Chapter 5

How does a lattice differ from a crystal structure?

Crystal structures and crystal lattices are different, although these terms are

frequently (and incorrectly) used as synonyms. A crystal structure is built of atoms.

A crystal lattice is an infinite pattern of points, each of which must have the same

surroundings in the same orientation. A lattice is a mathematical concept. If any

lattice point is chosen as the origin, the position of any other lattice point is defined

by

P(uvw) = ua + vb + wc

where a, b, and c are vectors, called basis vectors, and u, v and w are positive or

negative integers. There are only 14 three-dimensional lattices, called Bravais

lattices, which are sometimes called direct lattices. There are a vast number of

different crystal structures as each crystalline compound has a different crystal

structure.

What is a unit cell?

A unit cell is the smallest, or close to smallest, regular volume can be used to

construct a lattice or a crystal structure. For a lattice, the parallelepiped formed by

three basis vectors a, b and c, defines the unit cell of the lattice, with edges of length

a, b, and c. Clearly there are any number of ways of choosing a, b and c and the

unit cell and conventions are used to avoid ambiguity. Stacking these unit cells by

translation, without rotation, builds the whole lattice. In a crystal, the repetitive

organisation is also defined in terms of a unit cell which contains all of the atomic

species in the crystal, and which, when stacked in three-dimensions, reproduces the

macroscopic crystal.
 As with space lattices all crystal structures can be allocated to one of just

seven unit cell types.

How are crystal structures determined?

Crystal structures are determined by using diffraction. X-ray diffraction is the

most widespread technique used for structure determination, but diffraction of

electrons and neutrons is also of great importance, as these reveal features that are

not ready observed with X-rays.

The physics of diffraction by crystals has been worked out in detail. It is

found that the incident radiation is diffracted in a characteristic way, called a

diffraction pattern. If the positions of the diffracted beams are recorded, they map

out the reciprocal lattice of the crystal, which allows the unit cell of the structure to be

determined. The intensities of the beams are a function of the arrangements of the

atoms in space and some other atomic properties, especially the atomic number of

the atoms. Thus, if the positions and the intensities of the diffracted beams are

recorded, it is possible to deduce the arrangement of the atoms in the crystal and

their chemical nature. The technique has been used to solve enormously complex

structures, like that of huge proteins, or DNA.

Quick quiz

1. a; 2. c; 3. c; 4. b; 5. a; 6. b; 7. a; 8. c; 9. b; 10. b; 11. a; 12. c; 13. b;

14. b; 15. a; 16. c; 17. b; 18. b; 19. a; 20. a; 21. b; 22. a; 23. a; 24. c;

25. a; 26. c; 27. b.

Calculations and questions

 _
1. a. (010); b. (110); c. (520); d. (1 1 0).

_
2. a. (320); b. (040); c. ( 2 20); d. (130).

_ _
3. a. (3 2 0); b. (2 1 0); c. (140); d. (100).

_
4. a. (200); b. (3 2 0); c. (310); d. (020).

_ _ _
6. (110), (101), (011), (1 1 0), ( 1 01), (01 1 ); (110) + 6 equivalent planes.

_ _ _ _ _ _
7. (111), (11 1 ), (1 1 1), ( 1 11); ( 1 1 1 ) + 4 equivalent planes.

_ _ _
8. (hh0), (0hh), (h0h), (h h 0), (0h h ), ( h 0h) + 6 equivalent planes.

_ _ _ _ _ _
9. (hk0), (0hk), (h0k), (h k 0), (0h k ), (h0 k ), (kh0), (0kh), (k0h), (k h 0), (0k h ), ( k 0h)

+ 12 equivalent planes.

_ _ _ _ _
10. a. [ 1 10]; b. [110]; c. [ 1 30]; d. [1 1 0]; e. [ 2 1 0].

_ _ _ _ _ _
11. a. [0 1 0]; b. [ 3 1 0]; c. [ 1 1 0]; d. [ 1 40]; e. [350].

_ _ _ _ _
12. a. [ 1 1 0]; b. [0 1 0]; c. [1 3 0]; d. [230]; e. [ 1 20].

_ _ _ _ _ _
13. a. [010]; b. [ 1 00]; c. [ 1 2 0]; d. [ 1 2 0]; e. [ 1 30].

