Crystal

In a crystal, the arrangement of atoms is in a periodically repeating pattern, whereas no

such regularity of arrangement is found in a non crystalline material. A crystalline solid
can be either a single crystal, where the entire solid consists of only one crystal, or an
aggregate of many crystals separated by well-defined boundaries. In the latter form, the
solid is said to be polycrystalline. We first discuss the geometry of arranging points in
regular patterns in space. A crystal can be generated starting from such patterns. We then
introduce the conventions associated with representing directions and planes in crystals.
We describe in some detail the experimental method of determining simple crystal
structures using the x-ray diffraction technique.

Single crystal X-ray Diffraction

Crystals have inherent symmetry. A cubic crystal is said to have a four-fold rotation
symmetry about an axis passing through the centres of two opposite faces of the unit cube.
During each complete rotation about this axis, the crystal passes through identical
positions in space four times. The rotational, translational and reflection symmetry
operations constitute the symmetry elements of a crystal. The typical interatomic spacing
in crystals is 2–3 Å. So, the wavelength of the radiation used for crystal diffraction should
be in the same range. X-rays have wavelengths in this range and are, therefore, diffracted
by crystals. This property is widely used for the study of crystal structures. A beam of x-
rays directed at a crystal interacts with the electrons of the atoms in the crystal. The
electrons oscillate under the impact and become a new source of electromagnetic
radiation. The waves emitted by the electrons have the same frequency as the incident x-
rays. The emission is in all directions. As there are millions of atoms in a crystal, the
emission in a particular direction is the combined effect of the oscillations of electrons of
all the atoms. The emissions will be in phase and reinforce one another only in certain
specific directions, which depend on the direction of the incident x-rays, their wavelength
as well as the spacing between atoms in the crystal. In other directions, there is destructive
 interference of the emissions from different sources. The easiest way to visualize the
diffraction effects produced by the three-dimensional grating provided by the crystal is to
consider the Bragg law.

Fundamental Concepts

Atoms self-organize in crystals, most of the time. The crystalline lattice, is a periodic array
of the atoms. When the solid is not crystalline, it is called amorphous. Examples of
crystalline solids are metals, diamond and other precious stones, ice, graphite. Examples of
amorphous solids are glass, amorphous carbon (a-C), amorphous Si, most plastics
To discuss crystalline structures it is useful to consider atoms as being hard spheres, with
well-defined radii. In this scheme, the shortest distance between two like atoms is one
diameter.

Unit Cells

The unit cell is the smallest structure that repeats itself by translation through the crystal. We
construct these symmetrical units with the hard spheres. The most common types of unit
cells are the faced-centered cubic (FCC), the body-centered cubic (FCC) and the hexagonal
close-packed (HCP). Other types exist, particularly among minerals. The simple cube (SC) is
often used for didactical purpose, no material has this structure.

Metallic Crystal Structures

Important properties of the unit cells are

 The type of atoms and their radii R.

 cell dimensions (side a in cubic cells, side of base a and height c in HCP) in terms
of R.
 n, number of atoms per unit cell. For an atom that is shared with m adjacent unit cells,
we only count a fraction of the atom, 1/m.
 CN, the coordination number, which is the number of closest neighbors to which an
atom is bonded.
 APF, the atomic packing factor, which is the fraction of the volume of the cell actually
occupied by the hard spheres. APF = Sum of atomic volumes/Volume of cell.

Unit Cell n CN a/R APF

SC 1 6 2 0.52

BCC 2 8 4 3 0.68

FCC 4 12 2 2 0.74

HCP 6 12 0.74

The closest packed direction in a BCC cell is along the diagonal of the cube; in a FCC cell is
along the diagonal of a face of the cube.
Density Computations
The density of a solid is that of the unit cell, obtained by dividing the mass of the atoms (n
atoms x Matom) and dividing by Vc the volume of the cell (a3 in the case of a cube). If the
mass of the atom is given in amu (A), then we have to divide it by the Avogadro number to
get Matom. Thus, the formula for the density is:

Polymorphism and Allotropy

Some materials may exist in more than one crystal structure, this is called polymorphism. If
the material is an elemental solid, it is called allotropy. An example of allotropy is carbon,
which can exist as diamond, graphite, and amorphous carbon.

