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Recent progress in luminescence tuning of Ce3+

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and Eu2+-activated phosphors for pc-WLEDs

Cite this: DOI: 10.1039/c4cs00446a
Guogang Li,*a Ying Tian,a Yun Zhaoa and Jun Lin*b

Received 2nd December 2014
DOI: 10.1039/c4cs00446a
www.rsc.org/chemsocrev
Nowadays, phosphor converted white light-emitting diodes (pc-WLEDs) have been widely used in solid-
state lighting and display areas due to their superior lifetime, efficiency, and reliability as well as
significant reduction in power consumption. Phosphors are indispensable components of pc-WLED
devices, and their luminescence properties determine the quality of WLED lighting and displays. In order
to further achieve high luminous efficacy, chromatic stability, and color-rending properties in pc-WLEDs,
much effort has been focused on improving current pc-WLED phosphors and developing novel
pc-WLED phosphors recently. This review article concerns commonly used rare earth ion (Eu2+ and Ce3+)
activated inorganic phosphors, highlighting the important effect of spectral tuning via local structural variations
on improving the luminescence performance of phosphors. The main spectral tuning strategies are discussed
in detail and summarized, including (1) doping level control; (2) cationic substitution; (3) anionic substitution;
(4) cationic–anionic substitution; (5) the crystal-site engineering approach; (6) mixing of nanophases.

1. Introduction sources owing to their extraordinary luminous efficiency and

Nowadays, phosphor-converted white light-emitting diodes
(pc-WLEDs) are burgeoning and are extensively considered as
the most promising new generation solid state lighting (SSL)
a
Faculty of Materials Science and Chemistry, China University of Geosciences,
Wuhan 430074, P. R. China. E-mail: ggli8312@gmail.com
b
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of
Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R. China.
E-mail: jlin@ciac.ac.cn; Fax: +86-431-85698041
brightness, low power consumption, reliability, long operation
life and environmental friendliness compared to other lighting
technologies, like incandescent, halogen, xenon, fluorescent
lamps and so on.1 Especially in terms of energy saving,
pc-WLEDs have tremendous advantages compared to the above
other light sources. According to the statistics of the US
Department of Energy (DOE) in 2012, in the next two decades
(2010–2030), WLED lighting technology will save at least 20% of
total electricity consumption per year if a nationwide move
toward SSL for general illumination.1 No other lighting

Guogang Li is currently an Ying Tian is currently studying

associate professor in the China
University of Geosciences (Wuhan).
He received his BSc degree from
the Hebei Normal University of
Science & Technology in 2007
and was a graduate student at
the Changchun Institute of Applied
Chemistry (CIAC), Chinese Academy
of Sciences, and received a PhD
degree in 2012. After graduation,
he worked as a postdoctor in
Guogang Li Taiwan University for one year.
His current research interests
mainly include synthesis of luminescent materials for field
emission displays (FEDs) and white light emitting diodes
(W-LEDs) via solid state reaction and soft chemistry methods.
for her master’s degree in the
China University of Geosciences
(Wuhan). She received her BSc
degree from the College of
Technology, Hubei Engineering
University in 2014 and entered
into Prof. Guogang Li’s group in
the same year. Her current research
interests focus on the synthesis of
pc-WLED phosphors for white light
emitting diodes (W-LEDs) for solid-
Ying Tian state lighting and displays via solid
state reaction and soft chemistry
methods.

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Fig. 1 Schematics of the two principal white-lighting strategies of pc-WLED devices. (a) A blue chip with a yellow downconverting phosphor. (b) A n-UV
chip with red, green, and blue (RGB) downconverting phosphors. In order to obtain warm white light in the strategy (a), it can be modified as follows:
(c) mixing the blue chip with yellow and red downconverting (RY) phosphors; or (d) mixing the blue chip with green and red downconverting (RG)
phosphors.