_ _ _
14. [100], [ 1 00], [010], [0 1 0]; [001]; [00 1 ].

_ _ _ _ _ _ _ _ _ _ _ _
15. [110], [ 1 1 0], [011], [0 1 1 ], [101], [ 1 0 1 ], [1 1 0], [ 1 10], [01 1 ], [0 1 1], [ 1 01], [10 1 ].

16. 90.

17. 90.

19. (111), 44.6; (220), 76.6; (400), 122.4.

20. (110), 38.6; (211), 69.8; (310), 95.2.

21. 0.294 nm.

22. 0.8077 nm.

24. Ca0.45Sr0.55O.

25. x = 0.23; ZnAl1.54Ga0.45O4.

26. 0 0 0; ½ ½ 0; 0 ½ ½; ½ 0 ½.

27. Cl-, 0 0 0; Cs+, ½ ½ ½.

28. Ca, ½ ½ ½; Ti, 0 0 0; O, ½ 0 0, 0 ½ 0; 0 0 ½.

29. NiO, (B1).

30. AuCu3.

31. 2698 kg m-3.

32. 19260 kg m-3.

33. 1750 kg m-3.

34. 0.3611 nm.

35. Substitution plus anion vacancies; oxygen vacancies, 5522 kg m-3; interstitials,

5969 kg m-3.

37. Zirconium vacancies predominate; Zr vacancies, 5004 kg m-3; S interstitials,

6501 kg m-3.

37. a, b, no change; c, down, d, up.

38. FeTiO3, Al2O3 (corundum type).

Solutions

1 Index the planes (a) – ( d) shown on Figure 5.35A.

Remember that (hkl) refers to a set of parallel planes. Follow the method given in

Section 5.1.4.

_
a. (010); b. (110); c. (520); d. (1 1 0).
2 Index the planes (a) – ( d) shown on Figure 5.35B.

_
As Q 1: a. (320); b. (040); c. ( 2 20); d. (130).

3 Index the planes (a) – ( d) shown on Figure 5.35C.

_ _
As Q 1: a. (3 2 0); b. (2 1 0); c. (140); d. (100).

4 Index the planes (a) – ( d) shown on Figure 5.35D.

_
As Q 1: a. (200); b. (3 2 0); c. (310); d. (020).

5 Sketch the (111) and (1 1 1) planes in a cubic crystal.

(111) (1 1 1)

6 List the planes belonging to the {110} set in a cubic crystal.

_ _ _
There are 6 equivalent planes: (110), (101), (011), (1 1 0), ( 1 01), (01 1 ). However,

_ _ _ _
(̅ ) is equivalent to ( ̅ ) giving another 6 equivalent planes: ( 1 10), ( 1 1 0). (0 1 1),

_ _ _ _ _
(0 1 1 ), ( 1 01), ( 1 0 1 ).
7 List the planes belonging to the {111} set in a cubic crystal.

_ _ _
There are 4 equivalent planes: (111), (11 1 ), (1 1 1), ( 1 11). However, ( ̅ ) is

_ _ _ _ _ _ _ _ _
equivalent to ( ̅ ) giving another 4 equivalent planes: ( 1 1 1 ), ( 1 1 1 ), ( 1 1 1 ), (1 1 1 ).

8 List the planes belonging to the {hh0} set in a cubic crystal.

_ _ _
There are 6 equivalent planes: (hh0), (0hh), (h0h), (h h 0), (0h h ), ( h 0h). However,

_ _ _ _ _
(̅ ) is equivalent to ( ̅ ) giving another 6 equivalent planes: ( h h 0), (0 h h ), ( h 0

_ _ _ _
h ), ( h h0), (0 h h), (h0 h )

9 List the planes belonging to the {hk0} set in a cubic crystal.

_ _ _
There are 12 equivalent planes: (hk0), (0hk), (h0k), (h k 0), (0h k ), (h0 k ), (kh0),

_ _ _
(0kh), (k0h), (k h 0), (0k h ), ( k 0h). However, ( ̅ ) is equivalent to ( ̅ ) giving

_ _ _ _ _ _ _ _ _ _ _
another 12 equivalent planes: ( h k 0), (0 h k ), ( h 0 k ), ( h k0), (0 h k), ( h 0k), ( k h 0), (0

_ _ _ _ _ _ _
k h ), ( k 0 h ), ( k h 0), (0 k h), ( k 0h).

