Crystalline and Non-crystalline solids

Introduction
Matter can be subdivided into two states-solid and fluid, of which the later is subdivided into
liquid and gaseous state. Matter can also be subdivided into condensed stated and gaseous state
where condensed state is subdivided into the solid and liquid state.
Although very little of the matter in the universe is in the solid state, solids constitute much
of the physical world around us and a large part of the modern technology is based on the special
characteristics of the various solid materials.

Crystalline and non-crystalline (Amorphous Solids)

Nature favors the crystalline state of the solids, because the energy of the ordered atomic
arrangement is lower than that of an irregular packing of atoms.

Solid

Non-Crystalline/Amorphous
(Glass, plastic, Resin, Pitch, Sugar, Candy, etc)

Single crystal Polycrystalline/Semi crystalline

(Rock salt, Calcites, Quartz solids) (Rock, sand, metals, salts, etc)

Crystalline Solids
A solid in general is said to be a crystal if the constituent particles (atoms, ions or
molecules) are arranged in a three dimensional periodic manner. In crystalline solids the atoms are
stacked in a regular manner, forming a 3-D pattern which may be obtained by a 3-D repetition of a
certain pattern unit. It has long-range orderness and thus has definite properties such a sharp
melting point. Thus we can say, crystal is a three dimensional periodic array of atoms. When the
crystal grows under constant environment, the external geometrical shape of the crystal often
remains unchanged. Thus, the shape is a consequence of the internal arrangement of constituent
particles. The ideal crystal has an infinite 3D repetition of identical units, which may be atoms or
molecules. All ionic solids and most covalent solids are crystalline. All solid metals, under normal
circumstances, are crystalline.

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Single crystal
When the periodicity in crystal pattern extends throughout a certain piece of materials, one
speaks of a single crystal or unit crystal or mono-crystal. Rock salt, calcites, quartz, etc. are
examples of common single crystal.

Polycrystalline solids (Polymorphism)

When the periodicity in the crystal structure is interrupted at so-called grain boundaries, the
crystal is said to be polycrystalline. In this case the size of the grains or crystallites is smaller than
the size of the pattern unit which forms the periodicity. The size of the grain in which the structure
is periodic may vary from macroscopic dimensions to several angstroms. In general, the grains in
such a solid are not related in shape to the crystal structure, the surface being random in shape rather
than well defined crystal planes. Rock, sand, metals, salts, etc. are some examples of
polycrystalline solids.

Fig. Single crystal, polycrystalline, amorphous

Noncrystalline solids
It is the opposite extreme of a single crystal. These types of solids have neither reticular nor
granular structure. At most causes exhibit short range orderness in their structure. Glass and plastic
are common example of this class. When the size of the grains or crystallites becomes comparable
to the size of the pattern unit, we speak of amorphous substances. A typical feature of these
substances is that they have no definite melting points. As their temperature is increased, they
gradually become soft; their viscosity drops, and begins to behave like ordinary viscous liquids.

Amorphous solids have no long-range order. The atoms or molecules in these solids are not
periodically located over large distances. An amorphous structure is shown below.

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Many amorphous materials have internal structures similar to liquids. In fact, the only obvious
distinction between amorphous materials, such as glass, and liquids is the high viscosity (resistance
to flow) of the amorphous solids.
All solids tend to exist in the crystalline state rather than the amorphous state because the crystalline
structure always has a larger binding energy. However, in numerous instances amorphous solids are
formed when liquids are cooled below the melting temperature. This occurs for two reasons:
1) the structure of the molecules is so complex that they cannot easily rearrange themselves
to form a crystalline structure, and/or
2) the solid forms so rapidly that the atoms or molecules do not have time enough to
rearrange themselves in a crystalline structure.
Generally, amorphous solids have one of two distinct atomic arrangements: either a tangled mass of
long-chained molecules or a 3-dimentional network of atoms with no long-range order.
Amorphous materials with long-chained molecules (e.g. polymers) have a structure similar to that
shown below.

