Research and Reviews in Materials Science and Chemistry

Vol. 6, Issue 1, 2016, Pages 41-74

ISSN 2319-6920
Published Online on May 9, 2016
 2016 Jyoti Academic Press
http://jyotiacademicpress.net

LUMINESCENT MATERIALS AND APPLICATIONS

M. NAZAROV

Institute of Applied Physics

Academy Sciences of Moldova
Republic of Moldova
e-mail: [email protected]

Abstract

Short review of the past and present of luminescent materials is given to show a
major phosphor’s applications in traditional display, flat panel display, lighting,
medical, security etc. Multiphase micro and nanoparticle persistent phosphors
are synthesized and applied for different fields including painting, medical and
biological investigations. A lot of examples show a broad range of applications of
persistent luminescence from bulk materials to high tech products, especially in
medicine. The development of high efficiency nanosized phosphor makes it
possible to propose persistent materials as very good candidates for
photodynamic therapy of cancer. An artificial block from slag, concrete, and

sand covered with SrAl2O4 :Eu2 + , Dy3 + based phosphor is prepared, and a
new direction in biology for algae cultivation and artificial reef is discussed. For
the first time, underwater luminescence is experimentally studied under real
sea conditions. Bright blue-green long-lasting afterglow is registered at a depth
of 5m.

Keywords and phrases: luminescent materials, persistent luminescence, underwater

luminescence.
Communicated by Emad M. El-Menyawy.
Received March 12, 2016; Revised April 21, 2016
42 M. NAZAROV

1. Introduction

A phosphor is a material that emits light as a result of absorbing

energy (Figure 1). Luminescence is the term given to the emission of this
light.

Figure 1. Diagram illustrating the energy absorbed by a phosphor (left),

which is then transformed to emitted light of lower energy (right).

Hundreds of thousands of phosphors have been synthesized, each one

having its own characteristic colour of emission and period of time during
which light is emitted after excitation ceases. Most phosphors are
composed of a transparent microcrystalline host (or a matrix) and an
activator, i.e., a small amount of intentionally added impurity atoms
distributed in the host crystal.

Inorganic luminescent materials have been known since

approximately the tenth century in China and Japan as well as since the
end of the middle ages in Europe. The detailed history of luminescence
can be found in one of the early book of Harvey [1] or in a special review
dedicated to the 100 years of research and application of inorganic
luminescent materials [2].
 LUMINESCENT MATERIALS AND APPLICATIONS 43

2. The Past and Present of Phosphors

It is said that an alchemist, Vincentinus Casciarolo of Bologna, Italy,

found a heavy crystalline stone with a gloss at the foot of a volcano, and
fired it in a charcoal oven intending to convert it to a noble metal. He
obtained no metals but found that the sintered stone emitted red light in
the dark after exposure to sunlight. This stone was called the “Bolognian
stone” [3]. From the knowledge now known, the stone found appears to
have been barite ( BaSO4 ) , with the fired product being BaS, which is
now known to be a host for phosphor materials.

At the end of the nineteenth century, a first major milestone

concerning luminescent materials and devices was the realization of gas
discharges and electron beams in evacuated glass tubes by Geissler and
Braun, as well as the discovery of X-rays by Roentgen. The visualization
of gas discharges, cathode rays, or X-rays represent also the first
practical uses of luminescent materials. Based on these fundamental
results, the first luminescent devices were developed only a few years
later, and included cathode-ray tubes, fluorescent lamps, and X-ray
intensifying screens. Thereafter, research on cathode-ray tubes and the
relevant phosphors was stimulated during the Second World War for use
in radar screens. In addition, the rapid and successful application of
fluorescent lamps for illumination purposes, as well as the use of X-rays
for medical imaging, intensified research on novel luminescent materials
in the first half of the twentieth century. The first luminescent devices
contained only a single phosphor material. The emitted light was
normally not white, but coloured. For instance, blue-emitting CaWO4 ,
which is a highly efficient phosphor, was used in X-ray-intensifying
screens in Braun’s early cathode-ray tubes as well as in the first
fluorescent lamps by Edison. Lighting became more colourful with so-
called zeon or neon tubes. Based on neon, argon, or mercury discharges in
combination with different phosphors and coloured glass, different
coloured lamps were realized. These lamps were presented by Claude at
the world exhibition in 1937 in Paris and used for advertising [4]. For
illumination purposes, however, the emission of white light is required.
44 M. NAZAROV

