Outline

24. QUANTUM PHYSICS

24.1 Photons
24.2 Wave-particle duality
24.3 Atomic structure
24.4 X-rays
24.5 Nanoscience

Liew Sau Poh

Objectives

Objectives

(a) describe important observations in

photoelectric emission experiments
(b) recognise features of photoelectric emission
that cannot be explained by wave theory and
explain these features using the concept of
quantisation of light
(c) use the equation for a photon E= hf
(d) explain the meaning of work function and
threshold frequency

(e

Objectives

Objectives

(j) explain the advantages of an electron

microscope as compared to an optical
microscope

(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

(l) derive an expression for the radii of the orbits

(m) derive the formula

effect, hf=W + mv2max

(f) understand the meaning of stopping potential
and use eVs= mv2max
(h) use the relation
= h/p to calculate de
Broglie wavelength
(i) interpret the electron diffraction pattern as an
evidence of the wave nature of electron

Objectives

24.1 Photon

(r) derive and use the equation min = hc / eV

(s) describe X-ray diffraction by two parallel
adjacent atomic planes
d sin = m
(u) explain the basic concept of nanoscience
(v) state the applications of nanoscience in
electronics devices

Photoelectric effect:
When electromagnetic radiation is incident to
the surface of a metal, electrons are ejected
from the surface.
Photoelectrons:
The electrons emitted by this effect.
Visible light

UV
Photoelectrons

Metals

Visible light
Photoelectrons
No photoelectrons

Metals other than Alkali Metals

Alkali Metals

Photon
A packet or bundle of energy is called a
photon.
hc
Energy of a photon is E = hf =

Properties of photons
A photon travels at a speed of light c in vacuum.
(i.e. 3 x 108 m/s)
It has zero rest mass. i.e. the photon can not exist
at rest.
E
h
The kinetic mass of a photon is, m =
=

c
c2
E
h
p=
=
c

where h
f is the frequency of the radiation or photon,
c is the speed of light (e.m. wave) and
is the wavelength.

Properties of photons
Wavelength of the photon changes in
different media; so, velocity of a photon is
different in different media.
Photons are electrically neutral.
Photons may show diffraction under given
conditions.
Photons are not deviated by magnetic and
electric fields.

The momentum of a photon is,

Photons travel in a straight line.
Energy of a photon depends upon frequency of the
photon; so the energy of the photon does not
change when photon travels from one medium to
another.

Photoelectric Effect
UV

Photoelectrons
Visible light

Photoelectrons

Metals
Visible light
No photoelectrons

Alkali Metals

Metals other than Alkali Metals

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
suitable frequency is known as photoelectric effect.
The electrons emitted by this effect are called
photoelectrons.
The current constituted by photoelectrons is known as
photoelectric current.
Note: Non metals also show photoelectric effect.
Liquids and gases also show this effect but to limited
extent.

Experimental (Photoelectric Effect)

UV light
W
C

A
A
+
K

Metallic cathode

Metallic Anode

Quartz Window
- Photoelectron

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
constituted.

Experimental (Photoelectric Effect)

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

Intensity (L)

Experimental (Photoelectric Effect)

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
plate A, current becomes
maximum and is known as
saturation current.

2) Effect of Potential on
Photoelectric Current:
When the potential is
decreased, the current
decreases but does not
become zero at zero
potential.
This shows that even in the
absence of accelerating
potential, a few
photoelectrons manage to
reach the plate on their
own due to their K.E.

I
A

Saturation
Current

L2
L1

L2 > L1
VS

Potential of A (V)

I
A

Saturation
Current

L1
L2 > L1
VS

Potential of A (V)

Experimental (Photoelectric Effect)

Experimental (Photoelectric Effect)

2) Effect of Potential on
Photoelectric Current:

3) Effect of Frequency of Incident

Light on Photoelectric Current:
For a fixed intensity of incident
light, the photoelectric current
does not depend on the
frequency of the incident light.
Because, the photoelectric
current simply depends on the
number of photoelectrons
emitted and in turn on the
number of photons incident
and not on the energy of
photons.

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.
Intensity of incident light
does not affect the stopping
potential.

I
A

Saturation
Current

L2
L1

L2 > L1
VS

Potential of A (V)

A
2>
1

VS2

VS1 0

Potential of A (V)

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.
However, the saturation
current is same for
different frequencies of the
incident lights.

4) Effect of Frequency of
Incident Light on Stopping
Potential:
When potential is
decreased and taken below
zero, photoelectric current
decreases to zero but at
different stopping
potentials for different
frequencies.

