Physica B 304 (2001) 309–318

An approximation of phosphorescence decay kinetics of ideal

phosphors by a general order kinetics model
Z. Vejnovic! a, M.B. Pavlovic! b, M. Davidovic! b,c,*
a
Institute of Security, Kraljice Ane b. b. 11000 Belgrade, Yugoslavia
b
Vinca Institute of Nuclear Sciences, P.O. Box 522, 11001 Belgrade, Yugoslavia
c
Faculty of Electrical Engineering, P.O. Box 816, 11000 Belgrade, Yugoslavia

Received 27 June 2000; accepted 7 February 2001

Abstract

The phosphorescence of ideal phosphors has been investigated using a general order kinetics model. The regions
where the model describes the phosphorescence processes exactly and approximately have been identified. In order to
characterize these processes, the mean value of the kinetics order has been defined for the part of the curve of immediate
interest. It has been shown that the value of the order of kinetics for ideal phosphors in the transition region cannot
have a unique physical interpretation. The general order kinetics model enables theoretical explanation of some
important physical characteristics of TL processes for the ideal phosphors. For the theoretical curves, obtained by the
band model, the parameters of phosphorescence curves have been determined using the general order kinetics model.
The results differ from the exact values by 3%. We conclude that the general order kinetics model enables a better
understanding of the physical processes, and an approximate determination of the phosphorescence decay parameters.
This points out the theoretical and practical value of the model. # 2001 Elsevier Science B.V. All rights reserved.

PACS: 78.60.K

Keywords: Thermoluminescence; Phosphorescence processes; The general order kinetics model; Retrapping factor

1. Introduction known as ideal phosphor [1]. The general theory of

luminescence decay process, explained by the
The simplest band model (BM) when explains energy band model, is mathematically complicated
the mechanism of TL relaxation must include the and cannot be solved for the general case. Starting
luminescence centers and traps. If in an ideal case from the band model [2] and taking that
all luminescence centers and traps are assumed to n þ nc ¼ pl , a general equation can be obtained [3]:
be identical, then the model describes a system


1 d2 pl 1 dpl 2 gt
þ 1 þ
pl dt2 p2l dt gl
*Corresponding author. Vinca Institute of Nuclear Sciences,
P.O. Box. 522, 11001 Belgrade, Yugoslavia. Tel.: +381-11-458- 1 dpl   
222; fax: +381-11-344-0100.
þ gl  gt pl þ gt N þ S þ gl Spl ¼ 0; ð1Þ
pl dt
E-mail address: davidm@rt270.vin.bg.ac.yu
(M. Davidović). where pl is the concentration of holes occupying
0921-4526/01/$ - see front matter # 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 1 - 4 5 2 6 ( 0 1 ) 0 0 4 9 1 - 4
310 Z. Vejnović et al. / Physica B 304 (2001) 309–318

the luminescence centers, nc is the concentration of Taking S ¼ 0, an equation is obtained with

electrons in the conduction band, n is the solutions describing the first step of the decay
concentration of electrons occupying the traps, N process which is temperature independent. Solu-
is the trap density, gl and gt are capture tions are exact and shown in parametric form:
probabilities for electrons by luminescence centers nc  p gt =gl p
l l
and traps, respectively. Here S ¼ s expðE=kTÞ ¼ C1 þ  1; ð5Þ
N N N
where s is the frequency factor, E is the trap
activation energy, T is the material temperature and
Z
and k is the Boltzmann constant. Klasens and dpl
  gt =gl  ¼ C2  gl Nt: ð6Þ
Wise [3] have solved this equation for a special pl C1 pl =N þpl =N  1
case of the second order kinetics when gl ¼ gt ¼ g.
In this case, Eq. (1) becomes considerably simpler The integration constants C1 and C2 depend on
and the solution is the initial conditions of the density of electrons nc0

 
gL þ g nc0 =pl0  L exp½ðgN þ S Þt
I ¼
    2 ; ð2Þ
1=pl0 þ gLt þ g nc0 =pl0  L =gN þ S ð1  exp½ðgN þ S ÞtÞ