Some single-phosphor lamps were proposed, but their emission was too
low. Nowadays, tri-colour phosphor mixtures are used in fluorescent
lamps worldwide. Fluorescent tubes and compact fluorescent lamps
became widely available in the 1950s and early 1990s, respectively.
Along with high-intensity discharge lamps, they offer a longer life and
lower power consumption than incandescent sources, and have become
the mainstream lighting technology in homes, offices, and public places.

Figure 2. From incandescent sources to solid-state light sources.

More than a century after the introduction of incandescent lighting

and half a century after the introduction of fluorescent lighting, solid-
state light sources are revolutionizing an increasing number of
applications. Whereas the efficiency of conventional incandescent and
fluorescent lights is limited by fundamental factors that cannot be
overcome, the efficiency of solid-state sources is limited only by human
creativity and imagination. The high efficiency of solid-state sources
already provides energy savings and environmental benefits in a number
of applications. For example, conventional incandescent or fluorescent
lamps rely on either incandescence or discharge in gases. Both
 LUMINESCENT MATERIALS AND APPLICATIONS 45

phenomena are associated with large energy losses that occur because of
the high temperatures and large stokes shifts involved. Light-emitting
diodes using semiconductors offer an alternative method of illumination.
The operation of LEDs is based on spontaneous light emission in
semiconductors, which is due to the radiative recombination of excess
electrons and holes that are produced by the injection of current with
small energy losses. Subsequently, the radiative recombination of the
injected carriers may attain quantum yields close to unity. As a result,
compared with conventional lamps, LED-based light sources have
superior lifetime, efficiency, and reliability, which promise significant
reductions in power consumption and pollution from fossil fuel power
plants. Currently, LEDs are widely used as indicators, rear lamps for
vehicles, decorated lamps, backlights for cellular phones and liquid
crystal displays, and small-area lighting. With advances in the
brightness and colour-rendering properties of LEDs, it is generally
accepted that they will replace conventional lamps for general lighting in
the near future.

Figure 3. Evolution of lighting.

46 M. NAZAROV

Hundreds of phosphors are available for excitation at 250nm, the

dominant emission band of Hg lamps. In solid-state lighting, however,
the excitation wavelength is much longer, typically in the range 380 to
480nm. New high-efficiency phosphors, which can be efficiently excited at
these wavelengths, are now being developed. Whereas high efficiency
yellow phosphors are readily available (e.g., cesium-doped yttrium
aluminum garnet- Y3 Al 5O12 (YAG) phosphors), the efficiency of red
phosphors still lags. As a novel class of inorganic phosphors, oxynitride
and nitride luminescent materials have received considerable attention
because of their potential applications in solid-state lightings and
displays. Some of them are discussed in this review.

Why the luminescent materials?

(1) High lumen output

LED has eight time more brightness than incandescent lamps

without emissions harmful to the environment.

(2) Tremendous energy savings

High power LED light sources are extremely efficient returning a 50

to 80% saving over conventional sodium or mercury lamps.

(3) Long life

Operating for an average of 10 hours per day LED has a life span of
up to 13 years, 50,000 hours. Unlike traditional light bulbs, LED is not
fragile and susceptible to breakage or vandalism.

(4) High colour index

LED has an unique colour index providing bright, true colours during
night-time hours.

(5) No dust absorption or yellowing

Because LED operates at low voltage and low temperature there is no

reduction in brightness or yellowing, which is associated with traditional
street lighting, over the life span of the LED.