Saturation Current
A
2>
1

VS2

VS1 0

Potential of A (V)

Saturation Current

I
A

2>
1

VS2

VS1 0

Potential of A (V)

Higher the frequency, higher the stopping potential. i.e. VS

5) Threshold Frequency
The graph between stopping
potential and frequency does not
pass through the origin.
VS (V)
It shows that there is a minimum
value of frequency called threshold
frequency below which photoelectric
emission is not possible however
0
0
high the intensity of incident light
may be.
It depends on the nature of the metal
emitting photoelectrons.

Saturation Current

Experimental (Photoelectric Effect)

L2

28.2 Concept of light quantisation

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.

the energy of the photon is absorbed by the electron

and is used in two ways:
A part of energy is used to overcome the surface
barrier and come out of the metal surface. This part
work function
0).
The remaining part of the energy is used in giving a
to the maximum kinetic energy of the photoelectrons
( mv2max

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,

hf =

+ mv2max

= hf0 + mv2max

Photon h

mv2max

mv2max = h ( f - f0 )

Photoelectron

=h

Metal

Verification of Laws of Photoelectric Emission based

mv2max = h (

If < 0, then 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.

Application of Photoelectric Effect

Automatic fire alarm
Automatic burglar alarm
Scanners in Television
transmission
Reproduction of sound in
cinema film
In paper industry to
measure the thickness of
paper
To locate flaws or holes in
the finished goods
In astronomy
To determine opacity of
solids and liquids

Automatic switching of
street lights
To control the
temperature of furnace
Photometry
Beauty meter To
measure the fair
complexion of skin
Light meters used in
cinema industry to check
the light
Photoelectric sorting
Photo counting
Meteorology

Verification of Laws of Photoelectric Emission based

mv2max = h (

It is clear that 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.

Photoelectric Threshold
Binding Energies
K: 100
L: 50
M: 20

Photon energy: 15

Photon in

Which shells are

candidates for
photoelectric
interactions?

Photoelectric Threshold

Photoelectric Threshold
Binding Energies
K: 100
L: 50
M: 20

Photon energy: 15
NO

Binding Energies
K: 100
L: 50
M: 20

Photon energy: 25

NO
NO

Which shells are

candidates for
photoelectric
interactions?

Photon in

Photoelectric Threshold

Photon in

Photoelectric Threshold

Binding Energies
K: 100
L: 50
M: 20

Photon energy: 25
YES
NO
NO

Binding Energies
K: 100
L: 50
M: 20

Photon energy: 25
A

Which shells are

candidates for
photoelectric
interactions?

Photon in

Photon in

Photon energy: 22

Photoelectric Threshold

1
P.E. ~ ----------energy3

Which photon has

a greater
probability for
photoelectric
interactions with
the m shell?

Photoelectric Threshold

Binding Energies
K: 100
L: 50
M: 20

Photon energy: 55

Which shells are

candidates for
photoelectric
interactions?

Binding Energies
K: 100
L: 50
M: 20

Photon energy: 55
YES
YES

Photon in

Which shells are

candidates for
photoelectric
interactions?

Photoelectric Threshold

NO

Photon in

Photoelectric Threshold

Binding Energies
Photon energy: 105

Which shells are

candidates for
photoelectric
interactions?

K: 100
L: 50
M: 20

Binding Energies
Photon energy: 105
YES

K: 100
L: 50
M: 20

YES

Photon in

Which shells are

candidates for
photoelectric
interactions?

YES

Which shells are

candidates for
photoelectric
interactions?

Photoelectric Threshold

Photoelectric Threshold
When photon energy just reaches binding
energy of next (inner) shell, photoelectric
interaction now possible with that shell

1
P.E. ~ ----------energy3

shell offers new candidate target electrons

Photoelectric interactions
decrease with increasing photon
energy

Photon energy: 49

Photon energy: 51
YES
YES

YES

Binding Energies
K: 50
L: 25

NO

Photoelectric Threshold

Photoelectric Threshold

When photon energies just reaches binding energy of

next (inner) shell, photoelectric interaction now
possible with that shell, where shell offers new
candidate target electrons
Interaction
Probability
M-shell
interactions
possible

L-shell
interactions
possible

L-shell
binding
energy

K-shell
binding
energy

causes step increases in interaction

probability as photon energy exceeds shell
binding energies

Interaction
Probability

L-edge
K-edge

K-shell
interaction
s possible

Photon Energy

Photon Energy

Dual Nature of Radiation and Matter

24.2 Wave-particle Duality

Dual Nature of Radiation and Matter

Louis de Broglie suggested that the particles like
electrons, protons, neutrons, etc have also dual nature.
i.e. they also can have particle as well as wave nature.
Note: In no experiment, matter exists both as a
particle and as a wave simultaneously. It is either the
one or the other aspect. i.e. The two aspects are
complementary to each other.
His suggestion was based on:
The nature loves symmetry.
The universe is made of particles and radiations and
both entities must be symmetrical.

