accepted for journal of - physics | oklahoma state...

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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 1 Systematic Development of New Thermoluminescence and Optically Stimulated Luminescence Materials E. G. Yukihara 1,* , E. D. Milliken 1 , L. C. Oliveira 1 , V. R. Orante-Barrón 2 , L. G. Jacobsohn 3 , and M. W. Blair 4 1 Physics Department, Oklahoma State University, Stillwater, OK 74078, USA 2 Departamento de Investigación en Polímeros y Materiales, Universidad de Sonora, Hermosillo, Sonora 83000 México 3 Center for Optical Materials Science and Engineering Technologies (COMSET), and School of Materials Science and Engineering, Clemson University, Clemson, SC, USA 4 Materials Science and Technology Division, Los Alamos National Laboratory, Los Alamos, NM 87545, USA * Corresponding author Corresponding author: Eduardo G. Yukihara 145 Physical Sciences II Stillwater OK 74078, USA Phone: +1-405-744-6535 E-mail: [email protected] *Manuscript Click here to view linked References Accepted for publication in the Journal of Luminescence

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Page 1: Accepted for Journal of - Physics | Oklahoma State Universityphysics.okstate.edu/yukihara/Personal/OSL_News/Entries... · 2015-07-26 · Synthesis; Radioluminescence . Accepted for

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1

Systematic Development of New Thermoluminescence and Optically Stimulated

Luminescence Materials

E. G. Yukihara1,*

, E. D. Milliken1, L. C. Oliveira

1, V. R. Orante-Barrón

2, L. G. Jacobsohn

3, and

M. W. Blair4

1Physics Department, Oklahoma State University, Stillwater, OK 74078, USA

2Departamento de Investigación en Polímeros y Materiales, Universidad de Sonora, Hermosillo,

Sonora 83000 México

3Center for Optical Materials Science and Engineering Technologies (COMSET),

and School of Materials Science and Engineering, Clemson University, Clemson, SC, USA

4Materials Science and Technology Division, Los Alamos National Laboratory, Los Alamos, NM

87545, USA

* Corresponding author

Corresponding author:

Eduardo G. Yukihara

145 Physical Sciences II

Stillwater OK 74078, USA

Phone: +1-405-744-6535

E-mail: [email protected]

*ManuscriptClick here to view linked References

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Systematic Development of New Thermoluminescence and Optically Stimulated

Luminescence Materials

E. G. Yukihara1,*

, E. D. Milliken1, L. C. Oliveira

1, V. R. Orante-Barrón

2, L. G. Jacobsohn

3, and

M. W. Blair4

Abstract

This paper presents an overview of a systematic study to develop new thermoluminescence (TL)

and optically stimulated luminescence (OSL) materials using solution combustion synthesis

(SCS) for applications such as personal OSL dosimetry, 2D dose mapping, and temperature

sensing. A discussion on the material requirements for these applications is included. We present

X-ray diffraction (XRD) data on single phase materials obtained with SCS, as well as

radioluminescence (RL), TL and OSL data of lanthanide-doped materials. The results

demonstrate the possibility of producing TL and OSL materials with sensitivity similar to or

approaching those of commercial TL and OSL materials used in dosimetry (e.g., LiF:Mg,Ti and

Al2O3:C) using SCS. The results also show that the luminescence properties can be improved by

Li co-doping and annealing. The presence of an atypical TL background and anomalous fading

are discussed and deserve attention in future investigations. We hope that these preliminary

results on the use of SCS for production of TL and OSL materials are helpful to guide future

efforts towards the development of new luminescence materials for different applications.

Keywords: Thermoluminescence; Optically Stimulated Luminescence; Solution Combustion

Synthesis; Radioluminescence

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1. INTRODUCTION

Thermoluminescence (TL) and Optically Stimulated Luminescence (OSL), also called

Photo-Stimulated Luminescence (PSL), are techniques widely used in radiation dosimetry [1-4],

luminescence dating [1, 5, 6], and computed radiography [7]. They rely on the stimulated

recombination of electrons and holes created by ionizing radiation and trapped at defects in the

crystalline lattice of the host material, leading to luminescence whose intensity is related to the

energy deposited in the detector by ionizing radiation (i.e., absorbed dose). In TL the stimulation

is provided by controlled heating of the detector [3, 4]. In OSL, stimulation is provided by

controlled illumination [1, 2].

In spite of the widespread use of TL and OSL, a demand exists for new materials with

tailored properties for specific applications, including OSL neutron dosimetry, 2D dose mapping

and temperature sensing, as discussed below.

There are a limited number of OSL materials for personal dosimetry application,

particularly for neutron dosimetry. Only two materials are commercially used in OSL dosimetry,

Al2O3:C and BeO, and this limited availability has been pointed out as a weak point of the OSL

technique [2, 8]. Moreover, these materials do not have a high cross-section for neutron

interaction, which means that they cannot be used as neutron detectors [8]. This problem has

been partially solved by preparing detectors made of a mixture of OSL material and neutron

converters [9, 10] such as 6Li or

10B, which convert neutrons into charged particles [11].

Although this solution is commercially satisfactory [12], higher neutron sensitivities could be

achieved using new OSL materials containing 6Li or

10B as part of the crystalline structure,

which would require the development of new OSL materials based on compounds such as

Li2B4O7 or MgB4O7.

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Two-dimensional dose mapping in medical dosimetry, particularly in quality assurance

and dose verification in radiotherapy, is another area of potential application of OSL materials.

Although 2D dosimetry has been performed using TL [13-16], an all-optical technique such as

OSL would be a better choice for this type of application, as evidenced by the use of the OSL in

computed radiography [7]. The main problem with using photostimulable phosphors used in

computed radiography, such as BaXBr (X = F, Cl, Br) and CsBr, for dosimetry is their high

effective atomic number [17, 18] (Zeff~50) and signal fading (> 50% in 36 h) [7, 19]. One-

dimensional dose mapping using Al2O3:C OSL detectors has been used in computed tomography

[20-22], but the luminescence lifetime of the main luminescence centers in Al2O3:C (35 ms) is

too long for 2D dosimetry readout by spot-scanning laser. OSL systems based on BeO or SrS

have been described [23, 24], but these systems present problems such as limited spatial

resolution or high effective atomic number of the detector material (e.g. Zeff = 34.6 in the case of

SrS) [2].

