A Search for New Red Phosphors Using a

Computational Evolutionary Optimization

Process**
By Kee-Sun Sohn,* Jae Mun Lee, and Namsoo Shin
A three-band white-light-emitting diode (LED) consists of
an LED device that emits either soft ultraviolet (UV) or blue
light and redgreenblue (RGB) phosphors.[13] For the threeband white LEDs developed so far, InGaN and GaN chips
have been under consideration as excitation sources for RGB
phosphors. In this case either organic dyes or inorganic phosphors have attracted interest as RGB components for threeband white LEDs.[13] It should, however, be noted that the
lifetime of organic materials is too short and that all the inorganic phosphors under consideration pose some environmental problems both in preparation and in use because they
include toxic elements, such as sulfur, chlorine, and cadmium.[2,3] In order to avoid such problems, our objective was to
develop new oxide RGB phosphors. As a first step red oxide
phosphors were developed in the present investigation. Blue
and green phosphors will be also developed in the near future
based on the same methodology and a similar chemical composition system. We initially adopted a Eu3+-activated alkali
earth borosilicate system as a red phosphor for a three-band
white LED. This system includes seven cations, including Eu,

[*] Prof. K.-S. Sohn, J. M. Lee

Department of Materials Science and Metallurgical Engineering
Sunchon National University
Chonam 540742 (Korea)
E-mail: kssohn@sunchon.ac.kr
Dr. N. Shin
Beamline Division, Pohang Accelerator Laboratory
Kyungbuk 790784 (Korea)

[**] This work was supported by grant No.R012002000002030 from the

Basic Research Program of the Korea Science & Engineering Foundation.

Adv. Mater. 2003, 15, No. 24, December 17

DOI: 10.1002/adma.200305291

Mg, Ca, Sr, Ba, B, and Si. There are a large number of stoichiometric compounds (single-phase line compounds) and an
infinite number of their solid solutions in this system as well.
By considering the fact that the highest luminescence is not always elicited from a single-phase line compound, a mixed
compound would be better suited to the host of Eu3+ emission.
It is practically impossible to examine the complete composition range of a seven-dimensional system without a new
optimization process surpassing any other conventional highthrough-put combinatorial-chemistry (combi-chem) method
in terms of efficiency. Genetic algorithm-assisted combi-chem
(GACC) has recently attracted interest due to its ability to
compensate for the weak points in the traditional highthrough-put combi-chem, thereby enhancing the efficiency of
exploring new materials for specific purposes.[48] In fact this
methodology originated in the pharmaceutical research
area.[46] In the area of inorganic material synthesis concerned
with GACC, Baerns and co-workers[9,10] recently used GACC
for the development of heterogeneous catalytic materials.
Their approach[9,10] was found to be very efficient and promising in a search for new inorganic-catalytic materials. It is our
opinion that inorganic phosphors are more suitable for the
GACC method based on the fact that the screening process
can be greatly facilitated compared to that for catalytic
materials. In fact, we have already developed a promising
methodology that enables large-scale libraries and swift
screening.[1117] Thus, we were able to construct a 108-composition library in a single generation, and only two or three
days were required to complete the synthesis and characterization of a generation. A solution-based combi-chem method
was employed for the synthesis of phosphor powders. In the
solution-based combi-chem method, reagents are typically
delivered individually to each sample site. In order to create
these libraries efficiently with respect to process speed and
accuracy, we developed a scanning multi-injection delivery
system for the rapid and accurate delivery of several hundreds
of microliters of precursor solutions to sample sites. As a result, a substantial amount of material can be obtained, which
could be sufficient for any type of conventional characterization process without the need for any special additional instrumentation. When the combi-chem technique was applied
to the phosphor materials, most approaches were concerned
with thin film technologies and the fundamental goal of these
approaches was the development of a larger library on small
substrates. In fact, it is now possible to prepare more than a
2000-composition library on a 1 in. (1 in. = 2.54 cm) square
substrate using a masking technology.[1824] It should, however,
be noted that such an approach has limitations. First, the
amount of each compound is too small to be characterized
conventionally, and the luminescent properties in the thin film
state may be different from the powder properties. Because
phosphors are typically applied to most application systems in
the form of a powder, the approach used here could be more
promising for phosphor research. It is true that our solution
combi-chem system, which only develops a small library (only