Each segment in above figure represents one of the repeating units of the polymer chain. The
arrangement of the molecules is fairly random, resulting in a loosely packed structure. Network
amorphous solids are usually Oxides, the most common being Silica (SiO 2). The amorphous SiO2
structure is also shown above. Only oxygen atoms are shown (corners of tetrahedral) in this
amorphous SiO2 structure. There is a Silicon atom at the center of each tetrahedral which is not
shown here. This structure has short-range order but none of the long-range order found in
crystalline Silica. Thus, in both amorphous and crystalline Silica, each Silicon atom and each

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Oxygen atom have essentially the same local surroundings, even though there is no long-range
periodicity in the amorphous structure.

Solids that do not have long range atomic order are called amorphous solids. They often have
subunits that have consistent form, but their long-range order is disturbed because the sub-units
pack randomly. Amorphous solids are formed when liquids are cooled too quickly from the molten
state to allow the sub-units to arrange themselves in the low energy, crystalline state.
Solids with pure ionic bonds do not form amorphous solids but all the other bond types can produce
amorphous solids. Silica (SiO2) can form either covalent amorphous solids, usually called glasses
or regular crystal structrures (Quartz).

In glasses, the tetrahedral SiO2 structure If the molten Silica is cooled very slowly,
forms the sub-unit, and it is the flexibility of the sub-units fall into the regular crystal
corner to corner links that accounts for the structure of Quartz, shown below.
ability of SiO2 to form the random structures
shown below.

Impurities in SiO2 hinder crystallization. Common window glass (soda lime glass) has
Na20 and CaO added. Ovenware glass (borosilicate glass) has B203 added.
Liquid crystals (LCs) are a state of matter that have properties between those of a conventional
liquid and those of a solid crystal.[1] For instance, an LC may flow like a liquid, but its molecules
may be oriented in a crystal-like way. There are many different types of LC phase, which can be
distinguished by their different optical properties (such as birefringence). When viewed under a
microscope using a polarized light source, different liquid crystal phases will appear to have distinct
textures.
Examples of liquid crystals can be found both in the natural world and in technological applications.
Most modern electronic displays are liquid crystal based. Lyotropic liquid-crystalline phases are
abundant in living systems. For example, many proteins and cell membranes are LCs. Other well-
known LC examples are solutions of soap and various related detergents, as well as tobacco mosaic
virus.

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Liquid crystal display
Liquid crystals find wide use in liquid crystal displays, which
rely on the optical properties of certain liquid crystalline
substances in the presence or absence of an electric field. In a
typical device, a liquid crystal layer (typically 10 μm thick) sits
between two polarizers that are crossed (oriented at 90° to one Structure of liquid crystal display:
1 – vertical polarization filter,
another). The liquid crystal alignment is chosen so that its 2,4 – glass with electrodes,
relaxed phase is a twisted one (see Twisted nematic field effect). 3 – liquid crystals,
5 – horizontal polarization filter,
This twisted phase reorients light that has passed through the 6 – reflector

first polarizer, allowing its transmission through the second

polarizer (and reflected back to the observer if a reflector is provided). The device thus appears
transparent. When an electric field is applied to the LC layer, the long molecular axes tend to align
parallel to the electric field thus gradually untwisting in the center of the liquid crystal layer. In this
state, the LC molecules do not reorient light, so the light polarized at the first polarizer is absorbed
at the second polarizer, and the device loses transparency with increasing voltage. In this way, the
electric field can be used to make a pixel switch between transparent or opaque on command. Color
LCD systems use the same technique, with color filters used to generate red, green, and blue pixels.
Similar principles can be used to make other liquid crystal based optical devices.
They are used in a wide range of applications, including computer monitors, television, instrument
panels, aircraft cockpit displays, signage, etc. They are common in consumer devices such as video
players, gaming devices, clocks, watches, calculators, and telephones.