More recently, renewed interest has been expressed in the use of TL for temperature

sensing, in particular as passive temperature sensors in biological agent defeat tests [25], but the

lack of suitable materials is also one of the main obstacles. The concept is based on the fact that

charges trapped at different energy levels within the conduction band are affected differently by

the temperature experienced by the particles, and this can be quantified by measuring the TL

curves of particles previously irradiated: depending on the time-temperature profile, the TL

peaks would be erased differently. For this application, materials with multiple TL peaks that are

light-insensitive are required. Unfortunately, a survey of existing TL materials reveals most of

them to be light sensitive [3]. LiF:Mg,Ti is an exception, but this material is known for having a

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complex defect structure, which causes the TL properties to be dependent on the entire

temperature history, both before and after irradiation [3].

Because of the complex nature of the TL and OSL processes, which require the presence

of both recombination and trapping centers introduced by intrinsic or extrinsic defects in the host

material, development of new materials has been serendipitous. Often, the nature of the

recombination centers is known because of its characteristic emission spectrum, but that of

trapping centers responsible for the TL/OSL signal is not.

Recently, two developments increased the chances of more precisely engineering the TL

and OSL properties of materials. The first development is the demonstration that chemical routes

such as solution combustion synthesis (SCS) [26-29] may offer a more efficient way to

synthesize TL/OSL materials [30-33] and investigate the role of dopants in the TL and OSL

process. The second is the understanding that the energy levels introduced by lanthanide (Ln)

dopants and their role in the TL (and possibly OSL) process can be predicted based on a few

parameters [34-37].

Based on these developments and motivated by the lack of suitable TL and OSL

materials for different applications, we initiated a systematic study to develop new TL and OSL

materials with properties tailored for the specific applications discussed above. Our approach

uses SCS as the main synthesis method, accompanied by characterization of the crystal structure

and luminescence properties of the materials produced.

The objective of this work is to present an overview of these efforts by showing the range

of materials synthesized by SCS, typical radioluminescence (RL) spectra to show the

incorporation of luminescence centers, as well as TL and OSL of some of the samples that

exhibited high sensitivity to ionizing radiation. We also discuss the effect of Li co-doping in the

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RL and TL properties and some unexpected results related to background of the TL

measurements and fading. This work does not intend to be an exhaustive study of any single

material; see for example references [38, 39]. Instead, we focus on general observations that we

hope can be useful for other investigators working on the development of new TL and OSL

materials.

2. MATERIAL REQUIREMENTS

Table 1 summarizes the most important requirements for the specific applications

discussed above. In all cases, it is expected that the trapped charge population is stable at room

temperature.

In personal OSL dosimetry, additional requirements include a light sensitive trapped

charge population, emission in the blue-UV range of the spectrum, tissue equivalency, and

predominance of single trapping centers. Emission in the blue-UV range of the spectrum allows

for detection of light at shorter wavelengths than stimulation (blue or green), in addition to being

a better match for the spectral response of photomultiplier tubes (PMTs). In OSL dosimetry,

emission in wavelengths shorter than the stimulation wavelength makes it easier to separate

between the stimulation light and the OSL emission using optical filters [2]. Tissue equivalency

means that the host material has an effective atomic number similar to water or tissue (Zeff ~ 7.5

– 7.6), so that the detector has a response with dependence on photon energy similar to the

material of interest [17]. Predominance of a single trapping center means that that the signal is

not associated with overlapping components with different dosimetric properties (e.g., thermal

stability). Moreover, luminescence centers characterized by radiation transitions with long

lifetime are useful because of the possibility of increasing the signal-to-noise ratio using a time-

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resolved luminescence technique called pulsed OSL (POSL), in which the optical stimulation

and the luminescence detection occur asynchronously [40].

For 2D OSL dosimetry, the materials need to have an OSL resultant from luminescence

centers characterized by short luminescence lifetime, so that it is feasible to read a two-

dimensional detector in a reasonable period. In comparison with computed radiography,

applications in 2D dosimetry are less stringent in terms of sensitivity and resolution. Most of the

applications would be in quality control for radiotherapy, so the doses involved are high and

there is no patient involved. Also, dose information with spatial resolution higher than 0.1 mm is

hardly justifiable. On the other hand, requirements in terms of precision and accuracy would be

higher, since one is interested in absolute or relative dose measurements as a function of

position. To achieve that, OSL materials should have a low effective atomic number and an OSL

signal stable at room temperature to reduce the need for correction factors.

For temperature sensing applications, effective atomic number is not a constraint, but the

materials should have multiple trapping centers that are light insensitive (and if possible

characterized by simple recombination kinetics).

3. MATERIALS AND METHODS

Table 2 shows the samples obtained by SCS in this work. Because of the range of

applications discussed above, we focused on wide band-gap materials with a range of effective

atomic numbers.

The materials were prepared using oxidizers and fuels combined to obtain an elemental

stoichiometric coefficient of unity (e = 1) [41]. Typical quantities and the corresponding volume

of purified water (Type I, Milli-Q, Millipore Corporation, Billerica, MA, USA) are indicated in

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Table 2. The dopants were introduced as nitrates, and their concentrations refer to the molar

percentage relative to the metal nitrate of the host with the potential to be substituted. The

borates were prepared with a 35% excess of boric acid to account for losses during combustion

and annealing. All reagents are ACS grade obtained from Alfa-Aesar (Ward Hill, MA, USA) or

Sigma-Aldrich (Sigma-Aldrich Co, LLC, St. Louis, MO, USA).

