New Photostimulable Phosphor M aterials for Digital Radiography

',

H. Nanto 1,2,3, M.Miyazaki A.Imai', H.Komori', Y.Douguchi 4,

E. Kusano lP3and A . K i n a b ~ a ' . ~
'Advanced Materials Science R&D Center, Kanazawa Institute of technology,
3-1 Yatsukaho, Mattou, Ishikawa 924 Japan
'Electron Device System Research Laboratory and 3Department of Materials Science and Engineering,
Kanazawa Institute of Technology,
7-1 Oogigaoka, Nonoichi-machi, Ishikawa-gun, Ishikawa 921 Japan
41ndustrialResearch Institute of Ishikawa, 1 Tomizu-machi, Kanazawa, Ishikawa 920-20 Japan

Abstract
Intense photostimulated luminescence (PSL) is observed,
for the first time, in X-ray-irradiated KBr:Eu and KCl,Br,.
,:Eu phosphor ceramics. The peak in the stimulation
spectrum for the PSL red-shifted with increasing the Br
content of KC1,Brl.,:Eu phosphor ceramics. The intensity of
the PSL with a peak of about 420 nm increases linearly with
increasing X-ray irradiation dose over a wide range. The
KBr:Eu phosphor exhibites excellent fading characteristics at
room temperature (RT) in the dark. The mechanism of
fading of the PSL is also discussed.

I. INTRODUCTION
Photostimulated luminescence (PSL) phenomenon is based
on the presence of electron andor hole traps and
luminescence centers in storage phosphor materials. During
exposure to X-rays, the traps are occupied with charged
carriers such as electrons and holes that are created by x-ray
irradiation. Detrapping of these carriers requires energy.
The energy is provided by stimulating the phosphor material
with visible or infrared light. During a detrapping transition,
free carriers created by the absorption of photons from the
stimulating radiation field, recombine with the luminescence
centers, whereby visible photons (PSL) are emitted. Since
the PSL intensity is in the most cases proportional to dose of
X-rays, the phosphor materials which exhibit the PSL
phenomenon offer an alternative to conventional X-ray
radiography, which consists of a photographic film and an
intensifying screen. These phosphor materials adapt to
digital radiography systems which are based on the
conversion of the X-ray image pattern into digital signals
utilizing laser beam scanning of a photostimulable phosphor
imaging plate (IP).
Recently,

new

system

of

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(c) 2000 IEEE

computerized

radiography utilizing this phenomenon has been developed.

This system consists of a superior IP with a photostimulable
Eu-doped BaFBr (BaFBr:Eu) phosphor-powder-scrrened IP
[l] or T1-doped RbBr (RbBr:Tl) film-type IP [2] and a
computer. When the IP is exposed to X-rays, X-ray image is
temporarily stored into phosphor screen of the IP as a
distribution of quasi-stable color centers. The luminescence
can be observed by scanning the stored phosphor screen with
a stimulating focused laser beam. The PSL intensity is
converted into a time series of digital signals via a
photomultiplier, amplifiers and an analog to digital ( A D )
converter. The X-ray image can be, thus, stored and
reconstructed by a computer. The residual image on the
phosphor screen can be erased by illumination with visible
light.
The erasable phosphor IP developed for medical
radiography has found new uses in physical, medical and
biological fields such as X-ray diffraction analysis, protein
crystallography, radiation dosimety and auto-radiography
[3],[4],[5]. Since it was demonstrated that the IP has many
striking performances in these fields, such as a high
sensitivity (100-1000 times as high as an X-ray film), good
dose linearity (extreamly wide dynamic range of X-ray dose,
more than five decades) and easy erasing for reuse. The
features of the X-ray dose accumulation, high sensitivity and
wide dynamic range of dose will give a new world of
radiation dosimetry. There is, however, an urgent need for
the development of new materials with good fading
characteristics, because commercially-available IP using
BaFBr:Eu or RbBr:Tl phosphor has relatively poor fading
characteristics of the X-ray image.
After surveying many possible phosphor materials,
especially alkali halide phosphor materials such as Eu-doped
KCl, Eu-doped KBr and Eu doped KCl,Brl.,, we found that
KBr:Eu phosphor exhibits an intense PSL, good linearity for

digital
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X-ray dose and good fading characteristics. In this paper, the

PSL characteristics in X-ray-irradiated KClXBrl.,:Eu
phosphor ceramics are reported and the fading mechanism is
also discussed.