(6) Instant start

Unlike sodium lights, LED lights do not require a time delay to reach
optimum brightness levels.
 LUMINESCENT MATERIALS AND APPLICATIONS 47

3. Major Phosphor’s Applications

Luminescent materials are well known for a long time from

traditional lighting and display applications, like cathode-ray (television)
tubes, fluorescent lamps but also X-ray screens. Exploration of novel
materials classes during the last years has enabled development of new
applications, e.g., white LEDs, plasma display panels, bio-markers, and
solar cells. Recent progress and future prospects show that luminescent
materials remain not only interesting from a scientific point of view but
also relevant from an application point of view. For many years to come,
scientific challenges as well as societal needs in this research field can be
addressed by chemists, physicists, and materials scientists. This
presentation reviews the latest developments on these novel luminescent
materials, their preparation, crystal chemistry, characterization, and
optical properties. The intention is to focus on the relationship between
the luminescence properties on the one hand and the chemical
composition and structure on the other.

The research on luminescent materials is stimulated by various

applications. Luminescent materials are widely applied today. In the last
decades, a large number of luminescent materials based on rare earth
ions or rare earth host lattices have been invented. In many cases, rare
earth phosphors dramatically improved the performance of the devices in
which they are applied (Figure 4).

Figure 4. Major phosphor’s applications.

48 M. NAZAROV

Major applications of europium and terbium activated phosphors are

in emissive displays and fluorescent lamps. Three types of flat
luminescent displays are under development: plasma display panels, in
which phosphor powders are excited by VUV photons (145-180nm); field
emission displays, in which the luminescent material is bombarded by
low-energy electrons emitted by microtips; and thin-film electro-
luminescence displays in which electrons injected into the luminescent
layer are accelerated under the applied field up to the energies needed to
excite luminescent centers [5-7].

A more specialized and important application is the use of X-ray

intensifying screens for medical purposes [8]. Some X-ray detector
systems are based on luminescent materials as well. Research on X-ray
phosphors is mainly focused on photostimulable phosphors for digital
imaging; the luminescence of which is obtained by optical excitation in an
absorption band formed under X-ray irradiation [9]. Scintillator crystals
convert the energy of ionizing radiations into UV or visible radiation.
They are used for medical diagnostics, scientific experiments and
industrial control (e.g., inspection of baggage and containers, thickness
control of metal sheets, paper, geophysical exploration).

During the last ten years, white LEDs have become very important
lighting sources and the importance of LED phosphors for white and
coloured light generation must be considered an important market driver
in the future [10-16].

4. Experimental Procedures

The examined materials for different applications were prepared by

two methods: solid state reaction and combustion synthesis. The
conventional solid state reaction is mostly used for preparation of bulk
phosphors that used in traditional applications as safety signs, watch
dials, decorative objects and toys. Combustion method is used for
preparing nanoparticle materials which we need in medicine and
sometimes in biology.
 LUMINESCENT MATERIALS AND APPLICATIONS 49

4.1. Solid state reaction

Strontium aluminate phosphor doped with Eu 2 + and co-doped with

Dy 3 + ( SrAl 2O4 :Eu 2 + , Dy 3 + ) for traditional applications were prepared
by solid state reaction approach using strontium carbonate ( SrCO3 ;
Aldrich, 99.9%), aluminum oxide ( Al 2O3 ) europium oxide ( Eu 2O3 ;
Aldrich, 99.99%), and dysprosium oxide ( Dy 2O3 ; Aldrich, 99.99%) as the
starting materials. Small amount (0.2mol%) of H3 BO3 was used as a
flux. Prior to heating at 1250°C, the reagents were ground using a ball
mill to form a homogeneous mixture. First, the dry milling was used for
30 minutes and then continued by wet-mixing machine for 30 minutes.
The resulting slurry was dried at 150°C for 3 hours to remove the water
content. After fully dried, the mixed white powder was placed in a small
alumina crucible and then fired at 1250°C for 2 hours under a mild
reducing atmosphere. Graphite crucible was used to create the reducing
atmosphere and to ensure complete reduction of Eu3 + to Eu 2 + and to
crystallize and form the luminescence centers. Usually the particle size in
this process is about 10-20 micrometers. The mixing-milling process to
get smaller particle size and homogeneous mixture was used after
calcination.