Wave theory of electromagnetic radiations

explained the phenomenon of interference,
diffraction and polarization.
On the other hand, quantum theory of e.m.
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.

de Broglie wave
According to de Broglie, a moving material
particle can be associated with a wave. i.e. a
wave can guide the motion of the particle.
The waves associated with the moving material
particles are known as de Broglie waves or
matter waves.

The Compton Effect

So

h
mc

E = mc2
or

where p = mc
is momentum of a photon

h
p

If instead of a photon, we have a material

particle of mass m moving with velocity v, then
the equation becomes
which is the expression for de Broglie wavelength.

h
mv

Conclusion

h
mv

de Broglie wavelength is inversely proportional to the

velocity of the particle. If the particle moves faster,
then the wavelength will be smaller and vice versa.
If the particle is at rest, then the de Broglie wavelength
is infinite. Such a wave can not be visualized.
de Broglie wavelength is inversely proportional to the
mass of the particle. The wavelength associated with a
heavier particle is smaller than that with a lighter
particle.
de Broglie wavelength is independent of the charge of
the particle.

Davisson and Germer Experiment

A beam of electrons
emitted by the electron
gun is made to fall on
Nickel crystal cut along
cubical axis at a
particular angle.
The scattered beam of
electrons is received by
the detector which can be
rotated at any angle.

Electron Gun
F
C
A

Crystal Lattice

Nickel Crystal

Davisson and Germer Experiment

i.e.

= 180

= 65

For Ni crystal, lattice

spacing d = 0.91
For first principal
maximum, n = 1
Electron diffraction is
similar to X-ray
diffraction.

h
mv

Matter waves, similar to electromagnetic waves,

can travel in vacuum and hence they are not
mechanical waves.
Matter waves are not electromagnetic waves
because they are not produced by accelerated
charges.
Matter waves are probability waves, amplitude
of which gives the probability of existence of
the particle at the point.

Davisson and Germer Experiment

The energy of the
incident beam of
electrons can be varied by
changing the applied
voltage to the electron
gun.
Intensity of scattered
beam of electrons is
found to be maximum
when angle of scattering
is 50 and the
accelerating potential is
54 V.

Electron Gun
F
C
A

Crystal Lattice

Nickel Crystal

Intensity of scattered beam at 44 V

Electron Gun

Intensity of scattered beam at 48 V

F
C
A

Incident Beam

+ 50 +

Conclusion

Crystal Lattice

Nickel Crystal

Incident Beam

the photon is

Let the light is made up of particles (photons),

and that photons have momentum, with energy
hf collides with a stationary electron.
Some of the energy and momentum is
transferred to the electron (this is known as the
Compton effect), but both energy and
momentum are conserved (elastic collision).
After the collision the photon has energy hf and
the electron has acquired a kinetic energy K.
Conservation of energy: hf = hf + K

Incident Beam

According to quantum theory, the energy of the

photon is
hc
E= h =

Incident Beam

Expression for de Broglie wave

= 50

Intensity of scattered beam at 54 V

hypothesis,
=

2dsin = n gives

= 1.65

h
2meV

or

Intensity of scattered beam at 64 V

12.27
V

de Broglie wavelength of
moving electron at V = 54
Volt is 1.67 which is in
close agreement with 1.65 .

Intensity vs

The Electron Microscope

Diffraction
pattern after
100 electrons

10 15

20

25

Using wave-nature and particle nature of

electron
Electron is accelerated through a high voltage
Better than optical microscope
Shorter Wavelength : (up to 10 -10 ) vs (10-7)
Higher resolving power: nanometer vs. micro

Diffraction
pattern after
3000 electrons

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
sphere

electron

The electrons much likes currants in a plum pudding.

atom
SF027

66

atom.

In 1911, Ernest Rutherford performed a critical

correct and proposed his new atomic model known
shown in Figure

nucleus

electron

pictured as electrons orbiting around a central

nucleus which concentrated of positive charge.
The electrons are accelerating because their
directions are constantly changing as they circle the
nucleus.
nucleus

electron

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.

Based on the wave theory, an accelerating

charge emits energy.
Hence the electrons must emit the EM
radiation as they revolve around the nucleus.

e
e

+Ze

+Ze
energy loss
energy loss

1. Only certain discrete orbits (stationary states) are

allowed for the electron

2. Electron in a stationary state does not radiate
3. Classical mechanics apply to electron in a stationary
state (not between states)
4. When an electron moves from one SS to another, a
change in energy occurs involving the emission (or
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

new atomic model based on
hydrogen atom.
assumes that each electron
moves in a circular orbit which is
centred on the nucleus, the
necessary centripetal force being
provided by the electrostatic force
of attraction between the
positively charged nucleus and
the negatively charged electron.