technology can offer so much potential to save energy. Therefore,
they are very important for the reduction of global power require-
ments and the use of fossil fuels. On the other hand, pc-WLEDs
are excellent backlight sources for use in display areas such as
liquid crystal displays (LCDs).2 To build highly efficient WLED
devices, many aspects should be considered and optimized,
including semiconducting components (generally InGaN semi-
conductor chips), phosphor conversion components, and
luminaires as well as packaging technologies. Phosphors are
indispensable components of pc-WLED devices, and the explora-
tion and development of pc-WLED phosphors for use as lighting
and display backlight sources is one of the most important and
urgent challenges, which can be met by advanced science and
technology.3,4 Generally, in pc-WLEDs, downconverting phos-
phors are used to connect with bright blue or near ultra violet
light (n-UV) LEDs to generate white light, and two main strategies
are exploited as follows: one is to combine highly efficient
(Ga,In)N blue LEDs (420–480 nm) with yellow-emitting phos-
phors, as in a device with a schematic structure shown in
Fig. 1a.2 For example, the most common and easiest way is the
combination of a 460 nm blue InGaN LED chip and a yellow
phosphor of a cerium(III)-doped yttrium aluminum garnet
(YAG:Ce3+), which is still in widespread use today. However,
such a device has a poor color rendering index (Ra = 70–80) and
a high correlated color temperature (CCT = 4000–7500 K)
because of the lack of a red component. The modified ways
for achieving white light with a high Ra and a suitable CCT are
to coat yellow-emitting phosphors with a more red component
(Fig. 1c, right) or to mix green and red multi-phased phosphors
on 460 nm blue LEDs (Fig. 1d, right).5–15

Yun Zhao is now a postgraduate Jun Lin is a professor at the

student in China University of
Geosciences (Wuhan). She received
her BSc from JiangHan University
in 2011. She worked as a chemical
laboratory technician for 3 years
after undergraduate graduation.
Now, Prof. Guogang Li is her super-
visor for her Master’s degree. Her
current research interests focus
on the synthesis of pc-WLED phos-
phors for white light emitting
Yun Zhao diodes (W-LEDs) for solid-state
lighting and displays via solid
state reaction and soft chemistry
methods.
Changchun Institute of Applied
Chemistry (CIAC), Chinese
Academy of Sciences (CAS). He
received BSc and MSc degrees in
inorganic chemistry from Jilin
University, in 1989 and 1992,
respectively, and a PhD degree
(inorganic chemistry) from
CIACCAS, in 1995. He has
worked as a postdoctor for more
than 4 years in CityU (HK, 1996),
Jun Lin INM (Germany, 1997) and VCU/
UNO (USA, 1998–1999). His
research interests include luminescent materials and multifunc-
tional composite materials together with their applications in
display, lighting and biomedical fields. He has published more
than 400 peer-reviewed journal articles in related fields.