The aqueous mixture of reagents was dried at 200 ºC for ~1.5 h on a hot plate inside a

fume hood. The temperature was then increased to 500 ºC, causing the mixture to undergo

combustion after a few minutes. The resultant powder was crushed using an agate mortar and

pestle and placed in alumina crucibles for annealing. The samples were annealed in a

temperature controlled tube furnace (Marshall model 1123, ThermCraft Inc., Winston Salem,

NC, USA) or muffle furnace (Omegalux LMF-3550, Omega Engineering, Inc., Stamford, CT,

USA) at temperatures up to 1100ºC for up to 10 h, depending on the sample. The post-

combusted and annealed powder was then crushed again using an agate mortar and pestle.

Other materials were used for comparison of the TL, OSL and RL properties. For TL we

used commercial LiF:Mg,Ti (TLD-100, Thermo Fisher Scientific, Inc., Franklin, MA, USA), for

OSL we used commercial Al2O3:C (Landauer, Inc., Glenwood, IL, USA), and for RL we used

the scintillators Lu2SiO5:Ce (LSO, Single Crystal Growth Laboratory, Los Alamos National

Laboratory, Los Alamos, NM, USA) and Gd2SiO5:C (GSO, Hitachi Chemical Co., Ltd., ) (see

[42]).

The crystalline structures of the samples were characterized by X-ray diffraction (XRD)

using a Phillips Analytical X-ray diffractometer (model PW3020) with CuK radiation and

scanning the 2 in 0.02 degree step size and 0.5 step time.

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RL spectra were obtained by exciting the samples with a 40 kV X-ray tube (MagnumTM

,

Ag transmission target, Moxtek Inc.) delivering a dose rate of approximately 150 mGy/s at the

sample position, and detecting the luminescence using a CCD fiber spectrometer (model USB-

2000, Ocean Optics Inc., Dunedin, FL, USA) via an optical fiber (1 mm core diameter,

transmission between 200 – 1100 nm). Each RL spectrum was measured using ~10 mg of

powder deposited in stainless steel cups. The spectra were not corrected for the response of the

system, which peaks at 500 nm and reaches 10% efficiency at 250 nm and 730 nm [38].

TL and OSL measurements were carried out using a Risø TL/OSL reader (model

TL/OSL-DA-15, Risø National Laboratory, Røskilde, Denmark). The TL or OSL signals were

detected using a PMT (model 9235QB, Electron Tubes, Inc.). For the TL measurements we used

Schott BG-39 filters (6 mm thickness, transmission between ~340-610 nm, Schott AG, Mainz,

Germany) in front of the PMT. The samples were heated at 5 ºC/s in high purity nitrogen gas

atmosphere. For OSL measurements, the samples were stimulated with blue LEDs (centered at

~470 nm, irradiance of ~30 mW/cm2) using Hoya U-340 filters (7.5 mm thickness, transmission

between ~290-370 nm, Hoya Corporation USA, Santa Clara, CA, USA) in front of the PMT. For

TL and OSL measurements, the samples were irradiated with ~0.5 Gy using a 90

Sr/90

Y beta

source. More details on the Risø readers can be found in Bøtter-Jensen et al. [43] and references

therein.

All RL, TL and OSL data were obtained using 10 mg of powder in stainless steel cups.

4. RESULTS AND DISCUSSION

Figure 1 shows the XRD pattern for various undoped samples produced by SCS,

demonstrating that the materials are single phase. Data on MgO have been presented elsewhere

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[38]. These results assure we obtained the desired host lattice. In the case of doped MgO:Ce,Li,

XRD reveals an additional CeO2 phase, indicating that not all dopants are incorporated into the

MgO lattice [38]. However, we have not carried out extensive XRD investigations of doped

samples yet. The XRD patterns of undoped ZrO and LaMgB5O10 presented a mixture of phases

and are not shown here.

RL measurements demonstrate the incorporation of the dopants as luminescence centers

in the materials. Figure 2 shows the RL emission spectra for three lanthanide-doped compounds

which displayed the strongest RL intensities. The main characteristic emission lines from the

trivalent lanthanides can be observed, although the intensities varied with the host material. The

emission band from Ce3+

is also observed in CaO and MgO. The RL intensity for various

lanthanide materials are compared in Table 3.

TL curves with a variety of shapes and peaks located at temperatures in the dosimetric

range were observed from these samples, some of them with intensity comparable to or higher

than commercial TL materials. Figure 3 compares the curves for materials which exhibit strong

TL with that from LiF:Mg,Ti. It is worth mentioning that for shape of the TL curve of MgO:Ln,

Li and MgB4O7:Ln, Li changes depending on the type of lanthanide used for doping. In the case

of CaO, the most intense TL (>106 counts per 0.2s) was observed for undoped samples, with

doping generally decreasing the TL intensity (results not shown here). At this point concentration

quenching curves for RL and TL were obtained for MgO:Ce,Li only [38].

OSL investigations have been focused on materials with low effective atomic number,

from which MgO showed the best results. Examples of OSL curves for MgO:Ln1%,Li3% and

various dopants are compared in Figure 4 with the OSL from commercial Al2O3:C. MgO

samples which presented the most intense OSL signals are Gd-, Nd- and Tm-doped samples, in

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which the emission from the respective trivalent lanthanides occurs in the transmission range of

the optical filters (~290-370 nm) used in the OSL measurements (see Figure 2a).

For some samples, Li co-doping substantially improved the RL or TL intensities, or both.

Figure 5 shows the effect of Li co-doping on the RL and TL of MgO doped with Dy (Figure 5a)

and Eu (Figure 5b). Note that Li co-doping not only increases the intensity of the RL and TL, but

also changes the structure of the TL curve in comparison to the undoped samples or samples

doped only with lanthanide. Improved photoluminescence properties due to the effect of Li have

been observed before for MgO [44, 45]. We speculate that Li may be acting as a charge

compensator: Li+ substituting for Mg

2+ creates a defect with net negative charge (LiMg)

that may

compensate for the incorporation of the trivalent lanthanide in the Mg site, which creates a defect

with positive effective charge (LnMg)+. Therefore, in the presence of Li, the incorporation of

trivalent lanthanide into the crystal lattice may be more effective. Moreover, the ionic radius of

Li+ (0.90Å) and Mg

2+ (0.86Å) are similar, therefore favoring the substitution. However, changes

in TL curves with Li co-doping show that Li also introduces or favors the formation of other

defects acting as trapping centers. It should be pointed out that Li co-doping did not result in a

consistent improvement in the luminescence properties of CaO.