2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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[14] Inorganic Crystal Structure Database, http://www.fiz-karlsruhe.de/fiz/

products/icsd/icsd.html, ICSD Collection Code 72155.
[15] G. Mogensen, M. Mogensen, Thermochim. Acta 1993, 24, 47.
[16] E. Zolotoyabko, J. P. Quintana, J. Appl. Crystallogr. 2002, 35, 594.
[17] J. P. Nair, N. Stavitski, I. Zon, K. Gartsman, I. Lubomirsky, A. L. Roytburd, Europhys. Lett. 2002, 60, 782.
[18] I. Riess, R. Koerner, M. Ricken, J. Noelting, Solid State Ionics 1988, 28,
539.
[19] I. Riess, H. Janczikowski, J. Nolting, J. Appl. Phys. 1987, 61, 4931.
[20] E. A. Kummerle, G. Heger, J. Solid State Chem. 1999, 147, 485.
[21] Inorganic Crystal Structure Database, http://www.fiz-karlsruhe.de/fiz/
products/icsd/icsd.html, ICSD Collection Code 88758.
[22] C. C. Chin, R. J. Lin, Y. C. Yu, C. W. Wang, E. K. Lin, W. C. Tsai, T. Y.
Tseng, Phys. C 1996, 260, 86.
[23] M. S. Al-Robaee, K. Narasimha Rao, S. Mohan, J. Appl. Phys. 1992, 71,
2380.
[24] W. Lohwasser, J. Gerblinger, U. Lampe, H. Meixner, J. Appl. Phys. 1994,
75, 3991.
[25] E. J. Preisler, O. J. Marsh, R. A. Beach, T. C. McGill, J. Vac. Sci. Technol.
B 2001, 19, 1611.
[26] G. T. A. Kovacs, Micromachined Transducers Sourcebook, 1st ed., WCB
& McGraw Hill, New York 1999.
[27] R. M. A. Azzam, Ellipsometry and Polarized Light, North-Holland, Amsterdam 1987.
[28] G. G. Stoney, Proc. R. Soc. London, Ser. A 1909, 82, 172.

2082

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Normalized Fitness

Normalized Fitness

1.0 a

Normalized Fitness

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about hundred compositions are available per generation), is

not comparable to a thin-film combi-chem system comprised
of more than 2000 compositions in view of screening efficiency. However, the introduction of the GACC to our small-library solution combi-chem system made it possible to promote the efficiency of our method to a level comparable to
that of the high-throughput thin-film combi-chem system.
The GACC begins with non-orderly arrayed compositions.
Namely, the combinatorial library was constituted randomly
in advance. This randomly chosen library is called the first
generation. The population of this is much smaller than the
regular high-throughput thin-film combi-chem system. Evolutionary operations, such as elitism, selection, crossover, and
mutation, were then applied to this first generation using the
actually measured luminance values of all the members in the
first generation. This process yielded another new 108 compositionsthis is called the second generation. The second generation will show a somewhat improved luminance. The same
processing was done on the second generation and yielded the
third generation, and so on. This process will improve the
luminance of all the members in the generation as the generation number increases, finally leading us to the optimum.
Namely, the GACC includes repetitions of the synthesis/measurement based on the combi-chem technique and the computational evolutionary operation based on the measurement
results. It can be thus summarized that the GACC consists of
two parts; one is the experimental part and the other is the intermediate computation part.
Prior to the experiment, involving synthesis, characterization, and the computational evolutionary process, simulations
were carried out using three different hypothetical objective
functions. It is not efficient to examine the effect of the calibration of model parameters, such as selection, crossover and
mutation method, and the population size, etc., on optimization speed and correctness, because the optimum choice of
model parameters is strongly dependent on the objective
function, but we are totally unaware of the objective function
of concern in the actual experiment. Baerns and co-workers[10]
have already investigated the effect of the above-described
model parameters based on a certain objective function and
found that the variations between them had little effect on the
outcome. An investigation of how the whole optimization process is altered by the different objective functions is significant. In this regard, three different hypothetical objective
functions were introduced and optimization speed and correctness was then monitored with respect to the objective
function while keeping all the model parameters fixed. The
selection, crossover, and mutation rates were all set at 100 %.
The roulette wheel selection was adopted and the highest two
compositions in the former generation were elicited and copied to the next generation. The single-point crossover was
adopted and the crossover point was determined randomly.
The composition was normalized after the crossover. The
mutation was achieved by adding and subtracting 0.01 mol for
two arbitrary chosen components, respectively. Figures 1ac
show the maximum and average fitness (luminance, in our