10 Index the directions (a) – (e) shown on Figure 5.36A.

_ _ _ _ _
a. [ 1 10]; b. [110]; c. [ 1 30]; d. [1 1 0]; e. [ 2 1 0].

11 Index the directions (a) – (e) shown on Figure 5.36B.

_ _ _ _ _ _
a. [0 1 0]; b. [ 3 1 0]; c. [ 1 1 0]; d. [ 1 40]; e. [350].
12 Index the directions (a) – (e) shown on Figure 5.36C.

_ _ _ _ _
a. [ 1 1 0]; b. [0 1 0]; c. [1 3 0]; d. [230]; e. [ 1 20].

13 Index the directions (a) – (e) shown on Figure 5.36D.

_ _ _ _ _ _
a. [010]; b. [ 1 00]; c. [ 1 2 0]; d. [ 1 2 0]; e. [ 1 30].

14 List the directions belonging to the <100> set.

_ _ _
[100], [ 1 00], [010], [0 1 0]; [001]; [00 1 ].

15 List the directions belonging to the <110> set.

_ _ _ _ _ _ _ _ _ _ _ _
[110], [ 1 1 0], [011], [0 1 1 ], [101], [ 1 0 1 ], [1 1 0], [ 1 10], [01 1 ], [0 1 1], [ 1 01], [10 1 ].

16 What is the angle between (110) and [110] in a cubic crystal?

In a cubic crystal a plane (hkl) is normal to a direction [hkl] so the angle is 90.

17 What is the angle between (132) and [132] in a cubic crystal?

As in Q16, the angle is 90.

18 Sketch the reciprocal lattice of a cubic crystal with a = 5 nm.

19 Nickel has the A1 (face-centred cubic) structure, with a = 0.352 nm. A powder

sample is irradiated with X-rays with a wavelength of 0.1542 nm. What angles

would the diffracted beams from the (111), (220) and (400) planes make with the

incident beam direction.

The angle between the incident beam and the diffracted beam is 2. Using Bragg’s

law:  = 2dhkl sin 

For a cubic crystal: 1/dhkl2 = (h2 + k2 + l2) / a2

For Ni: 1/d1112 = (12 + 12 + 12) / 0.3522 nm

d111 = 0.352 / 3 nm

sin 111 = 0.1542 / 2dhkl = 0.1542 x 3 / 2 x 0.352

111 = 22.3, 2111 = 44.6

1/d2202 = (22 + 22 + 02) / 0.3522 nm

d220 = 0.352 / 8 nm

sin 220 = 0.1542 / 2d220 = 0.1542 x 8 / 2 x 0.352

220 = 38.3, 2220 = 76.6

1/d4002 = (42 + 02 + 02) / 0.3522 nm

d400 = 0.352 / 4 nm

sin 400 = 0.1542 / 2d400 = 0.1542 x 4 / 2 x 0.352

400 = 61.2, 2400 = 122.4

20 Tantalum has the A2 (body-centred cubic) structure, with a = 0.3303 nm. A

powder sample is irradiated with X-rays with a wavelength of 0.1542 nm. What

angles would the diffracted beams from the (110), (211) and (310) planes make with

the incident beam direction.

The angle between the incident beam and the diffracted beam is 2. Using Bragg’s

law:  = 2dhkl sin 

For a cubic crystal: 1/dhkl2 = (h2 + k2 + l2) / a2

For Ta: 1/d1102 = (12 + 12 + 02) / 0.33032 nm

d110 = 0.3303 / 2 nm

sin 110 = 0.1542 / 2dhkl = 0.1542 x 2 / 2 x 0.3303

110 = 19.3, 2110 = 38.6

1/d2112 = (22 + 12 + 12) / 0.33032 nm

d211 = 0.3303 / 6 nm

sin 211 = 0.1542 / 2dhkl = 0.1542 x 6 / 2 x 0.3303

211 = 34.9, 2211 = 69.8

1/d3102 = (32 + 12 + 02) / 0.33032 nm

d310 = 0.3303 / 10 nm

sin 310 = 0.1542 / 2dhkl = 0.1542 x 10 / 2 x 0.3303

310 = 47.6, 2310 = 95.2

21 A sample of the cubic alloy -brass (an alloy of copper and zinc) gives an X-ray

powder patter in which the first three reflections are (100),  = 22.9; (110),  =

33.35; (111),  = 42.35; when the X-ray wavelength is 0.229 nm. Calculate the

lattice parameters of the brass.

