Outline

24.1 Photons
24.2 Wave-particle duality
24.3 Atomic structure
24. QUANTUM PHYSICS 24.4 X-rays
24.5 Nanoscience
Liew Sau Poh

Objectives Objectives
(a) describe important observations in (e
photoelectric emission experiments effect, hf=W + ½mv2max
(b) recognise features of photoelectric emission (f) understand the meaning of stopping potential
that cannot be explained by wave theory and and use eVs= ½mv2max
explain these features using the concept of
quantisation of light (h) use the relation = h/p to calculate de
(c) use the equation for a photon E= hf Broglie wavelength
(d) explain the meaning of work function and (i) interpret the electron diffraction pattern as an
threshold frequency evidence of the wave nature of electron

Objectives
(j) explain the advantages of an electron
microscope as compared to an optical
microscope
(l) derive an expression for the radii of the orbits
(m) derive the formula
Objectives
(n) explain the production of emission line
spectra with reference to the transitions
between energy levels
(o) explain the concepts of excitation energy and
ionisation energy
(p) interpret X-ray spectra obtained from X-ray
tubes
(q) explain the characteristic line spectrum and
continuous spectrum including min in X-rays

Objectives 24.1 Photon

(r) derive and use the equation min = hc / eV Photoelectric effect:
(s) describe X-ray diffraction by two parallel When electromagnetic radiation is incident to
adjacent atomic planes the surface of a metal, electrons are ejected
d sin = m from the surface.
(u) explain the basic concept of nanoscience Photoelectrons:
(v) state the applications of nanoscience in The electrons emitted by this effect.
Visible light Visible light
electronics devices UV
Photoelectrons Photoelectrons
No photoelectrons

Metals Metals other than Alkali Metals Alkali Metals

Photon Properties of photons
A packet or bundle of energy is called a A photon travels at a speed of light c in vacuum.
photon. (i.e. 3 x 108 m/s)
hc It has zero rest mass. i.e. the photon can not exist
Energy of a photon is E = hf =
at rest.
The kinetic mass of a photon is, m =
E h
=
c2 c
where h
The momentum of a photon is,
E h
p= =
f is the frequency of the radiation or photon, Photons travel in a straight line.
c
c is the speed of light (e.m. wave) and Energy of a photon depends upon frequency of the
photon; so the energy of the photon does not
is the wavelength. change when photon travels from one medium to
another.

Properties of photons Photoelectric Effect

Wavelength of the photon changes in
different media; so, velocity of a photon is UV
Photoelectrons
different in different media.
Photons are electrically neutral. Visible light Photoelectrons
Photons may show diffraction under given Metals
conditions.
Photons are not deviated by magnetic and Visible light Alkali Metals
electric fields. No photoelectrons

Metals other than Alkali Metals

Photoelectric Effect Experimental (Photoelectric Effect)

The phenomenon of emission of electrons from mainly
metal surfaces exposed to light energy (X rays,
rays, UV rays, Visible light and even Infra Red rays) of
UV light
suitable frequency is known as photoelectric effect.
The electrons emitted by this effect are called W
photoelectrons.
C A
The current constituted by photoelectrons is known as
photoelectric current. A
Note: Non metals also show photoelectric effect. + + C Metallic cathode
Liquids and gases also show this effect but to limited K V A Metallic Anode
extent. W Quartz Window
- Photoelectron

Experimental (Photoelectric Effect) Experimental (Photoelectric Effect)

Glass transmits only visible and infra-red lights
but not UV light.
Quartz transmits UV light.
When light of suitable frequency falls on the
metallic cathode, photoelectrons are emitted.
These photoelectrons are attracted towards the
+ve anode and hence photoelectric current is
1) Effect of Intensity of Incident Light on
Photoelectric Current:
For a fixed frequency, the photoelectric current
increases linearly with increase in intensity of
incident light.
I A

constituted.

0 Intensity (L)
Experimental (Photoelectric Effect)
2) Effect of Potential on
Photoelectric Current:
For a fixed frequency and
intensity of incident light,
the photoelectric current
increases with increase in
+ve potential applied to the
anode.
When all the
photoelectrons reach the VS
plate A, current becomes
maximum and is known as
saturation current.
Experimental (Photoelectric Effect)
2) Effect of Potential on
Photoelectric Current:
When ve potential is
applied to the plate A w.r.t.
C, photoelectric current
becomes zero at a
particular value of ve
potential called stopping
potential or cut-off
potential. VS
Intensity of incident light
does not affect the stopping
potential.
Experimental (Photoelectric Effect)
4) Effect of Frequency of
Incident Light on Stopping
Potential:
For a fixed intensity of
incident light, the
photoelectric current
increases and is saturated
with increase in +ve
potential applied to the
anode. VS2
However, the saturation
current is same for
different frequencies of the
incident lights.
5) Threshold Frequency
The graph between stopping
potential and frequency does not
pass through the origin.
It shows that there is a minimum
value of frequency called threshold
frequency below which photoelectric
emission is not possible however
high the intensity of incident light
may be.
It depends on the nature of the metal
emitting photoelectrons.
Experimental (Photoelectric Effect)
2) Effect of Potential on
Photoelectric Current:
When the potential is
I Saturation decreased, the current I Saturation
A Current L2 decreases but does not A Current L2
L1
become zero at zero L1
potential.
L2 > L1 This shows that even in the L2 > L1
absence of accelerating
0 Potential of A (V)
+ potential, a few VS 0 Potential of A (V)
+
photoelectrons manage to
reach the plate on their
own due to their K.E.
Experimental (Photoelectric Effect)
3) Effect of Frequency of Incident
Light on Photoelectric Current:
For a fixed intensity of incident
Saturation light, the photoelectric current
I
Current does not depend on the
A L2
frequency of the incident light. I Saturation Current
L1
Because, the photoelectric A
L2 > L1
current simply depends on the 2>
number of photoelectrons 2 1
+ emitted and in turn on the
0 Potential of A (V) number of photons incident 1
+
and not on the energy of VS2 VS1 0 Potential of A (V)
photons.
Experimental (Photoelectric Effect)
4) Effect of Frequency of
Incident Light on Stopping
Potential:
Saturation Current
When potential is Saturation Current
I I
A decreased and taken below A
zero, photoelectric current
2> 2>
1
decreases to zero but at 1
2 2
different stopping
1 potentials for different 1
+ +
VS1 0 Potential of A (V) frequencies. VS2 VS1 0 Potential of A (V)
Higher the frequency, higher the stopping potential. i.e. VS
VS (V)
28.2 Concept of light quantisation
0 0
Laws of Photoelectric Emission
For a given substance, there is a minimum
value of frequency of incident light called
threshold frequency below which no
photoelectric emission is possible, howsoever,
the intensity of incident light may be.
The number of photoelectrons emitted per
second (i.e. photoelectric current) is directly
proportional to the intensity of incident light
provided the frequency is above the threshold
frequency.
Laws of Photoelectric Emission
The maximum kinetic energy of the photoelectrons is
directly proportional to the frequency provided the
frequency is above the threshold frequency.
The maximum kinetic energy of the photoelectrons is
independent of the intensity of the incident light.
The process of photoelectric emission is
instantaneous. i.e. as soon as the photon of suitable
frequency falls on the substance, it emits
photoelectrons.
The photoelectric emission is one-to-one. i.e. for
every photon of suitable frequency one electron is
emitted.

