MODULE 5

5.1 Neutron Activation Analysis (NAA)

Element identification and composition analysis of material is a
challenge to scientific community, when it comes down to very low level
detection, i.e. when we have to search one unit of some material out of one
million unit of another material, which is known as parts per million (ppm).
The complexity enhances more when we consider the material even less
than ppm level. Similarly, when the question of analying very thin layers
(nano meter dimension or less) comes, it !ecomes extremely difficult "o!.
There are several nuclear physics !ased techniques, such as #utherford !ack
scattering, nuclear reaction analysis, neutron activation analysis etc. These
are extremely sensitive techniques in terms of identification and
quantification of materials. $ne can also analye very thin l layer of material
and with an appropriate analying system it is possi!le to get information of
monolayer material deposition.
%onventionally, ma"or, minor and trace element of materials are defined in
the following manner&
Major: %oncentration exceeding '( !y mass
Minor: %oncentration in the range of ).'( to '.) ( !y mass
Trace: %oncentrations less than ).'( !y mass
*ifferent trace levels are
ppm: g+g (micro gram+gram , ')
-.
gm+gm)
pp: ng+g (nano gram+gram , ')
-/
gm+gm)
ppt: pg+g (pico gram+gram , ')
-'0
gm+gm)
pp!: fg+g (femto gram+gram , ')
-'1
gm+gm)
ppa: ag+g (atto gram+gram , ')
-'2
gm+gm)
"#at is NAA$
3n neutron activation analysis (455), the sample is exposed to the
intense radiation field of a nuclear reactor. The sample is thus !om!arded
with neutrons, causing the elements to form radioactive isotopes. The
radioactive emissions and radioactive decay paths for each element are well-
known. 6sing this information, it is possi!le to study spectra of the
emissions of the radioactive sample, and determine the concentrations of the
elements within it. 5ccording to the kinetic energies, neutrons can !e
classified in five groups -- thermal, epithermal, resonance, intermediate and
fast. 7hen target nuclei are !om!arded with neutrons, the four ma"or
reactions that take place are neutron capture, transmutation, fission reaction
and inelastic scattering. 3n neutron capture, the target nucleus a!sor!s
(captures) a neutron, resulting in a product isotope, the mass num!er of
which is incremented !y one. 3f the product nucleus is unsta!le, it usually de
excites !y emission of gamma rays and+or 8
-
. 9or example,
+ + Fe n Fe
59
26
1
0
58
26
----------- (m1.')
3n transmutation reaction, the target nucleus a!sor!s a neutron, emitting
charged+non-charged particles like alpha, proton etc. The unsta!le product
nucleus generally de-excites through 8
-
emission !ack to the target nucleus.
Transmutation neutron reactions are caused !y neutrons of high energies
(fast or intermediate neutrons). 9ission reaction is !asically fragmentation of
heavier nuclei into relatively lower mass nuclei under neutron !om!ardment,
and is discussed in detail in module :. The sequence of events occurring
during the most common type of nuclear reaction used for 455, namely the
neutron captures or (n, gamma) reaction is illustrated in 9ig.m1.'. 5s we
know that when a neutron interacts with the target nucleus, the compound
nucleus almost instantaneously de-excites into a more sta!le configuration
through emission of one or more characteristic prompt gamma rays. 3n
some cases, there may !e emission of delayed gamma rays, !ut at a much
slower rate. This is in accordance with the half-lives of the radioactive
nucleus, which could !e from a fraction of a second to several years.
FIGURE m5.1 Neutron capture by a target nucleus followed by the emission of
gamma rays

Let us see the basic NAA processes
;roadly, there are two types of 455& prompt-gamma ray NAA or
<=455 and delayed gamma ray NAA or *=455. 3n case of <=455,
measurements take place during irradiation, and in case of *=455,
measurements follow radioactive decay. The <=455 technique is generally
performed !y using a !eam of neutrons extracted through a reactor !eam
port. 3t is most applica!le to elements (;, %d, Sm and =d) with extremely
high neutron capture cross-sections. *=455 is useful for the vast ma"ority of
elements that produce radioactive nuclides. The technique is flexi!le with
respect to time, such that the sensitivity for a long-lived radionuclide that
suffers from interference !y a shorter-lived radionuclide can !e improved !y
waiting for the short-lived radionuclide to decay.
>et us now see the mathematical formulation required to determine the
concentration of any element present in any material.
The activity equation for 455 can !e o!tained in the following manner&
',0
>et,
A , num!er of decays per second (activity)
N , num!er of atoms of the target isotope ,
w
m
a ..)0: ')
0:

m , mass of the element in the irradiated sample
a , isotopic a!undance
w , atomic weight of the element
, decay constant
, neutron flux
, activation cross section
3f tirr is the time of irradiation then we can write
( ) [ ]
irr
t N A = exp 1
--------- (m1.0)
By measuring activity A of the radioactive nuclei and for known values of all other
quantities of the above equation the number of atoms N of the required element can be
determined.
5.% Nuclear reaction Analysis (N&A)
3n nuclear reaction analysis presence of any element (particularly low
mass elements, like %, 4, $) is detected through the nuclear reactions
emitted almost instantaneously from nuclear reactions produced in the
target !y the irradiating !eam.
$ne advantage of this analysis is com!ining it with !ackscattering
spectrometry, highly sensitive depth profiling of elements particularly
distri!uted in the surface and near-surface region of a material can !e done.
The characteristics of the emitted radiations from various depths depend on
the energy loss of the incident ions as they go into the sample and also the
charged particles emitted from the reactions as they come out from the
sample.
The primary emphasis of this lecture is to discuss how to determine
concentration depth profile of various trace element impurities !y analying
some nuclear reactions. 9irst let us see the !asic methodologies&
'asic Met#o(olo)y
9or depth profiling using 4#5, two different methods are generally
adopted, namely the energy-analysis method and the resonance method.
1
3n
the first case the energy of the analying !eam is kept fixed and during
analysis, the energy spectra of the particles from which the depth profiles
are derived, are recorded. The second method known as resonance is used
when a sharp peak (resonance) as a function of energy is o!tained. 3n this
case, the depth profile is derived from a measurement of the nuclear
reaction yield as a function of the energy of the analying !eam.
Ener)y analysis met#o(.
3n this technique !oth neutrons and charged particles are used as pro!es.
>et me !egin with the following neutron induced reaction
')
;(n,)
?
>i. The
energy of emitted alpha particles is @'.1 AeB and the reaction cross section
is @C))) !arns.
.
The charged particles (alpha and >i), which are emitted
isotropically due to this reaction start travelling to the outward path and
leave the sample and detected in a suita!le detection system. The energy of
the detected particle depends on the energy loss of the particle in the
outward path and the depth (from the surface) where the nuclear reaction
takes place. The energy difference (E) of the alpha particle from the surface
and from a layer at a depth t is given !y&
E * t ((E+(,) ------- (m5..)
5 quantitative analysis of the elemental distri!ution with depth, i.e. depth
profile is generated directly from the charged particle spectrum. The range
which can !e considered the distance the particles can travel after creation
and still exit the surface varies with composition.
Let us now see the nuclear reactions induced by charged particles:
3n charged particles induced reactions the incident particle energy is high
enough so that it can penetrate through the %oulom! !arrier resulting in
various nuclear reactions. 9or example, a deuteron of @'.? keB when
!om!arded on aluminium nitride target results in following nuclear
reactions&
?
0?
5l (d,p)
02
5l,
'C
4(d,p)
'1
4,
'C
4(d,)
'0
%.
The schematic of the geometry and the reactions associated with this
specific example is shown in 9ig. m1./.
/01U&E m5.2 3c#ematic o! (euterium in(uce( reaction an( asic
arran)ement !rom (ept# pro!ilin) o! Al,N+Ni
The elastically scattered particles are stopped in a thin a!sor!er to prevent
count rate saturation of the detector and electronic system.
>et us now see the !asic equations those govern the layer composition and
depth profile using this nuclear reaction process.
Similar to #;S The num!er of detected particles D* is proportional to the
areal concentration (atoms+cm
0
) 4t and is given !y the following equation&
4D * Nt ()56 ----------- (m5.7)
where () is the differential cross section, E is the num!er of incident
particles, and F the detection solid angle. Gowever, the cross section in
this process cannot !e represented !y a simple analytical formula. This can
!e o!tained from the nuclear physics literature. 9or depth profiling, the
energy difference !etween the detected particles originating from the
surface and from a depth d depends on the energy losses in inward and
outward path.
E * ( 8 a ((E+(,)in 9 ((E+(,)out : ------- (m5.;)
The difference !etween this and #;S is that the kinematic factor H of #;S
is replaced !y reaction factor a.
.
3f the cross section of a reaction is known,
the concentration profile can !e deduced from the shape of the experimental
spectrum.