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Chem Soc Rev
It is noticed that multi-phased phosphor converted systems
frequently result in the addition of the manufacture cost, and
low luminescence efficiency owing to the strong reabsorption
of the emission of blue or green phosphors by yellow and red-
emitting phosphors. The second approach involves mixing of
the emission from red, green, and blue (RGB) phosphors with
n-UV LED chips (380–420 nm), as in a device with a schematic
structure shown in Fig. 1b.16–24 It is similar to the first strategy
that low efficiency due to reabsorption, and problems of sedi-
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mentation and uniformity distribution of phosphors in silicon
resin cannot be avoided. In return, several benefits including
an extremely high color rendering index (Ra 4 90), a wide color
gamut coverage and a stable light color output at different drive
currents can be owned.16–24 In addition, in order to decrease
the reabsorption effect among phosphors and enhance their
luminescence efficiency and color rendering index, WLEDs
based on single-phased white light emitting phosphors have
been extensively investigated and developed.25–30 In general,
phosphors are vital to the development of the WLED lighting
and backlight display industry. Highly efficient and emission-
tunable phosphors not only can enhance the energy efficiencies
of WLEDs but also present potential advantages in the color
rendering index, correlated color temperature and color gamut,
which enlarge their use in vehicle lights, architecture decorations,
streetlights, directional lighting, clinical medical lighting, etc.
Therefore, novel and acceptable fluorescent materials for improving
the performances of solid-state lighting must be developed.31,32
So far, there have been a number of useful reviews summarizing
on the pc-WLED phosphors for solid-state lighting or backlight
displays by Jüstel et al.,33 Lin & Liu,3 Xie,34 Höppe,35 Schnick,36
and Shang & Lin37 et al. Especially, some recent reviews have
systematically summarized the design, optical properties and the
application of pc-WLED phosphors with the emphasis on the
dependence of luminescence properties on composition.38–40
For example, Smet and co-authors presented, identified and
discussed six main criteria dealing with the shape and position
of the emission and excitation spectra, the thermal quenching
behaviour, the quantum efficiency, the chemical and thermal
stability and finally with the occurrence of saturation effects.38
Based on these criteria, the most common dopant ions (broad-
band emitting Eu2+, Ce3+ and Mn2+, and light-emitting rare earth
ions) and host compounds (garnets, sulfides, and (oxy)nitrides)
are evaluated. Ye et al. reviewed the most recent advances in the
synthesis and application of phosphors for pc-WLEDs with the
emphasis specifically on: (a) principles to tune the excitation and
emission spectra of phosphors, predictions according to crystal
field theory, and structural chemistry characteristics (e.g. cova-
lence of chemical bonds, electronegativity, and polarization
effects of elements); (b) pc-WLEDs with phosphors excited by
blue-LED chips: phosphor characteristics, structure, and acti-
vated ions (i.e. Ce3+ and Eu2+), including YAG:Ce, other garnets,
non-garnets, sulfides, and (oxy)nitrides; (c) pc-WLEDs with
phosphors excited by near ultraviolet LED chips: single-phased
white-emitting phosphors (e.g. Eu2+–Mn2+ activated phosphors),
red–green–blue phosphors, energy transfer, and mechanisms
involved; and (d) new clues for designing novel high-performance
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phosphors for pc-WLEDs based on the available LED chips.39,41–47
The emphasis was also be placed on the relationships among
crystal structures, luminescence properties, and device perfor-
mances. He et al. summarized the dependence of spectroscopic
properties on composition for Eu2+, Ce3+ or Yb2+-activated
nitride and oxynitride phosphors based on a-SiAlON, b-SiAlON,
oxonitridosilicates, nitridoalumosilicates and nitridosilicates.40
Generally, all possible variations in host composition usually
alter the symmetry, coordination environment, crystal field
strength, covalence, and the energy transfer, thus influencing
luminescence properties. In fact, the focus on the tunable
luminescence of phosphors in the above reviews is mainly based
on the average change in crystal structures of phosphors. Though
the variation of the local crystal field also have extremely impor-
tant effect on the luminescence properties of Ce3+ and Eu2+-
activated pc-WLED phosphors, which has become a research
hotspot. In recent years, many famous research groups have
focused their attention on this topic. For example, Liu’s group
have proposed some new luminescence mechanisms in Ce3+ and
Eu2+-doped (oxy)nitrides based on the variation of the local crystal
structure including the ‘‘Cation-Size-Mismatch effect’’, the
‘‘Neighboring-Cation Substitution effect’’, and the ‘‘Nano-
segregation and Neighbor-Cation Control effect’’ to clarify
some abnormal luminescence phenomena.48–51 Ram’s group
also confirmed that some small variations in the local structure
of La3xCexSi6N11, SrxBa2xSiO4:Eu2+ and so on phosphor systems
might generate a big improvement on their luminescence perfor-
mances.1,53,54 Cheetham’s group found that the large spectral
shift from blue to yellow light in Ca2SiO4:Ce should be attributed
to the distortion of the local crystal structure.55 In summary, more
and more researchers have recently focused their attention on the
adjustment and improvement of luminescence properties of
phosphors through the variation of the local crystal structure.
However, so far there is no related review to mainly concern and
systematically discuss the effect of the local crystal field on the
luminescence performances of rare earth activated pc-WLED
phosphors. Therefore, a related review article is necessary. In view
of this blank, we summarize the current approaches to realize
spectral tuning by the variation of the local crystal structure
including doping level control, cationic substitution, anionic
substitution, cationic–anionic substitution, the crystal-site engineer-
ing approach, mixing of nanophases, and explain some abnormal
luminescence mechanisms based on the actual variation of the local
bond length, covalence, coordination environment, crystal field
strength and so on for spectral tuning in rare earth ion activated
pc-WLED phosphors through the variation of the local crystal field.
Therefore, it presents a new angle of view to concern the improve-
ment of pc-WLED phosphors, which is different from the previous
reviews involving pc-WLED phosphors. This review does not intend
to comprehensively understand all aspects of pc-WLED phosphors
and many of these aspects will not be discussed here such as Eu3+,
Mn2+ and Mn4+-doped materials, semiconducting quantum dots,
sulfide-based materials and defect-related luminescent materials.
The concerns are primarily focused on several commonly used rare
earth ion (Eu2+ and Ce3+) activated inorganic phosphors [mainly
including garnets, silicate oxides, (oxo)nitrido(alumino)silicates],
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emphasizing the important effect of spectral tuning via local

structural variations on improving the luminescence performances
of phosphors.