4.2. Combustion synthesis

Similar nanoparticles of SrAl 2O4 :Eu 2 + phosphor were prepared by

combustion synthesis. The starting material included: Aluminium nitrate
( Al ( NO3 )3 .9H2O; Systerm, 98%), strontium nitrate ( Sr( NO3 )2 ; Aldrich,
99%), europium oxide ( Eu 2O3 ; Aldrich, 99.99%), and urea ( CO( NH2 )2 ;
Systerm, 99%). Small amount of acid boric ( H3 BO3 ; Fisher, 100.04%)
were used as flux and small amounts of urea were used as reducer and
fuel. Figure 5 below shows the flow chart of SrAl 2O4 :Eu 2 + powders
synthesis.
50 M. NAZAROV

Figure 5. Flow chart of SrAl 2O4 :Eu 2 + phosphors powder by combustion

synthesis.

There are some details below to describe the combustion synthesis.

The stoichiometric quantities of raw materials were calculated and

weighed by using high precision mass balance. The composition of the
acid boric was set as 0.08mol%. Each raw materials Al ( NO3 )3 .9H2O,

Sr( NO3 )2 , H3 BO3 , and CO( NH2 )2 were dissolved into 20ml of deionized

water respectively to obtain transparent solution. Wet mixing was used

to obtain homogeneous mixture. Deionized water is selected instead of
distilled water due to the removal of the mineral ions such as cations
from sodium, calcium, iron, copper and anions from chloride and bromide
 LUMINESCENT MATERIALS AND APPLICATIONS 51

which will influence on the experiment result. Eu 2O3 was dissolves with
minimum amount HNO3 solution to convert into Eu( NO3 )3 according to

the Equation (1).

Eu 2O3 + 6HNO3 → 2Eu( NO3 )3 + 3H2O. (1)

The two solutions were mixed together and stirred by using magnetic
bar for several hours at 75°C to obtain viscous gel solution. The mixing
temperature is set at the range between 70°C to 80°C in this project due
to several reasons. Firstly, according to the MSDS, Aluminium nitrate
has quite low melting point (73°C) but high boiling point or decomposition
temperature (135°C). Heating aluminium nitrate above its melting point
encourage formation of homogeneous solution. Furthermore, it’s able to
dissolve acid nitric which has low boiling point (83°C).

The mixed viscous gel obtained continues for combustion reaction. In

this project, combustion is done by using hot plate instead of using
furnace. White combustion ash was obtained in 3-5 min by combusting
the precursor gel at temperature 500°C. Initially, the solution boiled and
underwent dehydration, followed by decomposition with emission of large
amounts of gasses (oxides of carbon, nitrogen and ammonia). Later, the
viscous gels spontaneously start to burn and burn slowly without flame
(smouldering combustion), thus producing white fined powder. The whole
process takes less than 5 minutes. When heated at 500°C, the powder
was hold for a few minutes to ensure the combustion reaction was
complete. The chemical equation of combustion is complicated and not
yet verified; however, the brief equation can be shown as below:

2Al ( NO3 )3 .9H2O + Sr ( NO3 )2 + CO( NH2 )2 + Eu( NO3 )3 + 1.5O 2 → SrAl 2O4 :

Eu 2 + + 20H2O + 5N 2 + 14.5O2 + CO2 . (2)

Next, the combustion ash was cooled to room temperature.

52 M. NAZAROV

The final pigments synthesis is done by heating the combustion ash

at 950°C-1100°C in a weak reductive atmosphere for 2 hours to obtain

SrAl 2O4 :Eu 2 + phosphor. The weak reductive atmosphere was created by
using graphite crucible to inhibit further oxidation take place.

Other compositions of persistent phosphors were synthesized by

similar methods.

Exciting by UV or sun light this phosphor shows bright blue-green

luminescence (Figure 6).

Figure 6. Bright luminescence of SrAl 2O4 :Eu 2 + , Dy 3 + based phosphor

in the open air under sun light excitation.