where in the conduction band and density of empty

S centers pl0 .
L¼ ; ð3Þ For the second step of the process Adirovitch,
gN þ S
has obtained the exact solutions also shown in
while nc0 and pl0 are the initial concentrations of parametric form:
electrons in the conduction band and empty
luminescence centers, respectively. dn gl S
I ¼ ¼ n2 ; ð7Þ
Klasens and Wise have noticed that the decay dt gl n þ gt ðN  nÞ
curves, obtained for various values of excitation, and
consist of two parts. The first part of the curve is


temperature independent and results from the 1 g n0 g N 1 1
t¼ 1  t ln þ t  : ð8Þ
concentration of electrons in the conduction band S gl n g l S n n0
which is higher than the quasistationary value
Phosphorescence intensity is obtained by sub-
characterizing the phosphorescence process. This
stituting the value of concentration n from the first
step of the process is very short and takes place
into the second equation. Adirovitch denoted the
immediately after the end of excitation. Its
resulting solutions the quasistationary ones [1] and
duration varies from 108 up to 102 s [1,3]. The
the corresponding region the quasistationary
second part of the curve obtained by neglecting
region.
exponential terms is strongly temperature depen-
dent. This step of the decay process is known as
phosphorescence.
Starting from these facts, Adirovich [1] has 2. General order kinetics model
found the solutions for the first and the second
step of luminescence decay process. After a In the general case, where neither of the two
rearrangement, Eq. (1) can be expressed as fol- basic processes (luminescence and retrapping) is
lows: dominant, the models of the first and the second


 order kinetics cannot be applied. For the general
dnc g t g t nc N 1 1 case of isothermal TL relaxation (see discussion in
¼1 þ þ þS  : ð4Þ
dpl g l g l pl pl g l n c g l pl Ref. [4]), Klasens and Wise have suggested an
 Z. Vejnović et al. / Physica B 304 (2001) 309–318 311