2. Improving the photoluminescence

performances by spectral tuning
It is known that the colors of light from pc-WLED lighting and
display devices based on rare earth ion (Eu2+ or Ce3+) activated
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phosphors are usually recorded through luminescence spectra,

namely, the excitation and emission spectra. While the lumi-
nescence spectra are closely related to several vital lumines-
cence performance parameters in pc-WLED devices such as
correlated color temperature (CCT), Commission Internationale
de I’Eclairage (CIE) color coordinates, color rendering index (CRI
or Ra), luminous efficacy, quantum yield (QY) and so on.1,3,37 By
adjusting the position (blue shift or red shift) and full width at
half maximum (FWHM, more broad or more narrow) of photo-
luminescence emission spectra of rare earth activated phosphors,
these parameters such as CCT, CIE color coordinates, and Ra can
be precisely controlled and thus further improve the lumines-
cence performances of WLED devices. For example, the color
coordinates of white light from single pc-WLED devices based on
multivariate phosphors could span the whole while light region Fig. 2 (a) A schematic luminescence process from activator ions (Ce3+ or
with various CCTs (cold or warm white light) and Ras through Eu2+) in a host crystal. (b) Schematic explanation of the effects of the
host crystal on the luminescence of Ce3+ or Eu2+ ions, including the
shifting of the emission position of phosphors. In addition,
nephelauxetic effect (NE, centroid shift), crystal field splitting (ecfs) and
changing the excitation spectra (enlarging the absorption range) the Stokes shift (SS) and so on. Such effects will lead to an increase or
of pc-WLED phosphors might enhance the luminescence effi- decrease in the energy difference between the 5d and 4f levels, known as
ciency of phosphors and the luminescence efficiency of WLED the blueshift or redshift, respectively.
devices. Generally, the above mentioned performance parameters
(CIE color coordinates, CCT, Ra, luminous efficacy, and QY) of
type.37 The most widely used activators are Ce3+ or Eu2+ ions,
rare earth activated phosphors can be reasonably optimized by
whose function in phosphors is to convert n-UV or blue light
spectral tuning including the change of spectral position, shape
radiation to visible light, as shown in Fig. 2a. Due to the 5d–4f
and FWHM to improve the luminescence performances of WLEDs,
transition, the luminescence of Ce3+ and Eu2+ doped phosphors
which can be summarized by the following several aspects: tuning
is related to the intrinsic feature of activator ions and the host
the spectral position to approach the eye sensitivity curve can
crystal structure. Especially the latter has a greater effect on
improve the luminous efficiency of WLEDs; matching the spectral
the resulting photoluminescence properties. Herein, we mainly
position with the standard illuminators can optimizing the color
discuss the effects of host lattices on the 5d–4f transition
rendering properties of WLEDs; adjusting the spectral position can
luminescence of Ce3+ and Eu2+ activated phosphors, highlighting
achieve the desired color temperature; matching spectral position
the relationship between local crystal structural variations around
and shape with the color filters can enhance the color gamut of
activator ions and spectral tuning. According to energetics, the 4f
WLED backlights.3,34 Accordingly, reasonably tuning the lumines-
and 5d energy levels of Ce3+ and Eu2+ ions in phosphors determine
cence spectra of rare earth ion activated phosphors are very
their excitation and emission properties. The Ce3+ ion with the 4f1
important and necessary for the rapid development of WLED
configuration in solids shows efficient broadband luminescence
lighting and backlight display undertakings. For the researchers
due to the 4f–5d parity allowed electric dipole transition. While the
in the phosphor area, great effort is needed to focus on the modi-
Eu2+ ion has the 4f7 electron configuration and its emission is
fication of phosphors’ structures and components for tuning their
partly forbidden by the spin selection role, which whether present
luminescence spectra.
broadband emission depends on the crystal field strength. The
above reasons result in different photoluminescence properties of
3. The spectral tuning approaches Ce3+ and Eu2+ ions in some same hosts. For free Ce3+ or Eu2+ ions,
in pc-WLED phosphors they have large energy difference between the 4f ground state and
the 5d excited state, which are B6.2 eV (50 000 cm1) for Ce3+ and
Commonly, phosphors used in WLEDs consist of an inactive B4.2 eV (34 000 cm1) for Eu2+ ions.56–58 Since the 5d orbitals are
host like aluminates, silicates, (oxo)nitrido(alumino)silicates, strongly affected by the surrounding crystal field, symmetry, anion
etc., and activators, which are defined as the ‘‘host + activator’’ polarizability, and covalency of the host crystal, the excitation and

