THE HISTORY OF PHOSPHORESCENT PIGMENTS

INTRODUCTION

Phosphors are designed classically as materials that exhibit emission of visible radiation for significant periods of time
following the removal of the excitation means (radiation, electron beam, electric field, etc.); such delayed emission of light is
called phosphorescence [1].

Phosphorescence is a luminescence that delayed radiation of trapped photo-produced electrons or holes occurs in materials
internal or exterior defect zones. When this trapped charge carries released with thermal energy, they come together again in
luminescence centres. In this way, phosphorescence is a physical formation when thermally activated charge carries get
released in traps of structure at characteristic temperatures. Many inorganic phosphors with superior properties consist of a
crystalline main material containing minute amounts of specific impurities and soluble activators. Basically, activators
are responsible for the formation of the luminescence mechanism. Other impurities, that is, auxiliary activators are in some
cases necessary for releasing the activators contained in the main crystal. Both activators and when necessary, auxiliary
activators are incorporated in the structure of the crystal at high temperatures during firing. Firing temperature is usually a
little below the melting temperature of the material. However, if crystallization is difficult due to excessively high melting
points of main crystal, crystallization may be facilitated by bringing down the melting temperature withthe addition of
various solvents to the initial phosphor recipe [1-2] .
One of the first natural phosphorescence observed in 1568 by Cellini, while the Bolognan Cobbler, Vincenzo Cascariolo,
who was an exponent of alchemy, synthesized in 1604 the first artificial phosphor by calcining sulphur-rich barium sulphate
to give it a golden appearance in daylight [3].
ZnS:Cu has been known since the beginning of 20
th
century as a long-term green light emitting material; however, the glow it
provides in applications and the continuity of such glow is limited. The visible phosphorus effect cannot be maintained more
than a few hours and the phosphorescent glow is lost easily. Therefore, to maintain glow, sometimes radioactive elements
(e.g. 1147Pm 1H) are added to ZnS:Cu phosphor-based pigments allowing them to emit the energy by the radioactive
substance. However, the procedure of processing and disposal of radioactive elements are very difficult leading to many
problems. Consequently, the use of such a pigments is also limited [4-7].
Earth alkali sulfides, such as CaS, SrS are the next generation long-lasting phosphors. They are among those sulfide
phosphors which were so called Lenards phosphors studied since 1930s [8-9]. They were re-discovered by Lehmann et. al.
in the early 1970s. The phosphors of the type were alkali earth sulfides, such as CaS:Bi
3+
, CaS:Eu
2+
, CaS:Ce
3+
, etc. Not that
much attention was paid to long persistence of these phosphors at earlier time. But during the World War II, military
application brought a lot of interests into their photo-stimulation properties. In term of long persistence, their major
advantages were not only the long persistence time but also that they could be excited under natural solar light. The
disadvantage is that they were chemically unstable. In practical application, the odor of H
2
S released from its reaction with
moisture was extremely bad [10].
In 1996, T. Matsuzawa et al. reported a new type of long-persistent phosphor SrAl
2
O
4
:Eu
2+
,Dy
3+
with a strong emission at
520 nm (green), which is developed from a phosphor SrAl
2
O
4
:Eu
2+
found by V. Abbruscato in 1971. The persistence time of
SrAl
2
O
4
:Eu
2+
,Dy
3+
was extended to longer than 16 hours (reported persistent time varied with detection limits from 10 hours
to 20 hours) after co-doping with Dy
3+
. After a short time period, a similar long-persistent phosphor CaAl
2
O
4
:Eu
2+
, Nd
3+
was