empirical differential equation instead of Eq. (7) to

describe the process of phosphorescence decay in
accordance with the ‘‘multimolecular’’ mechanism.
Later on, May and Partridge [5] have used the
model of general order kinetics expressed by such
a differential equation to explain the TL glow
curves which cannot be described by the models of
the first and second order of kinetics. In order to
give a better physical interpretation, Rasheedy [6]
proposed a correction of the empirical differential
equation, which can be expressed as:
dn S l
I ¼ ¼ n: ð9Þ
dt N l1
Fig. 1. The luminescence decay curves for different retrapping
As shown in Ref. [7], this is an empirical factor values r ¼ gt =gl , parameter relations gl N=S ¼ 50, and the
interpolation equation which enables the calcula- initial conditions nc0 =N ¼ 0:1 and pl0 =N ¼ 1. Broken lines
tion of an analytical approximate solution for the represent the curves of the second order kinetics model.
cases which cannot be described by the models of
the first [8] and the second order kinetics [9]. In
Eq. (9), the order of kinetics l is constant. In this
equation, the constant r is substituted for l so that limiting shape. This third part of the phosphores-
the differential equation has an analytical solution. cence curve, which appears after sufficiently long
In reality, however, l is not constant and depends time, characterizes emptiness of traps, i.e. n  N,
on the initial conditions as has been shown for the and can be called the limiting or asymptotic
curves close to the first and second order kinetics region. The quasistationary range in that case
[1,10]. This is particularly prominent in the general can be termed a transition range. For the well
order kinetics model, since, during the process of known models of phosphors: ideal phosphors
thermal relaxation there is a significant change in [1,11], phosphors with deep inactive traps [11],
the ratio of parameters r to n0 , and hence in l as phosphors with order of kinetics 1.5 [5], one
well. Therefore, the constant value of the para- obtains the concentration of electrons in the
meter l in the model of general order kinetics is in conduction band nc pK l , where K is a rational
fact an average value of this parameter for the part positive number or zero. Therefore, the third part
of the phosphorescence curve being examined. of the curve can be presented by the model of
Solving the differential Eq. (9) and substituting general order kinetics, or in other words, the
the value of n0 for t ¼ 0, a generalized empirical phosphorescence process can be shown in a simple
Becqurel formula for the isothermal TL emission way and directly. One can also see that the general
Ir ¼ dnr =dts at a given moment ts ¼ St is order kinetics model describes the limiting case of
obtained: phosphorescence process, a part of the general
Ir ¼ ½ðl  1Þts þ n1l l=l1 solution of this process (Fig. 1).
r0  ; ð10Þ
where nr ¼ n=N and nr0 ¼ n0 =N. This equation,
according to the general order kinetics model 3. The order of kinetics l in the general order
approximates the isothermal curve described by kinetics model
Eqs. (7) and (8).
By analyzing particular solution (2), for the Comparing Eqs. (7) and (9) one can see that
second order kinetics model, one can see that for they are related by [12]
different values of nc0 and pl0 , all the curves merge
into one. It means that all the curves tend to one nr þ rð1  nr Þ ¼ n2l
r : ð11Þ
312 Z. Vejnović et al. / Physica B 304 (2001) 309–318
Taking the logarithm of (11) we get:
ln½nr ð1  rÞ þ r
l ¼2 ¼ 2  f ðnr ; rÞ:
ln nr
From this expression it is clear that l is not
constant since it depends on the variable nr . An
essential approximation in the model of general
order kinetics is that l is independent of nr , that is,
of r. For the phosphorescence process, a constant
value of l can be obtained for the range of ts values
by finding its average value:
Rt
%l ¼ R0 l dts ¼ 2  f%ðnr ; rÞ: ð13Þ
t determined by nr0 , and by the final value nr , i.e.
0 dts
From Eq. (12), it is clear that the average value of l
requires the finding of an average value of the
function f ðnr ; rÞ:
R ts  
% 0 ln½nr ð1  rÞ þ r=ln nr dts
f ðnr ; rÞ ¼ R ts
0 dts
R nr   
nr0 ln½nr ð1  rÞ þ r=ln nr dts =dnr dnr
¼ R nr   :
nr0 dts =dnr dnr
When the distribution function dts =dnr is found
from Eq. (8) and substituted into Eq. (14) one
obtains the final expression for the calculation of
the average value of f ðnr ; rÞ for the interval of
values of nr in which the phosphorescence is
observed.
R nr  
ln½nr ð1  rÞ þ r=ln nr 1=n2r þ ð1  rÞ=nr dnr
f%ðnr ; rÞ ¼
nr0
R nr   :
2
nr0 1=nr þ ð1  rÞ=nr dnr
The integrals in Eq. (15) for the arbitrary value of r
in the interval from nr0 to 0 cannot be found
analytically. Difficulties arise from the upper limits
of the integral since the functions go to infinity
when nr ! 0. Physically, this corresponds to the
fact that the traps cannot become completely
depleted during the isothermal relaxation. With
the depleted traps, however, the probability of
retrapping increases with respect to the probability
of luminescent recombination. Therefore, only the
range of phosphorescence within the limits from
nr0 up to nr , for which numerical solutions can
always be found is of practical interest. The
changes in function f ðnr ; rÞ are generally small
ð12Þ within the nr range. The exception is that part of
the curve where nr ! 0. This part of the curve,
however, corresponds to the case where traps are
almost depleted and therefore the intensities of
phosphorescence in this region are very low. If this
part of the curve is outside the observed range or if
its influence is neglected, then we can take that
f%ðnr ; rÞ  f ðC; rÞ. In this expression C has a
constant value in the range of r from 0 to 1, for
the initial conditions of the observed region
by the time interval in which the phosphorescence
is observed. We conclude that C does not
correspond to the average value of nr since, as
can be seen from the above expression, the average
value of nr does depend on r. An increase in the
retrapping factor r leads to a slowdown of
phosphorescence and to a decrease in the average
value of nr . However, by calculating the average
value of nr , it can be shown that this is a slowly
changing function in the interval of r from 0 to 1.
ð14Þ
Therefore C is in fact an average value of nr which
gives the best description of phosphorescence in
the interval of r from 0 to 1, for the given initial
condition nr0 and specified time interval.
The value of C can be determined as follows.
The differential Eq. (7) is solved for some values of
the parameters r and nr0 . If this is done for a large