According to law of conservation of energy,

the energy of the photon is absorbed by the electron
and is used in two ways: hf = + ½ mv2max
A part of energy is used to overcome the surface
barrier and come out of the metal surface. This part
work function 0).
= hf0 + ½ mv2max Photon h
½ mv2max
The remaining part of the energy is used in giving a
½ mv2max = h ( f - f0 ) Photoelectron
to the maximum kinetic energy of the photoelectrons
( ½ mv2max =h 0

Metal

Verification of Laws of Photoelectric Emission based Verification of Laws of Photoelectric Emission based

½ mv2max = h ( - 0 ) ½ mv2max = h (
If < 0, then ½ mv2max is negative, which is
not possible. Therefore, for photoelectric
emission to take place > 0.
Since one photon emits one electron, so the
number photoelectrons emitted per second is
directly proportional to the intensity of
incident light.
- 0 )
It is clear that ½ mv2max as h and 0 are constant.
This shows that K.E. of the photoelectrons is directly
proportional to the frequency of the incident light.
Photoelectric emission is due to collision between a
photon and an electron. As such there can not be any
significant time lag between the incidence of photon
and emission of photoelectron. i.e. the process is
instantaneous. The delay is only 10-8 seconds.

Application of Photoelectric Effect Photoelectric Threshold

Automatic fire alarm Automatic switching of Binding Energies
Automatic burglar alarm street lights K: 100
Scanners in Television To control the Photon energy: 15 L: 50
transmission temperature of furnace M: 20
Reproduction of sound in Photometry
cinema film Beauty meter To
In paper industry to measure the fair
measure the thickness of complexion of skin Which shells are
paper Light meters used in candidates for
cinema industry to check Photon in photoelectric
To locate flaws or holes in
the finished goods the light interactions?
In astronomy Photoelectric sorting
To determine opacity of Photo counting
solids and liquids Meteorology
 Photoelectric Threshold
Photoelectric Threshold

Binding Energies Binding Energies

Photon energy: 15 K: 100 Photon energy: 25 K: 100
L: 50 L: 50
NO
M: 20 M: 20
NO
NO Which shells are Which shells are
candidates for candidates for
Photon in photoelectric Photon in photoelectric
interactions? interactions?

Photoelectric Threshold Photoelectric Threshold

Binding Energies Binding Energies
Photon energy: 25 K: 100 K: 100 1
Photon energy: 25
L: 50 L: 50 P.E. ~ -----------
YES energy3
M: 20 A
M: 20
NO
NO Which shells are
candidates for Which photon has
Photon in photoelectric Photon in a greater
interactions? probability for
photoelectric
B
interactions with
the m shell?
Photon energy: 22

Photoelectric Threshold Photoelectric Threshold

Binding Energies Binding Energies
Photon energy: 55 K: 100 Photon energy: 55 K: 100
L: 50 L: 50
YES
M: 20 M: 20
YES

Which shells are NO Which shells are

candidates for candidates for
Photon in photoelectric Photon in photoelectric
interactions? interactions?

Photoelectric Threshold Photoelectric Threshold

Binding Energies Binding Energies
Photon energy: 105 K: 100 Photon energy: 105 K: 100
L: 50 L: 50
YES
M: 20 M: 20
YES

Which shells are YES Which shells are

candidates for candidates for
Photon in photoelectric photoelectric
interactions? interactions?
Photoelectric Threshold Photoelectric Threshold

When photon energy just reaches binding

1 energy of next (inner) shell, photoelectric
P.E. ~ ----------- interaction now possible with that shell
energy3 shell offers new candidate target electrons

Photoelectric interactions Photon energy: 49 Photon energy: 51

decrease with increasing photon YES

energy YES
YES
Binding Energies
NO K: 50
L: 25

Photoelectric Threshold Photoelectric Threshold

When photon energies just reaches binding energy of causes step increases in interaction
next (inner) shell, photoelectric interaction now probability as photon energy exceeds shell
possible with that shell, where shell offers new binding energies
candidate target electrons
L-shell
Interaction L-shell interactions
Probability binding possible Interaction
energy Probability L-edge
K-shell
M-shell
interactions
binding K-edge
energy
possible
K-shell
interaction
s possible Photon Energy
Photon Energy

Dual Nature of Radiation and Matter

Wave theory of electromagnetic radiations
explained the phenomenon of interference,
diffraction and polarization.
On the other hand, quantum theory of e.m.
24.2 Wave-particle Duality
radiations successfully explained the
photoelectric effect, Compton effect, black
body radiations, X- ray spectra, etc.
Thus, radiations have dual nature. i.e. wave
and particle nature.