Figure 6 shows the effect of Li co-doping on Ce-doped MgB4O7. In this material, Li co-

doping increased the TL intensity, but did not affect the RL intensity from the trivalent

lanthanides.

Annealing was also observed to improve the RL and TL of some samples, particularly in

the case of Y3Al5O12 and MgO. This is exemplified in Figure 7 for Y3Al5O12:Ce,Yb, showing

that the TL peak at 200ºC increases as the annealing temperature is increased from 900ºC to

1100ºC, whereas high temperature peaks responsible for TL above 300ºC are reduced. Other

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investigators also emphasized the importance of annealing in improving the luminescence

properties of materials produced by SCS [46, 47]. In the case of MgO:Ce,Li, annealing to

increasing temperatures improve the overall RL and TL intensities and change the relative

intensities of the TL peaks [38].

In spite of the promising results obtained using SCS for the development of new TL and

OSL materials, a few observations deserve attention. In MgAl2O4 we observed an atypical TL

background, as exemplified in Figure 8. The TL curves in Figure 8 were obtained using un-

irradiated samples, after the samples have already been annealed to 900ºC for 2h in a furnace and

heated once to 450 ºC at 5 ºC/s in the TL reader. The TL curves should exhibit a low background

(~300-500 cps) characteristic of PMT dark counts, increasing above ~400ºC due to blackbody

radiation, as illustrated Figure 8 for a MgB4O7:Ce,Li sample. It is not clear whether this atypical

emission in MgAl2O4 is due to incomplete reaction during the combustion process or annealing

that is not optimized. In any case, it is worth determining whether or not this effect is related to

the material synthesis technique.

Another important observation is the presence of anomalous fading in some samples.

This is exemplified in Figure 9 for Y3Al5O12:Ce,Yb. This sample presents a TL peak at ~200 ºC

which should be relatively stable at room temperature, but which exhibits a substantial decrease

in intensity even after a short interval following irradiation (2h). Other studies have shown that,

in YAG prepared by co-precipitation, the rate of fading increases with the concentration of Ce

and Yb, leading to the suggestion that the anomalous fading is caused by tunneling between the

Yb2+

(trapping center) and the Ce4+

(recombination center) [37]. It would also be important to

understand whether this anomalous fading is restricted to Y3Al5O12 or related to the material

synthesis technique.

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5. CONCLUSIONS

This study demonstrates the possibility of producing TL and OSL materials with

sensitivity similar to or approaching those of commercial TL and OSL materials used in

dosimetry (e.g., LiF:Mg,Ti and Al2O3:C) using SCS. Of equal importance, the SCS method

offers an efficient way for testing the influence of different dopants, allowing the introduction of

luminescence centers with emission in the wavelength of interest for different applications. The

luminescence properties can be improved by Li co-doping and annealing at an appropriate

temperature. Atypical or anomalous effects (background and fading) have been observed in some

samples and deserve more attention in future investigations. This study represents a new

paradigm in TL/OSL research whereby new materials can be discovered and designed by

systematic investigation rather than by serendipity.

More in-depth studies focused on specific materials are required to further develop useful

TL and OSL materials. There are a large number of synthesis parameters to be investigated,

including dopant concentrations, fuel-oxidizer ratios, annealing temperatures, co-dopants, and so

on. Nevertheless, we hope these preliminary results on the use of SCS for production of TL and

OSL materials are helpful to guide future efforts towards the development of new materials

needed for the applications discussed here.

ACKNOWLEDGEMENTS

The authors thank Jim Puckette (Boone Pickens School of Geology, Oklahoma State

University, Stillwater, OK) for the use of the Phillips Analytical X-ray diffractometer, and

Gregoire Denis for discussions and suggestions. This work was supported by the Oklahoma

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Center for the Advancement of Science and Technology (OCAST) through OHRS award project

number HR09-104, and by the US Defense Threat Reduction Agency (DTRA) through contract

HDTRA1-10-1-0007.

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15

REFERENCES

[1] L. Bøtter-Jensen, S. W. S. McKeever, A. G. Wintle, Optically Stimulated Luminescence

Dosimetry. Amsterdam: Elsevier (2003).

[2] E. G. Yukihara, S. W. S. McKeever, Optically stimulated luminescence: fundamentals

and applications: John Wiley & Sons (2011).

[3] S. W. S. McKeever, M. Moscovitch, P. D. Townsend, Thermoluminescence dosimetry

materials: properties and uses. Ashford: Nuclear Technology Publishing (1995).

[4] R. Chen, S. W. S. McKeever, Theory of thermoluminescence and related phenomena.

Singapore: World Scientific Publishing Co. (1997).

[5] M. J. Aitken, Thermoluminescence Dating. Orlando: Academic Press (1985).

[6] M. J. Aitken, An Introduction to Optical Dating. Oxford: Oxford University Press (1998).

[7] P. Leblans, D. Vandenbroucke, P. Willems, Materials 4 (2011) 1034-1086.

[8] S. W. S. McKeever, M. Moscovitch, Radiat. Prot. Dosim. 104 (2003) 263-270.

[9] J. C. R. Mittani, A. A. R. d. Silva, F. Vanhavere, M. S. Akselrod, E. G. Yukihara, Nucl.

Instrum Methods. Phys. Res. B 260 (2007) 663-671.

[10] E. G. Yukihara, J. C. R. Mittani, F. Vanhavere, M. S. Akselrod, Radiat. Meas. 43 (2008)

309-314.

