Struktur dan Cacat Kristal

Struktur dan Sifat Kimia Material

23 Oktober 2015
 Crystal
Structure
Introduction

States of matter

Solids Liquids Gases

Introduction

A crystal or crystalline solid is a solid material

whose constituent atoms, molecules, or
ions are arranged in an ordered pattern
extending in all three spatial dimensions. In
addition to their microscopic structure, large
crystals are usually identifiable by their
macroscopic geometrical shape, consisting of
flat faces with specific, characteristic
orientations.
Introduction

Microscopic structure of a Halite crystal. Macroscopic (~10cm) halite crystal

(Purple is Sodium ion, green is chlorine cluster. The right-angles between
ion.) There is cubic symetry in the atoms' crystal faces are due to the cubic
arrangement. symmetry of the atoms' arrangement.
Introduction

• Kristal adalah susunan

atom-atom secara teratur
dan kontinu pada arah tiga
dimensi b a
c
• Satuan sel adalah susunan d
a
terkecil dari kristal
• Parameter kisi struktur b
x
kristal
Panjang sisi a, b, c
Sudut antara sumbu a, b, d

Tahun 1848, kristalografer Prancis Auguste Bravais (1811 –

1863) mengklasifikasikan kisi kristal berdasarkan simetrinya,
dan menemukan bahwa terdapat 14 jenis kisi kristal, disebut
kisi Bravais yang diklasifikasi menjadi 7 sistem kristal.
Crystal systems
Parameter kisi diklasifikasikan dalam tujuh sistem kristal dan empat belas kisi Bravais
P I F

Cubic

P C
Monoclinic
P I

Tetragonal
P C I F
P
P R
Triclinic Hexagonal
Trigonal
(Rhombohedral)

Orthorhombic
Crystal systems
P = Primitive

Layer Sequence
Unit Cell
G. Lisensky - Beloit College
Crystal systems

I = Body centered

Layer Sequence
Unit Cell
G. Lisensky - Beloit College
Crystal systems
F = Face Centered

Layer Sequence
Unit Cell
G. Lisensky - Beloit College
Crystal systems

System Relations between Lengths and

edges and angles of unit angles to be
cell specified
Cubic a=b=c a
α = β =  = 90
Tetragonal a=bc a, c
α = β =  = 90
Orthorhombic abc a, b, c
α = β =  = 90
Monoclinic abc a, b, c
α =  = 90  β β
Triclinic abc a, b, c
α  β    90 α, β, 
Hexagonal and a=bc a, c
Trigonal α = β = 90
 = 120
Crystal systems
Parameter kisi diklasifikasikan dalam tujuh sistem kristal dan empat belas kisi Bravais
P I F

Cubic

P C
Monoclinic
P I

Tetragonal
P C I F
P
P R
Triclinic Hexagonal
Trigonal
(Rhombohedral)

Orthorhombic
Miller Indices

Miller Indices of directions and planes

Miller Indices: Reciprocals of the

(three) axial intercepts for a plane,
cleared of fractions & common
multiples. All parallel planes have
same Miller indices.

Miller indices form a notation system

in crystallography for planes in crystal
(Bravais) lattice.
In particular, a family of lattice
planes is determined by three
integers h, k, and ℓ, the Miller indices. William Hallowes Miller
(1801 – 1880)
University of Cambridge
Miller Indices
Bidang Kristal

• Dinyatakan dengan (hkl)

• hkl merupakan bilangan bulat
Miller Indices

Menentukan Indeks Miller Bidang

Kristal
z z’
• Prosedur menentukan bidang kristal
x y z
Intersep ~a b c/2
Intersep
(dlm a, b dan c) ~ 1 ½ c
Resiprokal 0 1 2 a y

Penentuan (012)
b
x x’ bid.(012)
Miller Indices

Crystallographic Planes
z
example a b c
1. Intercepts 1 1  c
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2   c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 1 0 0
y
4. Miller Indices (100) a b
x
Miller Indices

Crystallographic Planes
example a b c z
1. Intercepts 1/2 1 3/4
2. Reciprocals 1/½ 1/1 1/¾ c
2 1 4/3 

3. Reduction 6 3 4
 y

4. Miller Indices (634) a b
x
Family of Planes {hkl}

Ex: {100} = (100), (010), (001), (100), (010), (001)

Miller Indices
Miller Indices

[1, 0, 0]

[1, 1, 0]

[2, -1, 0]

[1, -2, 0]

[2, 1, 0]
Miller Indices
Miller Indices
Miller Indices
Miller Indices
Miller Indices

Crystallographic Planes (HCP)

• In hexagonal unit cells the same idea is used
z

example a1 a2 a3 c
1. Intercepts 1  -1 1
2. Reciprocals 1 1/ -1 1
1 0 -1 1
a2
3. Reduction 1 0 -1 1

4. Miller-Bravais Indices (1011) a3

a1
Miller Indices

Determine the indices for the planes shown in the

hexagonal unit cells below:
Miller Indices
Determine the indices for the planes shown in the
hexagonal unit cells below:
Miller Indices
Miller Indices
Crystal
defects
Schottky Defects
The defect forms when oppositely charged ions
leave their lattice sites, creating vacancies. These
vacancies are formed in stoichiometric units, to
maintain an overall neutral charge in the ionic solid.
The vacancies are then free to move about as their
own entities. Normally these defects will lead to a
decrease in the density of the crystal.

Walter H. Schottky (1886 – 1976)

German physicist
Ion migration
Na Cl
Cl Na
E
Cl
Schottky Defect
Na Cl
(i.e. NaCl)
Frankel Defects
The defect forms when an atom or cation leaves its
place in the lattice, creating a vacancy, and becomes
an interstitial by lodging in a nearby location not
usually occupied by an atom. Frenkel defects occur
due to thermal vibrations, and it is theorized that
there will be no defects in a crystal at 0 K.

