1

SUMMARY
Mechanoluminescence (ML) is a type of luminescence induced by any
mechanical action in solids. The light emissions induced by elastic
deformation, plastic deformation and fracture of solids are known as elastico
ML (EML), plastico ML (PML) and fracto ML (FML), respectively. Whereas
only a few solids exhibit ML during their elastic and plastic deformation,
nearly 50% of all inorganic salts and organic molecular solids exhibit ML
during their fracture. The ML of many solids such as triphenylphosphine
oxide manganese bromide, europium tetrakis (dibenzoylmethide) triethyl
ammonium, Eu and Dy doped strontium aluminates, impure saccharin, etc. is
so intense that it can be seen in a day with naked eye.
Fracto mechanoluminescence has a great deal of potential to understand
the following facts and devices: (i) Earthquakes and mine-failure, (ii)
earthquake lights and moonquake lights, (iii) dynamics and mechanics of
fracture, (iv) design of damage sensors, (v) design of fracture sensors, (vi)
design of fuse system for army warhead, and (vii) design of safety
management monitoring system. Such potentials of the fracto ML require
deep understanding of the correlation between ML and fracture. Considering
the fact, it is planned to study theoretically the fracto-ML of organic and
inorganic solids. The present thesis is devoted to the theoretical studies of the
fracto-mechanoluminescence produced during impulsive deformation of
organic and inorganic solids. For the sake of convenience the thesis has been
divided into six chapters.
Chapter I begins with the description of luminescence. Then, it
describes mechanoluminescent materials, devices for mechanoluminescence
2

measurements, characteristics of ML, mechanisms of ML, applications of
ML, and subsequently the objectives and scope of the present investigation
are outlined and it is mentioned that the objective of the present investigation
is to make the theoretical studies on the ML produced during impulsive
deformation of organic and inorganic solids.
Chapter I I reports theoretical studies on the ML produced during
impulsive deformation of non-irradiated insulating fluorescent and
phosphorescent organic and inorganic crystals. When a fluorescent crystal is
fractured impulsively by the impact of a moving piston, then initially the ML
intensity increases linearly with time, attains a peak value I
m
at a particular
time t
m
, and later on it decreases with time. When a phosphorescent crystal is
fractured impulsively by the impact of a moving piston, then initially the ML
intensity increases linearly with time, attains a peak value I
m
at a particular
time t
m
and then, initially the ML intensity decreases at a fast rate and later on
it decreases at a slow rate. After attaining a peak value, the ML intensity of
the crystals exhibiting fluorescent emission ML and also the phosphorescent
emission ML decays exponentially, in which the decay time is related to the
relaxation time of the moving piston or the decay time of the strain rate of
crystals. Whereas the ML in fluorescent crystals appears only in the fracture
region, the ML in phosphorescent crystals also appears in the post-fracture
region, in which the decay time of the slow decay of ML intensity is equal to
the decay time of phosphorescence.
The value of time t
m
decreases with increasing value of the impact
velocity, in which t
m
is proportional to ln(1000/v
0
), the value of I
m
increases
linearly with v
0
, and the value of I
T
initially increases linearly with v
0
and
then it attains a saturation value for higher values of v
0
. The values of t
m
3

increases linearly with the logarithm of the thickness of crystals, the value of
I
m
increases linearly with the area of cross-section of the crystals and the value
of I
T
increases linearly with the volume of the crystals. From the time
dependence of ML induced by impulsive deformation of crystals, the time-
constant for the decrease of strain rate of crystals and the decay time of the
phosphorescent crystals can be determined.
So far as rise of ML, attainment of peak value, and fast decay of ML
are concerned, there is no any significant difference in the time evolution of
fluorescent and phosphorescent crystals. However, in the case of
phosphorescent crystals, in addition to the fast decay, slow decay of ML is
also observed, in the post-fracture region. As I
m
is related to the rate of
creation of new surfaces, and I
T
is related to the total area of the newly created
surfaces, the measurements of I
m
and I
T
may be useful in the design of sensors
for structural damage. Depending on the prevailing conditions, the ML
spectra resemble solid state luminescence spectra or gas discharge spectra or
they consist of the combination of the both.
The expressions derived for the transient ML intensity I, I
r
, t
m
, I
m
, I
T
, I
d
and I
ds
are as given below:




4



and,

A good agreement is found between the theoretical and experimental
results. The fracto-ML induced by impulsive deformation of crystals may be
useful in providing scientific background to the damage sensors; fuse systems
for army warheads, fracture produced by milling machines, crushers,
hammers, etc. It may also provide a sensitive optical tool for studying
fracture-dynamics in microsecond and nanosecond ranges. Furthermore, the
study of fracto-ML of crystals, especially the geological crystals, may be
helpful to understand the earthquakes and earthquake lights.
Chapter I I I deals with the theoretical studies on the ML produced
during impulsive deformation of II-VI semiconductors. When II-VI
semiconductors are fractured, charged dislocations moving near the tip of
moving cracks produce intense electric field, which causes the band bending.
Consequently, tunneling of electrons from filled electron traps to the
conduction band takes place, whereby the radiative electron-hole
recombination gives rise to the luminescence characteristic of the
recombination centres. The luminescence centres like Mn
2+
, rare earth ions,
etc. may get excited either by the impact excitation by the accelerated
electrons in the field of dislocations or by the energy produced during the
electron-hole recombination. When a crystal of a II-VI semiconductor is
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fractured, impulsively then initially the ML intensity increases with time,
attains a maximum value I
m
at a time t
m
, and later on it decreases with time.
In the ML produced during the fracture of II-VI semiconductors, I
m

increases linearly with the impact velocity v
0
of the piston and the total ML
intensity I
T
initially increases linearly with v
0
and later on it attains a
saturation value for higher values of v
0
. The ML intensity of II-VI
semiconductors decreases with temperature. For photoluminescence, the
temperature dependence comes mainly from the decrease of luminescence
efficiency,
0,
however, for the ML excitation, there is an additional factor, r
t

depending on temperature. As the charge on the dislocation decreases with
increasing temperature, the strength of electric field decreases with increasing
temperature. As such, there is a faster decrease of ML intensity with
increasing temperature as compared to that of the photoluminescence. The
ML spectra of II-VI semiconductors are similar to their PL or EL spectra.
The expressions derived for the transient ML intensity I, rise of ML
intensity I
r
, peak ML intensity I
m
, time t
m
, total ML intensity I
T
, fast decay of
ML intensity I
df
and for the slow decay of ML intensity I
ds
for II-VI
semiconductors are given below:



6




and,
From the measurement of the time dependence of ML the relaxation
time of the moving piston after impact, critical velocity for compression of
the crystals and the lifetime of electrons in the shallow traps can be
determined. As I
m
is related to the rate of creation of new surfaces, and I
T
is
related to the total area of the newly created surfaces, their measurements and
study may be useful in the design of sensors for structural damage. A good
agreement is found between the theoretical and experimental results.
Chapter I V reports the theoretical studies on the ML produced during
impulsive deformation of X or - radiated alkali halide crystals. When a -
irradiated KCl crystal is fractured impulsively by dropping a load from a given
height, then initially the ML intensity increases with time, attains a peak value
and then it decreases with time and later on it again increases and attains a
peak value again and later on it decreases with time. Thus two peaks of
intensities I
m1
and I
m2
at times t
m1
and t
m2
respectively are found in the ML
intensity versus time curve of the crystals. The peak ML intensity I
m1
and I
m2

corresponding to the first and second peaks in the ML intensity versus time
curve increase with the impact velocity v
0
. However, the time t
m1
and t
m2

corresponding to the first and second peaks of ML intensity versus time curve
decrease with the increasing impact velocity of the piston.
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The value of relaxation time of the piston , is determined from
the slope of ln I versus (t-t
m1
) plot and it is found to decrease with increasing
impact velocity v
0
. The value of , is determined from the slope of ln I
versus (t-t
m2
) plot and it is found to be independent of the impact velocity v
0
.
The ML intensities I
m1
and I
m2
increase linearly with the impact velocity,
however, the total ML intensity I
T
initially increases and then it tends to attain
a saturation value for higher value of the impact velocities. The values of I
m1
,
I
m2
and I
T
increase with increasing size of the crystals. The values of I
m1
, I
m2

and I
T
increase with increasing doses given to the crystals. However, the
values of t
m1
and t
m2
do not change significantly with the increasing doses
given to the crystals. A linear relation is found between the dependence of I
m1
,
I
m2
and I
T
on the density of colour cetres in crystals. In a given temperature
range the values of I
m1
, I
m2
and I
T
are found to increase with increasing
temperature of -irradiated KCl crystals. The value of t
m1
and t
m2
also
decrease with changing temperature of -irradiated KCl crystals. The ML
spectra of comparatively soft crystals like KCl, KBr, KI etc. consist of only
the solid state luminescence spectra, however, the ML spectra of
comparatively hard crystals such as NaCl, NaF and LiF crystals consist of the
combination of solid state luminescence spectra and the gas discharge spectra.
The mechanism of fracto ML in X or -irradiated alkali halide crystals can be
understood in the following way. When -irradiated alkali halide crystals are
fractured, then the moving dislocations near the tip of cracks capture the
electrons from the F-centres and subsequently the electrons are transferred to
the conduction band because of the creation of charged surfaces due to the
asymmetric movement of charged dislocations in the crystals. Subsequently
the recombination of electrons with the hole centres release energy and
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consequently the luminescence centres in the holes are excited and the de-
excitation gives rise to the light emission.
Based on the detrapping of dislocation captured electrons by the
electrostatic field produced by the charged dislocation, expressions are
derived for the transient ML intensity I, rise of ML intensity I
r
, ML intensity
I
m1
for the first peak, ML intensity I
m2
for the second peak, time t
m1
for the
first peak, time t
m2
for the second peak, temperature dependence of ML,
colour centre density dependence of ML, crystal size dependence of ML, total
ML intensity I
T
, fast decay of ML intensity I
df
and for the slow decay of ML
intensity I
ds
. A comparison made between the experimental and theoretical
results indicates a good agreement. The expressions derived are given below:







