Chapter 1 Solid State Physics

Chapter 1: Structure of Crystalline Matter

Solid State Physics
Eric Toberer, Colorado School of Mines

Chapter introduction The goal of this chapter is to briefly introduce the structure of materials.
For those who have experience in solid state chemistry, crystallography, or materials science, this
chapter won’t be particularly shocking news. However, it is worth at least acquainting yourself with
the local dialect of Solid State Physics and associated variables that will be used throughout these
notes. Our ultimate goal in this class is to link structure to physical properties in crystalline matter.
For all properties considered, we need to understand the placement, magnitude, and motion of the
potential wells that the nuclei create. These potential wells will be necessary to develop a V (~r, t)
in Schrodinger’s equation.

Topics covered:
• Introduce crystal structures as a concept
• A slightly quantitative view of translational symmetry
• Populating the unit cell with atoms

Associated videos: 2.1, 2.2. The videos can be found here.

Variables introduced:
• ~ai – translation vector along the î direction
• ~c – centering vector for non-primitive cells
• f - some arbitrary function
• T~ – translation vector sum that moves you from the global origin to any unit cell
• ui – unit cell in the î direction from a global origin

1.1 A qualitative introduction to crystalline solids

As you may have experienced in your childhood, you can grow large, beautiful crystals of sugar
from an evaporating water solution. You can achieve a similar
effect with other small organic molecules from solution. For exam-
ple, Figure 1 shows a pile of such crystals after precipitation. In
both cases, the organic molecules pack into a regular arrangement
due to a combination of sterics (a fancy chemistry word for geom-
etry) and local electrostatic forces. Similarly, nearly all inorganic
solids are crystalline. Such materials include metals, semiconduc-
tors, and ceramics. In some cases, the arrangement of atoms in
inorganic crystals can be thought of as simply hard sphere packing
with an eye towards electrostatic repulsion. In many other cases, Figure 1: Ketamine crys-
thought, the packing of atoms in a crystal depends strongly on tals form with beautiful facets
charge repulsion and local bonding motifs. Figure 2 shows these when you slowly remove the sol-
vent between the molecules of
two extremes with U3 O8 and C21 H23 NO5 .1 C H ClNO
13 16
1 Don’t worry, this is the last time we’ll mention molecules in this class.

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Figure 2: (Upper) Yellowcake is the common term for U3 O8 , an intermediate compound formed when
separating U-235 from U-238. The oxygen anions are in red, the uranium cations are in grey; the ‘bonds’
are simply to denote the structural relationship and do not indicate any covalent bonding in the structure.
The unit cell, denoting the repeat unit of the crystal, is highlighted in the lower left. (lower) The crystal
structure of heroin shows how the heroin molecules pack into an arrangement that reduces void space but
also creates opportunities for bonding with ions (i.e., chlorine in green) and water molecules (shown in white
and red). The unit cell is impressively large.

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The diversity of crystalline solids is absolutely delightful.2 The ways mother nature (aka ther-
modynamics) causes atoms to arrange themselves are diverse and peculiar; similarly, the properties
that arise from this structural diversity are immense. For example, the periodic checker-board of
Cu and O atoms in the high temperature superconductors is crucial for the development of the elec-
tronic wave functions and vibrational modes that ultimately yield superconductivity. Likewise, the
symmetry-breaking distortions in PbTiO3 crystals yield ferroelectric and piezoelectric properties.
Most solid state classes invoke without justification a taxonomy of crystal structures and as-
sociated bonding types up front (e.g. covalent, ionic, metallic). In this class, we will introduce
specific crystal structures when needed. To understand the bonding within materials, we will first
look closely at electronic structure. From this, we can develop a bonding classification scheme
towards the end of the semester that is rooted in physics rather than hand-waving.