Using Bragg’s law:  = 2dhkl sin 

For -brass: d100 = a

 / 2 sin  = dhkl

0.229 / (2 sin 22.9) = a = 0.294 nm

d110 = a / 2

 / 2 sin  = dhkl

0.229 x 2 / (2 sin 33.35) = a = 0.2945 nm

d111 = a / 3

 / 2 sin  = dhkl

0.229 x 3 / (2 sin 42.35) = a = 0.294 nm

22 A sample of the cubic spinel CuAl2O4 gives an X-ray powder patter in which the

first three reflections are (111),  = 9.51, (200),  = 11.00, (220),  = 15.65 when

the X-ray wavelength is 0.1541 nm. Calculate the lattice parameter of the spinel.

Using Bragg’s law:  = 2dhkl sin 

For CuAl2O4: d111 = a / 3

 / 2 sin  = dhkl

0.1541 x 3 / (2 sin 9.51) = a = 0.8077 nm

d200 = a / 2

 / 2 sin  = dhkl

0.1541 x 2 / (2 sin 11) = a = 0.8076 nm

d220 = a / 8

 / 2 sin  = dhkl

0.1541 x 8 / (2 sin 15.65) = a = 0.8079 nm

a(mean) = 0.8077 nm

23 A mineral sample contains a crystalline oxide with a formula NiAl2Ox, where x is

uncertain. The crystals gave an X-ray powder pattern with reflections characteristic

of a cubic material. The first reflection, (111), was at  = 9.55 when the X-ray

wavelength is 0.1541 nm. Confirm that this is consistent with the spinel nickel

aluminate, NiAl2O4, for which a = 0.8048 nm.

For a cubic phase: d111 = a / 3

 / 2 sin  = dhkl

a (calculated) = 0.1541 x 3 / (2 sin 9.55) = 0.8044 nm

The calculated value of a is close to the known value for NiAl2O4 and it is reasonable

to conclude that the sample is NiAl2O4.

24 The unit cell size of CaO is 0.48105 nm and that of SrO is 0.51602 nm. Both

adopt the halite (B1) structure-type. Estimate the composition of a crystal of formula

SrxCa1-xO, which was found to have a unit cell of 0.5003 nm.

Using Vegard’s law:

The amount of SrO, x = [a(CaxSr1-xO) - a(CaO)] / [[a(SrO) - a(CaO)]

= [0.5003 - 0.48105] / [0.51602 - 0.48105] = 0.55

The composition is Ca0.45Sr0.55O

25 A mixed cubic spinel ZnAl2-xGaxO4, is made up by heating together ZnAl2O4 (a =

0.8086 nm) and ZnGa2O4 (a = 0.8328 nm). The X-ray powder pattern, taken using

radiation of wavelength 0.1541 nm, gave the first reflection, (111), at a position  =

9.435. Estimate the value of x.

Using Vegard’s law:

 x = [a(solid solution) – a(ZnAl2O4)]/[a(ZnGa2O4) - a(ZnAl2O4)]

It is first necessary to determine he lattice parameter of the solid solution.

For a cubic phase: d111 = a / 3

 / 2 sin  = dhkl

a (calculated) = 0.1541 x 3 / (2 sin 9.435) = 0.8141 nm

x = [0.8141 – 0.8086] / [0.8328 – 0.8086] = 0.23

The composition is (1 – 0.23) ZnAl2O4: (0.23) ZnGa2O4 = ZnAl1.54Ga0.46O4

26 The cubic unit cell of iridium is drawn in Figure 5.37a. What are the atomic

coordinates? What is the unit cell type?

The coordinates of the atoms in the unit cell are:

000; ½ ½ 0; 0 ½ ½; ½ 0 ½;

These reproduce the structure when the unit cell is translated along the axes a, b

and c. The structure is the copper (A1) type.

27 The cubic unit cell of CsCl is drawn in Figure 5.37b. What are the atomic

coordinates of each ion?