[11] G. F. Knoll, Radiation Detection and Measurements: John Wiley & Sons, Inc. (2000).

[12] C. Passmore, M. Kirr, Radiat. Prot. Dosim. 144 (2011) 155-160.

[13] B. Marczewska, P. Bilski, P. Olko, M. P. R. Waligórski, Radiat. Meas. 38 (2004) 833-

837.

[14] L. Czopyk, M. Klosowski, P. Olko, J. Swakon, M. P. R. Waligorski, T. Kajdrowicz, G.

Cuttone, G. A. P. Cirrone, F. Di Rosa, Radiat. Prot. Dosim. 126 (2007) 185-189.

Accep

ted fo

r pub

licati

on in

the

Journ

al of

Lumine

scen

ce

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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

16

[15] B. Marczewska, P. Bilski, L. Czopyk, P. Olko, M. P. R. Waligórski, S. Zapotoczny,

Radiat. Prot. Dosim. 120 (2006) 129-132.

[16] P. Olko, B. Marczewska, L. Czopyk, M. A. Czermak, M. Kłosowski, M. P. R.

Waligórski, Radiat. Prot. Dosim. 118 (2006) 213-218.

[17] F. H. Attix, Introduction to radiological physics and radiation dosimetry. Weinheim:

Wiley-VCH (2004).

[18] A. J. J. Bos, Nucl. Instrum Methods. Phys. Res. B 184 (2001) 3-28.

[19] E. Ariga, S. Ito, S. Deji, T. Saze, K. Nishizawa, Med. Phys. 34 (2007) 166-174.

[20] E. G. Yukihara, C. Ruan, P. B. R. Gasparian, W. J. Clouse, C. Kalavagunta, S. Ahmad,

Phys. Med. Biol. 54 (2009) 6337-6352.

[21] C. Ruan, E. G. Yukihara, W. J. Clouse, P. B. R. Gasparian, S. Ahmad, Med. Phys. 37

(2010) 3560-3568.

[22] J. A. Bauhs, T. J. Vrieze, A. N. Primak, M. R. Bruesewitz, C. H. McCollough,

RadioGraphics 28 (2008) 245-253.

[23] A. Jahn, M. Sommer, J. Henniger, Radiat. Meas. 45 (2010) 674-676.

[24] K. Idri, L. Santoro, E. Charpiot, J. Herault, A. Costa, N. Ailleres, R. Delard, J. R. Vaille,

J. Fesquet, L. Dusseau, IEEE Trans. Nucl. Sci 51 (2004) 3638-3641.

[25] M. L. Mah, M. E. Manfred, S. S. Kim, M. Prokić, E. G. Yukihara, J. J. Talghader, IEEE

Sensors 10 (2010) 311-315.

[26] J. J. Kingsley, N. Manickam, K. C. Patil, Bull. Mater. Sci. 13 (1990) 179-189.

[27] J. J. Kingsley, K. C. Patil, Mater. Lett. 6 (1988) 427-432.

[28] L. E. Shea, J. McKittrick, O. A. Lopez, J. Am. Ceram. Soc. 79 (1996) 3257-3265.

Accep

ted fo

r pub

licati

on in

the

Journ

al of

Lumine

scen

ce

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17

[29] L. A. Chick, L. R. Pederson, G. D. Maupin, J. L. Bates, L. E. Thomas, G. J. Exarhos,

Mater. Lett. 10 (1990) 6-12.

[30] V. S. M. Barros, W. M. Azevedo, H. J. Khoury, M. E. A. Andrade, P. LInhares Filho,

Radiat. Meas. 45 (2009) 435-437.

[31] V. S. M. Barros, W. M. Azevedo, H. J. Khoury, P. L. Filho, Radiat. Meas. 43 (2008) 345-

348.

[32] M. W. Blair, L. G. Jacobsohn, B. L. Bennett, S. C. Tornga, E. G. Yukihara, E. A.

McKigney, R. E. Muenchausen, Phys. Status Solidi A 206 (2009) 904-909.

[33] M. W. Blair, L. G. Jacobsohn, S. C. Tornga, O. Ugurlu, B. L. Bennett, E. G. Yukihara, R.

E. Muenchausen, J. Lumin. 130 (2010) 825-831.

[34] P. Dorenbos, J. Alloys Compd. 488 (2009) 568-573.

[35] P. Dorenbos, A. J. J. Bos, Radiat. Meas. 43 (2008) 139-145.

[36] A. J. J. Bos, P. Dorenbos, A. Bessière, B. Viana, Radiat. Meas. 43 (2008) 222-226.

[37] F. You, A. J. J. Bos, Q. Shi, S. Huang, P. Dorenbos, J. Phys.: Condens. Matter 23 (2011)

215502 (6pp).

[38] V. R. Orante-Barrón, L. C. Oliveira, J. B. Kelly, E. D. Milliken, G. Denis, L. G.

Jacobsohn, J. Puckette, E. G. Yukihara, J. Lumin. 131 (2011) 1058-1065.

[39] L. C. Oliveira, G. Denis, E. D. Milliken, J. Puckette, E. G. Yukihara, J. Lumin. (in

preparation))

[40] M. S. Akselrod, S. W. S. McKeever, Radiat. Prot. Dosim. 81 (1999) 167-176.

[41] S. R. Jain, K. C. Adiga, V. R. P. Verneker, Combust. Flame 40 (1981) 71-79.

[42] E. G. Yukihara, L. G. Jacobsohn, M. W. Blair, B. L. Bennett, S. C. Tornga, R. E.

Muenchausen, J. Lumin. 130 (2010) 2309-2316.

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[43] L. Bøtter-Jensen, K. J. Thomsen, M. Jain, Radiat. Meas. 45 (2010) 253-257.

[44] F. Gu, C. Li, H. Cao, W. Shao, Y. Hu, J. Chen, A. Chen, J. Alloys Compd. 453 (2008)

361-365.