Dual Nature of Radiation and Matter de Broglie wave

Louis de Broglie suggested that the particles like According to de Broglie, a moving material
electrons, protons, neutrons, etc have also dual nature.
i.e. they also can have particle as well as wave nature.
particle can be associated with a wave. i.e. a
Note: In no experiment, matter exists both as a wave can guide the motion of the particle.
particle and as a wave simultaneously. It is either the The waves associated with the moving material
one or the other aspect. i.e. The two aspects are particles are known as de Broglie waves or
complementary to each other.
matter waves.
His suggestion was based on:
The nature loves symmetry.
The universe is made of particles and radiations and
both entities must be symmetrical.
Expression for de Broglie wave The Compton Effect
According to quantum theory, the energy of the Let the light is made up of particles (photons),
photon is hc and that photons have momentum, with energy
E= h =
hf collides with a stationary electron.
Some of the energy and momentum is
the photon is E = mc2 transferred to the electron (this is known as the
So =
h or =
h where p = mc Compton effect), but both energy and
mc p is momentum of a photon
momentum are conserved (elastic collision).
If instead of a photon, we have a material After the collision the photon has energy hf and
particle of mass m moving with velocity v, then
the electron has acquired a kinetic energy K.
the equation becomes
which is the expression for de Broglie wavelength. h Conservation of energy: hf = hf + K
=
mv

Conclusion = h Conclusion h
mv =
mv
de Broglie wavelength is inversely proportional to the Matter waves, similar to electromagnetic waves,
velocity of the particle. If the particle moves faster,
then the wavelength will be smaller and vice versa. can travel in vacuum and hence they are not
If the particle is at rest, then the de Broglie wavelength mechanical waves.
is infinite. Such a wave can not be visualized.
de Broglie wavelength is inversely proportional to the
Matter waves are not electromagnetic waves
mass of the particle. The wavelength associated with a because they are not produced by accelerated
heavier particle is smaller than that with a lighter charges.
particle.
de Broglie wavelength is independent of the charge of Matter waves are probability waves, amplitude
the particle. of which gives the probability of existence of
the particle at the point.

Davisson and Germer Experiment Davisson and Germer Experiment

A beam of electrons The energy of the
emitted by the electron incident beam of
gun is made to fall on electrons can be varied by
V Electron Gun V Electron Gun
Nickel crystal cut along changing the applied
F voltage to the electron F
cubical axis at a C
gun.
C
particular angle. A A
Intensity of scattered
The scattered beam of beam of electrons is
electrons is received by found to be maximum
the detector which can be when angle of scattering
rotated at any angle. Crystal Lattice is 50° and the Crystal Lattice
Nickel Crystal accelerating potential is Nickel Crystal
54 V.

Davisson and Germer Experiment

Incident Beam

Incident Beam

+ 50° + = 180°
i.e. = 65°
V Intensity of scattered beam at 44 V Intensity of scattered beam at 48 V
Electron Gun
For Ni crystal, lattice F
spacing d = 0.91 Å C
Incident Beam

Incident Beam

A
For first principal
maximum, n = 1
= 50
Electron diffraction is
similar to X-ray Intensity of scattered beam at 54 V Intensity of scattered beam at 64 V
Crystal Lattice
diffraction.
Nickel Crystal de Broglie wavelength of
hypothesis, h 12.27 Å
= or = moving electron at V = 54
Volt is 1.67 Å which is in
2dsin = n gives = 1.65 Å 2meV V
close agreement with 1.65 Å.
Intensity vs
The Electron Microscope
Diffraction
pattern after Using wave-nature and particle nature of
100 electrons electron
Electron is accelerated through a high voltage
Diffraction Better than optical microscope
pattern after
0 5 10 15 20 25
3000 electrons Shorter Wavelength : (up to 10 -10 ) vs (10-7)
Higher resolving power: nanometer vs. micro

Diffraction
pattern after
70000 electrons

24.3 Atomic structure

Early models of atom

In 1898, Joseph John Thomson suggested a model of an atom

that consists of homogenous positively charged spheres with tiny
negatively charged electrons embedded throughout the sphere
as shown in the Figure.
positively
charged electron
sphere

The electrons much likes currants in a plum pudding.

atom atom.
SF027 66

In 1911, Ernest Rutherford performed a critical

pictured as electrons orbiting around a central
correct and proposed his new atomic model known nucleus which concentrated of positive charge.
The electrons are accelerating because their
shown in Figure directions are constantly changing as they circle the
nucleus.

nucleus nucleus
electron electron
 Based on the wave theory, an accelerating
charge emits energy.
Hence the electrons must emit the EM
radiation as they revolve around the nucleus.
As a result of the continuous loss of energy, the radii
of the electron orbits will be decreased steadily.
This would lead the electrons spiral and falls into the
nucleus, hence the atom would collapse as shown in
Figure.