0.8
0.6
0.4
0.2
1.0

0.8
0.6
0.4
0.2
1.0

0.8
0.6
0.4
0.2
0

10

15

20

25

30

35

40

Generation
Fig. 1. Maximum (j) and average (s) luminance of each generation as a function of generation. This simulation was carried out based on three hypothetical
objective functions (hypothetical luminance functions), see Appendix.

case) of each generation as a function of the generation number for three hypothetical objective functions (hypothetical
luminance functions), whose local and global optimum points
were analytically obtained. This means that the luminance
was assumed to be a function of seven variables (the mole
fractions of seven constitutive elements). The function values,
which are below zero, were set as zero to permit the simulation of a more plausible objective function with discontinuities. The data shown in Figure 1 are the results from ten runs.
The objective function (OF), global maximum point (OP),
and number of local maximum points (# of LOP) used in each
simulation are given in the Appendix. Figure 1a shows the
uniquely convex objective function with no local maximum
point. On the other hand, Figures 1b,c show somewhat more
complex shaped functions with several local maximum points.
The optimization speed and correctness did not vary significantly with the objective function but it was found that unlike
the others, Figure 1b showed a relatively scattered result. This
implies that the change in objective function has an influence,
but there is no systematic way of unveiling it at the present
stage. This simulation only provided information for reaching
the optimum point in only ten generations irrespective of the
choice of objective function and model parameters.
Figure 2a shows the actual experimental results, in which
the maximum and average luminance values are plotted as a
function of generation number. As can be seen in Figure 2a,
both values increase with increasing generation number. The
composition in the first generation was not completely random but some knowledge based on the material science was
involved into the library design by taking into account the
nature and characteristics of phosphors. The confinements

http://www.advmat.de

Adv. Mater. 2003, 15, No. 24, December 17

employed in the first generation are as below; Eu3+ doping

did not exceed 50 mol-% of the sum of alkali earth elements
and compositions that do not contain any alkali earth elements were non-existent. The inset in Figure 2a shows the
first and tenth generation photographed under an excitation
of 365 nm. Even though the lamp light was not illuminated
evenly over the library in this case and the excitation light
wavelength of the lamp (365 nm) differs from the 400 nm excitation that was adopted for subsequent quantitative measurements, it can be seen that the tenth generation contains
much more promising compositions than the first. The maximum luminance began to saturate from the sixth generation.
Consequently, the composition of the highest luminance was
fixed at Eu0.14Mg0.18Ca0.07Ba0.12B0.17Si0.32Od after that. The
first generation contained a considerable number of glassy
members (38 of 108). These were all precluded prior to the
computation by setting their luminance values at zero irrespective of the intensity of their luminescence, thereby reducing the number of glassy members in the next generation. As
a result, there were very few glassy members in the tenth generation (4 of 108). It should be noted that the discontinuities
that we introduced into the hypothetical objective functions
reflected the occurrence of these glassy members. Figure 2b
shows the average mole fraction of each component for the
top eleven compositions for each generation.
Even though we started with a seven-element system, strontium was rapidly weeded out (the sample with the highest
luminance is approximated to Eu0.14Mg0.18Ca0.07Ba0.12B0.17-

Adv. Mater. 2003, 15, No. 24, December 17

http://www.advmat.de

2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2083

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Fig. 2. a) Maximum (d) and average (j) luminance of each generation as a

function of generation; b) the average mole fraction of each component for the
top eleven compositions of each generation. The inset in (a) represents the
libraries of both the first and tenth generation at the 365 nm excitation.