[45] F. Gu, C. Z. Li, H. B. Jiang, J. Cryst. Growth 289 (2006) 400-404.

[46] L. G. Jacobsohn, S. C. Tornga, B. L. Bennett, R. E. Muenchausen, O. Ugurlu, T. K.

Tseng, J. Choi, P. H. Holloway, Radiat. Meas. 45 (2010) 611-614.

[47] E. Zych, Opt. Mater. 16 (2001) 445-452.

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19

TABLE CAPTIONS

Table 1. Examples of desirable properties for new TL/OSL materials for different applications.

Table 2. Materials produced by SCS, bandgap energy, effective atomic number, typical reagent

quantities and solution volume, and dopants investigated. The effective atomic number was

calculated as in Bos [18].

Table 3. RL intensities for various lanthanide-doped materials produced by SCS; the values are

in counts per second and correspond to the maximum intensity of the indicated emission band.

All lanthanide concentrations are 0.1%, except when indicated otherwise. The data were

obtained using powder (10 mg) and identical measurement conditions. The data are only for

qualitative comparison, since the x-ray energy deposited in different materials varies with the

mass energy absorption coefficients of each material [17] and the spectra were not corrected for

the detection response of the system [38]. The position of the lines varies depending on the

material.

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FIGURE CAPTIONS

Figure 1. XRD patterns of samples produced by SCS, accompanied by information on annealing

temperature and duration, powder diffraction card number, crystal system and space group: (a)

Y2O3 (1100 C for 2h, 01-083-0927, cubic, Ia-3), (b) CaO (900 C for 2h, 01-077-2376, cubic,

Fm-3m), (c) MgAl2O4 (900 C for 2h, 01-071-6329, cubic, Fd-3m), (d) MgB4O7 (900 C for 2h,

00-017-0927, orthorhombic, Pbca), (e) Al2O3 (900 C for 2h, 00-042-1468, rhombohedral, R-

3c), (f) CaAl12O19 (1200 C for 4h, 00-038-0470, hexagonal, P63/mmc), (g) LiB4O7 (860 C for

40min, 01-084-2191, tetragonal, 141cd), (h) Y3Al5O12 (900 C for 2h, 01-071-1853, cubic, Ia-

3d), (i) LiAlO2 (1200 C for 4h, 00-038-1464, tetragonal, P4212). Miller indices are presented

only for the most intense peaks. The asterisk (*) indicates an artifact introduced by the sample

holder.

Figure 2. RL spectra from (a) MgO:Li3%, (b) CaO and (c) Y2O3 undoped or doped with different

lanthanides. The spectra are offset vertically for better visualization. For comparison, the

maximum intensity from LSO:Ce and YSO:Ce scintillators in powder measured in the same

conditions are ~140 cps and 180 cps, respectively. The spectra were not corrected for the

detection response of the system [38].

Figure 3. TL curves for different lanthanide(Ln)-doped compounds synthesized by SCS: (a)

MgO; (b) Li2B4O7 and (c) MgB4O7. Panel (d) shows the TL from commercial LiF:Mg,Ti (TLD-

100) for comparison.

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Figure 4. OSL curves of MgO samples synthesized by SCS compared to the OSL curve of

commercial Al2O3:C measured in the same conditions. It should be pointed out the experimental

conditions used here are not optimum for Al2O3:C. Based on the emission spectrum of Al2O3:C

and transmittance spectra of optical filters, we estimate that OSL measurements of Al2O3:C using

Hoya U-340 filters (7.5 mm thickness) are 70% lower than identical measurements using filters

centered at the Al2O3:C emission band (Kopp 5113, 8 mm thickness).

Figure 5. Effect of Li co-doping on the RL and TL properties of (a) MgO:Dy and (b) MgO:Eu.

The data were obtained using 10 mg of powder in identical conditions. The samples were

annealed at 900ºC for 2h.

Figure 6. Effect of Li co-doping on the TL of MgB4O7. The samples were annealed at 900 °C for

2h.

Figure 7. Effect of annealing on the TL of yttrium aluminum garnet (YAG), Y3Al5O12, produced

by SCS.

Figure 8. Atypical background emission from un-irradiated MgAlO4 samples previously

annealed at 900ºC for 2h and then heated to 450ºC at 5ºC/s, compared with a normal background

from MgB4O7:Ce0.1%, Li1%, both prepared by SCS.

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Figure 9. Example of anomalous fading for yttrium aluminum garnet (YAG) Y3Al5O12 irradiated

with 0.5 Gy of beta radiation, showing the TL curve immediately after irradiation, with or

without a 2 h period in the dark before TL readout. The samples were annealed at 1100ºC for 2h.

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Table 1.

Application Desirable properties

All Trapped charge population stable at room temperature

Personal OSL

dosimetry Trapped charge population sensitive to light

Emission in the blue-UV region

Tissue equivalency (Zeff ~ 7.5)

Single trapping center associated with the OSL signal

Long luminescence lifetime (>100 s) in case of POSL applications

Intrinsic neutron sensitivity, i.e. having Li or B in its composition (for neutron dosimetry)

2D OSL

dosimetry Trapped charge population sensitive to light

Short luminescence lifetime (<100 s)

Emission in the blue-UV region

Tissue equivalency (Zeff ~ 7.5)

Single trapping center associated with OSL signal

Small grain sizes (~m or less)

Temperature

sensing (TL) Multiple TL peaks over a wide range of temperatures

Simple TL kinetics (first order)

Trapped charge population insensitive to light

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Table 2

Host Eg (eV)

Zeff Reagents Dopants investigated (co-doping indicated in parenthesis)

ZrO2 ~5 36.3 11.9 g Zr(NO3)26H2O; 3.5 g

urea, 50ml

Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb

Y2O3 5.6 36.1 7.6 g Y(NO3)36H2O, 3 g urea,

50ml

Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, (Ce,Sm), (Ce,Dy), (Ce,Tm), (Eu,Sm),