1.5

KCI,Br,.,:Eu
X-ray IRRAD.

11. EXPERIMENTAL
Each powder mixture of reagent grade KCl and KBr
containing various content (0.01, 0.05 and 0.1 mol%) of
Eu20306H20powder was pressed into discs at 6 tons for 10
min. The discs with 13 mm diameter and 1 mm thickness
were sintered at about 7000 for 3 hours in air [6]. X-rayirradiation was carried out at room temperature (RT) in the
dark with tungsten-target tube operated at 20-40 kV and 2-20
mA.
The PSL emission spectra and photoluminescence (PL)
spectra were observed using a Hitachi F-3010
spectrofluorometer at RT. The PSL and PL spectra were
corrected for the diffraction efficiency of grating and the
optical response of the photomultiplier.

111. RESULTS AND DISCUSSION

A. PSL Characteristics and Emission Mechanism
in KChBr1-p*Eu Phosphors
An intense PSL peak at about 420 nm was observed
regardless of KBr content when the X-ray-irradiated samples
were stimulated with 470-750 nm light. Figure 1 shows
typical PSL emission spectra and its stimulation spectra of X
ray-irradiated KC1:Eu and KE3r:Eu phosphor samples. It can
be seen that the stimulation spectrum of KBr:Eu phosphor
sample is peaked at longer wavelength than that of KC1:Eu
phosphor sample. Figure 2 shows typical stimulation spectra
for KCl,Brl-,:Eu phosphor samples with various KBr

400

600
700
W A V E L E N G T H @ [nm]

500

800

Fig. 2 Typical stimulation spectra for X-ray-irradiated KCI:Eu

(x=l), KC10,33Br0.67:E~
(X=0.33), KClo.~Bro.~:Eu(x=O.5),
KC10,67Bro,33:Eu(x=0.67) and KBr:Eu (x=O)phosphor
samples.
contents. It should be noted that the peak of stimulation
spectrum is red shifted with increasing KBr content. These
results as described above strongly suggest that there exist
two kinds of electron traps such as C1 vacancy and Br
vacancy in KCl,Brl.,:Eu phosphor samples because the peak
wavelength of the optical absorption band of F centers in KCl
and KBr are 560 and 620 nm, respectively. Typical PL
emission spectrum and its excitation spectrum in KC1:Eu and
KJ3r:Eu phosphor samples are shown in Fig. 3 and Fig. 4,
respectively. The 420 nm PL emission is attributed to Eu2+
ions, since the peak wavelength of the excitation spectra
corresponds to that of characteristic optical absorption band
maximum of isolated Eu2+ ions [6],[7]. The 420 nm PSL
peak which coincides with the PL peak is, therefore, assigned
to the inner ionic transition (4f5d-4f7) of isolated Eu2+ions,
which occupy cation sites [8],[9]. The result described above
strongly suggests that the following PSL emission
mechanism is likely. Part of free electrons and holes

1.5

. X-ray IRRAD.

v)

;
- 1.0

PSL

STlM U LATlON

-I
v)

[L

n
W

0.5

I
U

300

400

500
600
700
W A V E L E N G T H e [nm]

200

800

300
400
W A V E L E N G T H @ [nm]

500

Fig. 1 PSL emission spectrum and its stimulation spectra of X-ray- , Fig. 3 Typical PL emission spectrum and its excitation spectrum for
KC1:Eu phosphor sample.
irradiated.
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exhibited excellent fading characteristics than that of other

KClxBrl.,:Eu and BaFBr:Eu phosphor samples, which
indicating that the fading is depended on the crystallinity of
phosphors.

1.5
t

t
v)
z

5- 1.0

2
v)

1.5 I

a
0
W

0.5

X-ray IRRAD

z
W

$1.0
-

a
n

v)

0
200

300

400

500

W A V E L E N G T H @ [nm]

<

0.5

I
U
0

Fig. 4 Typical PL emission spectrum and its excitation spectrum for

KBr:Eu phosphor sample.

f+

0 KClo.33Bro,66:Eu

KCIo.5Bro,,:Eu

V KClo66Br033:Eu

produced during X-ray irradiation are trapped at two kinds of

vacancies such as C1 and Br vacancies to produce the F
centers and at Eu2' ions to produce Eu3+ ions, respectively.
By subsequent stimulation with 470-750 nm light, the
electrons which are optically released from the F centers,
recombine with Eu3+ ions leading to the excited Eu2+ ions
whereby the 420 nm PSL is emitted.