Si0.32Od). As may be expected, Eu0.14Mg0.18Ca0.07Ba0.12B0.17Si0.32Od does not appear to result in a stoichiometric single
line compound, which was tentatively verified by referring to
both the JCPDS (Joint Committee of Powder Diffraction
Standards) data and phase diagrams of MgOB2O3SiO2,
CaOB2O3SiO2, and BaOB2O3SiO2 systems. It can thus
be deduced that the top eleven members, whose compositions
are close to Eu0.14Mg0.18Ca0.07Ba0.12B0.17Si0.32Od, might be a
mixture of well-known stoichiometric compounds, which are
presented in the JCPDS data and phase diagrams. Kim et
al.[13] confirmed that a non-stoichiometric compound exhibits
a higher luminance than the constituent stoichiometric line
compounds in the CaGdAlO4/CaGdAl3O7 mixture system
and provided a reasonable interpretation for such a finding.
Accordingly, the Eu3+ luminescence of the mixed compound
Eu0.14Mg0.18Ca0.07Ba0.12B0.17Si0.32Od could also be superior to
its constituent stoichiometric compounds, even though its constituent compounds were not yet identified. Phase identification is currently being carried out on X-ray diffraction (XRD)
data of Eu0.14Mg0.18Ca0.07-Ba0.12B0.17Si0.32Od obtained using a
synchrotron light source to obtain information concerning the
constituent compounds and their precise proportion. However, such an analysis is not easy at the current stage because
of the large number of candidates that could constitute Eu0.14Mg0.18Ca0.07Ba0.12B0.17-Si0.32Od. The phase identification as
well as several other routine analyses, such as emission/excitation spectra, decay curves, reflectance, thermal analysis, and
powder characterization, of Eu0.14Mg0.18Ca0.07Ba0.12B0.17Si0.32Od and its constituent compounds will be published
separately as a full paper in the near future.
From the practical point of view, it is more interesting to
investigate how promising the luminance level of the Eu0.14Mg0.18Ca0.07Ba0.12B0.17Si0.32Od could be rather than a phase
identification. The luminance of Eu0.14Mg0.18Ca0.07Ba0.12B0.17Si0.32Od was five times higher than the commercially available
Y2O3:Eu3+ and nearly ten times higher than the commercially
available Y2O2S:Eu3+ red phosphors at 400 nm excitation.
However, these data were not compared to the ZnCdS:Ag
red phosphor, which has been considered to be a good candidate for the red component of a three band white LED.[3]
Instead, a commercially available ZnS:Cu,Al green phosphor
was used as a reference by considering the fact that the
quantum efficiency of the ZnS:Cu,Al green phosphor is
approximately twice as high as the ZnCdS:Ag red phosphor.
Consequently, it was found that the luminance of Eu0.14Mg0.18Ca0.07Ba0.12B0.17Si0.32Od at 400 nm excitation was lower
than the ZnCdS:Ag red phosphor by a factor of 10 %.
In summary, the validity and applicability of the GACC
method was confirmed with regard to the development of inorganic phosphor materials. Through the simulation using
three different hypothetical objective functions, it was found
that the global optimum point can be reached in at least 10
generations even though slight differences might exist with respect to the objective function. In the actual experiment, the
maximum luminance was enhanced by about 100 % only six
generations after the onset of the GACC process. The maxi-

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mum luminance was obtained at a composition of Eu0.14Mg0.18Ca0.07Ba0.12B0.17Si0.32Od. This suggests that the optimum composition Eu0.14Mg0.18Ca0.07Ba0.12B0.17Si0.32Od did
not constitute a single line compound but, rather, a mixture of
several well-known stoichiometric compounds. The luminance
of Eu0.14Mg0.18Ca0.07Ba0.12B0.17Si0.32Od was higher than any
other well-known red phosphors at 400 nm excitation.