L
mvr
where

nh
2
nh
2

and

Fe

+e

m vr
(11.1)

n : principalquantum number 1,2,3,...

r : radius of theorbit
m : mass of theelectron

force as the centripetal force he obtained

e 4 me
4 (4

0)

n12

n22

On this basis he was able to show that the energy of

an orbiting electron depends on the radius of its orbit.
This model has several features which are described
by the postulates (assumptions) stated below :
1. The electrons move only in certain circular orbits,
called STATIONARY STATES or ENERGY LEVELS.
When it is in one of these orbits, it does not radiate
energy.
2. The only permissible orbits are those in the discrete
set for which the angular momentum of the electron L
equals an integer times h/2 . Mathematically,

3. Emission or absorption of radiation occurs only

when an electron makes a transition from one
orbit to another.
The frequency f of the emitted (absorbed) radiation
is given by
E hf E f E i
where

E : change of energy
h : Planck's constant
Ef : final energy state
Ei : initialenergy state
If Ef > Ei

Absorption of EM radiation

If Ef < Ei

Emission of EM radiation

Energy level of hydrogen atom

Fe

+
e

Consider one electron of charge e and mass m moves in a

circular orbit of radius r around a positively charged nucleus with
a velocity v.
The electrostatic force between electron and nucleus contributes
the centripetal force as write in the relation below:

Fe

electrostatic force

mv 2

r
rn

n 2h 2
me 2
n2

By taking square of both side of the equation, we get

(11.4)

By dividing the eqs. (11.4) and (11.3), thus

n2 h 2
4 2

m 2v 2 r 2
mv 2

e2
0r

4
2

n h
me 2

and

electrostatic
constant

1
0

4 k

the radius of the

most stable (lowest) orbit or ground state (n=1) in
the hydrogen atom and its value is

1
4 k

h2
; n 1, 2 , 3 ...
4 mke 2

(11.5)

a0

which rn is radii of the permissible orbits for the

a0
n 2a0

rn

n2h2
4 2

m2v2r 2

Fc centripetal force
mv 2
and Q 1 Q 2 e
r
e2
(11.3)
4 0r

Q1Q 2
r2

1
4

nh
2

mvr

(11.6)

6 . 63 10
4

9 . 11 10

5 . 31 10

Unit conversion:

11

31

34 2

9 . 00 10 9 1 . 60 10

OR

19 2

0.531 (angstrom)

1 = 1.00 10

10

and

h2
4 2 mke 2

a0

where a0 is called the

atom.

The radii of the orbits associated with allowed orbits

or states n
are 4a0,9a0 , thus the
radii are quantized.

of hydrogen

Energy level in hydrogen atom

Energy level in hydrogen atom

is defined as a fixed energy corresponding to the

orbits in which its electrons move around the
nucleus.
The energy levels of atoms are quantized.
The total energy level E of the hydrogen atom is
given by
E

Potential energy of the electron

Kinetic energy of the electron

1 2
e
mv but mv 2
2
4 0r
1
e2
1
where
k
2 4 0r
4 0
1 ke 2
2 n 2 a0

and

Therefore the eq. (11.7) can be written as

ke 2
n 2a0

En

ke 2 1
2a0 n 2

kQ1Q 2
r
ke 2
n 2 a0

where

Q1

nucleus

e; Q 2

and

n 2a0

electron
(11.8)

ke 2 Z 2
(11.11)
2 a0 n 2
where Z : a to m ic n u m b e r
Using numerical value of k, e and a0, thus the eq. (11.10) can be
2
written as
9 . 00 10 9 1 . 60 10 19
1
En
11
2 5 . 31 10
n2
18
2 . 17 10
1
eV 2
1 . 60 10 19
n
13 . 6
En
eV; n 1,2,3,...
(11.12)
n2
th
where E n : e n ergy le v el o f n s tate (o rb it)
Note:
En

(11.9)

En

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

by

(11.7)

Kinetic energy K of the electron is given by

Potential energy U of the electron is given

1 ke 2
2 n 2a0
(11.10)

n 2 a0

Eqs. (11.10) and (11.12) are valid for energy level of the
hydrogen atom.

The negative sign in the eq. (11.12) indicates that work has to
be done to remove the electron from the bound of the atom to
infinity, where it is considered to have zero energy.
The energy levels of the hydrogen atom are when

n=1, the ground state (the state of the lowest energy level) ;
13 . 6
E1
eV
13 .6 eV
2
1
13 . 6
E2
eV
3 .40 eV
n=2, the first excited state;
2
2
13 . 6
E3
eV
1.51 eV
2
n=3, the second excited state;
3
13 . 6
E4
eV
0 .85 eV
2
n=4, the third excited state;
4
n= , the energy level is 13 . 6
electron is completely
E
eV 0
2
removed from the atom.

