Solid State Physics Chapter 1
Solid State Physics Chapter 1
Solid State Physics Chapter 1
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
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
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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.
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:
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.
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Figure 8: A simple 2D crystal with atoms shown in black. The various boxes shown are candidate unit
cells.
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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.
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