Exploiting periodicity Let’s briefly consider how large a

mole of atoms is: 1 mole of iron (Fe) is 55 g or for the Amer-
icans in the audience the weight of 5 Oreos. In this mole of
Fe, we by definition have 6 × 1023 nuclei. So about a trillion
trillion nuclei. Considering electrons in a mole of Fe, we have
∼ 1025 . The point is that these are simply enormous num-
bers.3 However, the crystallinity of Fe allows us to describe
these 1023 nuclei in terms of one (1!!) atom, a handful of elec-
trons, and a series of symmetry operations. Figure 3 shows
Figure 3: Iron typically exists as ei-
stable structures of elemental iron, both of which can be de- ther (left) body centered or (right) face
scribed with a single unique atom. Learning to harness this centered structures. These cells can be
incredible simplification to predict properties is at the heart generated using just one atom and then
of solid state physics. Conversely, the study of amorphous applying a series of symmetry opera-
materials is exceedingly challenging due to the inability to tors. Neither of these cells are primi-
tive.
robustly apply such a simplification.

1.2 A slightly quantitative introduction to crys-

talline solids
Introducing the translational vector T~ The only required symmetry operation a crystal must
have is translational periodicity. We define translational periodicity in terms of a translation vector
T~ . Starting at some point inside the crystal, moving by T~ takes you to an identical point. For this
to be true, there must be some repeated unit in the crystal. Let’s define this repeated unit as the
unit cell. Assuming T~ is in R3 , we can decompose this vector into a set of coordinate vectors ~a1 ,
~a2 , and ~a3 that individually preserve the translational periodicity of T~ . Note that these vectors
may not be orthogonal, given the symmetry of your crystal. We can thus move by integer steps ui
in ~ai and be at effective identical points in the lattice. Thus:

T~ = u1~a1 + u2~a2 + u3~a3 (1)

2 This is not to short-change amorphous materials. Beyond the obvious window glass, we have
amorphous layers within our microelectronic chips and amorphous indium tin oxide as a trans-
parent conductor on our screens. Amorphous metals are extremely rare and difficult to produce.
As we’ll discuss below, this class will focus strictly on crystalline materials.
3 Other fun comparisons: There are 1011 stars in the Milky Way, 1015 ants on Earth, and about
1019 grains of sand in the deserts and on beaches.

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where ui are integers. Throughout the book, we’ll denote integers with Z; as in ui ∈ Z.
Let’s restate the above paragraph with a general example. If you can describe your crystal in
terms of some function f (~r), then the following must be true:

f (~r) = f (~r + T~ ) (2)

This f could be the electron density, the nuclear density, net charge density or other such terms.
This cute little equation is going to be the foundation of a lot of the math that we end up doing.

Crystal systems It’s helpful at this point to introduce some vocabulary. The nature of T~ defines
the crystal system of a crystal. The crystal systems are cubic, hexagonal, trigonal, tetragonal,
orthorhombic, monoclinic, and triclinic. On one extreme, a cubic system is what it sounds like: the
vectors a~i are all of equal length and they are all orthogonal to each other. On the other extreme,
the triclinic system has vectors a~i of unequal length and the angles between these vectors must all
be different and may not include 90◦ . As such, triclinic systems are generally avoided. In this class,
we will tend to focus on cubic, tetragonal, and hexagonal crystals.
The crystal system doesn’t tell you anything about what’s inside the unit cell. The size of the
cell, how many atoms are in it, their arrangement – the crystal system says next to nothing about
these questions.

a b c g

d e f h

Figure 4: Here are some simple 2D lattices for thinking about symmetry and unit cell selection.

Putting some numbers to periodicity Before we think about the unit cell vectors that build
T~ , let’s just start with atoms. A hydrogen atom is about 1 Å in diameter. On the other atomic
extreme, iodine has a diameter of 4 Å.4 Thus, in the most simple unit cell, we might expect lattice
parameters of at least 2 Å per side. This proves to be a safe bet; for example the unit cell of
Fe from Figure 3a has lattice parameters of 2.8 Å and interatomic distances of 2.5 Å. For most
structural metals and electronic semiconductors, the unit cells are fairly simple and the lattice
parameters will thus range between 3 – 6 Å. However, it is clear from Figure 2 above that the unit
4 Let’s look at the ratio of electron density assuming the electrons are evenly distributed within
1e− 43
their diameter (probably a terrible assumption but no worries): ddHI = 53e − 13 = 1.2. OK, so it
looks like the electron density isn’t very different between H and I. Neat!