reported with a blue emission at 450 nm. These two phosphors drew considerable attentions from many scientists because
avalue of 16 hours persistent time could bring the phosphorescence over a whole night. Since then, long-persistent phosphor
becomes one of the major research areas in luminescence materials [11].
In 2002, Akiyama et al. investigated the mechanoluminescence (ML) of Eu,Dy co-doped strontium aluminates [12]. In 2003,
Abanti Nag et al. searched the role of B
2
O
3
addition on the long-phosphorescence of SrAl
2
O
4
:Eu
2+
, Dy
3+
. B
2
O
3
is not an
inert high temperature solvent (flux) to accelerate grain growth, according to SEM results.With increasing concentrations,
B
2
O
3
reacts with SrAl
2
O
4
to form Sr
4
Al
14
O
25
together with Sr-borate (SrB
2
O
4
) as the glassy phase, as evidenced by XRD and
SEM studies. At high B
2
O
3
contents, Sr
4
Al
14
O
25
converts itself to SrAl
2
B
2
O
7
(cubic and hexagonal), SrAl
12
O
19
and Sr-borate
(SrB
4
O
7
) glass. Sr
4
Al
14
O
25
:Eu
2+
, Dy
3+
has also been independently synthesized to realize the blue emitting (
em
=490 nm)
phosphor. The afterglow decay as well as thermoluminescence studies reveal that Sr
4
Al
14
O
25
:Eu
2+
, Dy
3+
exhibits equally
long-phosphorescence as that of SrAl
2
O
4
:Eu
2+
, Dy
3+
[13].
In 2005, Sho Abe et al. prepared a red long-lasting phosphor using a conventional solid state reaction in the
BaMg
2
Si
2
O
7
:Eu
2+
, Mn
2+
system. Phosphors doped only with Mn
2+
emitted a red light that was barely visible. Phosphors
doped with both Eu
2+
and Mn
2+
showed a reddish luminescence. They realiased that, the red emission intensity of co-doped
sample was seven times higher than that doped only with Mn
2+
[14].
In 2006, Jinyong Kuang et al. studied the white long-lasting phosphor in the Dy
3+
-doped SrSiO
3
system.After irradiation by a
254 nm UV lamp for 5 min, the Dy
3+
-doped SrSiO
3
phosphor emits whitelight-emitting long-lasting phosphorescence for
more than 1 h even after the irradiation source has been removed.Photoluminescence, long-lasting phosphorescence and
thermoluminescence (TL) spectra are used to explain this luminescent phenomenon [15].
In 2007, M.K. Jung et al. studied the red phosphor prepared by solid-state reaction method in the Y
2
O
3
:Eu,Sm system. The
emmission spectra of Y
2
O
3
:Eu,Sm increased with increasing firing temperature. The co-doping with Eu and Sm ions
broadened the excitation band of the Y
2
O
3
:Eu, Sm phosphors and enhanced their emission intensity under 390 and 405 nm
light excitation. The weak ff transition in the range from 350 to 420 nm, due to the
5
H
5/2

4
D
1/2
and
5
H
5/2

4
K
11/2

transitions of the Sm ions, has a broad excitation spectra and increased emission intensitym [16].
In 2008, Chai Yueshang et al. prepared flower-like phosphor powders with red long-afterglow under the reducing atmosphere
by sol-gel method in the Sr
3
Al
2
O
6
:Eu
2+
, Dy
3+
system.Sr
3
Al
2
O
6
:Eu
2
, Dy
3+
phosphor powders indicate a broad red emission
band with emission peak at 612 nm under 472 nm excitation. At the Eu
2+
concentration of 8mol% shows the highest
luminescent intensity, at 612 nm. The red afterglow of phosphors lasted for over 1100 s after the excitation source was cut off
[17].
In 2009, Rui-Ping Wei et al.studied the white light emitting long-lasting phosphorescent material synthesized by
conventional solid-state reaction method in the Ca
3
SnSi
2
O
9
:Dy
3+
system. It indicates a white light
emitting phosphorescence at room temperature after the 254 nm UV light irradiation stopped, and it is considered that
the phosphorescence originates from the mixture of Dy
3+
characteristic luminescence. . The thermoluminescence (TL) spectra
show that Dy
3+
ion induces a proper trap in the phosphor with the depth of 0.402 eV and results in long
afterglow phosphorescence [18].
In 2010, HE Xianghonget al. prepared pseudo-pompon-like red-emitting phosphors by solid state method in the Eu
3+
-
activated Gd
2
(MoO
4
)
3
system. The morphology,structure and luminescent properties of these powder samples were
investigated by a scanning electron microscopy (SEM), X-ray diffraction (XRD) and fluorescent spectrophotometry,
respectively. The phosphor could be efficiently excited by the incident light of 348425 nm, well matched with the output
wavelength of near-UV (In,Ga)N chip, and re-emitted an intense red light peaking at 615 nm. By combing this phosphor with


