Physica B ()

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Physica B
journal homepage: www.elsevier.com/locate/physb

Kinetics and dosimetric features of secondary thermoluminescence in carbon-doped aluminium oxide

M.L. Chithambo n, C. Seneza
Department of Physics and Electronics, Rhodes University, P O BOX 94, Grahamstown 6140, South Africa

art ic l e i nf o

a b s t r a c t
Carbon-doped aluminium oxide has some unstable electron traps whose presence is revealed as luminescence at temperatures close to ambient. Thermoluminescence of such a secondary glow peak at 46 1C has been studied for heating at 1.0 1C s 1. The study showed that the peak follows rst order kinetics and has an activation energy of about 0.7 eV independent of irradiation. Its dose response is linear at low dose with a supralinearity index equal to 1 but suffers from fading between irradiation and measurement with a half-life of about 120 s. The luminescence is attributed to the 3P-1S transition at an F-centre. & 2013 Elsevier B.V. All rights reserved.

Keywords: Thermoluminescence Kinetic analysis Dosimetry Aluminium oxide

1. Introduction Carbon-doped aluminium oxide (-Al2O3:C) is an ultra-sensitive dosimeter whose luminescence is attributed to large concentrations of F centres induced in the material during its growth in a highly reducing atmosphere in the presence of carbon [1]. The F centres act as luminescence sites for electrons thermally or optically released from electron-trapping point defects. These electrons result from ionisation in previously irradiated materials. The signal associated with the thermal release, thermoluminescence (TL), appears as a temperature-resolved set of peaks, a glow curve. The TL of -Al2O3:C typically consists of a dominant main peak used in dosimetry and a number of secondary peaks [1,2]. Luminescence in -Al2O3:C is discussed in terms of optically or thermally stimulable traps as well as deep electron and hole traps that compete for charge [1]. Understanding of thermoluminescence mechanisms is aided by kinetic analysis for parameters associated with particular traps e.g. the activation energy. To date, the focus in -Al2O3:C has been on the main peak e.g. [3,4] with few exceptions on the secondary ones e.g. [2,5]. This report is concerned with kinetics of the rst secondary TL peak in -Al2O3:C. Complementary studies of the dosimetric features of the peak have been included.

was measured using a RIS TL/OSL DA-20 Luminescence Reader. The luminescence was detected by an EMI 9235QB photomultiplier tube through a 7 mm Hoya U-340 lter (transmission band 250 390 nm FWHM). Samples were irradiated in-situ at room temperature using a 90Sr/90Y source at a dose rate of 0.10 Gy s 1. All measurements were carried out in a nitrogen atmosphere to prevent spurious signals from air and to improve thermal contact between sample holder and heater planchet. Unless otherwise stated, samples were heated at 1.0 1C s 1 from 30 to 500 1C after irradiation to 0.5 Gy. 3. Results and discussion 3.1. General characteristics of TL glow curves Fig. 1 shows a glow curve of -Al2O3:C. The dominant peak at 186 1C (peak II) is anked by secondary ones at 46 1C (peak I) and 314 1C (peak III). This paper is concerned with the kinetic and dosimetric features of peak I. The order of kinetics for peak I was assessed using the TmTstop method, a procedure used to determine the number and position of component peaks of a complex glow curve [6]. An irradiated sample was rst partially heated from 30 to 32 1C, the peak position Tm noted, and after cooling, the complete glow curve measured from 30 1C. The procedure was repeated several times on the same sample, freshly irradiated each time, with the Tstop temperature increased in turn by 2 1C from 32 up to 44 1C. Fig. 2 shows a graph of Tm against Tstop where it is evident that Tm is essentially independent of Tstop. This feature suggests that peak I is free of overlapping components and that it follows rst-order kinetics. The kinetics are rst-order since in such a process, the

2. Experimental details Samples used were -Al2O3:C discs of 5 mm diameter and 1 mm thickness (Rexon TLD Systems, Ohio, USA). Thermoluminescence
n

Corresponding author. Tel.: 27 46 603 8450; fax: 27 46 603 8757. E-mail address: m.chithambo@ru.ac.za (M.L. Chithambo).

0921-4526/$ - see front matter & 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.physb.2013.11.045

Please cite this article as: M.L. Chithambo, C. Seneza, Physica B (2013), http://dx.doi.org/10.1016/j.physb.2013.11.045i

M.L. Chithambo, C. Seneza / Physica B ()

1e+6

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10.2

8e+5

10.0

Intensity (a.u)

6e+5

9.8

4e+5

ln I
9.6
2e+5

9.4

0 0 100 200 300 400 500

9.2 37.6

37.8

38.0

38.2

38.4

38.6

38.8

Temperature (oC)
Fig. 1. A glow curve after 0.5 Gy dose and heating at 1.0 1C s 1. Peak III data has been scaled up for visual clarity.
55

1/kT

(eV)-1

Fig. 3. Application of the initial rise method. There was no systematic dependence of E on dose (inset).