ð15Þ
number of various values of r, a set of isothermal
TL relaxation curves is obtained, which can be
fitted by using expression (10). The value of nr0 is
taken to be constant when fitting the parameter l.
In this way a dependence of l on r is obtained
(Fig. 2). By fitting the obtained curve to the
function:
ln½Cð1  rÞ þ r
l ¼2 ¼ 2  f ðC; rÞ; ð16Þ
ln C
the value of parameter C is found. A constant
value of l is always obtained by applying this
 Z. Vejnović et al. / Physica B 304 (2001) 309–318
Fig. 2. The dependence of the order of kinetics l on the
retrapping factor r. The solid line is obtained by fitting the
order of kinetics l using Eq. (10), with numerical solutions of
the differential Eq. (7) for the exact value of nr0 ¼ 0:1. The
parameter C is obtained by fitting the resulting curve to Eq. (16)
(dotted line).
procedure for any constant value of nr0 , as a
function of r. In the example shown in Fig. 2 we
find C ¼ 0:032. The fitting was performed using
the chi square method without weight factor when
summing the squares. In this case, the sum of
squares is computed using the expression
Sðyi  fi Þ2 , where yi is the experimental value of
the intensity of phosphorescence at some point i,
while fi is the value of the fitting function. It means
that the highest TL emission values have the
strongest influence on the fitting process of the
experimental or simulated curve to the assumed
function of the model. In practice this means that,
in the case of a decrease in the TL emission by two
orders of magnitude, any further increase in the
range of nr , where the TL relaxation is observed,
has a negligible influence on the change of the
obtained values of l.
Assuming that close to the end of the curve the
phosphorescence proceeds by second order hyper-
bola, we may introduce the weighting factor in the
process of chi square fitting for each point si ¼ yi ,
and get the sum of squares Sððyi  fi Þ=si Þ2 . When
using this method, all the points are fitted with the
same relative error and for l we get the values
closest to those computed by Eqs. (13) and (15).
Thus we show that the parameter C depends
313
Fig. 3. Interpolation function (broken line) and exact values of
the expression in the denominator of Eq. (7) (solid line). The
parameter nr0 ¼ 0:1.
strongly on the method of fitting and on the
interval of time for which the curve is observed, as
shown by the theoretical expressions.
Substituting Eq. (16) into Eq. (11) we get the
form of the interpolation function which approx-
imates the expression in the denominator of
Eq. (7):
nr ð1  rÞ þ r  nrf ðC; rÞ : ð17Þ
For the values of parameters of the phosphores-
cence curves, given as an example in Fig. 2, the
ratio of these two functions is graphically pre-
sented for a few characteristic values of the
parameter r (Fig. 3). The figure shows, how the
interpolation is made by the model of general
order kinetics, using the values of the function
f ð0:032; rÞ, with the parameter r in the range from
0 to 1 when nr0 ¼ 0:1.
4. Discussion
For the transition region, relationship (12) is
only an initial one in the process of defining the
order of kinetics parameter using the general order
kinetics model, the value of the order is taken to
be constant during the TL process. We consider
the method by which the constant l is obtained to
be essential for the physical interpretation of this
314 Z. Vejnović et al. / Physica B 304 (2001) 309–318
Fig. 4. The dependence of the kinetics order l on the initial
condition nr .
parameter. The constant value of l can be defined
as an average value of the function (12), which
varies during phosphorescence process. This is an
approximation as one can easily see. Leaving its
quality aside for the moment, we have focussed
our attention to the physical essence of the
parameter l in the model of general order kinetics.
Therefore, although we can conditionally take that
the function (12) describes the value of the kinetics
order, l is constant (Eq. (16)) throughout the
phosphorescence process.
Using Eq. (16) the functional dependence of l on
r can be found in the entire region of l which is of
practical interest (0.7, 2.5) [13]. Fig. 4 shows the
curves for various values of the initial condition
nr0 . If we examine these curves and look at the left
and right hand side from the point r ¼ 1, the
following can be concluded with a decrease in nr .
The parameter l approaches the value of 2, which
is its limiting value, the order of kinetics l > 2
exists only if r > 1, and kinetics order l52 appears
for r51. On the left, as well as on the right hand
side of the point r ¼ 1, depletion of traps leads to
an absolute domination of the retrapping process
but also to a less influence of the retrapping factor
r and to an increase in depleted trap influence on
the retrapping process. On the left hand side this
means an increase of the retrapping probability,
and on the right hand side a decrease of the
retrapping probability with respect to its initial
value. This leads to asymptotic characteristics of
phosphorescence processes [10]. Following the
excitation with different intensities, the decay
curves approach each other as the time goes on.
For an ideal phosphor the relaxation processes are
close to the process described by the second order
kinetics. We can define the stable kinetics of the
phosphorescence process, which should be under-
stood as a process where l is constant and as a
process to which all the other processes of
phosphorescence decay asymptotically approach.
For the ideal phosphors, the process flowing
according to the second order kinetics model can
be defined as a stable one. Phosphorescence
process in these systems which is described by
the model of the second order kinetics tends to go
on unchanged. Those processes having the order
of kinetics different from two tend to change into
those, which can be described by the model of
second order kinetics. For phosphorescence curves
of ideal phosphors the region outside the second
