crystal plane forx,y and z axes. Eg: (111)
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Miller Indices - Examples

z (100) Intercepts of the plane at x,y & z axes are 1, and Taking reciprocals we get (1,0,0). Miller indices are (100). ******************* Intercepts are 1/3, 2/3 & 1. taking reciprocals we get (3, 3/2, 1). Multiplying by 2 to clear fractions, we get (6,3,2). Miller indices are (632).

y
x x

Figure 3.14 3-21

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Miller Indices - Examples

Plot the plane (101) Taking reciprocals of the indices we get (1 1). The intercepts of the plane are x=1, y= (parallel to y) and z=1. ****************************** Plot the plane (2 2 1) Taking reciprocals of the indices we get (1/2 1/2 1). The intercepts of the plane are x=1/2, y= 1/2 and z=1.

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Miller Indices - Example

Plot the plane (110) The reciprocals are (1,-1, ) The intercepts are x=1, y=-1 and z= (parallel to z axis) z To show this plane in a (110) single unit cell, the origin is moved along the positive direction y of the y axis by 1 unit.

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Miller Indices Important Relationship

Direction indices of a direction perpendicular to a crystal plane are same as miller indices of the plane. z Example:-

(110)

[110]
x
Interplanar spacing between parallel closest planes with same miller indices is given by

d
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hkl

k l
2

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Symmetry
a) PLANES (SYMMETRY BY REFLECTION)

b) AXES (SYMMETRY OF ROTATION)

4 FOLD

c) CENTER (POINT SYMMETRY)

3 FOLD 2 FOLD
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Minimum symmetry
CUBIC TEGRAGONAL ORTHORHOMBIC
HEXAGONAL RHOMBOHEDRAL MONOCLINIC TRICLINIC EXAMPLES

FOUR 3 FOLD ROTATION AXES ONE 4 FOLD ROTATION AXIS THREE PERPENDICULAR 2 FOLD ROTATION AXES ONE 6 FOLD ROTATION AXIS ONE 3 FOLD ROTATION AXIS) ONE 2 FOLD ROTATION AXIS NONE

ORTHORHOMBIC 2 FOLD

TETRAGONAL 4 FOLD

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Planar and linear density

BCC

LINEAR DENSITY ALONG CUBE DIAGONAL IS 2 POINTS PER 3 a

AREA DENSITY OF SHADED PLANE IS 2 POINTS PER 2 a2

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Example: Directions
Q. List the coordinates for the Cl- ions in the NaCl crystal structure. A. First define the origin and unit vectors. Cl- in the (001) plane [0 1 0],[0.5 0.5 0], [1 1 0],[1 0 0],[0 0 0] Cl- in the (002) plane [0 0.5 0.5],[0.5 1 0.5], [1 0.5 0.5],[0.5 0 0.5]

Cl- in the (001) plane [0 1 1],[0.5 0.5 1], [1 1 1],[1 0 1],[0 0 1]

c b a
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Example: Planes
Q. In the orthorhombic unit cell, sketch the (001), --(210), and (111) planes. A. (001) Plane - intercepts are ,,1 (210) Plane - intercepts are 1/2,1, --(111) Plane - intercepts are -1,-1,-1

ab c a=b=g=90o
c b a
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