Polymorphism
Polymorphism refers to the ability of a solid to exist in more than one crystalline form or structure.
According to Gibbs' rules of phase equilibria, these unique crystalline phases will be dependent on
such intensive variables as pressure, temperature and volume. Polymorphism can potentially be
found in many crystalline materials including polymers, minerals, and metals, and is related to
allotropy, which refers to elemental solids. The complete morphology of a material is described by
polymorphism and other variables such as crystal habit, amorphous fraction or crystallographic
defects. Polymorphs have different stabilities and may spontaneously convert from a metastable
form (or thermodynamically unstable form) to the stable form at a particular temperature. They also
exhibit different melting points, solubilities, and X-ray diffraction patterns.

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One good example of this is the quartz form of silicon dioxide, or SiO2. Quartz is one of the several
thermodynamically stable crystalline forms of silica, SiO2. The most important forms of silica
include: α-quartz, β-quartz, tridymite, cristobalite, coesite, and stishovite. In the vast majority of
silicates, the Si atom shows tetrahedral coordination by 4 oxygens. All but one of the crystalline
forms involve tetrahedral SiO4 units linked together by shared vertices in different arrangements. In
different minerals the tetrahedra show different degrees of networking and polymerization. For
example, they occur singly, joined together in pairs, in larger finite clusters including rings, in
chains, double chains, sheets, and three-dimensional frameworks. The minerals are classified into
groups based on these structures. In each of its 7 thermodynamically stable crystalline forms or
polymorphs of crystalline quartz, only 2 out of 4 of each the edges of the SiO 4 tetrahedra are shared
with others, yielding the net chemical formula for silica: SiO2.
Another example is elemental tin (Sn), which is malleable near ambient temperatures but is brittle
when cooled. This change in mechanical properties due to existence of its two major allotropes, α-
and β-tin. The two allotropes that are encountered at normal pressure and temperature, α-tin and β-
tin, are more commonly known as gray tin and white tin respectively. Two more allotropes, γ and σ,
exist at temperatures above 161 °C and pressures above several GPa.[12] White tin is metallic, and
is the stable crystalline form at or above room temperature. Below 13.2 °C, tin exists in the gray
form, which has a diamond cubic crystal structure, similar to diamond, silicon or germanium. Gray
tin has no metallic properties at all, is a dull-gray powdery material, and has few uses, other than a
few specialized semiconductor applications. Although the α-β transformation temperature of tin is
nominally 13.2 °C, impurities (e.g. Al, Zn, etc.) lower the transition temperature well below 0 °C,
and upon addition of Sb or Bi the transformation may not occur at al.

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Space lattice and Translation vectors
The property that distinguishes crystals from other solids is that the constituent particles in crystals
are arranged in a three dimensional periodic manner. In 1848 Bravais introduced the concept of
space lattice.

Lattice: In order to describe the arrangement of atoms in a crystal, it is always to describe the
arrangement of imaginary points in space which has a definite relationship with the atoms of the
crystal. This set of imaginary points form a framework on which the actual crystal structure is based
on. Such an arrangement of infinite number of imaginary points in three dimensional space with
each point having identical surroundings is known as point lattice or space lattice or simply lattice.

The term ‘identical surroundings’ means that the lattice has the same appearance when
viewed from a point r in the lattice as it has when viewed from any other point r with respect to
some arbitrary origin.

Lattice arrangement in 1-D is the line of Lattice, in 2-D is the Lattice plane, in 3-D is the space
Lattice.
Thus the three dimensional lattice arrangements with translation vectors is the space lattice.
Let us consider the translation of an object to a finite distance and then repeated systematically
along 3-D crystallographic directions x, y, z to obtain 3-D space lattice. The lattice is defined by 3

fundamental translation vectors such that the atomic arrangement looks the same in

every respect when viewed from the point r as when viewed from the point

= + n1 + n2 + n3 .......................................... (1)

Where n1, n2, n3 are arbitrary integers and the set of points defined by (1) for all n1, n2, n3 defines a
lattice.