B. PSL Characteristics as a Storage Material for

Medical Imaging
It was found that the PSL intensity increases with
increasing x-ray irradiation dose. Figure 5 shows the PSL
intensity as a function of the X-ray irradiation dose for
KCIxBrl.,:Eu phosphor samples comparing with that of
commercially available imaging plate using BaFBr:Eu
phosphor. It can be seen that there are good linearity
between the PSL intensity and X-ray dose in all phosphor
samples. The fading characteristics of the PSL intensity at
RT in the dark for various phosphor samples are shown in
Fig. 6. It should be noted that the KBr:Eu phosphor sample

40

60

Fig. 6 Fading characteristics of the PSL in KCl,Br,.,:Eu phosphor

samples, compared with that of commercially available
imaging plate (BaFBr:Eu).
These results described above strongly suggest that the
KBr:Eu phosphor is one of the most attractive storage
phosphor material for the imaging plate of computed
radiography utilizing the PSL phenomenon.
It was found that the fading characteristics of the KBr:Eu
phosphor samples is depended on Eu concentrations doped as
shown in Fig. 7. It can be seen that the KBr:Eu (O.Olmol%)
phosphor sample exhibits excellent fading characteristics.

n
w

."

20

TIME AFTER IRRADIATION@ [min]

0.5

I X-ray IRRAD.

/I

I
U

04

0'

4
Y o3

>
t

20

40

60

T I M E AFTER I R R A D I A T I O N @ [min]

v)

E102

Fig. 7 Dependence of the fading characteristics on the doped Eu

concentrations for various KBr:Eu phosphor samples with
different Eu concentrations (0.005mol%, O.Olmol%,
0.05mol%, O.lmol% and 0.5mol%).

I-

z_

$1 0'

1 oo

ioo

IO'

io2 i o 3

io4

It was also found that the fading characteristics is affected

by the temperature and humidity in the ambient air. Figure 8
shows the change of the PSL intensity as a function of the
temperature in KBr:Eu phosphors with various Eu

io5

W AVELENGTHe [nm]

Fig. 5 PSL intensity vs. x-ray-irradiation dose in KCl,Brl.,:Eu

phosphor samples, compared with that of commercially
available imaging plate (BaFBr:Eu).
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concentrations. Among three phosphor samples with

different Eu concentrations, the KBr:Eu (O.Olmol%)
phosphor sample exhibted the best in the stability for the
temperature.
As can be seen from Fig. 9, the fading
characteristics measured in air ambient with low humidity is
1.5
t

IRRAD.

0 x=O.Ol

x=0.05

lJY

x=O.l

z
w

5- 1.0
-I

a
0

a
W

0.5
d

I
a:
0

0
20

30

50
60
TEMPERATURE@ [ * ]
40

80

70

Fig. 8 Dependence of the fading characteristics of the KBr:Eu

(O.Olmol%)phosphor sample on ambient temperatures.

better than that with high humidity. One can expect that this
is due to the deliquescence of alkali halides.
Figure 10 shows the dependence of the fading
characteristics of the KBr:Eu phosphor sample on the
irradiated X-ray energies. The characteristics for UV
irradiation is also shown in the figure. It should be noted that
the fading characteristics become poor with decreasing the
energy of irradiated X-rays. This result shows that the fading
characteristics near the surface of phosphor is poor due to the
effect of humidity, that is, in the irradiation using low energy
X-rays the F centers as the electron traps create near the
surface of the phosphor and these electron traps are affected
by the humidity, because the almost of low energy X-rays is
absorbed near the surface of phosphor. But, there are no
problem [10],[11] because the energy of X-rays used in
practical medical image measurements is about 70-120kV, of
which energy is higher than 40kV showing good fading
characteristics as shown in Fig. 10.

IV. CONCLUSIONS

I
0

20

60

40

TIME AFTER IRRADIATION@ [min]

It was found that the X-ray-irradiated KBr:Eu phosphor

exhibits an intense PSL, a good linearity between the PSL
intensity and X-ray irradiation dose and excellent fading
characteristics of the PSL. This result strongly suggests that
the KBr:Eu phosphor is useful as a novel candidate as a
strorage phosphor material for the medical imaging (digital
radiography) utilizing the PSL phenomenon. It was also
found that the PSL characteristics, especially the fading
characteristics, in KCl,Br,.,:Eu alkali halide phosphors is
affected by crystallinity of the phosphor, Eu concentrations
and ambient temperature and humidity.