Line spectrum
The emission lines correspond to the photons
of discrete energies that are emitted when
excited atomic states in the gas make
transitions back to lower energy levels.

Figure 11.4 shows diagrammatically the various energy levels in the

hydrogen atom.

E n (eV )
0 .0 Free electron

Figure 11.4

0 . 5 4 4th excited state

0 . 8 5 3rd excited state
1 . 51 2nd excited state excited state

5
4
3

Ionization energy
is defined as the
energy required
2
by an electron in
the ground state
to escape
completely from
the attraction of
the nucleus.
An atom
becomes ion.

3 . 4 0 1st excited state

Excitation energy
is defined as the energy
required by an electron that
raises it to an excited state
from its ground state.

13 . 6 Ground state

is defined as
the energy
levels that
higher than
the ground
state.
is defined as the
lowest stable
energy state of
an atom.

Line spectrum
Figure below shows line spectra produced by
emission in the visible range for hydrogen
(H), mercury (Hg) and neon (Ne).

Figure 11.5

Hydrogen Spectrum
= 656, 486, 434, 410 & 397 nm, what is the pattern?

Hydrogen emission line spectrum

The series in the hydrogen emission line
spectrum are
Paschen series involves electron transitions that
end at the 2nd excited state of hydrogen atom. It
is in the infrared (IR) range.
Brackett series involves electron transitions that
end at the 3rd excited state of hydrogen atom. It is
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.

Hydrogen emission line spectrum

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

series of hydrogen emission line spectrum.
E n ( eV )

0 . 0 Free electron

5
4
3
2

th
Pfund series00 .. 85 54 4rd excited state
3 excited state
Brackett series
1 . 5 1 2nd excited state
Paschen series

Balmer series

3 . 3 9 1st excited state

Lyman series
Stimulation 11.1

1 3 . 6 Ground state

Wavelength of hydrogen emission line

spectrum

in the Bohr model of a hydrogen atom.

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

Wavelength of hydrogen emission line

spectrum

rd

1
hc

ke 2 1
2 a 0 nf 2

1
hc

ke 2 1
2 a 0 nf 2

E
hc

hc

ke 2
1
2 hca 0 n f 2

postulate, the eq. (11.13)

can be written as
1

1
hc

E nf

E ni

where

and

E nf

ke 2 1
2 a 0 nf 2

E ni

ke 2 1
2 a 0 ni 2

1
where

RH

nf 2

ni 2

ke 2 1
2 a 0 ni 2
1
ni 2

1
ni

E
hc

and

ke 2
2 hca 0

RH

(11.14)

RH : Rydberd' s constant 1.097 107 m

nf : final value of n
ni : initial value of n

Note:

For the hydrogen line spectrum,

1
Lyman series( nf=1 )
Balmer series( nf=2 )

1
1

Paschen series( nf=3 )

1
Brackett series( nf=4 )

1
Pfund series( nf=5 )

RH

1
12

1
ni 2

RH

1
22

ni

RH

1
32

ni

RH

1
42

ni

RH

1
52

predicts successfully the energy levels of the

hydrogen atom but fails to explain the energy
levels of more complex atoms.
can explain the spectrum for hydrogen atom but
some details of the spectrum cannot be explained
especially when the atom is placed in a magnetic
field.

1
2

1
2

1
2

2
Energy Levels

1
ni

Transitions

To calculate the shortest wavelength in any series, take ni=

Spectra
Figure 11.7 No 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

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

Electron
Proton
Neutron

Atoms
In their normal state, atoms are electrically
neutral
If an atom has an extra electron or has had an
electron removed, it has been ionized.

Atoms
Electrons can only exist
in certain shells that
represent electron
binding energies
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).

How X-rays are Created

To produce x-rays, you need 3 things:
1. A source of electrons
2. A force to move them rapidly
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 Rntgen discovered X-Rays in
1895.
1901 Nobel prize in Physics

Wilhelm Conrad Rntgen (1845-1923)

A modern radiograph of a hand

Early use of X-Rays

History of X-ray and XRD

Radiographs like the
ones in the last slide are
simply shadowgrams.
The X-rays either pass
straight through or are
stopped by the object.
The diagram on the
upper left illustrates the
principle and shows a
perfect shadow.

Within few months of

their discovery, X-rays
were being put to
practical use.
This is an X-ray of bird
shot embedded in a
hand.
Unfortunately, much of
the early use of X-rays
was far too aggressive,
resulting in later cancer.
Section 9.4

History of X-ray and XRD

In reality, a large fraction
of the X-rays are not
simply absorbed or
transmitted by the object
but are scattered. The
diagram on the bottom
left illustrates this effect
and illustrates the fuzzy
edge of the object that is
produced in the image by
the scattered X-rays.