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Bravais and Non-Bravais lattice
There are two classes of lattices: the Bravais and the non-Bravais. In a Bravais lattice all
lattice points are equivalent and hence by necessity all atoms in the crystal are of the same kind. On
the other hand, in a non-Bravais lattice, some of the lattice points are non-equivalent. Non-Bravais
lattices are often referred to as a lattice with a basis. The basis is a set of atoms which is located
near each site of a Bravais lattice.
The lattice is defined by fundamental translation vectors. For example, the position vector of any
lattice site of the two dimensional lattice in figure can be written as
T=n a +n a
1 1 2 2

where a and a are the two vectors shown in figure, and n , n is a pair of integers whose values
1 2 1 2

depend on the lattice site. So, the two non-collinear vectors a1 and a2 can be used to obtain the
positions of all lattice points which are expressed
by the equation. The set of all vectors T expressed
by this equation is called the lattice vectors.
Therefore, the lattice has a translational symmetry
under displacements specified by the lattice vectors
T. In this sense the vectors a and a can be called
1 2

the primitive translation vectors. The choice of the

primitive translations vectors is not unique. One
could equally well take the vectors a1 and a = a +a as primitive translation vectors. This choice is
1 2

usually dictated by convenience.

Crystal structure
In the simplest crystals such as copper, silver, iron, aluminum, and the alkali metals, the
structural unit is a single atom. Often the structural unit is several atoms or molecules, upto 1000 in
inorganic crystals and 10000 in protein crystals. Thus each lattice point has a number of groups of
atoms attached to each lattice point. This group of atoms attached to each lattice point is called the
basis, it is repeated in space to form the crystal structure.
Basis is identical – in composition,
in arrangement,
in orientation .

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and repeated periodically in space to form the crystal structure which can be represented by the
logical relation
Lattice + Basis = Crystal Structure ------------- (2)

Lattice + Basis crystal structure

2-D non-collinear translation define a plane lattice

3-D non-coplanar translation defined a space lattice

The lattice and the translation vectors a, b, and c are said to be primitive if any two points r and
r`from which the atomic arrangement looks the same always satisfy eq (1) with a suitable choice of
the integers n1, n2 and n3. A lattice translation operation is defined as the displacement of a crystal
by a crystal translation vector in x, y, z crystallographic direction as
T = n1a + n2b + n3c ----------------------------- (3)
Thus, r` = r + T ----------------------------------- (4)

Fig. The atomic arrangement in the crystal looks exactly the same to an observer at r`as to an
observer at r, provided that the vector T which connects r` and r may be expressed as an integral
multiple of the vectors a and b.

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For example: If the 3-D fundamental basis vectors of a crystal are a = 3i, b =3j and c =1.5 (i+j), the
primitive translation operation is then given by T = n1 (3i)+n2 (3j)+1.5 (i+j) gives the body centered
cubic structure.

Primitive unit cell & Non-primitive unit cell

All solids are composed of discrete basic units which are the atoms. These atoms are not
distributed randomly, but are arranged in a highly ordered manner relative to each other. Such a
group of ordered atoms is referred to as a crystal.
In 3-D, the simplest parallelepiped formed by the primitive translation operation T is called unit
cell.
The parallelepiped defined by primitive axes a, b, c is called primitive cell. The number of atoms in
a primitive cell or primitive basis is always the same for a given crystal structure.
It is the minimum volume cell.
It is the building block element.
It has always only one lattice point per cell.

Fig. Choices for primitive translation vectors and primitive unit cells which have equal area (cells 1,
2, 3)

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Volume of the unit cell

Here parallelogram 1, 2, 3 are equal in area and any one of them could be taken as the primitive
cell. The parallelogram 4 has twice the area of a primitive cell and thus a compound cell. The
compound cell is also a non-primitive cell. There is more than one lattice point and the area is
constant multiple of primitive cell.

Example of
Primitive cell – Simple cubic;

Non-primitive cell – Body centered cubic, Face centered cubic; Base centered orthorhombic,
Hexagonal structure, etc.