Close-Packed Crystal Structures

The FCC and HCP are related, and have the same APF. They are built by packing spheres on
top of each other, in the hollow sites (Fig. 3.12 of book). The packing is alternate between
two types of sites, ABABAB.. in the HCP structure, and alternates between three types of
positions, ABCABC… in the FCC crystals.
Crystalline and Non-Crystalline Materials

Single Crystals
Crystals can be single crystals where the whole solid is one crystal. Then it has a regular
geometric structure with flat faces.

Polycrystalline Materials
A solid can be composed of many crystalline grains, not aligned with each other. It is
called polycrystalline. The grains can be more or less aligned with respect to each other.
Where they meet is called a grain boundary.

Anisotropy
Different directions in the crystal have a different packing. For instance, atoms along the
edge FCC crystals are more separated than along the face diagonal. This causes anisotropy in
the properties of crystals; for instance, the deformation depends on the direction in which a
stress is applied.

Non-Crystalline Solids
In amorphous solids, there is no long-range order. But amorphous does not mean random,
since the distance between atoms cannot be smaller than the size of the hard spheres. Also, in
many cases there is some form of short-range order. For instance, the tetragonal order of
crystalline SiO2 (quartz) is still apparent in amorphous SiO2 (silica glass.)
What is X-ray Diffraction (XRD)
X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for phase identification of a crystalline material and can provide
information on unit cell dimensions. The analyzed material is finely ground, homogenized, and average bulk composition is determined.

Fundamental Principles of X-ray Diffraction (XRD)

Max von Laue, in 1912, discovered that crystalline substances act as three-dimensional diffraction gratings for X-ray wavelengths
similar to the spacing of planes in a crystal lattice. X-ray diffraction is now a common technique for the study of crystal structures
and atomic spacing. X-ray diffraction is based on constructive interference of monochromatic X-rays and a crystalline sample.
These X-rays are generated by a cathode ray tube, filtered to produce monochromatic radiation, collimated to concentrate, and
directed toward the sample. The interaction of the incident rays with the sample produces constructive interference (and a diffracted
ray) when conditions satisfy Bragg's Law (nλ=2d sin θ). This law relates the wavelength of electromagnetic radiation to the
diffraction angle and the lattice spacing in a crystalline sample. These diffracted X-rays are then detected, processed and counted.
By scanning the sample through a range of 2θangles, all possible diffraction directions of the lattice should be attained due to the
random orientation of the powdered material. Conversion of the diffraction peaks to d-spacings allows identification of the mineral
because each mineral has a set of unique d-spacings. Typically, this is achieved by comparison of d-spacings with standard
reference patterns.
All diffraction methods are based on generation of X-rays in an X-ray tube. These X-rays are directed at the sample, and the
diffracted rays are collected. A key component of all diffraction is the angle between the incident and diffracted rays. Powder and
single crystal diffraction vary in instrumentation beyond this.

X-ray Powder Diffraction (XRD) Instrumentation

X-ray diffractometers consist of three basic elements: an X-ray tube, a sample holder, and an X-ray detector.X-rays are generated in
a cathode ray tube by heating a filament to produce electrons, accelerating the electrons toward a target by applying a voltage, and
bombarding the target material with electrons. When electrons have sufficient energy to dislodge inner shell electrons of the target
material, characteristic X-ray spectra are produced. These spectra consist of several components, the most common being K α and
Kβ. Kα consists, in part, of Kα1 and Kα2. Kα1 has a slightly shorter wavelength and twice the intensity as Kα2. The specific
wavelengths are characteristic of the target material (Cu, Fe, Mo, Cr). Filtering, by foils or crystal monochrometers, is required to
produce monochromatic X-rays needed for diffraction. Kα1and Kα2 are sufficiently close in wavelength such that a weighted average
of the two is used. Copper is the most common target material for single-crystal diffraction, with CuKα radiation = 1.5418Å. These
X-rays are collimated and directed onto the sample. As the sample and detector are rotated, the intensity of the reflected X-rays is
recorded. When the geometry of the incident X-rays impinging the sample satisfies the Bragg Equation, constructive interference
occurs and a peak in intensity occurs. A detector records and processes this X-ray signal and converts the signal to a count rate
which is then output to a device such as a printer or computer monitor. The geometry of an X-ray diffractometer is such that the
sample rotates in the path of the collimated X-ray beam at an angle θ while the X-ray detector is mounted on an arm to collect the
diffracted X-rays and rotates at an angle of 2θ. The instrument used to maintain the angle and rotate the sample is termed a
goniometer. For typical powder patterns, data is collected at 2θ from ~5° to 70°, angles that are preset in the X-ray scan.