e
e +Ze
+Ze

energy loss
energy loss

1. Only certain discrete orbits (stationary states) are

allowed for the electron force as the centripetal force he obtained
2. Electron in a stationary state does not radiate
3. Classical mechanics apply to electron in a stationary
state (not between states)
e 4 me 1 1
4. When an electron moves from one SS to another, a v 2
change in energy occurs involving the emission (or 4 (4 0) h n12 n22
absorption) of a single photon of frequency v = E/h
5. Permitted orbits (SS) are those in which angular
momentum can take on only the discrete values
nh/2

In 1913, Neils Bohr proposed a On this basis he was able to show that the energy of
new atomic model based on an orbiting electron depends on the radius of its orbit.
hydrogen atom. e This model has several features which are described
by the postulates (assumptions) stated below :
Fe v
assumes that each electron 1. The electrons move only in certain circular orbits,
+e
called STATIONARY STATES or ENERGY LEVELS.
moves in a circular orbit which is r When it is in one of these orbits, it does not radiate
centred on the nucleus, the energy.
necessary centripetal force being 2. The only permissible orbits are those in the discrete
provided by the electrostatic force set for which the angular momentum of the electron L
of attraction between the equals an integer times h/2 . Mathematically,
positively charged nucleus and
the negatively charged electron.

3. Emission or absorption of radiation occurs only

when an electron makes a transition from one
nh orbit to another.
L and L m vr
2 The frequency f of the emitted (absorbed) radiation
is given by
nh E hf E f E i
mvr (11.1)
2
where n : principalquantum number 1,2,3,... where E : change of energy
h : Planck's constant
r : radius of theorbit Ef : final energy state
m : mass of theelectron Ei : initialenergy state
If Ef > Ei Absorption of EM radiation
If Ef < Ei Emission of EM radiation
Energy level of hydrogen atom nh
Fe
e v mvr
+ r 2
e By taking square of both side of the equation, we get
Consider one electron of charge e and mass m moves in a
circular orbit of radius r around a positively charged nucleus with n2h2
m2v2r 2 (11.4)
a velocity v. 4 2
By dividing the eqs. (11.4) and (11.3), thus
The electrostatic force between electron and nucleus contributes
the centripetal force as write in the relation below: n2 h 2
m 2v 2 r 2 4 2
electrostatic force Fe Fc centripetal force mv 2 e2
1 Q1Q 2 mv 2 4
and Q 1 Q 2 e 0r electrostatic
4 0 r2 r 2 2 constant
e2 n h 0 1
mv 2 (11.3) r and 0
4 0r me 2 4 k

the radius of the

n 2h 2 1
r most stable (lowest) orbit or ground state (n=1) in
me 2 4 k the hydrogen atom and its value is
h2 34 2
rn n2 ; n 1, 2 , 3 ... (11.5) 6 . 63 10
4 mke 2
2
a0
2 31 19 2
4 9 . 11 10 9 . 00 10 9 1 . 60 10
which rn is radii of the permissible orbits for the
11
a0 5 . 31 10 m OR 0.531 Å (angstrom)

rn n 2a0 (11.6)
Unit conversion: 1 Å = 1.00 10 10 m
and
h2 The radii of the orbits associated with allowed orbits
a0
4 2 mke 2 or states n are 4a0,9a0 , thus the
radii are quantized.
where a0 is called the of hydrogen
atom.

Energy level in hydrogen atom Energy level in hydrogen atom

is defined as a fixed energy corresponding to the Potential energy U of the electron is given
orbits in which its electrons move around the
nucleus. by
The energy levels of atoms are quantized.
The total energy level E of the hydrogen atom is kQ1Q 2
given by U where Q1 e; Q 2 e and r n 2a0
r
nucleus electron
ke 2
E U K (11.7) U (11.8)

Kinetic energy of the electron

n 2 a0
Potential energy of the electron

In general, the total energy level E for the atom is

Kinetic energy K of the electron is given by
2
ke 2 Z 2
1 2 e En (11.11)
K mv but mv 2 2 a0 n 2
2 4 0r where Z : a to m ic n u m b e r
1 e2 1 Using numerical value of k, e and a0, thus the eq. (11.10) can be
K where k and r n 2 a0 2
2 4 0r 4 0 written as 9 . 00 10 9 1 . 60 10 19 1
En 11
1 ke 2 2 5 . 31 10 n2
K (11.9) 2 . 17 10 18
1
2 n 2 a0 eV 2
Therefore the eq. (11.7) can be written as 1 . 60 10 19 n
13 . 6
ke 2 1 ke 2 En eV; n 1,2,3,... (11.12)
En n2
n 2a0 2 n 2a0 th
where E n : e n ergy le v el o f n s tate (o rb it)
Note:
ke 2 1
En (11.10) Eqs. (11.10) and (11.12) are valid for energy level of the
2a0 n 2 hydrogen atom.
 The negative sign in the eq. (11.12) indicates that work has to Figure 11.4 shows diagrammatically the various energy levels in the
be done to remove the electron from the bound of the atom to hydrogen atom.
infinity, where it is considered to have zero energy. n E n (eV )
The energy levels of the hydrogen atom are when Figure 11.4 0 .0 Free electron
n=1, the ground state (the state of the lowest energy level) ; 5 0 . 5 4 4th excited state
13 . 6 4 0 . 8 5 3rd excited state
E1 2
eV 13 .6 eV 3 1 . 51 2nd excited state excited state
1 13 . 6 Ionization energy
n=2, the first excited state; E2 2
eV 3 .40 eV is defined as the
is defined as
2 energy required 2 3 . 4 0 1st excited state the energy
13 . 6 by an electron in
levels that
E3 eV 1.51 eV the ground state
n=3, the second excited state; 3
2
Excitation energy higher than
to escape
13 . 6 is defined as the energy the ground
completely from
E4 2
eV 0 .85 eV the attraction of required by an electron that state.
n=4, the third excited state; 4 the nucleus. raises it to an excited state
is defined as the
from its ground state.
n= , the energy level is 13 . 6 electron is completely lowest stable
E 2
eV 0 removed from the atom. An atom energy state of
becomes ion. 1 13 . 6 Ground state an atom.