Base centered tetragonal Unit cell

Hexagonal Unit cell

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Wigner-Seitz cell
It was first suggested by E. P Wigner and F. Seitz. A primitive cell can also be chosen as:
 Firstly, we have to draw lines to connect a given lattice point to all nearby lattice
points.
 Secondly, at the midpoint and normal to these lines we have to draw new lines or
planes.

The smallest volume enclosed in this way is the Wigner-Seitz primitive cell. All the space of the
crystal may be filled by these primitive cells, by translating the unit cell by the lattice vectors. In
the figure, the Wigner-Seitz cell is a polyhedron obtained by connecting a lattice point (red) to all
other lattice points and drawing the planes perpendicular to these connecting lines and passing
through their midpoints. This construction is called the Dirichlet construction. The cell thus
obtained is a primitive cell and all the space of the crystal may be filled by these primitive cells, by
translating the unit cell by the lattice vectors.

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The Wigner-Seitz cell of a body-centered cubic lattice I is a cuboctahedron and the Wigner-Seitz
cell of a face-centered cubic lattice F is a rhomb-dodecahedron. In reciprocal space this cell is the
first Brillouin zone. Since the reciprocal lattice of body-centered lattice is a face-centered lattice and
reciprocally, the first Brillouin zone of a body-centered cubic lattice is a rhomb-dodecahedron and
that of a face-centered cubic lattice is a cuboctahedron.

Lattice parameters and lattice constant

The lattice constant [or lattice parameter] refers to the constant distance between unit cells in
a crystal lattice. Lattices in three dimensions generally have three lattice constants, referred to as a,
b, and c. However, in the special case of cubic crystal structures, all of the constants are equal and
we only refer to a. Similarly, in hexagonal crystal structures, the a and b constants are equal, and we
only refer to the a and c constants. A group of lattice constants could be referred to as lattice
parameters. However, the full set of lattice parameters consist of the three lattice constants and the
three angles between them.
For example the lattice constant for a common carbon
diamond is a = 3.57Å at 300 K. The structure is equilateral
although its actual shape can not be determined from only
the lattice constant. Furthermore, in real applications,
typically the average lattice constant is given. As lattice
constants have the dimension of length, their SI unit is the
meter. Lattice constants are typically of the order of several
angstroms (i.e. tenths of a nanometre). Lattice constants can be determined using techniques such as
X-ray diffraction or with an atomic force microscope (AFM).

Thus, the tree fundamental translation vectors , , along with opposite angles , , , each of

between two crystallographic axis as shown in figure are the lattice parameters and the distance
between two identical atoms or molecules is the lattice constant.

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Co-ordination number
The points in a Bravais lattice that are closest to a given point are called its nearest
neighbors. Because of the periodic nature of a Bravais lattice, each point has the same number of
nearest neighbors. This number is thus a property of the lattice and is referred to as the co-
ordination number of the lattice.
In solid-state structures of crystals are defined by a simpler model in which the atoms are
represented by touching spheres. In this model the coordination number of an atom is the number of
other atoms which it touches. For an atom in the interior of a crystal lattice the number of atoms
touching the given atom is the bulk coordination number; for an atom at a surface of a crystal, this
is the surface coordination number.
A simple cubic lattice has co-ordination no. 6, Body centered cubic lattice has co-ordination no. 8
and face centered cubic lattice has co-ordination no. 12.

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The coordination number of BCC crystal is 8. The body centered atom is in contact with all the
eight corner atoms. Each corner atom is shared by eight unit cells and hence, each of these atoms is
in touch with eight body centered atoms.

In the FCC lattice each atom is in contact with 12 neighbor atoms. FCC coordination number Z =
12.
For example, the face centered atom in the front face is in contact with four corner atoms and four
other face-centered atoms behind it (two sides, top and bottom) and is also touching four face-
centered atoms of the unit cell in front of it.

In Hexagonal lattice Z = 12. The center atom of the top face is in touch with six corner atoms, three
atoms of the mid layer and other three atoms of the mid layer of the unit cell above it.

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