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An Approximation of Phosphorescence Decay Kinetics of Ideal PDF
An Approximation of Phosphorescence Decay Kinetics of Ideal PDF
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
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
Taking the logarithm of (11) we get: always be found is of practical interest. The
ln½nr ð1 rÞ þ r changes in function f ðnr ; rÞ are generally small
l ¼2 ¼ 2 f ðnr ; rÞ: ð12Þ within the nr range. The exception is that part of
ln nr
the curve where nr ! 0. This part of the curve,
From this expression it is clear that l is not however, corresponds to the case where traps are
constant since it depends on the variable nr . An almost depleted and therefore the intensities of
essential approximation in the model of general phosphorescence in this region are very low. If this
order kinetics is that l is independent of nr , that is, part of the curve is outside the observed range or if
of r. For the phosphorescence process, a constant its influence is neglected, then we can take that
value of l can be obtained for the range of ts values f%ðnr ; rÞ f ðC; rÞ. In this expression C has a
by finding its average value: constant value in the range of r from 0 to 1, for
Rt
the initial conditions of the observed region
%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
by the time interval in which the phosphorescence
From Eq. (12), it is clear that the average value of l is observed. We conclude that C does not
requires the finding of an average value of the correspond to the average value of nr since, as
function f ðnr ; rÞ: can be seen from the above expression, the average
R ts
value of nr does depend on r. An increase in the
% 0 ln½nr ð1 rÞ þ r=ln nr dts
f ðnr ; rÞ ¼ R ts retrapping factor r leads to a slowdown of
0 dts phosphorescence and to a decrease in the average
R nr
nr0 ln½nr ð1 rÞ þ r=ln nr dts =dnr dnr value of nr . However, by calculating the average
¼ R nr :
nr0 dts =dnr dnr
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
When the distribution function dts =dnr is found gives the best description of phosphorescence in
from Eq. (8) and substituted into Eq. (14) one the interval of r from 0 to 1, for the given initial
obtains the final expression for the calculation of condition nr0 and specified time interval.
the average value of f ðnr ; rÞ for the interval of The value of C can be determined as follows.
values of nr in which the phosphorescence is The differential Eq. (7) is solved for some values of
observed. the parameters r and nr0 . If this is done for a large
R nr
ln½nr ð1 rÞ þ r=ln nr 1=n2r þ ð1 rÞ=nr dnr
f%ðnr ; rÞ ¼
nr0
R nr : ð15Þ
2
nr0 1=nr þ ð1 rÞ=nr dnr
The integrals in Eq. (15) for the arbitrary value of r number of various values of r, a set of isothermal
in the interval from nr0 to 0 cannot be found TL relaxation curves is obtained, which can be
analytically. Difficulties arise from the upper limits fitted by using expression (10). The value of nr0 is
of the integral since the functions go to infinity taken to be constant when fitting the parameter l.
when nr ! 0. Physically, this corresponds to the In this way a dependence of l on r is obtained
fact that the traps cannot become completely (Fig. 2). By fitting the obtained curve to the
depleted during the isothermal relaxation. With function:
the depleted traps, however, the probability of
ln½Cð1 rÞ þ r
retrapping increases with respect to the probability l ¼2 ¼ 2 f ðC; rÞ; ð16Þ
ln C
of luminescent recombination. Therefore, only the
range of phosphorescence within the limits from the value of parameter C is found. A constant
nr0 up to nr , for which numerical solutions can value of l is always obtained by applying this
Z. Vejnović et al. / Physica B 304 (2001) 309–318 313
have a stable process obeying the same law to its r51 and it means that gt 50 or gl 50, which is
very end. physically impossible. Therefore, the general order
From Eq. (16), we now conclude that the kinetics model cannot explain kinetics orders less
constant, having the value of 2, determines the than one, and an extrapolation of the curve (16),
stable character of the TL relaxation, and the based on these values, for a given band model has
function f ðC; rÞ is an average value of the no physical meaning. However, since the region
deviation from the stable process for the initial for r ¼ 0 is the region of great instability of
condition nr0 . Therefore, the kinetics order l is the phosphorescence, it can be observed that a very
measure of the stability of TL relaxation process in small increase in both the luminescence centers,
respect to the initial condition nr0 , or in respect to not followed by an increase in electron density in
the retrapping factor r in the TL relaxation region. traps, and electrons in the conduction band or on
From Eq. (16) derived above and Fig. 4, we can excited levels, not arising from the traps, leads to
see that the conditions for the first and the second the phosphorescence with the order of kinetics
order kinetics can be simply expressed by r ¼ 0 smaller than one.