Line spectrum Line spectrum

The emission lines correspond to the photons Figure below shows line spectra produced by
of discrete energies that are emitted when emission in the visible range for hydrogen
excited atomic states in the gas make
transitions back to lower energy levels. (H), mercury (Hg) and neon (Ne).

Figure 11.5

Hydrogen Spectrum Hydrogen emission line spectrum

= 656, 486, 434, 410 & 397 nm, what is the pattern?
Emission processes in hydrogen give rise to series,
which are sequences of lines corresponding to
atomic transitions.
The series in the hydrogen emission line spectrum
are
Lyman series involves electron transitions that
end at the ground state of hydrogen atom. It is
in the ultraviolet (UV) range.
Balmer series involves electron transitions that
end at the 1st excited state of hydrogen atom. It
is in the visible light range.

Figure below shows diagrammatically the

Hydrogen emission line spectrum series of hydrogen emission line spectrum.
The series in the hydrogen emission line n E n ( eV )
0 . 0 Free electron
spectrum are
Paschen series involves electron transitions that 5 Pfund series00 .. 85 54 4rd excited state
th
4 3 excited state
end at the 2nd excited state of hydrogen atom. It 3
Brackett series
1 . 5 1 2nd excited state
is in the infrared (IR) range. Paschen series
Brackett series involves electron transitions that
2 3 . 3 9 1st excited state
end at the 3rd excited state of hydrogen atom. It is Balmer series
in the IR range.
Pfund series involves electron transitions that end
at the 4th excited state of hydrogen atom. It is in
the IR range. Lyman series
Stimulation 11.1
1 1 3 . 6 Ground state
 Wavelength of hydrogen emission line
in the Bohr model of a hydrogen atom. spectrum
If an electron makes a transition from an outer orbit of
level ni to an inner orbit of level nf, thus the energy is
radiated.
The energy radiated in form of EM radiation
(photon) where the wavelength is given by

hc 1 E
E
hc

Wavelength of hydrogen emission line

spectrum
1 1 ke 2 1 ke 2 1
hc 2 a 0 nf 2 2 a 0 ni 2

hc 1 E 1 ke 2 1 1
E
hc hc 2 a 0 nf 2 ni 2
rd postulate, the eq. (11.13) ke 2 1 1 ke 2
and RH
can be written as 2 hca 0 n f 2 ni
2
2 hca 0
1 1 1
1 1 ke 2 1 RH (11.14)
E nf E ni where E nf nf 2 ni 2
hc 2 a 0 nf 2
where RH : Rydberd' s constant 1.097 107 m 1
ke 2 1
and E ni nf : final value of n
2 a 0 ni 2 ni : initial value of n

Note:
For the hydrogen line spectrum,
1 1 1
Lyman series( nf=1 ) RH
12 ni 2 predicts successfully the energy levels of the
1 1 1 hydrogen atom but fails to explain the energy
Balmer series( nf=2 ) RH levels of more complex atoms.
22 ni
2

can explain the spectrum for hydrogen atom but

1 1 1 some details of the spectrum cannot be explained
RH
Paschen series( nf=3 ) 32 ni
2
especially when the atom is placed in a magnetic
1 1 1
field.
RH
Brackett series( nf=4 ) 42 ni
2
2
1 1 1 Energy Levels
RH Transitions
Pfund series( nf=5 ) 52 ni
2
1
To calculate the shortest wavelength in any series, take ni= . Spectra
Figure 11.7 No magnetic field Magnetic field

24.4 X-ray

cannot explain the Zeeman effect

Zeeman effect is defined as the splitting
of spectral lines when the radiating
atoms are placed in a magnetic field.

2
Energy Levels
Transitions
1
Spectra
No magnetic field Magnetic field
Review: Atoms Review: Atoms
Smallest particle of matter that has the
properties of an element.
Contains a small, dense, positively charged
center (nucleus).
Nucleus surrounded by a negative cloud of
electrons.
Electrons revolve in fixed, well-defined orbits
(energy levels).

3 Fundamental Particles of an Atom Atoms

Electrons can only exist
Electron in certain shells that
represent electron
Proton binding energies
Neutron K, L, M shells (K is
closest to the nucleus)
The closer an electron
is to the nucleus, the
higher the binding
energy (strength of
attachment to the
nucleus).

Atoms How X-rays are Created

In their normal state, atoms are electrically To produce x-rays, you need 3 things:
neutral 1. A source of electrons
If an atom has an extra electron or has had an 2. A force to move them rapidly
electron removed, it has been ionized. 3. Something to stop them rapidly

*All 3 conditions met in an x-ray tube

Early X-ray Tube Early X-ray Tube

The X-Ray tube is the single most important component of the
radiographic system. It is the part that produces the X-rays History of X-ray and XRD
Wilhelm Conrad Röntgen discovered X-Rays in
1895.
1901 Nobel prize in Physics

Wilhelm Conrad Röntgen (1845-1923)

A modern radiograph of a hand

Early use of X-Rays History of X-ray and XRD

Within few months of Radiographs like the
their discovery, X-rays ones in the last slide are
were being put to simply shadowgrams.
practical use.
The X-rays either pass
This is an X-ray of bird
shot embedded in a
straight through or are
hand. stopped by the object.
Unfortunately, much of The diagram on the
the early use of X-rays upper left illustrates the
was far too aggressive, principle and shows a
resulting in later cancer. perfect shadow.
Section 9.4

History of X-ray and XRD History of X-ray and XRD

In reality, a large fraction The first kind of scatter process to be
of the X-rays are not recognised was discovered by Max
simply absorbed or von Laue who was awarded the Nobel
prize for physics in 1914 "for his
transmitted by the object discovery of the diffraction of X-rays
but are scattered. The by crystals". His collaborators Walter
diagram on the bottom Max von Laue (1897-1960)
Friedrich and Paul Knipping took the
left illustrates this effect picture on the bottom left in 1912. It
and illustrates the fuzzy shows how a beam of X-rays is
edge of the object that is scattered into a characteristic pattern
produced in the image by by a crystal. In this case it is copper
sulphate.
the scattered X-rays.