Yakov Il'ich Frenkel (1894 – 1952)

Russian physicist

Ion migration
Direct Interstitial Jump
Interstitialcy Mechanism

Frenkel Defect
(i.e. AgCl)
 Ion Migration (Frenkel Defects)
The Frenkel defects in AgCl can migrate via two mechanisms.
Ag Cl Ag Ag Cl Ag

Cl Ag Cl Ag Cl
Cl
Ag1
Ag1
Cl Ag2 Cl Cl Ag2 Cl

Ag Cl Ag Ag Cl Ag

Direct Interstitial Jump

Ag Cl Ag Ag Cl Ag

Cl Ag Cl Ag Cl
Cl
Ag2
Ag1
Cl Ag2 Cl Cl Ag1 Cl

Ag Cl Ag Ag Cl Ag

Interstitialcy Mechanism
Chem 754 - Solid State
Chemistry
Stone-Wales Defects
A Stone–Wales defect is a crystallographic
defest that occurs on carbon nanotube and
graphene and is thought to have important
implications for nanotube's mechanical
properties. Describe in 1986 paper.

Professor Anthony Stone

University of Cambridge

Stone-Wales Defect
(i.e. CNT, graphene)
Line Defects (Edge Dislocations)

Edge dislocations are caused by the termination of a plane of atoms in the middle
of a crystal. In such a case, the adjacent planes are not straight, but instead bend
around the edge of the terminating plane so that the crystal structure is perfectly
ordered on either side.
Planar Defects

Grain boundaries occur where the crystallographic direction of the lattice

abruptly changes. This usually occurs when two or more crystals begin
growing separately and then meet.

Twin boundary Grain boundary

Bulk Defects

Voids are small regions where there are no atoms, and can be thought of as
clusters of vacancies.
Impurities can cluster together to form small regions of a different phase. These
are often called precipitates.

Precipitates
X-Ray Diffraction
X-Ray Diffractometer
XRD parts

β-Filter
Detector

Slit

Radiation
Source
XRD
XRD
XRD
XRD

Sir William Henry Bragg William Lawrence Bragg

(1862 – 1942) (1890 – 1971)

the 1915 Nobel Prize in Physics: "For their services in the analysis of crystal
structure by means of X-ray"
X-Ray Radiations

Wavelength (Å)
Anode β-Filter
Kα1 (100) Kα2 (50) Kβ (15)
Cu 1.54060 1.54439 1.39222 Ni
Cr 2.28970 2.29361 2.08487 V
Fe 1.93604 1.93998 1.75661 Mn
Co 1.78897 1.79285 1.62079 Fe
Mo 0.70930 0.71359 0.63229 Zr
Cu Radiations

Cu Kα = 1.5418 Å

Kα 1 = 1.54060 Å
Kα 2 = 1.54439 Å

Kβ = 1.39222 Å
XRD
Bragg’s Law
Example

Material Mesopori
Example

a
d

t = 6-12 A

Jika bidang d001 mendifraksikan sinar x pada 2 = 2,14o, maka

berapakah jari-jari pori material tersebut? (17.8 Å)
Analysis

JCPDS - Joint Committee on Powder Diffraction Standards

Analysis

JCPDS - Joint Committee on Powder Diffraction Standards

NiO diffractogram
[003] [012]

200
Intensity / cps d

30 35 40 45 50
2 / degree
Analysis

JCPDS - Joint Committee on Powder Diffraction Standards

Analysis

JCPDS - Joint Committee on Powder Diffraction Standards

Analysis
[101] [102] [110] [201] [103]
[112] [202]
4:3
5000

3:2
Intensity (cps)

2:1
[002] [201]
[200] 3:1

4:1

JCPDS Ni3Sn2 No. 6-414

JCPDS Ni3Sn No. 35-1362

30 40 50 60
2 (degree)
Shape factor

Scherrer equetion:

= mean size of the ordered (crystalline) Paul Scherrer (1890 – 1969)

= Shape factor (varies from 0.89 for spherical to 0.94 Swiss physicst
for cubic, set to 0.9 for unknown)
= x-ray wavelength (1.5418 Å)

= line broadening at half the maximum intensity (radians)

 = Bragg angle
Quiz 1

1. Sebutkan bagian2 dari X-Ray Diffractometer ! Dan fungsi2nya masing2 !

2. Logam-logam apa saja yang dapat dijadikan sumber sinar? Berapa
panjang gelombang sinar X yang dihasilkan? Apa saja logam yang
dipakai untuk menyaring sinar Kβ
3. Tuliskan persamaan Bragg ! Dan jelaskan bagaimana Bragg dapat
merumuskan persamaan tersebut (dengan gambar difraksi) !
4. Berapa jarak antar kisi kristal (nilai d) jika diketahui:
- Sudut difraksi: 2 = 30.7742
- Sinar X yang digunakan : Cu Kα = 1.5418 Å
5. Berapa ukuran partikel padatan jika diketahui:
- Sudut difraksi: 2 = 30.3
- Sudut-sudut pada setengah puncak: 30.02 dan 30.74
- Sinar X yang digunakan: Cu Kα = 1.5418 Å
- Shape factor (K) = 0.9
d = 2.903 nm
Τ = 11.447 nm
Miller Indices

Menentukan Indeks Miller Arah

Kristal
z
• Prosedur menentukan arah
kristal
x y z
Proyeksi a/2 b 0
Proyeksi pd sb y: b
Proyeksi (dlm a, b, c) c Proyeksi pd
sb x: a/2
½ 1 0 a y
Reduksi 1 2 0
Penentuan [120] b
x