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emission energies can be modulated through changing the
composition and structure of the host crystal. Dorenbos has
proposed a series of equations to preliminarily determine the
f–d excitation and d–f emission of rare earth ions in inorganic
compounds.59 For free lanthanide ions and the ions in any
inorganic compound, the energy difference E(n,Q,A) between
the lowest 4f n level and the first 4f n15d level in trivalent
(Q = 3+) and divalent (Q = 2+) lanthanide ions always shows
the same characteristic variation with the number of electrons
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n in the 4f shell.59 The effect of the host crystal, denoted by
the parameter A on the energy difference is expressed by the
redshift D(Q,A) and the Stokes shift S(Q,A): for the energy of
fd-absorption one may write
Eabs(n,Q,A) = EA,free(Q,A)  D(Q,A) (1)
and for the df-emission
Eem(n,Q,A) = EA,free(Q,A)  D(Q,A)  DS(Q,A) (2)
where EA,free(Q,A) is a constant for each lanthanide ion with a
value equal or close to the f–d transition energies for the free
(gaseous) lanthanide ions.60–69 When the first 5d level energy is
known for a specific lanthanide ion in compound A; one may
determine the redshift D(Q,A). From that, the first 5d level
energies for all other lanthanides in the same compound can
be predicted. The values for D(Q,A) and DS(Q,A) (Q = 3+, 2+) of
several hundred different compounds including fluorides,
chlorides, bromides, iodides, oxides, sulfides, selenides, (oxy)-
nitrides and so on were compiled in ref. 60–69. The above
contributions are very important, which not only guide the
researchers to develop desired rare earth ion doped phosphors
for WLEDs, but also help to deeply study the structure-related
luminescence properties. Simply, when accommodating Ce3+ or
Eu2+ ions into a host, this energy difference can range from UV
across visible wavelengths, depending on two main aspects:
crystal field splitting (CFS) and the nephelauxetic effect (NE).
The big 5d orbital crystal field splitting and the nephelauxetic
effect (centroid shift) of Ce3+ or Eu2+ ions can substantially
decrease their energy difference, leading to obvious n-UV or
blue light absorption and tunable emission all over the visible
light range. These features of Ce3+ and Eu2+ activated phosphors
perfectly match with n-UV or blue LEDs, and thus are extremely
conducive to their application in WLEDs. For the crystal field
splitting effect, it describes the energy difference between the
highest and lowest 5d energy levels, which is the complex results
of some effects like the bond lengths from the activator ion to the
coordinating anions, the degree of covalency between the acti-
vator ion and its ligands, the coordination environment, and the
symmetry of the activator site. Generally, the crystal field splitting
(Dq) can be determined by the following equation:37,59,70–72
1 r4
Dq ¼ Ze2 5 (3)
6 R
where Dq is the magnitude of the 5d energy level separation, Z is
the anion charge or valence, e is the electron charge, r is the
radius of the d wavefunction, and R is the bond length. Although
this equation was derived by using a point charge model, it can
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be used as an approximation for describing crystal field splitting
trends with the bond distance. The shorter the bond length and
the stronger the crystal field splitting, and then the longer
the emission wavelength. As the other important aspect, the
nephelauxetic effect (literally means ‘‘charge cloud expansion’’)
has been studied for the ff-transitions in lanthanides,73,74
the dd-transitions in transition metal elements,70 and the
sp-transitions in Tl+; Pb2+; and Bi3+.75,76 It leads to a displacement
of levels to lower energy depending on the type of compound. The
ideas developed for the nephelauxetic effect in the above metal
elements may also be used to describe the energy difference
between the 5d and 4f levels.59–69 The decrease of 5d levels
relative to the free ion situation is known as the centroid shift.
It could lead to the centroid shift to lower energy depending on
the type of compound due to a reduction of interelectron repul-
sion.70 The size of the nephelauxetic effect can be characterized
by the nephelauxetic ratio b as
1  b = hk (4)
where 1  b is written as a product of two functions, each
variable.70 h characterizes the anion ligands and k the metal.
When anions or ionic complexes are put in the order of
increasing h-parameter the well-known nephelauxetic series is
obtained, i.e., no ligands o F o H2O o NH3 o Cl o Br o
N3 o I2 o O2 o S2 o Se2 and H2O o SO42 o CO32 o
PO43 o BO33 o SiO44 o AlO45 o O2. The reduction of
interelectron repulsion and the increase of the h-parameter are
often ascribed to the covalence,70,74 i.e., the sharing of electrons
between the metal and the surrounding ligands. Therefore,
the centroid shift originated from the nephelauxetic effect is
also related to the covalency between the activator ions and
the surrounding anion ligands.71,72 The higher the degree of
covalency, the larger centroid downshift will be generated.
Except for the above two main aspects, some other factors such
as the Stokes shift (SS), the coordination geometry, the d orbital
hybridization of the activator ion due to the interaction between
molecular orbitals of neighboring anions, the distortion of the
activator ion site and so on, can also affect the energy difference
between the 5d and 4f levels and thus give rise to a spectral shift.1
In general, the position of the 5d energy levels of Ce3+ and Eu2+
ions can change by tens of thousands of wavenumbers from one
compound to another, for example the 5d configuration of Ce3+ is
known to lower the energy by 5000–25 000 cm1 under different
crystal environments, and thus their emission spectra can be
adjusted in the whole visible light region.58,59 In other words, this
essence of spectral tuning in Ce3+ or Eu2+ doped phosphors is
ascribed to the variation of the microstructural environment
surrounding Ce3+ or Eu2+ ions. Herein, we summarized several
main aspects to realize spectral tuning of rare earth activated
phosphors based on the local crystal structural change of
phosphors including doping level control, cationic substitu-
tion, anionic substitution, cationic–anionic substitution, the
crystal-site engineering approach, and mixing of nanophases.
The detailed explanations are presented in Sections 3.1–3.4.
The summary of spectral tuning in some representative phosphor
systems by compositional adjustment based on the variation of
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Table 1 Summary of the spectral tuning mechanism in some representative phosphor systems by compositional adjustments based on the variation of
the local crystal structure