Fig. 9 Dependence of the fading characteristics of the KBr:Eu

(O.Olmol%)phosphor sample on ambient humidity.

0 40[kV],20[mA]
0 30[kV],16[mA]
0 20[kV],2[mA]
8 UVIRRAD.

V. ACKNOWLEDGMENTS
We wish to thank Prof. M.Takebe and Prof. K.Abe of
Tohoku University, Prof. K.Inabe and S.Taniguchi of
Kanazawa University for their fruitful discussion and
N.Kashiwagi, Y.Oda, Y.Noguchi, Y.Hayashi, H.Shin,
T.Minato and T.Yasue for their excellent technical assistance
in the experiments. This work was partly supported by a
Grant-inAid for Scientific Research (No.08875014 and
09558060) and the foundation for High-Tech Research
Center from the Ministry of Education, Science and Culture
of Japan.

20
40
60
TIME AFTER IRRADIATION@ [min]

Fig. 10 Dependence of the fading characteristics of the KBr:Eu

(O.Olmol%)phosphor sample on irradiated x-ray energies.
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VI. REFERENCES
[ l ] K.Takahashi, J.Miyahara and Y.Shibahara,
"Photostimulated Luminescence (PSL) and Color
Centers in BaFX:Eu (X=Cl,Br) Phosphors", J.
Electrochem. Soc., ~01.132,pp.1492-1494, 1985.
[ 2 ] K.Amitani, K.Kano, H.Tsuchiya and F.Shimada, "X-ray
imaging system utilizing new photostimulable
phosphors", Advanced Printing Paper Summaries of
the 26th Fall Symp. on SPSEs Conf. And Exhibition
on Electronic Imaging, San Diego, California, pp. 180183, 1986.
[3] Y.Amemiya and J.Miyahara, "Imaging plate illuminates
many fields, Nature, vo1.336, pp. 89-90, 1988.
[4] H.Nanto, "Optically Stimulated Luminescence Application to Optical Memory and Imaging Sensor for
Ionizing Radiation", Kotai Butsuri, vol. 28, pp. 49-58,
1993.
[5] H.Nanto, "Photostimulated Luminescence in Insulators
and Semiconductors", Radiation Effects and Defects in
Solids, vo1.146, pp.311-321, 1998.
[6] H.Nanto, Y.Hirai, F.Endo, M.Ikeda, S.Nasu and
N.Takeuchi, "KC1:Eu Phosphors as a Storage Materials
for Two-Dimensional X-ray or UV-ray Imaging
Sensor", Tech. Digest of The 12th Sensor Symp.,
pp.51-54, 1994.

0-7803-5696-9/00/$10.00 (c) 2000 EEE

H.Nanto, F.Endo, Y.Hirai, S.Nasu, S.Taniguchi and

N.Takeuchi, "Eu-doped KCl phosphor crystals as a
storage material for two-dimensional ultraviolet-ray or
x-ray imaging sensors", J. Appl. Phys., vo1.75,
pp.7493-7497, 1994.
[8] J.Hernandez A, F.J.Lopez, H.Mumeta S and F.J.Lopez,
"Optical Absorption, Emission and Excitation Spectra
of Eu2+in Alkali Halides", J. Phys. Soc. Japan, ~01.50,
pp.225-229, 1981.
[9] J.Rubio 0, H.Murrieta S, J.Hernandez A and F.J.Lopez,
"Addendum to optical absorption and luminescence
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NaCl and KCl single crystals", Phys. Rev., B, vol. 24,
4847-4851, 1981.
[lo] K.Toh, K.Saito, K.Abe and H.Nanto, Responses of
storage phosphors to radiations and their particle
identification", Extended Abstract of The 59th Autumn
Meeting (Japan Soc. of Appl. Phys.), 16a-R-4, 1998.
[ 111 M.Miyazaki, A.Imai, T.Sato, N.Dougami, Y.Douguchi,
E.Kusano, S.Nasu, A.Kinbara
and H.Nanto,
"Mechanism of PSL fading in alkali halide Phosphors",
Extended Abstract of The 59th Autumn Meeteing
(Japan Soc. of Appl. Phys.), 16a-R-7, 1998.

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