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cell dimensions can be far larger for complex crystals; for example, the organic crystal in Figure 2
has a long axis length of 72 Å. Proteins form some of the largest crystals that retain atomic registry
between unit cells, these cells regularly have dimensions of hundreds of Angstroms on a side. If one
is willing to disregard atomic periodicity and just retain some meso- or macro-scale periodicity, no
upper bound exists for ‘crystalline’ materials. For example, a box of donuts could loosely be viewed
as crystalline, provided they were arranged with translational symmetry. While this sounds silly,
we will find that the underlying physics of such structures is remarkably similar to their atomic
counterparts.

1.3 Beyond Translational Symmetry

We already discussed the translational symmetry of crystals in terms of T~ , but that is not the only
symmetry operator that can be applied to a crystal. Mirror planes, rotations around a point and a
suite of other operators can also be found (or not) inside of a given crystal. For example, in Figure
4a we have highlighted the mirror planes found in this simple square array of atoms. Additionally,
there are several points in the cell that have 4-fold (90◦ ) rotational symmetry.
In practice, symmetry has two important roles in introductory solid state physics. First, it
offers ways to simplify problems that would otherwise be mathematically unpleasant. Second,
there are some material properties that are fundamentally driven by changes in symmetry. To take
advantage of symmetry, we’re going to need some vocabulary and some conventions. We begin by
asking:
 Where is the origin of T~ ? Can it be anywhere in the crystal?
So far, we haven’t put further constraints on T~ , and informally5 it can be anywhere. It doesn’t even
have to be at an atomic nucleus. However, a consideration of the symmetry of the cell will typically
suggest where to place the origin. As mentioned above, Figure 4a is a square lattice has many
symmetry operations, including the mirror planes denoted with dashed lines. By inspection, we
can see that putting our origin on the intersection of these mirror planes has a certain cleanliness.
It’s also notable that there are two possible origins that could be used if we follow this maxim
(Figure 5a), leading to two different unit cells.
 What would happen if we used a T~ that is bigger than
needed? a b
Using a larger unit cell than absolutely necessary is surpris-
ingly common. For example, in Figure 5b we can still tile
space with a T~ that is has |~ai | that is twice as large. Alter-
natively, we can rotate T~ 45◦ as it still tiles space. If the
unit cell is the smallest cell (in terms of volume) that can tile
space, then we call that cell the primitive cell. Figure 5: For this simple cubic lattice,
you can imagine (a) reasonable primi-
 When would you want to use a non-primitive cell? tive cells as well as (b) supercells. All
You typically use non-primitive cells to simplify the lengths of these tile space.
and angles that you’re working with. For example, in Figure
6 we have a primitive cell (a) that is a rhombus or a special rhombus (hexagonal cell). Instead,
we can consider a rectangular cell (b) that is twice as large as the original primitive cell. On one
hand this is great, because we’re back to 90 degree angles; on the other hand, we now have more
atoms in our cell that we’re going to have to keep track of. Non-primitive cells that increase the
user-friendliness of the cell are called the conventional cell.
5 In this class, all of our efforts in symmetry will be informal. For a more formal view of things,
you’ll want to take a class of either group theory or crystallography.

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 How do we denote the atom positions inside of c