Experimental
The overall process of the combi-chem system adopted in the present investigation is described in more detail in our previous reports [1117]. The Eu, Si,
and Ca solutions were prepared by dissolving Eu2O3 (0.1 mol), Si(C2H5O)4(TEOS) (0.5 mol), and CaCO3 (0.5 mol) in nitric acid. The Mg, Sr, Ba, and B
solutions were prepared by dissolving Mg(NO3)26H2O (0.5 mol), Sr(NO3)2
(0.5 mol), Ba(NO3)2 (0.25 mol), and H3BO3 (0.5 mol) in deionized water. The
appropriate amount of each solution was then injected into a 6 mL test tube
array according to the composition table with the assistance of a computer programmed injection system (108 different compositions per generation were
used). The solutions in the tubes were dried at 80 C for 24 h. At this stage gelation took place for those compositions that contained more than 0.3 mol of Si,
but the others were simply dried. These samples were further dried at 600 C
for 2 h. The dried samples were pulverized and collected in a specially designed
ceramic container (given the name combi-chem container) and successively
fired at 900 C for 2 h in an ambient atmosphere. The firing temperature was
selected out of several other temperatures such as 900, 1000, 1100, and 1200 C
in view of the average and maximum luminance value of the first generation.
Some of the samples chosen among the library were removed from the combichem containers and examined by XRD and scanning electron microscopy
(SEM) analyses. The emission spectra and the decay curves were monitored at
400 nm, which simulates an InGaN LED light source, with the samples being
left in the combi-chem containers using a plate reader accessory attached to a
Perkin Elmer LS50B spectrometer with a xenon flash lamp. The luminance was
calculated by integrating the product of the emission spectrum and the standard
visual spectral efficiency curve based on CIE (Commission Internationale de
l'Eclairage) regulation [25].

Appendix
The hypothetical objective functions (hypothetical luminance functions)
used for the simulations shown in Figure 1a are:
OF

P
1


OP

xi

p1 ; p1 ; p1 ; p1 ; p1 ; p1 ; p1
7 7 7 7 7 7 7

7
P
1

(1a)

(1b)

By Christoph Waldauf,* Pavel Schilinsky, Mario Perisutti,

Jens Hauch, and Christoph J. Brabec*


OP

7p
sin xi
2

1 1 1 1 1 1 1
; ; ; ; ; ;
7 7 7 7 7 7 7

(2a)

(2b)

# of LOP = 6.
Those used for Figure 1c are:
OF

7
P
1


OP

ai sin

1 1 1 1 1 1 1
; ; ; ; ; ;
9 9 9 6 6 6 6

# of LOP = 32.

2084

pxi
; a13 1=9 a47 1=6
2ai

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Solution-Processed Organic n-Type Thin-Film

Transistors

# of LOP = 0.
Those used for Figure 1b are:
OF

Over the last few years, impressive progress has been made
to develop high-performance solution-processable organic
semiconductors. First display applications have already entered the market and the next generation of organic semiconductor devices is close to being released.[1,2] For the products
currently available, the lower performance of the organic
semiconductors concerning electronic parameters but espe-

(3a)


(3b)

Received: April 22, 2003

Final version: September 14, 2003

2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

[*]

C. Waldauf, Dr. C. J. Brabec, P. Schilinsky, M. Perisutti, Dr. J. Hauch

Siemens AG, CT MM1, Innovative Polymer
Paul-Gossen-Str. 100, D-91052 Erlangen (Germany)
E-mail: christoph.waldauf.ext@erls.siemens.de,
Christoph.Brabec@siemens.com
C. Waldauf, P. Schilinsky
Department of Energy and Semiconductor Research
University of Oldenburg
D-26129 Oldenburg (Germany)

DOI: 10.1002/adma.200305623

Adv. Mater. 2003, 15, No. 24, December 17