5. Persistent Phosphors for Painting, Medical

and Biological Applications

Applications of persistent luminescence phosphors are rapidly

expanding from bulk materials visible to everyone (e.g., exit signalization
 LUMINESCENT MATERIALS AND APPLICATIONS 53

on airplane cabin floors) to high tech products. In this review, we

consider traditional applications, such as painting, and more interesting
and important applications in medicine and biology. We propose also a
new direction in study and application these materials, namely,
underwater investigations of persistent luminescence for an artificial reef
and algae cultivation.

5.1. Painting

Persistent phosphors are a type of phosphors that have very long

persistent afterglow emission. The phenomenon of afterglow is as follows.
After the excitation source is turned off, emission from previously
trapped electrons is still observed. The irradiation used may be UV,
visible light, X-ray, gamma radiation as well as usual sun light.

The mechanism of long persistent phosphors’ phosphorescence is

basically a three-level electron transition mechanism, including a ground
state, an excited state, and a meta-stable trapping state.
Phosphorescence lifetime is usually longer than the lifetime at the
excited state, and it depends on the trap depth and trapping/detrapping
mechanism.

Persistent luminescence has been intriguing to people for hundreds of

years. The situation drastically changed about 17 years ago when
Matsuzawa et al. [17] discovered bright and long-lasting luminescence in
SrAl 2O4 :Eu 2 + , Dy 3 + . In 1996, they reported a new type of long

persistent phosphor SrAl 2O4 :Eu 2 + , Dy 3 + with a strong emission at

520nm (green), which is developed from a phosphor SrAl 2O4 :Eu 2 + found
by Abbruscato in 1971 [18]. Takasaki et al. [19] reported similar results.
They found an afterglow with both a far higher initial intensity and a
much longer lifetime compared to traditional ZnS: Cu, Co. The
persistence time of SrAl 2O4 :Eu 2 + , Dy 3 + was extended to longer than
16h (reported persistent time varied with detection limits from 10 to 20h)
after codoping with Dy 3+ .
54 M. NAZAROV

A short time later, a similar long persistent phosphor CaAl 2O4 :Eu 2 + ,

Nd 3 + was reported with a blue emission at 450nm [20]. These two

phosphors drew considerable attention from many scientists because a
16-h persistent time could bring phosphorescence over a whole night
[21-24]. Since then, long persistent phosphor becomes one of the major
research areas in luminescence materials.

Some novel methods have been developed while people are

developing new long persistent phosphor systems. These methods include
co-doping with ions as electron traps, co-doping ions to create defects for
defect related electron traps, persistent energy transfer, etc.

These investigations have led to a renewed research interest, and it

promoted the use of these persistent phosphors in signalization, traffic
signs, power switch, traffic police uniforms, luminous paints, glow-in-the-
dark toys, decorative objects, emergency signage, watches and clocks,
dials and displays, textile printing, medical diagnostics, and many other
applications.

Figure 7. Blue, red, pink, violet, yellow, and green colours are possible in
glow dark paint.
 LUMINESCENT MATERIALS AND APPLICATIONS 55

Phosphorescent paint is commonly called “glow-in-the-dark” paint. It

is made from different phosphors, such as silver-activated zinc sulphide,
or, more recently, doped strontium aluminate, and typically glows a pale
green to greenish blue colour. The mechanism for producing light is
similar to that of fluorescent paint, but the emission of visible light
persists for some time after it has been exposed to light. Phosphorescent
paints have a sustained glow which lasts for up to 12h after exposure to
light, but will eventually fade over time.

This type of paint has been used to mark escape paths in aircraft and
for decorative use, such as “stars” applied to walls and ceilings (Figure 8).

Figure 8. Glow-in-the-dark rocket, planets and stars wall stick.

56 M. NAZAROV

Some other examples of glow-in-the-dark application are shown in

Figures 9-12.

Figure 9. Hand-painted glow-in-the-dark blue Angelfish art magnet.

Figure 10. Luminescent paint by Pieter van den Bosch.

 LUMINESCENT MATERIALS AND APPLICATIONS 57

Figure 11. Decorative floor tiles.