(Eu,Dy), (Eu,Tm), (Tb,Sm), (Tb,Dy), (Tb,Tm), (Tb,Eu)

MgAl2O4 5.8 11.2 7.8 g Mg(NO3)26H2O, 23.2 g

Al(NO3)39H2O

12.2 g urea, 50ml

Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb

Y3Al5O12 7.5 30.6 8.1 g Y(NO3)36H2O, 13.5 g

Al(NO3)39H2O

8.6 g urea, 50ml

Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, (Ce,Sm), (Ce,Eu), (Ce,Yb), (Tb:Sm), (Tb,Eu) , (Tb,Yb), (Ce,Eu,Yb), (Tb,Eu,Yb)

LaMgB5O10 41.5 4.3 g La(NO3)36H2O, 2.7 g

Mg(NO3)26H2O, 3.2g H3BO3;

2.1 g glycine, 100ml

Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Li

CaO 7.1 18.3 16.7 g Ca(NO3)24H2O, 7.1 g

urea, 50ml

Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Li

MgB4O7 8.5 5.2 g Mg(NO3)26H2O, 6.7g H3BO3, 2.0 g urea, 100ml

Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Tm, Yb , (Ce, Pr), (Ce, Nd), (Ce, Dy), (Ce, Tm), (Tb, Pr), (Tb, Nd), (Tb, Dy), (Tb, Tm), Li, Na, K

Al2O3 9.5 11.3 15.5 g Al(NO3)39H2O, 6.1 g

urea, 50ml

Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Li ,Zn, Zr, Si, Ag, Fe, Mn, Ni, Cu,

(Zr,Si), (Zr,P), (Zr, Tb), Li

CaAl12O19 12.4 0.74 g Ca(NO3)24H2O, 14.1 g

Al(NO3)29H2O, 6.0 g urea, 50ml

Ce, Eu, Li

Li2B4O7 7.5 7.3 7.0 g LiNO3, 12.6g H3BO3,

8.0g NH4NO3, 5.71 glycine, 50ml

Dy, Ce, Mn, Cu, Ag, (Cu, Ag), Ni, Cr

CaAl2O4 7.4 14.8 3.1 g Ca(NO3)24H2O, 10.0 g

Al(NO3)39H2O, 5.4 g urea, 50ml

Ce, Eu, Li

MgO 7.8 10.8 13.1 g Mg(NO3)26H2O, 5.1 g

urea, 50ml

Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Li, Al, (Ce,Gd), (Nd,Gd), (Ce,Ca), (Ce,

La), (Ce, Dy), (Ce, Eu), (Ce, Er), (Ce, Tm), (Ce, Yb), ( Ce, Tb), La , Ca, Na, Ba, K, Al ,

Fe, Cr, Mn, P, Si, Co, Zn, Zr, In, (In,Gd), (In, Nd), Ti , Cu, Ag, (Cu, Ag), Ni, (Ce:Gd),

(Nd:Gd), (Nd, Ho), (Nd, Tm), (Ce,Ca), (Fe, Mn), (Nd, Ho), (Nd, Dy), (Nd, Gd),

(Nd,Tm), (Nd, Ho), (Nd, Er)

LiAlO2 10.7 7.5 g Al(NO3)39H2O, 5.2 g

urea, 1.4 g LiNO3, 50ml

Ce

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Table 3

Ce Pr

~620nm Nd

~396nm Sm

~600nm Eu

~600nm Gd

313nm Tb

544nm Dy

~570nm Ho

548nm Er

~407nm

Tm

454nm

Al2O3 30* <1 13 13 30 10 100 25 <1 6 13

CaO 80 60 <1 210 100 90 250 390 25 <20 80

MgB4O7:Li1% <1 <1 <1 4 1 2 17 35 <1 <1 14

LaMgB5O10 <1 1 <1 25 <1 1 14 35 <1 <1 22

Y2O3 <1 50 <1 70 140 50 175 250 <20 <20 <20

Y3Al5O12 70 25 <20 60 60 30 35 <20 <1 <1 <1

MgO:Li3%

(Ln1%)

80 1 20 18 60 6 6 16 <1 <1 6

*The emission is probably due to F centers, since undoped samples also show similar emission band.

“<1” indicates undetected or weak emission.

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20 40 60

(622

)

(611

)

(440

)

(134

)(3

32)

(411

)(400

)(2

22)

(211

)

*

Inte

nsity

(ar

b. u

nits

) (a) Y2O

3

20 30 40 50 60

*

(311

)

(220

)

(200

)

(111

)

(b) CaO

20 30 40 50 60

*

(511

)(4

22)

(400

)

(311

)

(220

)

(111

)

(c) MgAl2O

4

20 30 40 50 60

(810

)(7

02)(5

13)

(232

)(5

12)

(421

)(402

)(321

)(3

02)(2

20)

(311

)(0

20)

(211

)(2

10)

(d) MgB4O

7

Inte

nsity

(ar

b. u

nits

)

20 40 60

(018

)(1

16)

(024

)

(113

)

(110

)

(104

)

*(0

12)

(e) Al2O

3

20 30 40 50 60

*

(217

)(2

01)

(206

)(205

)(2

03)

(114

)

(107

)(1

10)

(006

)

(102

)

(d) CaAl12

O19

20 30 40 50 60

(512

)

(224

)(2

04)

(004

)(3

12)

(202

)(2

11)

(112

)

(g) Li2B

4O

7

(200

)

Inte

nsity

(ar

b. u

nits

)

2 (deg.)

20 30 40 50 60

* (800

)(642

)(6

40)

(444

)

(611

)

(521

)

(422

)(4

20)

(400

)(3

21)

(211

)

(h) Y3Al

5O

12

2 (deg.)

20 30 40 50 60

(302

)(2

22)

(310

)

(113

)(2

20)

(211

)(2

01)

(200

)

(102

)(1

11)

(110

)

(101

)

(i) LiAlO2

2 (deg.)