order kinetics represents the region of transition
regime.
The facts discussed above have been proved
experimentally for some phosphors [10]. Assumed
quasistationary electron density in the conduction
band leads to a stable phosphorescence process.
Only in two cases, the first and the second order
kinetics, the process of phosphorescence can be
observed to follow from the beginning to the end
an unchanged law of decay. For the first order
kinetics, one can see that the electron density in the
conduction band nc ¼ S=gl is constant throughout
the phosphorescence. The stable phosphorescence
is a consequence of the constancy of nc . In the case
of phosphors there is always a finite number of
occupied traps, so it is clear that at the end of
phosphorescence nc cannot remain constant. A
detailed analysis is given in Ref. [1]. We conclude
that at the end of phosphorescence process, taking
place according to the first order kinetics model,
the quasistationary electron density nc in the
conduction band no longer holds. Therefore, in
this case, we have a quasistable phosphorescence
process. For the second order kinetics, the process
proceeds in a stable manner due to the constant
density ratio of electrons in the conduction band
ðnc ¼ Sn=gt NÞ and in traps. This means that we
 Z. Vejnović et al. / Physica B 304 (2001) 309–318
have a stable process obeying the same law to its
very end.
From Eq. (16), we now conclude that the
constant, having the value of 2, determines the
stable character of the TL relaxation, and the
function f ðC; rÞ is an average value of the
deviation from the stable process for the initial
condition nr0 . Therefore, the kinetics order l is the
measure of the stability of TL relaxation process in
respect to the initial condition nr0 , or in respect to
the retrapping factor r in the TL relaxation region.
From Eq. (16) derived above and Fig. 4, we can
see that the conditions for the first and the second
order kinetics can be simply expressed by r ¼ 0
and 1, respectively. It may be assumed that the
given models can be approximately used in the
neighborhood of these points. The condition
315
r51 and it means that gt 50 or gl 50, which is
physically impossible. Therefore, the general order
kinetics model cannot explain kinetics orders less
than one, and an extrapolation of the curve (16),
based on these values, for a given band model has
no physical meaning. However, since the region
for r ¼ 0 is the region of great instability of
phosphorescence, it can be observed that a very
small increase in both the luminescence centers,
not followed by an increase in electron density in
traps, and electrons in the conduction band or on
excited levels, not arising from the traps, leads to
the phosphorescence with the order of kinetics
smaller than one.
For ideal phosphors, expression (9) can be used
to fit the phosphorescence curves with shapes
ranging from exponential ðl ¼ 1Þ to hyperbolic
r  nr , defining the first order kinetics process, decay ðl  1Þ [4]. In order to take account of all
can simply be shown to be a close proximity of the these cases of decay, there has to be some
point r ¼ 0. Since N > n we must have gl  gt and interdependence of the parameters in the exponent
this is r  0. The same holds for the condition of relation (9) and the parameters next to the term
r  nr , which defines the second order kinetics
process. However, since this is the region of stable
processes, where even greater changes in the
parameter r do not necessarily change the order
of kinetics l, it may happen that for larger
deviations from the point r ¼ 1 the phosphores-
cence process proceeds according to the second
ts . In the cases of the first and second order
kinetics, the exponent in Eq. (10) is constant,
hence this exponent and the coefficient ts are
independent quantities. Therefore, they can be
obtained by a simple fitting of the experimental
curves to function (10). For those cases, where the
phosphorescence decay is described by the expres-
order kinetics. The condition r  nr may hold
even for some point r1 which is far from r ¼ 1, and
this means that at this point the phosphorescence
process can also be described by the model of the
second order kinetics. As one can see from Fig. 4,
if the phosphorescence can be approximately
described by the second order kinetics at the point
r1 , for a given initial condition nr0 , then this must
be valid at any point 1 > r > r1 if r1 51 or 15r5r1
if r1 > 1. Consequently, the condition r ¼ 1 is the
sion having the order of kinetics l ¼ 1 and 2 each
part of that curve can be described by Eq. (10). If
various parts of that curve are fitted to expression
(10), a different value of the parameter l will be
obtained for each part. If we now make an
approximation that l is constant throughout the
phosphorescence decay, then by fitting the experi-
mental curves to function (10) an error appears.
This error is minimal in the process of fitting the
parameter l and the coefficient ts . All this leads to a
limiting value of the condition r  nr . Therefore, deviation of the parameter l and the coefficient ts
the conditions r ¼ 1 and r  nr define the range of
r in which the phosphorescence processes can be
described by the second order kinetics model, and
they are interdependent.
For a given band model with two types of
centers: traps and luminescence centers we get
using an approximation with the general order
kinetics that l ¼ 1 represents a limit of physically
real phosphorescence processes. For l51 we get
from their exact values. This deviation depends on
how much the parameter l deviates from l ¼ 1 or
2. The errors are larger near l ¼ 1, since we deal
with an unstable process. Similar errors are present
near l ¼ 2, because here we deal with a stable
process.
Assuming that the occupancy of traps nr is
known, from the fitting of an experimental curve
to Eq. (10) and from the value obtained for the
316 Z. Vejnović et al. / Physica B 304 (2001) 309–318