Figure 12. A helmet and a high-voltage insulator (ceramic) in the day

time and at dark.
58 M. NAZAROV

5.2. Medical applications

With the development of high efficiency nanosized red phosphor, it

has become possible to incorporate it in organic matrices to produce
singlet oxygen, which kill cancer cells (Figure 13). This persistent
phosphor is a very good candidate for photodynamic therapy (PDT) of
cancer. Other light sources include light-emitting diodes (LEDs), which
may be used for surface tumors, such as skin cancer [25]. Researchers
continue to study ways to improve the effectiveness of PDT and expand
its use to other cancers.

Over 2 mln people annually lost due to cancer. Photodynamic therapy

has near 100% efficiency. PDT combines a drug (called a photosensitizer
or photosensitizing agent) with a specific type of light to kill cancer cells.
When photosensitizers are exposed to a specific wavelength of light, they
produce a form of oxygen that kills nearby cells [26-32] (Figure 13). PDT
may also be repeated and may be used with other therapies, such as
surgery, radiation, or chemotherapy [28, 29].

Figure 13. Cancer therapy using luminescent nanoparticles, which

produces red light and then singlet oxygen when irradiated with X-rays.
 LUMINESCENT MATERIALS AND APPLICATIONS 59

Each photosensitizer is activated by light of a specific wavelength

[30-34]. This wavelength determines how far the light can travel into
the body [25, 30-32]. Thus, doctors use specific photosensitizers and
wavelengths of light to treat different areas of the body with PDT.

In the first step of PDT for cancer treatment, a photosensitizing

agent is injected into the bloodstream. The agent is absorbed by cells all
over the body but stays in cancer cells longer than it does in normal cells.
Approximately 24 to 72h after injection [26, 27], when most of the agent
has left normal cells but remains in cancer cells, the tumor is exposed to
light. The photosensitizer in the tumor absorbs the light and produces an
active form of oxygen that destroys nearby cancer cells [26-32].

The light used for PDT in traditional application can come from a
laser or other sources [25, 28, 29] (Figure 14).

Figure 14. Laser light is directed through fiber optic cables.

Laser light can be directed through fiber optic cables (thin fibers that
transmit light) to deliver light to areas inside the body [28, 29]. For
example, a fiber optic cable can be inserted through an endoscope (a thin,
lighted tube used to look at tissues inside the body) into the lungs or
esophagus to treat cancer in these organs, but it is difficult in application
for internal organs. Therefore, the cancer therapy using luminescent
nanoparticles instead of optic cables seems to be promising and more
60 M. NAZAROV

efficient. One of the aims of our work is to use a red persistent nontoxic
nanosized phosphor exposed to X-ray inside the body as a new
photosensitizer and produce a form of oxygen that kills nearby cancer
cells.

5.3. Biological applications

There is a risk of forever damaging the existence of thousands

natural reefs because of tsunami or other cataclastic phenomena. We
need to know how to restore or sometimes to improve reefs and marine
ecosystems. Therefore, measuring and interpreting the impact of human
actions on the diversity on marine and oceanic life represent one way to
prevent ecological disasters and predict possible environmental changes.

Artificial rock and block made of steel slag hybrid matrix were
developed recently in Japan [35, 36]. Electric Arc Furnace (EAF) slag is
the byproduct from steelmaking process with an estimated amount
generated of about 10-15 weight percent (wt.%) for every ton of steel
produced [37]. Steel slag is used in the production of cement [37], coastal
marine blocks for seaweed bed [38] and substrate for mangrove
rehabilitation [39]. Steel slag has also been shown to be effective in corral
growing due to significant amount of calcium and silicon present in its
composition [40]. Steel slag can be modified to form potassium calcium
silicate ( K 2CaSiO4 ) [38]. This mineral has been of interest in the field of
applied mineralogy due to the crystal structure which dissolves slowly in
acidic soil providing valuable nutrients [41]. Its production from
steelmaking slag is renewable resource and allows for greater waste
recycling from steelmaking process. It can also be found in products such
as the ashes from biomass combustion [42]. The production of this
fertilizer is from iron slag after the desiliconization process of hot metal
in the steel mill [38]. The main mineral phase present was K 2Ca 2Si 2O7
[43]. However, researchers are yet to clarify the actual chemical
composition of mineral phase present in this compound and mechanism
of its dissolution as a fertilizer [42].
 LUMINESCENT MATERIALS AND APPLICATIONS 61