History of X-ray and XRD What are X-rays?

The X-ray diffraction pattern of Beams of electromagnetic radiation Interacts
with
a pure substance is like a Short wavelength, high energy
electrons!
fingerprint of the substance.
The powder diffraction method Wave (sinusoidal, oscillating electric field with, at right
is thus ideally suited for angles to it, a magnetic field)
Max von Laue (1897-1960)
characterization and wavelength
identification of polycrystalline frequency
phases. Particle (photon)
Photon energy E E=h
(h -34 Js)
Properties of a wave Electromagnetic radiation

Wave =c/ (c=300.000 km/s) Å (Ångström) is non-SI unit of length X-rays: 10-8 to 10-11 m
-10
1 Å = 10 m = 0.1 to 100 Å
0.1 nm dimension of atoms, bonds, unit-

X-Rays X-Rays
Electromagnetic radiation with short X-rays (discovered and named
wavelengths by Roentgen): electromagnetic
Wavelengths less than for ultraviolet radiation with short typically
Wavelengths are typically about 0.1 nm about 0.1 nm wavelengths
X-rays have the ability to penetrate most X-rays have the ability to
materials with relative ease penetrate most materials with Wilhelm Conrad Röntgen
1845 1923
High energy photons which can break relative ease
chemical bonds danger to tissue X-rays are produced when
Discovered and named by Roentgen in 1895 high-speed electrons are
suddenly slowed down

How are X-rays generated? How are X-rays generated?

A. Radioactive materials undergo decay (too many A. Machines
nuclear particles or too high neutron/proton ratio) X-ray tube (accelerates electrons which
interact with electrons of target)
32 32
15 P -> 16 S + X-ray Particle accelerator

e-

X-ray tube Two types of X-radiation are produced:

Bremsstrahlung
3. Electrons interact
with target (anode), radiation), produces a continuous spectrum of X-
X-rays Target (Co, Cu) producing X-rays ray wavelengths

2. Electrons are
Electron beam accelerated in
electric field

Tungsten
1. W filament is
Filament heated, electrons
Two types of X-radiation are produced: Two types of X-radiation are produced:
2. Characteristic Radiation (X-rays of distinct 2. Characteristic Radiation (X-rays of distinct
wavelengths, unique for each element) wavelengths, unique for each element)

a) Incoming electron a) The difference in

knocks inner shell binding energy
electron out of its between inner and
place outer shell electrons
is released as X-ray
b) Empty site is filled by of characteristic
an electron from a wavelength
higher shell

Typical X-ray spectrum Production of X-rays

Continuous radiation
= Bremsstrahlung
radiation
Characteristic radiation is
used in XRD, which
requires monochromatic
radiation
(eg. CuK = 1.5418 Å)
X-rays are produced
when high-speed
electrons are suddenly
slowed down
Can be caused by the
electron striking a
metal target
A current in the
filament causes
electrons to be emitted

Production of X-rays Production of X-rays (Bremsstrahlung)

These freed electrons An electron passes near a
are accelerated toward target nucleus and is
a dense metal target deflected from its path by its
attraction to the nucleus
The target is held at a
This produces an acceleration
higher potential than the
of the electron and hence
filament emission of electromagnetic
radiation

Production of X-rays (Bremsstrahlung) Production of X-rays (Bremsstrahlung)

If the electron loses all of its Not all radiation produced
energy in the collision, the is at this wavelength
initial energy of the electron Many electrons undergo
is completely transformed more than one collision
into a photon before being stopped
The wavelength then is This results in the
continuous spectrum
produced
hc
e V h max
min
hc
min
e V
Characteristic X-Rays Characteristic X-Rays
When a metal target is The details of atomic structure can be used to explain
bombarded by high-energy characteristic x-rays
electrons, x-rays are A bombarding electron collides with an electron in the
target metal that is in an inner shell
emitted
If there is sufficient energy, the electron is removed
The x-ray spectrum from the target atom
typically consists of a broad The vacancy created by the lost electron is filled by an
continuous spectrum and a electron falling to the vacancy from a higher energy
series of sharp lines level
The lines are dependent The transition is accompanied by the emission of a
photon whose energy is equal to the difference
on the metal of the target between the two levels
The lines are called
characteristic x-rays

X-ray Spectrum Production of Characteristic Radiation

The x-ray spectrum has
two distinct components
1) Bremsstrahlung: a
continuous broad
spectrum, which depends
on voltage applied to the
tube
2) The sharp, intense lines,
which depend on the
nature of the target material

Possible Interaction Between Electron Beam

The X-ray Production and the Target
X-rays are emitted when high energy electrons or any
other charged particles bombard a metal target.
The X-ray spectrum typically consists of a broad
continuous band containing a series of sharp lines.
The continuous spectrum is a result of collision
between incoming electrons and the target atoms.
The sharp lines are a result of the removal of inner
shell electrons of the target atoms.