History of X-ray and XRD

Max von Laue (1897-1960)

The X-ray diffraction pattern of

a pure substance is like a
fingerprint of the substance.
The powder diffraction method
is thus ideally suited for
characterization and
identification of polycrystalline
phases.

History of X-ray and XRD

Max von Laue (1897-1960)

The first kind of scatter process to be

recognised was discovered by Max
von Laue who was awarded the Nobel
prize for physics in 1914 "for his
discovery of the diffraction of X-rays
by crystals". His collaborators Walter
Friedrich and Paul Knipping took the
picture on the bottom left in 1912. It
shows how a beam of X-rays is
scattered into a characteristic pattern
by a crystal. In this case it is copper
sulphate.

What are X-rays?

Beams of electromagnetic radiation
Short wavelength, high energy

Interacts
with
electrons!

Wave (sinusoidal, oscillating electric field with, at right

angles to it, a magnetic field)
wavelength
frequency
Particle (photon)
Photon energy E
(h

E=h
-34

Js)

Electromagnetic radiation

Properties of a wave

Wave

=c/

(c=300.000 km/s)

X-Rays

(ngstrm) is non-SI unit of length

X-rays: 10-8 to 10-11 m
-10
1 = 10 m
= 0.1 to 100
0.1 nm
dimension of atoms, bonds, unit-

X-Rays

Electromagnetic radiation with short

wavelengths
Wavelengths less than for ultraviolet
Wavelengths are typically about 0.1 nm
X-rays have the ability to penetrate most
materials with relative ease
High energy photons which can break
chemical bonds danger to tissue
Discovered and named by Roentgen in 1895

X-rays (discovered and named

by Roentgen): electromagnetic
radiation with short typically
about 0.1 nm wavelengths
X-rays have the ability to
penetrate most materials with
relative ease
X-rays are produced when
high-speed electrons are
suddenly slowed down

Wilhelm Conrad Rntgen

1845 1923

How are X-rays generated?

How are X-rays generated?

A. Radioactive materials undergo decay (too many

nuclear particles or too high neutron/proton ratio)

A. Machines

32
15 P

->

32
16 S

+ X-ray

X-ray tube (accelerates electrons which

interact with electrons of target)
Particle accelerator

e-

X-ray tube

Two types of X-radiation are produced:

3. Electrons interact
with target (anode),

X-rays

Target (Co, Cu) producing X-rays

2. Electrons are
Electron beam
accelerated in
electric field
Tungsten
Filament

1. W filament is
heated, electrons

Bremsstrahlung
radiation), produces a continuous spectrum of Xray wavelengths

Two types of X-radiation are produced:

Two types of X-radiation are produced:

2. Characteristic Radiation (X-rays of distinct

wavelengths, unique for each element)

2. Characteristic Radiation (X-rays of distinct

wavelengths, unique for each element)
a) The difference in
binding energy
between inner and
outer shell electrons
is released as X-ray
of characteristic
wavelength

a) Incoming electron
knocks inner shell
electron out of its
place
b) Empty site is filled by
an electron from a
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 )

Production of X-rays
These freed electrons
are accelerated toward
a dense metal target
The target is held at a
higher potential than the
filament

Production of X-rays (Bremsstrahlung)

If the electron loses all of its
energy in the collision, the
initial energy of the electron
is completely transformed
into a photon
The wavelength then is

e V

hc
max
min

min

hc
e V

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 (Bremsstrahlung)

An electron passes near a
target nucleus and is
deflected from its path by its
attraction to the nucleus
This produces an acceleration
of the electron and hence
emission of electromagnetic
radiation

Production of X-rays (Bremsstrahlung)

Not all radiation produced
is at this wavelength
Many electrons undergo
more than one collision
before being stopped
This results in the
continuous spectrum
produced

Characteristic X-Rays
When a metal target is
bombarded by high-energy
electrons, x-rays are
emitted
The x-ray spectrum
typically consists of a broad
continuous spectrum and a
series of sharp lines
The lines are dependent
on the metal of the target
The lines are called
characteristic x-rays

X-ray Spectrum

Characteristic X-Rays
The details of atomic structure can be used to explain
characteristic x-rays
A bombarding electron collides with an electron in the
target metal that is in an inner shell
If there is sufficient energy, the electron is removed
from the target atom
The vacancy created by the lost electron is filled by an
electron falling to the vacancy from a higher energy
level
The transition is accompanied by the emission of a
photon whose energy is equal to the difference
between the two levels

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

The X-ray Production

Possible Interaction Between Electron Beam

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

The X-ray diffractometer

n

Experiment of Laue 1912

X-ray diffraction by a single crystal

= 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

crystal
A tool for the characterisation of solid materials
based on their crystal structure
Used by
Earth Scientists
Chemists
Physicists
Material Scientists
Archaeologists

Identification of minerals
Quantification of minerals
Determination of crystal structure
Unit-cell dimensions, symmetry, atom
Determination of grain sizes, strain
Typical samples
Minerals, rocks, corals, shells

Rosalind E. Franklin 1952

What is X-ray diffraction?