We propose experimental artificial glow reef to make from steel slag

as well as from concrete and sand to provide hard surface. Other decision
is to cover this artificial reef as well as real corals by persistent
phosphors. The main goal of these experiments is to cultivate the algae in
future and to attract the fishes. An artificial block from concrete and
sand covered by SrAl 2O4 :Eu 2 + , Dy 3 + based phosphor was made and a
new direction in study and application of persistent phosphors was
proposed. For the first time, the underwater luminescence was
experimentally studied in real sea conditions. Our pioneers works in this
field were published recently [44, 45].

In this present study, Scheil-Gulliver model was applied to slag

solidification to characterize the solidification behavior of mineral phase
formation in a modified EAF slag system. Details of the solidification
modeling have been described elsewhere [46]. In the experimental work,
EAF slag from a Malaysian steel company was modified with 20wt.%
K 2CO3 . Each powder mixture was placed in an alumina crucible and
melted in a Lenton EHF 1700 furnace. Details of the experimental work
have been described elsewhere [47]. The plant chosen for the study was
Typhonium flagelliforme or better known in Malay as “Keladi Tikus”.
Typhonium flagelliforme is a medicinal herb plant that belongs to the
Araceae family [48]. For the plant fertilization study, 3 conditions was
investigated. These conditions were in a deionized water (DI) without
fertilizer, DI with potassium silicate slag (PSS) fertilizer and DI with
PSS coated by an epoxy layer with persistent SrAl 2O4 :( Eu 2 + , Dy 3 + )
phosphors. The phosphors coating was done to investigate the effect of
fertilizer absorption due to enhance photosynthesis activity. Persistent
phosphors can emit light for a long time from seconds to many hours
after the excitation has ended. The irradiation used may be UV, visible
light, X-ray, gamma radiation, as well as usual sun light.
62 M. NAZAROV

The results of solidification model for slag system is given in Figure

15. For 0.6 CaO/SiO2 wt. ratio, after complete solidification, six mineral
phases were formed, with their percentage fraction given in Figure 15.
Potassium silicates (PS) started to form at 650°C and reached a
maximum composition of 27.5wt.% at 605°C where the solidification ends.
Detailed analysis of effect of CaO/SiO2 wt. ratio with respect to PS
formed is given elsewhere [49].

Figure 15. Fractions of simulated mineral phase during solidification at

1330°C-600°C ( CaO/SiO2 = 0.6 ) .

The mineralogical compositions of the modified PSS samples were

analyzed by XRD and shown in Figure 16. The diffraction patterns of the
slags showed that there are heterogeneous materials consisting of
mixtures of crystalline and amorphous phases. According to Figure 16,
three crystalline phases were identified in the air cooled synthetic slag
(EAF0A): potassium silicate ( K 2Si 2O5 ) , silicon dioxide ( SiO2 ) and
 LUMINESCENT MATERIALS AND APPLICATIONS 63

alpha calcium silicate ( α-CaSiO3 ) . In the water cooled synthetic slag

(EAF0W), three crystalline phases were detected: alpha calcium silicate
( α-CaSiO3 ) , potassium silicate ( K 6 Si 3O9 ) and potassium calcium
silicate ( K 8CaSi10 O25 ) .

Figure 16. XRD pattern of modified synthetic EAF slags system. EAF0A
= Air cooled with 0.6 wt. ratio of CaO/SiO2 and EAF0W = Water cooled
with 0.6 wt. ratio of CaO/SiO2 .