Spectral tuning/emission
Type Representative examples Blueshift Redshift Ref.
Doping level control La3xCexSi6N11 (0 o x r 3) B30 nm 53
Ba1xEuxSi2O2N2 (0 o x r 0.1) B10 nm 80
Sr1xEuxSi2O2N2 (0 o x r 0.16) B19 nm 81
Ca-a-SiAlON:xEu2+ (0 o x r 0.25) B20 nm 82
Y3xCexAl5O12 (0 o x r 0.0333) B22 nm 83
Ca12xCexLixAlSiN3 (0 o x r 0.05) B33
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nm 84
Ca2xEuxSiO4 (0 o x r 0.08) B70 nm 86

Cationic substitution SrxBa2xSiO4:Eu2+ (0 r x r 0.2) B63 nm 54

(Sr1xCax)Si2O2N2:Eu2+ (0 r x r 1) B10 nm 81
(Sr0.98xBaxEu0.02)Si2O2N2 (0 r x r 0.63) B25 nm 48, 100
(Sr2xBax)Ga2SiO7:Eu2+ (0 r x r 1) B48 nm 88
a-(Y,Gd)FS:Ce3+ (0 r y r 0.3) B8 nm intensitym 42
Y1.98Ce0.02(Ca1ySry)F4S2 (0 r y r 1) B40 nm 43
(Sr1xCax)2Si5N8:Eu2+ (0 r y r 0.3) B50 nm 93
Ba2xSrxSi5N8:Eu2+ (0 r y r 0.5) 14–33 nm 95
(Ca0.993xyMgxSry)9Y(PO4)7:Eu0.007 (0 r x r 0.5) B51 nm 90
(Ca0.993xyMgxSry)9Y(PO4)7:Eu0.007 (0 r x r 0.5) B22 nm
Sr3xBaxSiO5:Eu2+ (0 r x r 0.2) B15 nm 101
(Na1xCax)(Sc1xMgx)Si2O6:Eu2+ (0 r x r 1) B83 nm 105
(Ce0.005Y0.995)3Sc2Al3xGaxO12 (0 r x r 3) B24 nm 108
CaAlxSi(73x)/4N3:Eu2+ (0.7 r x r 1.3) FWHMm 110
Y3Al52xMgxSixO12:Ce3+ (0 r x r 2) B41 nm 111
Y3Al52xMgxGexO12:Ce3+ (0 r x r 1.6) B19 nm
(Ca1xLax)(Al1+xSi1x)N3:Eu (0 r x r 0.15) B20 nm 50
(Ca1xLix)(Al1xSi1+x)N3:Eu (0 r x r 0.15) FWHMm
La1x0.025Ce0.025Sr2+xAl1xSixO5 (0 r x r 0.975) B29 nm 112
(Ca1xCex)6Ba(P1xSix)4O17 (0 r x r 0.07) FWHMm 113