XRD complements other analytical methods Visual
Need large crystals! cm
Optical microscopy (colour, birefringence,
m to mm
SEM (composition: wt.% SiO2
What about polymorphs? (Calcite, Aragonite
= CaCO3)
> 3 m
XRF (composition: wt.% SiO2
What about polymorphs? (Calcite, Aragonite
= CaCO3)

Interaction of X-rays with crystal structures

Crystal structure:
three-dimensional, periodic arrangement
of atoms in space.
Unit-cell of NaCl
Na

Cl

Many different layers of atoms exist in a crystal

structure.
Each set of layers has a distinct interplanar distance
(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 (Xray) and and electron (in crystal)
- outgoing photons (X-ray) have same wavelength,

frequency and energy as incoming photons [XRD!]

Incoherent Scatter (= Compton scatter): inelastic collision
between photon and electron
- outgoing photons have lower energy

Positive
Interference

Negative
Interference

Incoming wave
Every electron/atom in structure acts as a
scattering center, and is a source of spherical
waves of the same wavelength and frequency as
the incoming wave.

X-rays passing through a crystal lattice

X-rays
out of phase!

Crests and troughs add up and

form a wave with twice the
amplitude.

Crests and troughs are offset

and cancel each other out.

This happens to most X-rays

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

X-rays
in phase!

Diffraction
some X-rays to experience positive (or
constructive) interference in crystals. This is
called diffraction.
radiation coherently, the concerted
constructive interference at specific angles is
called diffraction
Diffraction in crystalline materials is best
described with
= 2 dhkl sin

Diffraction of X-rays by Crystals

For diffraction to occur,
the spacing between the
grooves must be
approximately equal to
the wavelength of the
radiation to be measured
For X-rays, the regular
array of atoms in a crystal
can act as a threedimensional grating for
diffracting X-rays

= 2 dhkl sin

dhkl
hkl

For positive interference to occur, the path-difference must

be equal to one wavelength ( or multiple wavelengths
(n .

Schematic for X-ray Diffraction

A beam of X-rays with a
continuous range of
wavelengths is incident on the
crystal
The diffracted radiation is very
intense in certain directions
These directions
correspond to constructive
interference from waves
reflected from the layers of
the crystal
The diffraction pattern is
detected by photographic film

Photo of X-ray Diffraction Pattern

The beam reflected from the
lower surface travels farther
than the one reflected from
the upper surface
If the path difference equals
some integral multiple of the
wavelength, constructive
interference occurs
gives the
conditions for constructive
interference

The array of spots is called a

Laue pattern
The crystal structure is
determined by analyzing the
positions and intensities of the
various spots
This is for NaCl

X-Ray Diffraction

Bragg Equation

sin

d
Crystal solid such
as sodium

dsin
Constructive interference:

2dsin

d 0.5nm in NaCl
For =.017nm

= (n )/2d

= angle of incidence
= wavelength
d = interplane distance of crystal

1st maximum will be at 100

X-ray

Bragg Equation

Bragg Equation

When the X-rays strike a layer of a crystal, some of

them will be reflected. We are interested in X-rays
that are in-phase with one another. X-rays that add
together constructively in x-ray diffraction analysis
in-phase before they are reflected and after they
reflected.

These two x-ray beams travel slightly different

distances. The difference in the distances traveled is
related to the distance between the adjacent layers.
Connecting the two beams with perpendicular lines
shows the difference between the top and the
bottom beams.

Incident angle
Reflected angle
Wavelength of X-ray

The line CE is
equivalent
to the distance
between the two
layers (d)

2
Total Diffracted
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
by:

EF

d sin

DE

d sin

DE

EF

2d sin

2d sin

Constructive interference of the radiation from

successive planes occurs when the path difference
is an integral number of wavelenghts. This is the
Bragg Law.

2d

where, d is the spacing of the planes and n is the

order of diffraction.
Bragg reflection can only occur for wavelength

2d sin

This is why we cannot use visible light. No diffraction

occurs when the above condition is not satisfied .
The diffracted beams (reflections) from any set of
lattice planes can only occur at particular angles
pradicted by the Bragg law.