parameter l, we conclude that there is an agree-
ment between the theoretical procedure, based on
general order kinetics, and the simple band model
characterizing the ideal phosphor. Furthermore,
we conclude that the simple band model of
phosphor can explain the general empirical Bec-
querel law. It can also point out the complexity of
the phenomenon of phosphorescence decay when
other effects which can influence the phosphores-
cence are present (luminescence quenching, the
presence of traps with various depths, etc).
Expression (15) can be used to explain the fact
that in the model of general order kinetics, for the
processes of TL relaxation stimulated by the
heating function R which is a simple hyperbolic
function [11], we got analytical solutions. In the
region where the distribution function tends to
infinity, R tends to infinity as well, and this leads,
at least theoretically, to the total depletion of
traps.
5. Theoretical and practical aspects of the general
order kinetics model
With respect to the asymptotic character of the
phosphorescence process, observed long ago, the
parameter l shows the characteristics of the
stability curve in the physical sense. Therefore,
this parameter shows the stability of phosphores-
cence or the distance from the asymptote, which
defines stable conditions of the process for the real
materials, which can be approximated by the
model of general order kinetics. If we take the
parameter l to be constant and get back to Eq. (9)
and write it in another form, we get
Ir ¼ expðljln nr jÞ: ð18Þ
Here, we can define the parameter l as a constant
of the velocity of emptying the traps with respect
to variable ln nr for a given part of the phosphor-
escence curve. This means that the traps will empty