50

45

40

determined to be E 0.73 7 0.02 eV. Further investigations showed that E was independent of irradiation for dose between nominally 0.51 and 2.57 Gy used (Fig. 3, inset) with the average value being E 0.72 7 0.01 eV. The frequency factor s, a measure of the frequency with which an electron attempts to escape from a trap, was estimated on assumption of rst-order kinetics for heating rate using the expression   E E s 2 exp 2 kT m kT m as  3 1010 s 1. This is the right range for s being of the order of the Debye vibration frequency as required [6].
28 30 32 34 36 38 40 42 44

Tm (C)

35

Tstop (C)
Fig. 2. Dependence of peak position Tm on Tstop. The dashed line is only a visual guide.

position of a peak is not affected by the initial concentration of trapped charge [6] which in this case is changed by the partial heating. 3.2. Kinetic analysis Samples were analysed for kinetic parameters using four different methods, i.e., the initial-rise, peak-shape, variable heating rate and whole glow curve methods. The different techniques were used as a means to corroborate results. 3.2.1. The initial rise method The basis of the initial rise method is that the TL intensity I in the rising edge of a peak, usually up to 15% of peak maximum, is approximately dependent on temperature T as   E I T C exp 1 kT where E is the activation energy, k is Boltzmann's constant and C a constant of proportionality [6]. Thus, a plot of ln I against 1/kT should be linear with slope equal to E. In this study, the 15% rule-of-thumb could not be applied as data then corresponded to temperatures below 30 1C. For all methods, the uncertainty in E was obtained directly from curve tting or evaluated using standard procedures of error propagation and are actual errors in E. Fig. 3 shows a plot of ln I against 1/kT for measurements corresponding to 1.0 Gy from which the activation energy was

3.2.2. Variable heating rate technique The variable heating rate technique uses the shift in peak position Tm caused by a change in heating rate as a way of calculating kinetic parameters. The method is a good approximation for any order of kinetics [6]. Assuming that the frequency factor s is constant, it can be shown from the theoretical dependence of on Tm that !     T2 E 1 E m 3 ln ln k Tm sk from which a plot of ln (T2m/) against 1/Tm should be linear with slope E/k from which E can be evaluated. The method was applied on a set of measurements on the same sample for heating rates from 0.1 to 2 1C s 1 following irradiation to 0.5 Gy. Fig. 4 shows the results from which the activation energy was found as 0.72 7 0.04 eV, in good agreement with the initial rise method. The frequency factor was evaluated using Eq. (2) as 3 1010 s 1. The corresponding TL intensity increases with heating rate (Fig. 4, inset) unlike the case for the main peak [4] which suffers from thermal quenching, i.e. non-radiative transitions. 3.2.3. Peak-shape method In the peak shape method, the activation energy E associated with a peak of maximum temperature Tm is estimated using the equation ! kT 2 m E C 4 b 2kT m where can be any , or where is the peak width at halfmaximum, is the lower half-width, and the upper half-width. The order of kinetics b is deduced from its link to the geometrical factor g /. In particular g is equal to 0.42 and 0.52 for rst- and

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2 b = 0.9 b=1 b = 1.1 b = 1.2

0
13.0

ln (Tm2/)

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Norm. Im (a.u)

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-6

(oC s-1)

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-1

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1/kTm (eV)

1/kT (eV)-1
Fig. 5. ln (I/nb) versus 1/kT plots for various values of b.
1.2 1.0
ln I

Fig. 4. The variable heating rate method on peak I. The inset shows the normalised TL intensity against heating rate.

second-order kinetics, respectively. Values for the constants c and b are found from Chen's formulae [6]. The activation energy was calculated for glow curves measured at different doses. For 0.5 Gy, we found E 1.05 7 0.05 eV, E 1.07 7 0.07 eV and E 1.01 7 0.11 eV. These values, although consistent, are somewhat greater than those found using the initial rise and variable heating methods. The results may be an over-estimation because analysis of the geometrical shape of a TL peak is susceptible to error due to subjectivity in determining the temperatures corresponding to the intensity at half-height. However, here too E was independent of dose. Further, the geometrical factor was found to be 0.42 implying that peak I is of rst-order kinetics, consistent with the TmTstop method. 3.2.4. Whole glow-peak method This method uses the peak area n(T) where 1 I T T nT T T0 5

0 -2 -4

0.8

Intensity (a.u)

0.6 0.4 0.2 0.0

-6 0 300 600 900

Time (s)

200

400

600

800

1000

Time (s)
Fig. 6. The time dependence of TL fading in peak I.