The coordinates of the atoms in the unit cell are:

Cl 000

Cs ½ ½ ½

These reproduce the structure when the unit cell is translated along the axes a, b

and c.
28 The cubic unit cell of perovskite, CaTiO3, is drawn in Figure 5.37c. What are

the atomic coordinates of the atoms?

The coordinates of the atoms in the unit cell are:

Ca ½ ½ ½

Ti 0 0 0

O ½ 0 0; 0 ½ 0; 0 0 ½;

These reproduce the structure when the unit cell is translated along the axes a, b

and c.

29 The atom positions in cubic nickel oxide are:

Ni: 0,0,0 ½,½,0 0,½,½ ½,0,½

O: ½,½,½ 0,0,½ ½,0,0 0,½, 0

Sketch the unit cell. What is the formula of the oxide? What is the structure type?

The structure type is B1 (halite, NaCl)

30 A copper gold alloy has a cubic structure. The atom positions are:

Au: 0,0,0

Cu: 0,½,½ ½,0,½ ½,½,0

Sketch the unit cell and determine the formula of the alloy.
An atom at a unit cell corner counts 1/8, so Au composition is 1/8 x 8 = 1

An atom at a unit cell face centre counts ½ , so Cu composition is ½ x 6 = 3

The cell contents and thus the formula is AuCu3

31 Aluminium has the cubic A1 structure with a lattice parameter of 0.4050 nm.

Estimate the density of the metal.

The A1 structure has Z = 4, i.e. there are 4 Al per unit cell.

The mass of an aluminium atom = molar mass (kg) / NA

Density = mass / volume = 4 x molar mass / NA a3

= (4 x 0.02698) / [(6.02214 x 1023) x (0.4050 x 10-9)3]

= 2698 kg m-3

32 Tungsten has the cubic A2 structure with a lattice parameter of 0.31651 nm.

Estimate the density of the metal.

The A2 structure has Z = 2, i.e. there are 2 W per unit cell.

The mass of a tungsten atom = molar mass (kg) / NA

Density = mass / volume = 4 x molar mass / NA a3

= (2 x 0.18384) / [(6.02214 x 1023) x (0.31651 x 10-9)3]

= 19258 kg m-3
33 Magnesium has the A3 structure with hexagonal lattice parameters of a = 0.320

nm, c = 0.520 nm. Estimate the density of the metal.

The A3 structure has Z = 2, i.e. there are 2 Mg per unit cell.

The mass of a magnesium atom = molar mass (kg) / NA

The volume of a hexagonal unit cell is (3 / 2) a2c

Density = mass / volume = 2 x molar mass / NA (3 / 2) a2c

= (4 x 0.2431) / [(6.02214 x 1023) x (3 x 0.320 x 10-9)2 x 0.520 x 10-9]

= 1750 kg m-3

34 Copper has the cubic A1 structure and a density of 8.96 x 10 3 kg m-3. What is

the length of the unit cell edge?

The A1 structure has Z = 4, i.e. there are 4 Cu per unit cell.

The mass of a copper atom = molar mass (kg) / NA

Density = mass / volume = 4 x molar mass / NA a3

= (4 x 0.06354) / [(6.02214 x 1023) x (a)3]

a = 3.611 x 10-10 m = 0.3611 nm

35 A sample of calcia stabilised zirconia, prepared by heating 85 mole % ZrO2 with

15 mole % CaO at 1600°C. The material had a cubic unit cell with a lattice

parameter, a, of 0.5144 nm and a measured density of 5485 kg m-3. Calculate the

theoretical density of the sample and hence determine whether interstitials or

vacancies are more likely to be present in the structure. [The parent structure is
fluorite (CaF2), in which each cubic unit cell contains 4 metal positions and 8 non-

metal positions, to give an overall composition of MX2.]

The composition of the phase is 0.15CaO + 0.85ZrO 2, i.e. Ca0.15Zr0.85O1.85 which is

different from the ideal fluorite MO2.

The two simplest models to reconcile the structure and composition are:

(a) All of the cation sites in MO2 are full and there are oxygen vacancies in the

structure. The formula of the material can be written Ca0.15Zr0.85O1.85.