c
the unit cell?
This one is easy! The first way is to simply define a
b
vector (in Angstroms) that extends from one corner b
of the unit cell to the atom. We will often call this
a a
vector r~α , where α denotes the flavor of the atom at
that position. Alternative (and more frequently), we Figure 6: (left) In a 2D hexagonal system, we
take the component ~ai vectors of T~ that define our unit can use the (a) primitive hexagonal cell or (b)
cell and describe our atomic positions using fractional a centered rectangular cell. In (c), we have an
coordinates. So in Figure 5, we have one atom in the actual hexagon. This third version tiles space,
unit cell at (0,0) if we use the blue unit cell. Note that but doesn’t have edges defined by T~ . (right) In
this panel, we have a similar situation, but the
the other atoms that touch this square are in other inner angle is no longer 60◦ . Now we have a (a)
unit cells. Alternatively, we could us the purple unit primitive rhombus, (b) centered rectangular
cell and have the one atom at ( 21 , 12 ). cell, and (c) some hideous distorted hexagon.
 How do we decorate the whole crystal with atoms?
We can describe an atom’s position as T~ + r~α , where r~α is the local vector from the unit cell origin
to the atom’s position. Thus, to decorate a unit cell, we cycle over all atoms α in the cell. This set
of all atoms in the unit cell is called the basis.6 Note that T~ + r~α effectively creates a local origin
for r~α at the corner of the cell.
 What about conventional cells?
For conventional cells, things get a little more tricky. Since we have at least doubled the size of
the unit cell compared to the primitive cell, there must be at least two duplicate regions of crystal
within the unit cell. We end up placing atoms at T~ + ~c + r~α , where ~c creates new local origins
for r~α . For all cells, ~c includes the null vector (i.e., (0,0,0)) and may include either body centering
( 21 , 12 , 12 ) or base/face centering across some or all permutations of( 12 , 12 ,0). We call the local origins
created by T~ + ~c lattice points.
 Do I have to enumerate all the atoms in a cell?
Sometimes. We often use symmetry operations to duplicate atoms within a given cell. For example,
in Figure 4c, we don’t need to specify all the orange atoms but just one and then note that there
is a 90◦ rotation at position ( 12 , 12 ). When we refer to just the initial generating atom(s), we call
those the asymmetric basis. After the symmetry operations have been applied, thereby creating
more atoms in the unit cell, the resulting set of atoms is called the symmetric basis.
 What do I call a crystal system that has multiple lattice points?
We talked about the crystal system way above (Wikipedia), as a reminder it defines the translational
symmetry of the lattice based on the vectors that form the unit cell. There are 7 crystal systems in
3D. Once you have a crystal system, there are a finite number of ways in which you’re allowed to
decorate it with lattice points. Once you decorate a crystal system with lattice points, it’s called a
Bravais lattice (Wikipedia ).
6 This is tricky business, vocab-wise, as the “basis” in physics typically refers to the coordinate
system vectors. Here, a basis still refers to a set of vectors, but it’s no longer a coordinate system.
It’s simply a handful of vectors that describes where your atoms can be found.

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Case example As an example, let’s consider the

CsCl structure. The Bravais lattice is primitive cu-
bic; by primitive, we mean that it only has lattice
points at the corners of the cube and no centering vec-
tor(s) ~c is required. By invoking a cube, we’re say-
ing the ~ai that build T~ are orthogonal and of equal
length. The atomic basis consists of a Cs atom at po-
sition (0,0,0) and a Cl atom at position ( 21 , 12 , 21 ). From Figure 7: It’s the CsCl structure!
this information, the entire bulk crystal can be gener-
ated by iterating over the prefactors ui in T~

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Figure 8: A simple 2D crystal with atoms shown in black. The various boxes shown are candidate unit
cells.

Chapter 1 pre-class questions

1. What are the defining features for a material to be crystalline?

2. Figure 8 shows a series of atoms in a 2D crystal. Which of these (A-I) candidate unit cells
successfully translates space?
3. Which of these cells in Figure 8 are acceptable primitive unit cells? Why?
4. The pattern in Figure 9 is built out of two types of rhombi (light and dark purple); is this a
crystal, a quasicrystal or a glass and why? Please don’t stare at this for more than 5 minutes
or you’ll get a headache.
5. Describe the pizza crystal of Figure 10 in terms of lattice and basis. This is not a trick
question.
6. How many pizzas form the basis of the primitive cell? One unit of pizza is a full pie.

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Figure 9: Don’t stare at this for more than 10 minutes, or you will get a headache – advice from prior
Solid State students.

Figure 10: It’s a freaking pizza crystal!

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