400
1.2 1.2

Intensity (a.u)

as a means to evaluate E. Here I(T) is the TL intensity, the heating rate, T temperature and T the temperature interval in measurement. In the case of general-order kinetics, one nds that  0   I T s E 6 ln ln b kT n where s (m3(b 1) s 1) is the effective frequency factor for general-order kinetics [6]. Although Eq. (6) is in principle linear with the slope usable to nd E, its application requires testing different values of b and choosing the most linear option. Fig. 5 shows various such plots from which the best option (R2 0.99) corresponds to b 1 with E 0.90 7 0.02 eV. This method necessarily should work properly for an isolated peak and is otherwise only a good estimate here. 3.3. Dosimetric features 3.3.1. Fading The effect of delay between irradiation and measurement on peak I was studied for TL measured from the same sample. The results, Fig. 6, show that the peak fades with delay t exponentially as I(t) I0 exp ( at) where I0 is the initial intensity and a is the decay constant. The solid line through the data points is the best t of I(t). The semi-log plot (Fig. 6, inset) further attests to the exponential nature of the fading. Peak I is unstable and decays to half-maximum within 120 s. This feature suggests that there is negligible competitive electron re-trapping at the associated traps as was noted before [2]. The causes of the fading were studied by

I2/I1

0.6

0.6

200

0.0 0 200 400 600 800

0.0 1000

Time (s) 100

0 0 20 40 60 80 100

Time (s)
Fig. 7. Phosphorescence from an unpreheated sample (solid circles) and background signal from one preheated to 100 1C (open circles). The inset shows the concurrent change of TL intensity in peaks II and III as peak I fades.

measuring spontaneously emitted luminescence (phosphorescence) rst, from an irradiated sample preheated to 100 1C to remove peak I and then, without any preheating after irradiation. The results, Fig. 7, show that only the unheated case showed phosphorescence (solid circles). Thus, the loss of electrons at ambient temperature due to phosphorescence is a cause of fading in peak I. The concomitant TL intensity in peaks II and III (plotted as normalised ratios in the inset to Fig. 7) increased as peak I faded implying that their traps successfully compete for charge from the

Please cite this article as: M.L. Chithambo, C. Seneza, Physica B (2013), http://dx.doi.org/10.1016/j.physb.2013.11.045i

I3/I1

300

M.L. Chithambo, C. Seneza / Physica B ()

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4. Mechanisms Previous studies on the main dosimetry peak suggest that the mechanism leading to TL emission in -Al2O3:C is the recombination of an electron with an F centre producing an excited F centre. The luminescence is emitted following relaxation of the electron from the 3P to the 1S ground state. In order to account for the dose response, we refer to Fig. 9, an energy band model for -Al2O3:C [1,2,7]. After ionisation, transition 1, electrons may be trapped (downward arrows) at electron traps ST, MT and IDT associated with peaks I, II and III respectively. Electrons from the conduction band can also be trapped at competitor deep electron(DT) and lled deep hole traps (HT) which only compete for charge. At low dose (Fig. 8), the rate of production of F centres by capture of holes at F centres and their conversion to F centres by electron-capture is approximately equal. Thus an increase in dose is reected as a corresponding proportional increase in TL intensity. Competition for electrons would only be important if the concentration of empty deep electron- or lled hole traps were appreciable which is irrelevant in this low-dose case.

TL intensity (a.u)

60000 50000 40000

Tm (oC)
50 46 42

30000 20000 10000 0.0 0.5 1.0 1.5

Dose (Gy)

2.0

2.5

3.0

Beta dose (Gy)

Fig. 8. Growth-curve for peak I and, in the inset, dose dependence of its peak temperature.

5. Conclusion Kinetics of the rst secondary TL peak in -Al2O3:C have been studied. The peak follows rst-order kinetics with an activation energy of the order of 0.7 eV and frequency factor  3 1010 s 1. The peak suffers from fading with a half-life of about 120 s but has a linear dose response in the range 0.52.6 Gy studied. The luminescence is attributed to the transition between the 3P and 1S state at an F-centre with no thermal-quenching.

Q2 Fig. 9. An energy-band model showing the shallow, main and intermediate energy

traps (ST, MT, IDT) responsible for peaks I, II and III. Levels DT and HT are for deep electron and hole traps. Transition 1 denotes ionisation, transition 2 luminescence, and transition 3 is non-radiative.

unstable peak I. Interestingly, the rate of change of the intensity for peaks II and III are identical. References 3.3.2. Dose-dependence The dependence of TL intensity of peak I on dose D was studied for doses from 0.5 to 2.6 Gy. Fig. 8, the resultant growth curve is linear as can also be deduced from the superlinearity index g(D) where g(D) {[Dy(D)/y(D)] 1} where y and y are the rst and second derivatives of the analytical function of the growth curve. The index g(D) is a measure of the change in slope of a growth curve [6]. In addition, the peak position Tm was found to be independent of dose (inset), a further conrmation that peak I follows rst-order kinetics.
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