Initial plant fertilization study by PSS was investigated on

Typhonium flagelliforme in DI water with different conditions. Figure 17
shows the pH relationship to different fertilization conditions. From
Figure 17, the pH values increased within the first 24 hours in all plants
before slowly settling to an optimum condition after 400 hours. Plants
grown with DI only settled at a pH of 5, which is close to pH produced by
2wt.% of citric acid. The acidic nature of the Typhonium flagelliforme is
well suited to the application of PSS [50]. This is due to the
neutralization that will occur with the basic PSS. On the other hand, the
plants with PSS and coated PSS fertilization settled at a basic pH. Both
64 M. NAZAROV

conditions showed a similar trend in the pH values variation with time,

settling at around 8.9 and 8.7. However, the coated PSS had a slightly
lower pH value. This can be attributed to the phosphor coatings which
slowed the release of nutrients from the PSS fertilizer. Future work will
investigate the nitrogen, potassium, calcium, silicon, and phosphorus
content of the leaves with respect to the fertilization conditions. It has
been shown that a higher potassium and silicon uptake by plants is
expected with PSS fertilization [51]. This in turn will lead to better plant
growth and disease immunity [52].

Figure 17. pH measurement of Typhonium flagelliforme with different

fertilization condition.

5.4. Underwater luminescence

Below we show some applications of artificial reefs from metallic

construction and slag with persistent phosphors in real sea conditions
near the Malaysia in Indian Ocean.
 LUMINESCENT MATERIALS AND APPLICATIONS 65

The real underwater experiments in sea conditions were carried out

in Pulau Payar, Malaysia. First, the artificial blocks covered by
SrAl 2O4 :Eu 2 + , Dy 3 + and excited by the sun light were installed on the
ocean floor with different relief (agropora corals, rocks, sand) and at
different deep from 2 up to 6 meters. Figure 18 shows the process of
installation artificial luminescent block on real stone in the sea at the
deep about 5 meters.

Figure 18. Installation of concrete matrix covered by SrAl 2O4 :Eu 2 + ,

Dy 3 + .

Next step was the underwater luminescence investigations. All blocks

showed the bright blue-green luminescence from all the places
independently of relief and deep. One of the examples is demonstrated in
Figure 19.
66 M. NAZAROV

Figure 19. Blue-green colour luminescence of SrAl 2O4 :Eu 2 + , Dy 3 + from

5 meters deep in real sea conditions.

After some minutes the fishes were interested in a new luminescent

object and gathered around it (Figure 20).

Figure 20. The fishes are attracted by bright and long-lasting

luminescence of SrAl 2O4 :Eu 2 + , Dy 3 + .
 LUMINESCENT MATERIALS AND APPLICATIONS 67

Finally, the black-tip shark was also interested in luminescence and

came near our artificial sample (Figure 21).

Figure 21. The black-tip shark is also interesting in luminescence.

Figure 22. Real coral on a metallic construction (Pulau Kapas).

68 M. NAZAROV

Figure 23. Artificial coral reefs (Pulau Kapas).

Figure 24. Green luminescence from slag covered by persistent

SrAl 2O4 :Eu 2 + , Dy 3 + in sea-urchin environment.
 LUMINESCENT MATERIALS AND APPLICATIONS 69

Figure 25. Artificial luminescent block inside real corals.

Figure 26. Real coral with phosphor inside.

70 M. NAZAROV

Figure 27. Night luminescence of real coral covered by phosphor.

Figure 28. Night luminescence of artificial slag covered by phosphor.

 LUMINESCENT MATERIALS AND APPLICATIONS 71

Figure 29. The clown fishes are attracted by the bright light of artificial
reef.

6. Conclusions

Short review is given to show the past and present of luminescent

materials.

Major phosphor’s applications in traditional display, flat panel

display, lighting, medical, security are presented.

Multiphase micro and nanoparticle blue-green persistent phosphor

with turquoise luminescence was synthesized and applied for painting,
medical and biological investigations.

A lot of examples show a very large range of applications of persistent

luminescence phosphors from bulk materials visible to everyone to high
tech products, especially in medicine. The development of high efficiency
nanosized phosphor gives the possibility to incorporate it in an organic
matrix to produce singlet oxygen, which kill cancer cells. This persistent
phosphors are very good candidates for photodynamic therapy of cancer.
72 M. NAZAROV

For the first time, the experiments with an artificial stone covered
with SrAl 2O4 :Eu 2 + , Dy 3 + based phosphor were carried out under real
sea conditions in Pulay Payar Marine Park Malaysia. Strong, and bright
blue-green (turquoise) luminescence was observed and registered under
water.

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