Applications
X-ray powder diffraction is most widely used for the identification of unknown crystalline materials (e.g. minerals, inorganic
compounds). Determination of unknown solids is critical to studies in geology, environmental science, material science, engineering
and biology.
Other applications include:
 characterization of crystalline materials
 identification of fine-grained minerals such as clays and mixed layer clays that are difficult to determine optically
 determination of unit cell dimensions
 measurement of sample purity

Determination of crystal structure using XRD

As the sample and detector are rotated, the intensity of the reflected X-rays is recorded. When the geometry of the incident X-rays
impinging the sample satisfies the Bragg Equation, constructive interference occurs and a peak in intensity occurs. A detector
records and processes this X-ray signal and converts the signal to a count rate which is then output to a device such as a printer or
computer monitor.
 X-Ray diffractometer:
T = x-ray source
S = specimen
C = detector
O = the axis around which the
specimen and detector rotate.

Diffraction is a process in which‘linear information’ (the d-spacing of the planes) is converted to ‘angular information’ (the angle of diffraction,
). If the detector is placed ‘far away’ from the sample (i.e. ‘R’ in the figure below is large) the distances along the arc of a circle (the
detection circle) get amplified and hence we can make ‘easy’ measurements.This also implies that in XRD we are concerned with angular
resolution instead of linear resolution.
THE POWDER METHOD
• In the powder method the specimen has crystallites (or grains) in many orientations (usually random).

• Monochromatic X-rays are irradiated on the specimen and the intensity of the diffracted beams is measured as a function
of the diffracted angle.

• In this elementary text we shall consider cubic crystals.

Selection/Extinction Rules
• As we have noted before even if Bragg’s equation is satisfied, ‘reflections may go missing’this is due to the presence of
additional atoms in the unit cell.

• The reflections present and the missing reflections due to additional atoms in the unit cell are listed in the table below

Bravais Lattice Reflections which may be present Reflections necessarily absent

Simple all None

Body centred (h + k + l) even (h + k + l) odd

Face centred h, k and l unmixed (i.e. all even or all odd) h, k and l mixed

End centred (C centred) h and k unmixed h and k mixed

 Bravais Lattice Allowed Reflections

SC All

BCC (h + k + l) even

FCC h, k and l unmixed

EC k + l) divisible by
4

Sadoway’s Five-Step program to determine crystal structure

Step 1: Start with 2θ value and generate a set of Sin2θ values
2 2 2
Step 2: Normalize the Sin θ by generating Sin θn/Sin θ1
Step 3: Clear fractions from “normalized” column

Step 4: Speculate on the hkl values that if expressed as (h2 + k2 +l2) , it will generate the sequence of the clear

fraction column

Step 5: Compute for each θ the vlaue of Sin2θn/(h2 + k2 + l2) on the basis of the assumed hkl, values, if each

entry in this column is identical, then the entire process is validated.

 Selection Table

h2 + k2 + l2 SC FCC BCC DC

1 100
2 110 110
3 111 111 111
4 200 200 200
5 210
6 211 211
7 220 220 220 220
8 300, 221
9 310 310
10 311 311 311
11 222 222 222
12 320
13 321 321
14 400 400 400 400
15 410, 322
16 411, 330 411, 330
17 331 331 331
The ratio of (h2 + k2 + l2) derived from extinction rules (earlier page)
As we shall see soon the ratios of (h2 + k2 + l2) is proportional to Sin2which can be used in the determination of
the lattice type

SC 1 2 3 4 5 6 8 …
BCC 1 2 3 4 5 6 7 …
FCC 3 4 8 11 12 …
DC 3 8 11 16 …

 Note that we have to consider the ratio of only two lines to distinguish
FCC and DC. if the ratios are 3:4 then the lattice is FCC.
 But, to distinguish between SC and BCC we have to go to 7 lines
 Example

The values above correspond to a primitive cubic structure (we can tell this because N=7 is not possible from
the sum of three squares). (Refer table of selection rule)