an approximately 395 nm emitting (In,Ga)N chip, a red LED was fabricated, so that, the applicability of this novel phosphor
to white LEDs was confirmed. It is considered to be an efficient red-emitting conversion phosphor for solid-state lighting
based on (In,Ga)N LEDs [19].
In 2011, Bingfu Lei et al., worked on the new long-lasting phosphorescence phosphor which emits orangelight upon
UVexcitation prepared successfully by a conventional high-temperature solid-state reactionmethod in the
Ca
2
SnO
4
:Sm
3+
system. After irradiation with 252 nm ultraviolet light, Ca
2
SnO
4
:Sm
3+
emits intense orange afterglow
originating from the
4
G
5/2
->
6
H
J
(J = 5/2,7/2,9/2) transitions. The afterglow decay curve of the Sm
3+
-doped Ca
2
SnO
4

phosphorindicates both fast and slow decay components. Due to the presence of the latter one, the afterglow canbe clearly
observed by the naked eyes in the dark for more than 1 h after [20].
Karasu et al., have recently studied the SrAl
2
O
4
:Eu
2+
, Sr
4
Al
14
O
25
and CaAl
2
O
4
:Eu
2+
systems which are reliable, chemically
stable with high glow, not containing radiation, with long-term photoluminescence emissionbluish-green and yellowish-green
pigments that have got phosphorescent properties and they used these produced pigments in wall tile glazes and decorative
glass systems successfully [21-33].
Although there are many new phosphors were developed within the current ten years, only some of them can be excited
under visible natural light. The others required UV or deep UV excitation to trap electrons. The issue whether the long
persistence can be obtained by natural light excitation, is very important and actually it sometimes limits the application of
long lasting phosphors [3].
PHOSPHORESCENCE MECHANISM

Figure 1: Thephosphorescence mechanism [34].

A molecule in the excited triplet state may not always use intersystem crossing to return to the ground state. It could lose
energy by emission of a photon.Triplet->singlet transition is much less probable than a singlet->singlet transition.The lifetime
of the excited triplet state can be up to 10 seconds, in comparison with10
-5
s to 10
-8
s average lifetime of an excited singlet
state.Emission from triplet/singlet transitions can continue after initial irradiation [34-35].
For many of the main crystals, phosphorescence is due to Eu
2+
: 4f->5d transition. 4f electrons of Eu
2+
ions are strong to the
structural changes due to the outer shell acts as a shield, 5d electrons are easily separated to this kind of changes. Peak
positions in the emission spectrum are connected with the locations of Eu
2+
, for such a reason Eu
2+
ions can emit different
visible light in various cyrystalline regions [35].


In the strontium aluminates system, phosphors are activated with europium (Eu) and dysprosium (Dy) draw great interest due
to many superior properties they own. When compared to the classical sulphur phosphors, they are superior because of their
high radiation intensity, color purity, chemical stability, long emission duration and no radiation risk [26].
The phosphorescence characteristics of SrAl
2
O
4
: Eu
2+
, Dy
3+
system has been described as a mechanism where the Dy
3+
ion
functions as the trapping center and the Eu
2+
ion is the emitter, taking place due to heat emissions and trappings of load
charge carriers at room temperature. It has been observed that B
2
O
3
, on the other hand, improves the long-term emission
property of the phosphorus system. To accelerate grain growth of strontium aluminate, B
2
O
3
has been used as a high
temperature solvent in an inert environment. Up to now, different mechanisms have been proposed for auxiliary additive
incorporated SrAl
2
O
4
:Eu
2+
and Ca-Al
2
O
4
:Eu
2+
systems. One of these is the mechanisms developed by Matsuzawa, et. al. for
the SrAl
2
O
4
: Eu
2+
system which relies on the photoconductivity function of powder samples in the SrAl
2
O
4
:Eu
2+
system. This
phenomenon indicates that UV radiation leads to hole type photoconductivity. Therefore, this indicates the existence of hole
trapping [26] .

Figure 2: Phosphorescence mechanism purposed by Matsuzawa et al. for SrAl
2
O
4
:Eu
2+
system [11].
Phosphorescence pigments have got various application areas, such as, road signs, coating of the yield surfaces, plastic,
rubber, polyvinyl choloride (PVC), traffic control gloves, traffic safety signs, reflection plates of vehicles, rubber tyres,
shoes, raincoats, coating of phone keys, clocks, stairway edges, emergency signs, extinguisher tube surfaces, toys, writing
appliances, ceramic coating materials etc. [11].
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