The X-ray Spectrum Some Features of the Spectrum

The energy of Bremsstrahlung radiation range from
zero to a maximum value which depends on the
potential difference applied on the tube.
The intensity of the low energy photons within the
spectrum is reduced because the absorption of the
target material.
The average energy of the X-ray beam is about one
third of the maximum.
The sharp lines, K,L,M etc stay at the same positions.
The line X-ray can be produced only when the
incoming electrons exceed some values.
 A modern Diffractometer

X-ray tube sample Detector

31.2 X-ray diffraction

Experiment of Laue 1912

The X-ray diffractometer X-ray diffraction by a single crystal
n = 2 d sin

Powder diffractometer with Bragg-Brentano geometry.

Analyst controls (choice of target in X-ray tube)
(positions of X-ray tube / sample / detector

What is X-ray diffraction? What is XRD used for?

Scattering phenomenon, X-rays passing through Identification of minerals
crystal Quantification of minerals
A tool for the characterisation of solid materials
Determination of crystal structure
based on their crystal structure
Used by
Unit-cell dimensions, symmetry, atom
Earth Scientists
Chemists Determination of grain sizes, strain
Physicists
Material Scientists Typical samples
Archaeologists Minerals, rocks, corals, shells

Rosalind E. Franklin 1952

What is X-ray diffraction? Interaction of X-rays with crystal structures

XRD complements other analytical methods Visual Crystal structure:
Need large crystals! cm three-dimensional, periodic arrangement
Optical microscopy (colour, birefringence, of atoms in space. Unit-cell of NaCl

Na Cl
µm to mm
SEM (composition: wt.% SiO2
What about polymorphs? (Calcite, Aragonite
= CaCO3) Many different layers of atoms exist in a crystal
> 3 µm structure.
XRF (composition: wt.% SiO2
What about polymorphs? (Calcite, Aragonite
Each set of layers has a distinct interplanar distance
= CaCO3) (d-spacing).
Interaction of X-rays with crystal structures Interaction of X-rays with a scattering center
Interference
X-rays (electromagnetic wave) interact with the electrons
of the atoms in the crystal +
Coherent Scatter: elastic collision between a photon (X-
-
ray) and and electron (in crystal) +
- outgoing photons (X-ray) have same wavelength,
-
frequency and energy as incoming photons [XRD!]
Incoming wave
Incoherent Scatter (= Compton scatter): inelastic collision
between photon and electron
Every electron/atom in structure acts as a
scattering center, and is a source of spherical
- outgoing photons have lower energy waves of the same wavelength and frequency as
the incoming wave.

Positive Negative
Interference Interference X-rays passing through a crystal lattice

X-rays
out of phase!

Crests and troughs add up and

Crests and troughs are offset
form a wave with twice the
and cancel each other out.
amplitude.

This happens to most X-rays

scattered in crystals due to the
large number of scattering
centers ...

X-rays
Diffraction in phase!

some X-rays to experience positive (or n = 2 dhkl sin

constructive) interference in crystals. This is
called diffraction.

radiation coherently, the concerted dhkl

constructive interference at specific angles is
hkl
called diffraction
Diffraction in crystalline materials is best For positive interference to occur, the path-difference must
described with be equal to one wavelength ( or multiple wavelengths
= 2 dhkl sin (n .

Diffraction of X-rays by Crystals Schematic for X-ray Diffraction

For diffraction to occur, A beam of X-rays with a
continuous range of
the spacing between the wavelengths is incident on the
grooves must be crystal
approximately equal to The diffracted radiation is very
the wavelength of the intense in certain directions
radiation to be measured These directions
correspond to constructive
For X-rays, the regular interference from waves
array of atoms in a crystal reflected from the layers of
the crystal
can act as a three-
The diffraction pattern is
dimensional grating for detected by photographic film
diffracting X-rays
Photo of X-ray Diffraction Pattern
The array of spots is called a The beam reflected from the
lower surface travels farther
Laue pattern than the one reflected from
The crystal structure is the upper surface
determined by analyzing the If the path difference equals
some integral multiple of the
positions and intensities of the wavelength, constructive
various spots interference occurs
gives the
This is for NaCl conditions for constructive
interference

X-Ray Diffraction Bragg Equation

d sin = (n )/2d
Crystal solid such
dsin as sodium = angle of incidence
Constructive interference: 2dsin m = wavelength
d 0.5nm in NaCl
d = interplane distance of crystal
For =.017nm 1st maximum will be at 100
X-ray

Bragg Equation Bragg Equation

When the X-rays strike a layer of a crystal, some of These two x-ray beams travel slightly different
them will be reflected. We are interested in X-rays distances. The difference in the distances traveled is
that are in-phase with one another. X-rays that add related to the distance between the adjacent layers.
together constructively in x-ray diffraction analysis Connecting the two beams with perpendicular lines
in-phase before they are reflected and after they shows the difference between the top and the
reflected. bottom beams.
Incident angle The line CE is
Reflected angle
Wavelength of X-ray
equivalent
to the distance
2 between the two
Total Diffracted layers (d)
Angle 2
DE d sin

Bragg Equation
The length DE is the same as EF, so the total
distance traveled by the bottom wave is expressed n 2d
by: where, d is the spacing of the planes and n is the
order of diffraction.
DE d sin Bragg reflection can only occur for wavelength
EF d sin DE EF 2d sin
2d sin n
n 2d sin This is why we cannot use visible light. No diffraction
Constructive interference of the radiation from occurs when the above condition is not satisfied .
successive planes occurs when the path difference The diffracted beams (reflections) from any set of
is an integral number of wavelenghts. This is the lattice planes can only occur at particular angles
Bragg Law. pradicted by the Bragg law.
Arthur Holly Compton The Compton Effect
1892 1962 Compton directed a beam of x-rays toward a block of
Discovered the Compton graphite
effect He found that the scattered x-rays had a slightly
Worked with cosmic rays longer wavelength that the incident x-rays
Director of the lab at U of This means they also had less energy
Chicago The amount of energy reduction depended on the
Shared Nobel Prize in 1927 angle at which the x-rays were scattered
The change in wavelength is called the Compton shift