and 1, respectively. It may be assumed that the For ideal phosphors, expression (9) can be used
given models can be approximately used in the to fit the phosphorescence curves with shapes
neighborhood of these points. The condition 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 ts . In the cases of the first and second order
process. However, since this is the region of stable kinetics, the exponent in Eq. (10) is constant,
processes, where even greater changes in the hence this exponent and the coefficient ts are
parameter r do not necessarily change the order independent quantities. Therefore, they can be
of kinetics l, it may happen that for larger obtained by a simple fitting of the experimental
deviations from the point r ¼ 1 the phosphores- curves to function (10). For those cases, where the
cence process proceeds according to the second phosphorescence decay is described by the expres-
order kinetics. The condition r nr may hold sion having the order of kinetics l ¼ 1 and 2 each
even for some point r1 which is far from r ¼ 1, and part of that curve can be described by Eq. (10). If
this means that at this point the phosphorescence various parts of that curve are fitted to expression
process can also be described by the model of the (10), a different value of the parameter l will be
second order kinetics. As one can see from Fig. 4, obtained for each part. If we now make an
if the phosphorescence can be approximately approximation that l is constant throughout the
described by the second order kinetics at the point phosphorescence decay, then by fitting the experi-
r1 , for a given initial condition nr0 , then this must mental curves to function (10) an error appears.
be valid at any point 1 > r > r1 if r1 51 or 15r5r1 This error is minimal in the process of fitting the
if r1 > 1. Consequently, the condition r ¼ 1 is 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 from their exact values. This deviation depends on
r in which the phosphorescence processes can be how much the parameter l deviates from l ¼ 1 or
described by the second order kinetics model, and 2. The errors are larger near l ¼ 1, since we deal
they are interdependent. with an unstable process. Similar errors are present
For a given band model with two types of near l ¼ 2, because here we deal with a stable
centers: traps and luminescence centers we get process.
using an approximation with the general order Assuming that the occupancy of traps nr is
kinetics that l ¼ 1 represents a limit of physically known, from the fitting of an experimental curve
real phosphorescence processes. For l51 we get 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- 5. Theoretical and practical aspects of the general
ment between the theoretical procedure, based on order kinetics model
general order kinetics, and the simple band model
characterizing the ideal phosphor. Furthermore, With respect to the asymptotic character of the
we conclude that the simple band model of phosphorescence process, observed long ago, the
phosphor can explain the general empirical Bec- parameter l shows the characteristics of the
querel law. It can also point out the complexity of stability curve in the physical sense. Therefore,
the phenomenon of phosphorescence decay when this parameter shows the stability of phosphores-
other effects which can influence the phosphores- cence or the distance from the asymptote, which
cence are present (luminescence quenching, the defines stable conditions of the process for the real
presence of traps with various depths, etc). materials, which can be approximated by the
Expression (15) can be used to explain the fact model of general order kinetics. If we take the
that in the model of general order kinetics, for the parameter l to be constant and get back to Eq. (9)
processes of TL relaxation stimulated by the and write it in another form, we get
heating function R which is a simple hyperbolic
Ir ¼ expðljln nr jÞ: ð18Þ
function [11], we got analytical solutions. In the
region where the distribution function tends to Here, we can define the parameter l as a constant
infinity, R tends to infinity as well, and this leads, of the velocity of emptying the traps with respect
at least theoretically, to the total depletion of to variable ln nr for a given part of the phosphor-
traps. 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) 309–318 317
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