Anionic substitution Ca2.97Sc2Si3O126xN4x:0.03Ce3+ (0 r x r 0.8) FWHMm 116

Sr1.984Si(N,O)4:0.016Eu2+ (0.7 o z o 1.2) B30 nm 118
Ba5SiO4(FxCl6x):Eu2+ (0 r z r 0.15) B61 nm 119

Cationic–anionic substitution Ca1.95Eu0.05Si5xAlxN8xOx (0 r x r 1) B20 nm 49

Sr1.95Eu0.05Si5xAlxN8xOx (0 r x r 1) B15 nm
Ba1.95Eu0.05Si5xAlxN8xOx (0 r x r 1) B40 nm
Y2.94Ce0.06Al(5x)SixO(12x)Nx (0.20 r x r 0.3) B31 nm 123
Y2.91Ce0.09Al5xSixO12xNx (0 r x r 0.3) B45 nm 117
Sr2.975Ce0.025Al1xSixO4+xF1x (0 r x r 1) B63 nm 136
Gd1xSr2+xAlO5xFx:Ce3+ (0 r x r 1) B100 nm 137
Sr2Ba(AlO4F)1x(SiO5)x:Ce3+ (0 r x r 0.9) B29 nm 138
Ca12Al14zSizO32+zF2z:Eu (0 r z r 0.5) B173 nm 139
(SiC)x–(AlN)1x:Eu2+ (0 r x r 0.5) B35 nm 140
Sr1xY0.98+xCe0.02Si4N7xCx (0 r x r 1) B75 nm 51
(KSrPO4)1x(Ba2SiO4)x (0 r x r 1) B50 nm 149
(KSrPO4)1x(Sr2SiO4)x (0 r x r 1) B95 nm

Crystal-site engineering approach b-YFS:Ce3+ B45 nm 41

Sr32xCexNaxAlO4F (0 o x r 0.2) B66 nm 87
(Ca1xySrxEuy)7(SiO3)6Cl2 (0 r x r 0.5) B5 nm 150
Ca3La3(1x)Ce3x(BO3)5 (0 r x r 0.5) B50 nm 151

the local crystal structure is shown in Table 1. It is noted that
in addition to the 5d–4f transition luminescence, some 4f–4f
transition luminescence such as Eu3+ or Tb3+-activated phos-
phors has also been developed as potential phosphors for use
in pc-WLEDs.31,32,40,77 However, due to the narrow excitation
(Eu3+: 393 nm 7F0–5L6, 463 nm 7F0–5D2; Tb3+: 4f–4f, 378 nm)
and emission lines (Eu3+: 5D0–7F2 612 nm; Tb3+: 5D4–7F5 543 nm),
these phosphors commonly cannot be efficiently excited by the
wide UV-to-blue light region, and have poor color rendering
indices when they are complexed with other phosphors for
generating white light due to the incomplete cover over the whole
visible light region. Thus they are usually used in specific UV-LED
based WLED lighting and display devices. Some transition metal
ions Mn2+ (3d5 electronic configuration) and Mn4+ (3d3 electronic
configuration) activated phosphors have also been developed as
potential pc-WLED phosphors.78,79 The Mn2+ ion can give a broad
band emission in the visible range owing to the 4T1 - 6A1
transition, and the emission color of Mn2+ can vary from green
to red depending on the crystal field.78 If the crystal field around
the Mn2+ ion is weak, the splitting of the excited energy levels in d
orbits will be small resulting in Mn2+ emission with higher energy,
whereas it will give lower energy emission. However, the d–d