Figure 1

Accep

ted fo

r pub

licati

on in

the

Journ

al of

Lumine

scen

ce

Page 27: Accepted for Journal of - Physics | Oklahoma State Universityphysics.okstate.edu/yukihara/Personal/OSL_News/Entries... · 2015-07-26 · Synthesis; Radioluminescence . Accepted for

200 400 600 8000

20

40

60

80

100

120

140

160

180

200

220

240

260 (a) MgO:Li3%

Yb

Tm

Er

Ho

Dy

Tb

Gd

Eu

Sm

Nd

Pr

Ce

undoped

200 400 600 8000

100

200

300

400

500

600

700

800

900

1000

1100

1200

1300 (b) Y2O

3(b) CaO

Wavelength (nm)200 400 600 8000

50

100

150

200

250

300

350

400

450

500

550

600

650

RL

inte

nsity

(cp

s)

Figure 2

Accep

ted fo

r pub

licati

on in

the

Journ

al of

Lumine

scen

ce

Page 28: Accepted for Journal of - Physics | Oklahoma State Universityphysics.okstate.edu/yukihara/Personal/OSL_News/Entries... · 2015-07-26 · Synthesis; Radioluminescence . Accepted for

100 200 300 4000.0

0.2

0.4

0.6

0.8

1.0

Ce

Sm (1100oC/6h)

Nd (0.5%)

(a) MgO:Ln1%

,Li3%

100 200 300 4000.0

0.1

0.2

0.3

0.4(b) Li

2B

4O

7:Cu

0.3%,Ag

0.3%

100 200 300 4000

1

2

3

4

5

TmDy

Tb

Ce

(c) MgB4O

7:Ln

0.1%,Li

1%

TL

inte

nsity

(10

6 cou

nts

per

0.2s

)

Temperature (oC)

100 200 300 4000.0

0.2

0.4

0.6

0.8

1.0 (d) LiF:Mg,Ti (TLD-100)

Figure 3

Accep

ted fo

r pub

licati

on in

the

Journ

al of

Lumine

scen

ce

Page 29: Accepted for Journal of - Physics | Oklahoma State Universityphysics.okstate.edu/yukihara/Personal/OSL_News/Entries... · 2015-07-26 · Synthesis; Radioluminescence . Accepted for

0 10 20 30 40 50 600.0

0.5

1.0

1.5

2.0

2.5

3.0

MgO:Sm1%

,Li3%

MgO:Tm1%

,Li3%

MgO:Nd1%

,Li3%

MgO:Gd1%

,Li3%

OS

L in

tens

ity (

106 c

oun

ts p

er

0.2

s)

Time(s)

Al2O

3:C

Figure 4

Accep

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r pub

licati

on in

the

Journ

al of

Lumine

scen

ce

Page 30: Accepted for Journal of - Physics | Oklahoma State Universityphysics.okstate.edu/yukihara/Personal/OSL_News/Entries... · 2015-07-26 · Synthesis; Radioluminescence . Accepted for

400 500 600 700 8000

2

4

6

8

10

12

14

16

Dy1%

Dy1%

,Li3%

(a) MgO:Dy1%

RL

inte

nsity

(cp

s)

Wavelength (nm)100 200 300 400

0.0

0.2

0.4

0.6

0.8

undopedDy

1%

Dy1%

,Li3%

TL

inte

nsity

(10

5 cou

nts

per

0.2s

)

Temperature (ºC)

400 500 600 700 8000

10

20

30

40

50

60

Eu1%

Eu1%

,Li3%

(b) MgO:Eu1%

RL

inte

nsity

(cp

s)

Wavelength (nm)100 200 300 400

0.0

0.5

1.0

1.5

undopedEu

1%

Eu1%

,Li3%

TL

inte

nsity

(10

5 cou

nts

per

0.2s

)

Temperature (ºC)

Figure 5

Accep

ted fo

r pub

licati

on in

the

Journ

al of

Lumine

scen

ce

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100 200 300 4000

2

4

6

8 Ce0.1%

Li1%

Ce0.1%

Li0.1%

Ce0.1%

undopedTL

inte

nsity

(10

5 cou

nts/

0.2s

)

Temperature (oC)

MgB4O

7

Figure 6

Accep

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r pub

licati

on in

the

Journ

al of

Lumine

scen

ce

Page 32: Accepted for Journal of - Physics | Oklahoma State Universityphysics.okstate.edu/yukihara/Personal/OSL_News/Entries... · 2015-07-26 · Synthesis; Radioluminescence . Accepted for

100 200 300 4000

1

2

3

4

5

1100oC/2h

1100oC/10h

900oC/2h

TL

inte

nsity

(10

5 cou

nts/

0.2s

)

Temperature (oC)

YAG:Ce0.1%

,Yb0.1%

Figure 7

Accep

ted fo

r pub

licati

on in

the

Journ

al of

Lumine

scen

ce

Page 33: Accepted for Journal of - Physics | Oklahoma State Universityphysics.okstate.edu/yukihara/Personal/OSL_News/Entries... · 2015-07-26 · Synthesis; Radioluminescence . Accepted for

100 200 300 4000

1

2

3

4

MgB4O

7:Ce

0.1%,Li

1%

Ce

PrNd

SmEu

Gd

Tb

MgAl2O

4:Ln

0.1%

TL

inte

nsity

(10

4 coun

ts p

er 0

.2s)

Temperature (oC)

Figure 8

Accep

ted fo

r pub

licati

on in

the

Journ

al of

Lumine

scen

ce

Page 34: Accepted for Journal of - Physics | Oklahoma State Universityphysics.okstate.edu/yukihara/Personal/OSL_News/Entries... · 2015-07-26 · Synthesis; Radioluminescence . Accepted for

100 200 300 4000

1

2

3

4

+ 2h

YAG:Ce0.1%

,Yb0.1%

TL

(105 c

ount

s pe

r 0.

2s)

Temperature (oC)

Figure 9

Accep

ted fo

r pub

licati

on in

the

Journ

al of

Lumine

scen

ce