9









From the measurement of the fracto ML of coloured alkali halide
crystals the relaxation time of moving piston impacting on an object, lifetimes
of electrons in the shallow traps and critical impact velocity for compressing
the crystals can be determined. As the ML intensity depends on the doses or
X ray doses given to the crystals, the ML measurement may also be useful in
radiation dosimetry.
Chapter V deals with the theoretical studies on the ML produced
during impulsive deformation of III- V semiconductors. When a III-V
semiconductor is fractured impulsively by the impact of a moving piston, then
initially the ML intensity increases linearly with time, attains a peak value I
m

10

at a particular time t
m
, and later on it decreases with time. The value of time t
m

decreases with increasing value of the impact velocity, in which t
m
is
proportional to logarithm of the inverse of v
0
, the value of I
m
increases
linearly with v
0
, and the value of I
T
initially increases linearly with v
0
and
then it attains a saturation value for higher values of v
0
. The values of t
m
increases with the logarithm of the thickness of crystals and the value of I
m
increases linearly with the area of cross-section of the crystals and the value
of I
T
increases linearly with the volume of the crystals. From the time
dependence of ML induced by impulsive deformation of III-V
semiconductors, the time-constant for the decrease of strain rate of crystals
and the decay time of the III-V semiconductor can be determined. As I
m
is
related to the rate of creation of new surfaces, and I
T
is related to the total area
of the newly created surfaces, the measurements of I
m
and I
T
may be useful in
the design of sensors for structural damage.
The formation of crack-induced localized states is responsible for the
ML excitation produced during the cleavage of elemental and IIIV
semiconductors. According to this mechanism, as the atoms are drawn away
from each other in advancing crack tip, the decreasing wave-function overlap
across the crack may result in localized states which are associated with
increasing electron energy. If the energy of these localized states approaches
that of the conduction band via tunneling would be possible, creating minority
carriers, and consequently the electron hole recombination may give rise to
the mechanoluminescence. The de-excitation of electrons excited by cleavage
in to conduction band, shallow traps, into upper surface states and defect
centres, produce the light having different wave lengths. When an elemental
or IIIV semiconductor is cleaved, initially the ML intensity increases with
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time, attains a peak value I
m
at the time t
m
corresponding to completion of the
cleavage and then it decreases exponentially with time, in which the decay
time of ML depends on the type of signal emitted such as type A, B or C.
Three types of signal, namely A, B and C, and produced during the cleavage
of elemental and IIIV semiconductors. Type A signals arises due to the
cleavage induces population of the bulk conduction band and shallow traps
and their subsequent de-excitation. Type B signal produced due to the
cleavage induced population of the surfaces states and their subsequent de-
excitation, and type C signals occurs due to the cleavage induced population
of the defect centres and their subsequent de-excitation. The peak ML
intensity I
m
and the total ML intensity I
T
increase directly with the area of the
newly created surfaces of crystals. The wavelength of the light induced by
cleavage of elemental and IIIV semiconductors lies in the infrared region.
From the measurement of the ML, band gap of the material, energy of the
surface states, energy of the defect states, life time of the electrons in shallow
traps, life time of electrons in the surface states, lifetime of electrons in defect
centres and the velocity of the crack propagation in the materials can be
determined.
The expressions derived for the impulsive excitation of ML of
elemental and III-V semiconductors are as given below:



12










and,
The expression derived for the ML of elemental and IIIV
semiconductors are as given below
t)] ( exp [1 Wv Z 2 = I
1 1
'
1 1



t)] ( exp [1 Wv Z 2 I
2 2
'
2 2



t)] ( exp [1 Wv Z = I
3 3
'
3 3


13


t Wv Z 2 = I
1 1
'
1 1r



t Wv Z 2 = I
2 2
'
2 2r



t Wv Z 2 = I
3 3
'
3 3r


A Z Z Z I )
3 2 1 3
'
3 2
'
2 1
'
1 m
(

A ] [ = I
'
3
'
2 1
'
1 T 3 2
Z Z Z


)] t (t [ exp t g = I
m 1 m 1 1
'
1 1d



)] t (t [ exp t g = I
m 2 m 2 2
'
2 2d



)] t (t [ exp t g = I
m 3 m 3 3
'
3 3d


and,
v
H
t
m

Chapter VI gives the conclusions and future perspectives for the
research on ML.