Compton Scattering Compton Scattering

Compton assumed the photons acted like other The quantity h/mec is called the Compton wavelength
particles in collisions Compton wavelength = 0.002 43 nm
Energy and momentum were conserved Very small compared to visible light
The shift in wavelength is The Compton shift depends on the scattering angle
and not on the wavelength
h Experiments confirm the results of Compton
o (1 cos )
mec scattering and strongly support the photon concept

Three-Dimensional Conformal Radiation Three-Dimensional Conformal Radiation

Therapy (3D-CRT) Therapy (3D-CRT)
Tumors usually have an irregular Radiation beams are then
shape shaped exactly to the size and
Three-dimensional conformal shape of the tumor
radiation therapy (3D-CRT) uses Because the radiation beams are
sophisticated computers and CT very precisely directed, nearby
scans and/or MRI scans to create normal tissue receives less
detailed 3-D representations of radiation exposure
the tumor and surrounding
organs

Sample Sample
sample sample
We are choosing incoming angle = However, we want ALL
outgoing angle. crystallographic planes to
Therefore only diffraction from (001) (001)
contribute to the XRD pattern.
atomic planes in the crystal
structure that are parallel to the flat
All samples need to be ground
sample surface are detected up very finely (ideally 1-10 µm
For example, if we analysed this grain size), and the grains
single muscovite
muscovite crystal with XRD, oriented randomly
muscovite
in the
lying flat on the sample holder with sample holder.
its 001 plane, only (001) planes
would diffract.
Powder X-ray Diffraction Powder X-ray Diffraction
24.5 Nanoscience Nanotechnology
Nanoscience refers to the ability to manipulate Nanotechnology is the understanding and
individual atoms and molecules, making it control of matter at dimensions of roughly 1 to
100 nanometers.
possible to build machines on the scale of Nanotechnology involves imaging, measuring,
human cells. modeling, and manipulating matter at this
length scale.

Nanoscale Facts
At the nanoscale, the physical, chemical, and A nanometer is one billionth of a meter.
biological properties of materials differ in In 2005 the US government spent an estimated
fundamental and valuable ways from the $1,081 million
properties of individual atoms and molecules or While difficult to measure accurately, some
bulk matter. have estimated that worldwide government
Nanotechnology R&D is directed toward funding has increased to about five times what
understanding and creating improved it was in 1997, exceeding $2 billion in 2002.
materials, devices, and systems that exploit
these new properties

CMOS TECHNOLOGY

(released March 2004):

150 million transistors
90 nm design rules
3.4 GHz clock frequency
DRAM chips: One area of nanotechnology R&D is medicine.
4 Gb chips demonstrated Medical researchers work at the micro- and
(~ 109 transistors/cm2) nano-scales to develop new drug delivery
methods, therapeutics and pharmaceuticals.
Now chips based on the
design rules of 22 nm are on
For a bit of perspective, the diameter of DNA,
the way. our genetic material, is in the 2.5 nanometer
- 130 nm) processor range, while red blood cells are approximately
In 2004 we were already inside nanotechnology!
Introduction
2.5 micrometers.
178

Applications/Products
- Nanotechnology has the
potential to profoundly
limited), nanoparticles are being used in a change our economy and to
number of industries. Nanoscale materials are improve our standard of
used in electronic, magnetic and living, in a manner not unlike
optoelectronic, biomedical, pharmaceutical, the impact made by advances
cosmetic, energy, catalytic and materials over the past two decades by
applications. Areas producing the greatest information technology. It is
revenue for nanoparticles reportedly are quite possibly the next step in
chemical-mechanical polishing, magnetic technology that will lead to
recording tapes, sunscreens, automotive great innovations. If the
catalyst supports, biolabeling, capabilities of nanoscience are
fully harnessed, anything
could be possible.
 Nanomaterials
Numerous products featuring the unique Examples are nanoscale particles, tubes and
properties of nanoscale materials are available
rods.
to consumers and industry today. Most
Nanoparticles
computer hard drives, for instance, contain
giant magnetoresistance (GMR) heads that,
through nano-thin layers of magnetic
materials, allow for a significant increase in
storage capacity. Other electronic applications
include non-volatile magnetic memory,
automotive sensors, landmine detectors and
solid-state compasses
Nanorods Nanotube

Some other uses Medical uses

Burn and wound Protective and glare-
dressings reducing coatings for
Water filtration eyeglasses and cars
Catalysis Sunscreens and The pharmaceutical and chemical industries are
A dental-bonding cosmetics. being impacted greatly by nanotechnology, as
agent Longer-lasting tennis well. New commercial applications of
Step assists on vans. balls. nanotechnology that are expected in two to five
Light-weight, years in these industries include:
Coatings for easier
cleaning glass stronger tennis advanced drug delivery systems, including
racquets. implantable devices that automatically
Bumpers and administer drugs and sensor drug levels and
catalytic converters Stain-free clothing
on cars and mattresses. medical diagnostic tools, such as cancer tagging
Ink. mechanisms.

Bibliography
http://www.nsf.gov/news/overviews/nano/ind
ex.jsp
http://www.nanoscience.com/education/inde
x.html
http://www.nsf.gov/discoveries/index.jsp?prio
_area=10