Arthur Holly Compton

The Compton Effect

1892 1962
Discovered the Compton
effect
Worked with cosmic rays
Director of the lab at U of
Chicago
Shared Nobel Prize in 1927

Compton directed a beam of x-rays toward a block of

graphite
He found that the scattered x-rays had a slightly
longer wavelength that the incident x-rays
This means they also had less energy
The amount of energy reduction depended on the
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

particles in collisions
Energy and momentum were conserved
The shift in wavelength is
o

h
(1 cos )
mec

Three-Dimensional Conformal Radiation

Therapy (3D-CRT)

The quantity h/mec is called the Compton wavelength

Compton wavelength = 0.002 43 nm
Very small compared to visible light
The Compton shift depends on the scattering angle
and not on the wavelength
Experiments confirm the results of Compton
scattering and strongly support the photon concept

Three-Dimensional Conformal Radiation

Therapy (3D-CRT)

Tumors usually have an irregular

shape
Three-dimensional conformal
radiation therapy (3D-CRT) uses
sophisticated computers and CT
scans and/or MRI scans to create
detailed 3-D representations of
the tumor and surrounding
organs

Radiation beams are then

shaped exactly to the size and
shape of the tumor
Because the radiation beams are
very precisely directed, nearby
normal tissue receives less
radiation exposure

Sample

Sample

We are choosing incoming angle =

outgoing angle.
Therefore only diffraction from
atomic planes in the crystal
structure that are parallel to the flat
sample surface are detected
For example, if we analysed this
single muscovite
crystal with XRD,
muscovite
lying flat on the sample holder with
its 001 plane, only (001) planes
would diffract.

sample

(001)

Powder X-ray Diffraction

However, we want ALL

crystallographic planes to
contribute to the XRD pattern.
All samples need to be ground
up very finely (ideally 1-10 m
grain size), and the grains
oriented randomly
in the
muscovite
sample holder.

sample

(001)

Powder X-ray Diffraction

24.5 Nanoscience

Nanotechnology

Nanoscience refers to the ability to manipulate

individual atoms and molecules, making it
possible to build machines on the scale of
human cells.

Nanoscale

Nanotechnology is the understanding and

control of matter at dimensions of roughly 1 to
100 nanometers.
Nanotechnology involves imaging, measuring,
modeling, and manipulating matter at this
length scale.

Facts

At the nanoscale, the physical, chemical, and

biological properties of materials differ in
fundamental and valuable ways from the
properties of individual atoms and molecules or
bulk matter.
Nanotechnology R&D is directed toward
understanding and creating improved
materials, devices, and systems that exploit
these new properties

A nanometer is one billionth of a meter.

In 2005 the US government spent an estimated
$1,081 million
While difficult to measure accurately, some
have estimated that worldwide government
funding has increased to about five times what
it was in 1997, exceeding $2 billion in 2002.

CMOS TECHNOLOGY
(released March 2004):
150 million transistors
90 nm design rules
3.4 GHz clock frequency

One area of nanotechnology R&D is medicine.

Medical researchers work at the micro- and
nano-scales to develop new drug delivery
methods, therapeutics and pharmaceuticals.
For a bit of perspective, the diameter of DNA,
our genetic material, is in the 2.5 nanometer
range, while red blood cells are approximately
2.5 micrometers.

DRAM chips:
4 Gb chips demonstrated
(~ 109 transistors/cm2)
Now chips based on the
design rules of 22 nm are on
the way.
- 130 nm) processor
In 2004 we were
already inside nanotechnology!
Introduction

178

Applications/Products
limited), nanoparticles are being used in a
number of industries. Nanoscale materials are
used in electronic, magnetic and
optoelectronic, biomedical, pharmaceutical,
cosmetic, energy, catalytic and materials
applications. Areas producing the greatest
revenue for nanoparticles reportedly are
chemical-mechanical polishing, magnetic
recording tapes, sunscreens, automotive
catalyst supports, biolabeling,

Nanotechnology has the

potential to profoundly
change our economy and to
improve our standard of
living, in a manner not unlike
the impact made by advances
over the past two decades by
information technology. It is
quite possibly the next step in
technology that will lead to
great innovations. If the
capabilities of nanoscience are
fully harnessed, anything
could be possible.

Nanomaterials
Numerous products featuring the unique
properties of nanoscale materials are available
to consumers and industry today. Most
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

Examples are nanoscale particles, tubes and

rods.
Nanoparticles

Nanorods

Some other uses

Burn and wound
dressings
Water filtration
Catalysis
A dental-bonding
agent
Step assists on vans.
Coatings for easier
cleaning glass
Bumpers and
catalytic converters
on cars

Nanotube

Medical uses
Protective and glarereducing coatings for
eyeglasses and cars
Sunscreens and
cosmetics.
Longer-lasting tennis
balls.
Light-weight,
stronger tennis
racquets.
Stain-free clothing
and mattresses.
Ink.

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

The pharmaceutical and chemical industries are

being impacted greatly by nanotechnology, as
well. New commercial applications of
nanotechnology that are expected in two to five
years in these industries include:
advanced drug delivery systems, including
implantable devices that automatically
administer drugs and sensor drug levels and
medical diagnostic tools, such as cancer tagging
mechanisms.