Table 1

r ts l lf 1 rl1 (%) nr0f 1 rn1 (%) lf 2 rl2 (%) nr0f 2 rn2 (%)

0 15 1 1 0 0.1 0 1 0 0.1 0
0.01 20 1.0789 1.0944 1.44 0.0944 5.52 1.0662 1.18 0.0987 1.25
0.02 25 1.1307 1.1643 2.97 0.0915 8.47 1.1171 1.20 0.0982 1.79
0.03 30 1.1874 1.2197 2.72 0.0895 10.50 1.1598 2.32 0.0979 2.07
0.04 50 1.2291 1.2685 3.21 0.0873 12.62 1.1981 2.52 0.0975 2.44
0.05 50 1.2700 1.3075 2.96 0.0865 12.62 1.2303 3.13 0.0976 2.37
0.06 80 1.3015 1.3453 3.37 0.0849 15.05 1.2621 3.03 0.0972 2.76
0.08 80 1.3622 1.4052 3.16 0.0835 16.44 1.3128 3.62 0.0975 2.47
0.1 100 1.4076 1.4515 3.12 0.0836 16.39 1.3576 3.55 0.0976 2.37
0.125 100 1.4568 1.4954 2.65 0.0850 14.98 1.4015 3.79 0.0985 1.46
0.15 100 1.5012 1.5378 2.44 0.0848 15.15 1.4438 3.83 0.0987 1.30
0.175 150 1.5409 1.5777 2.39 0.0839 16.01 1.4835 3.72 0.0985 1.49
0.2 150 1.5746 1.6072 2.07 0.0848 15.11 1.5177 3.66 0.0987 1.27
0.25 175 1.6305 1.6593 1.75 0.0860 13.98 1.5753 3.39 0.0991 0.88
0.3 200 1.6781 1.7027 1.47 0.0871 12.86 1.6256 3.13 0.0993 0.63
0.35 200 1.7172 1.7379 1.21 0.0887 11.22 1.6686 2.83 0.0997 0.29
0.4 250 1.7534 1.7718 1.05 0.0894 10.53 1.7086 2.56 0.0997 0.26
0.5 300 1.8129 1.8265 0.75 0.0915 8.45 1.7759 2.04 0.0999 0.03
0.6 350 1.8618 1.8715 0.52 0.0935 6.48 1.8328 1.55 0.1000 0.08
0.8 500 1.9397 1.9438 0.21 0.0968 3.16 1.9259 0.71 0.1000 0.09
1 650 2 2 0 0.1 0 2 0 2 0
1.1 800 2.0255 2.0238 0.09 0.1025 2.59 2.0319 0.32 0.0999 0.05
1.2 900 2.0488 2.0455 0.16 0.1031 3.18 2.0613 0.61 0.0998 0.11
1.3 1000 2.0702 2.0654 0.23 0.1047 4.76 2.0884 1.12 0.0998 0.17
1.4 1100 2.0899 2.0838 0.29 0.1063 6.34 2.1137 1.14 0.0997 0.24
1.5 1200 2.1083 2.1009 0.35 0.1079 7.90 2.1373 1.38 0.0997 0.30
 Z. Vejnović et al. / Physica B 304 (2001) 309–318
more slowly if the order of kinetics is higher. This
is correct since in this case the retrapping factor is
too large.
As far as the calculation of phosphorescence
parameters is concerned, only two parameters are
of interest for some experimental curves, as one
can see from Eq. (9), and they are nr 0 and r. Two
cases will be examined. A direct fitting of the
variables to the experimental curve (Table 1, lf 1
and nr0f 1 ) and a fitting with one parameter only if
the exact value of the other one is known. Eq. (10)
can be used for the purpose. If the value nr0 is
known then the fitting l value can be taken to be
the exact average value (Table 1, nr0 ¼ 0:1 and l).
It comes out that the obtained values are not
identical, except for the interpolation knots where
the differential Eq. (7) is identical with differential
Eq. (9) and this area can be described by the model
of general order kinetics. These disagreements
around knots are larger for that part of the curve
where nr and r are of the same order of magnitude,
particularly for the lower values of nr when traps
are less occupied. The explanation of these
discrepancies lies in the fact that the model of
general order kinetics is an approximation of the
phosphorescence process so that for some experi-
mental phosphorescence curves this process is
better described by close values than by the exact
ones. However, one can see from Table 1 that
these close values are questionable and that the
deviations from the exact values do not influence
the general physical picture and explanation of the
phosphorescence process. If the general order
kinetics model can approximately describe the
phosphor specimen then it is possible to improve
the method of calculation of the phosphorescence
parameters. In the case where one parameter is
fitted and the other is already known, the
following relationship can be used to determine l:


Z 1
 process, and thus its practical and theoretical
 0 0
Ir ¼ exp l
ln
Ir ts dts
: ð19Þ importance.
ts
Here, one should know only Ir as a function of
temperature ts and then nr0 is determine by fitting
the function (7) to the experimental curve. This
method of calculation gives more accurate values
for nr0 and l (Table 1, lf 2 and nr0f 2 ) than the method
of direct fitting (Table 1, rl1 , rn1 , rl2 and rn2 ).
317
6. Conclusions
The phosphorescence, which for ideal phos-
phors is described by the band model with two
types of competing capture centers (traps and
luminescence centers), can be approximately de-
scribed by the model of general order kinetics.
According to the model, each phosphorescence
curve can be approximated to a constant value of
the kinetics order parameter l. It is shown that this
constant value is the average value of l for the time
interval in which the phosphorescence curve is
observed. Based on such a definition of the order
of kinetics, general Becquerel relation can be
derived which approximates the phosphorescence
curve. Its practical significance has been discussed
in a series of papers [4,10,11].
The model of general order kinetics shows that
all processes of phosphorescence decay tend to
become stable, which is physically determined by
domination of one type of capture centers, the
traps. Stable flow of the phosphorescence process
is defined by exact and constant value of para-
meter l at any moment. It is an asymptotic value
too. Eq. (7) has an analytical solution in that
point. Stable flow of the process, for ideal phos-
phors, is determined by the second order kinetics
model and by the value l ¼ 2, which is the limiting
case of the general order kinetics. The process
stability is determined by the order of kinetics l via
f ðnr ; rÞ function, and depends on the deviation
from the value l ¼ 2. Therefore, l is a dynamic
parameter that changes during the phosphores-
cence process, characterizing its stability.
We may thus conclude that the model of general
order kinetics is not only a mathematical formal-
ism, but an explanation of some characteristics of
the TL relaxation kinetics as well, and so it enables
a better understanding of the kinetics of this
The general order kinetics model, besides better
understanding of the physical process enables
better calculation of the parameters of the
phosphorescence processes.
In the general case with phosphors which
besides traps and luminescence centers also con-
tain inactive deep traps, phosphorescence pro-
318 Z. Vejnović et al. / Physica B 304 (2001) 309–318

cesses described by the same order of kinetics as [2] A. Halperin, A.A. Braner, Phys. Rev. 117 (1960) 408.
the processes in ideal phosphors have different [3] H.A. Klasens, M.E. Wise, Nature 158 (1948) 483.
[4] E.I. Adirovitch, J. Phys. Radiat. 17 (1956) 705.
physical interpretations [11]. These phosphors
[5] C.E. May, J.A. Partridge, J. Chem. Phys. 40 (1964)
have the asymptotic value of the order of kinetics 1401.
equal 1. [6] M.S. Rasheedy, J. Phys: Condens. Matter 5 (1993)
633.
[7] Z. Vejnovi!c, M. Pavlovi!c, D. Risti!c, M. Davidovi!c,
Acknowledgements J. Lumin. 78 (1998) 279.
[8] J.T. Randall, M.H.F. Wilkins, Proc. R. Soc. A 184 (1945)
The authors are grateful to Professors D. 356.
$ ajkovski and Z. Ikoni!c for careful reading and
C
[9] G.F.J. Garlick, A.F. Gibson, Proc. R. Soc. A 188 (1947)
485.
useful comments on the manuscript. [10] M.V. Fok, Vvedenie v kinetiku lyminescencii kristallofos-
forov, Nauka, Moskva, 1964, p. 40.
[11] R. Chen, Y. Kirsh, Analysis of Thermally Stimulated
References Process, Pergamon, Oxford, 1981.
[12] C.M. Sunta, R.N. Kulkalni, T.M. Piters, W.E. Feria Ayta,
[1] E.I. Adirovitch, Nekotorie voprosi teorii lyminescencii S. Watanabe, J. Phys. D 31 (1998) 2074.
kristallov, GITTL, Moskva, 1956, p. 148. [13] R. Chen, J. Electrochem. Soc. 116 (1969) 1254.