The density is:

4 x 0.15 x molar mass Ca / NA + 4 x 0.85 x molar mass Zr / NA + 4 x 1.85 x

molar mass O / NA

= [(4 x 0.15 x 0.04008) + (4 x 0.85 x 0.09122) + (4 x 1.85 x 0.015999)] / NA

= 0.4526 / NA kg

Density = 0.4526 / [(6.02214 x 1023) x (a)3]

= 0.4526 / [(6.02214 x 1023) x (0.5144 x 10-9)3]

= 5522 kg m-3

(b) All of the anion sites in MO2 are full. In this case the defects are interstitial Ca 2+

ions. The formula is now given by dividing the amounts in Ca0.15Zr0.85O1.85 by 1.85

and multiplying by 2 to give a “true” formula Ca0.162Zr0.919O2. In this formula, (0.919

Zr + 0.081Ca) fill the M sites in MO2 and 0.081 Ca are in interstitial sites.

Following part (a), the density =

= [(4 x 0.162 x 0.04008) + (4 x 0.919 x 0.09122) + (4 x 2 x 0.015999)] / NA

= 0.48929 / NA kg
Density = 0.48929 / [(6.02214 x 1023) x (a)3]

= 0.48929 / [(6.02214 x 1023) x (0.5144 x 10-9)3]

= 5969 kg m-3

The density in (a) is the closest to the experimental value so we conclude that the

material contains oxygen vacancies.

36 The unit cell of a zirconium sulphide, with a measured composition of 77 Zr : 100

S, is of the halite (B1) type, with a = 0.514 nm. The measured density is 4.80 x 10 3

kg m-3. Calculate the theoretical density of ideal ZrS with the B1 structure, and give

an opinion on the defect structure of the real material.

The procedure here is exactly as in the previous question.

The halite structure, MS, ideally contains 4 Zr and 4 S atoms. The measured

composition is Zr0.77S which is different from the ideal ZrS. The two simplest models

to reconcile the structure and composition are:

(a) All of the anion sites in ZrS are full and there are Zr vacancies in the structure.

The formula of the material can be written Zr0.77S.

The density is:

4 x 0.77 x molar mass Zr / NA + 4 x 1 x molar mass S / NA

= [(4 x 0.77 x 0.09122) + (4 x 1 x 0.03207)] / NA

= 0.409 / NA kg

Density = 0.409 / [(6.02214 x 1023) x (a)3]

= 0.409 / [(6.02214 x 1023) x (0.514 x 10-9)3]

 = 5004 kg m-3

(b) All of the cation sites in ZrS are full and there are S interstitials in the structure.

The formula of the material can be written ZrS1.30.

The density is:

4 x molar mass Zr / NA + 4 x 1.30 x molar mass S / NA

= [(4 x 0.09122) + (4 x 1.30 x 0.03207)] / NA

= 0.5316 / NA kg

Density = 0.5316 / [(6.02214 x 1023) x (a)3]

= 0.5316 / [(6.02214 x 1023) x (0.514 x 10-9)3]

= 6501 kg m-3

The density in (a) is the closest to the experimental value so we conclude that the

material contains Zr vacancies.

37 Will the density of a crystal go up or down if it contains: (a) Schottky defects; (b)

Frenkel defects; (c) vacancies; (d) interstitials?

(a) Schottky defects consist of vacancies on both cation and anion positions. The

average mass in a unit cell will decrease, but the number of these defects is small

and the density will be virtually unchanged.

(b) Frenkel defects consist of an interstitial atom and a paired vacancy. On average

the mass in a unit cell will remain unchanged compared to a defect free material, and

the density will be unchanged.

(c) When vacancies occur on one type of site the total mass in a unit cell will

decrease and the density will also decrease.

(d) When interstitials not balanced by vacancies occur, the total mass of a unit cell

will increase and the density will also increase.

38 An iron titanium oxide has the anions in a hexagonal close-packed array. The

Fe and Ti atoms each occupy 1/3 of the octahedral sites available in an ordered

array. What is the formula of the oxide? What is the likely parent structure of the

oxide?

In a close packed anion array there are N octahedral sites for every N anions. If 2/3

of these are occupied by metal atoms, the composition is M2O3. As each metal

atom occupies 1/3 of the sites the formula is FeTiO3.

The likely parent structure is that of corundum, Al2O3. FeTiO3 is an ordered form of

this structure, called ilmenite.