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transition of Mn2+ is forbidden and difficult to pump, the
Mn2+ ion activated phosphors have low luminescence efficiency.
Mn4+ doped materials, for example oxides and fluorides, are
commonly used as red emitting phosphors. Because they present
broad adsorption bands at 380–490 nm and sharp emission
peaks at 610–760 nm due to their distinct 2E–4A2 transition in
the symmetrically octahedral crystal field. However, some draw-
backs of Mn4+ doped materials including a lot of use of HF in the
synthesis process, so far redshift for efficient warm WLEDs with
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a high luminous efficiency, low resistance to moisture, and
unclear structure-related luminescence mechanisms, limit their
rapid progress in scientific investigation and application of
WLED lighting.79 In addition, the long decay lifetime at the
millisecond order of magnitude of Mn2+ and Mn4+-activated
phosphors also tremendously hinders for their application in
WLED lighting. Based on the above reasons Eu3+, Mn2+ and
Mn4+-doped materials are not discussed here temporarily.
On the other hand, the thermal stability of luminescence pro-
perties of phosphors is an important parameter to be considered
in practical WLED applications, which influences the lumines-
cence efficiency and lighting quality of the WLED devices.1,34,48–52
Because the emission intensity decreases (namely thermal
quenching) and the wavelength shifts clearly with increasing
temperature due to nonradiative transitions from the excited
state to the ground state, which could be explained by hole-trapping
or electron transition mechanisms.48–52 Thus an improvement in
the thermoluminescence stability of phosphors used in WLEDs is
indispensable. Generally, the thermal stability of phosphors is
closely related to the covalency of activator–anions, the rigidity of
the crystal lattice, and the Stokes shift. An excellent thermal stability
could be expected in some phosphors with high covalency, high
rigidity and small Stokes shift. Otherwise, a poor thermal stability
will be observed. Because the variation of local crystal structure of
phosphors could influence the covalency of activator–anions, the
rigidity of the crystal lattice, and the spectral shift. Therefore, it
could be used to improve the thermoluminescence stability
of phosphors, and some specific discussion is shown in the
following section.
3.1 Doping level control
As mentioned in the above section, the ‘‘host + activator’’ typed
luminescent materials are the most widely used phosphors
in pc-WLEDs, and the doped amount of activator ions (Ce3+
or Eu2+) needs to be reasonably selected in the host (usually
less than 10%). By controlling the doping levels, not only the
luminescence intensity and efficiency of phosphors can reach a
maximum value but also the position of luminescence spectra
can be tuned to some extent. To our knowledge, changing the
doping levels of Ce3+ or Eu2+ ions in phosphors is the easiest
and most common way to realize spectral tuning, namely, changing
the energy difference between the 5d and 4f levels of Ce3+ or Eu2+
ions among all available approaches. For example, George et al.
reported a redshift of B30 nm of the position of the maximum
emission wavelength in the La3xCexSi6N11 (0 o x r 3) system with
increasing Ce3+ doping concentration, as shown in Fig. 3c.53 This is
mainly ascribed to the increased crystal field splitting (CFS) due to
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Fig. 3 Room-temperature (a) absorption, (b) excitation, (c) emission
spectra of La3xCexSi6N11 (0.18 r x r 3). (Reproduced with permission
from ref. 53, copyright 2013, American Chemical Society.)
the decrease in the Ce–N bond length, as shown by eqn (3). The
increase in CFS strength can be confirmed in the excitation/
absorption spectra. There is a significant shift toward lower
energies in the position of the lowest energy excitation/
absorption band with increasing Ce content, as exhibited in
Fig. 3a and b. A larger CFS thus means a reduction in the energy
difference between the ground states and the lowest 5d-state of
Ce3+, shifting the emission peak to the lower energy part of the
spectrum. Except for the CFS effect, a reduction in the Ce–N
distance also increases the interaction of Ce3+ and N3, which
enlarges the nephelauxetic effect. Therefore, a redshift in the
emission spectrum appears. In addition, the self-absorption is
also one possible reason for the red shift due to the relatively
small stokes shift of Eu2+ and Ce3+ emission.3,31,32 More examples
for the spectral shift originating from the increase of activator
concentration can be found in Ce3+ or Eu2+ ion doped phosphor
systems like Ba1xEuxSi2O2N2 (10 nm),80 Sr1xEuxSi2O2N2 (19 nm),81
Ca-a-SiAlON:xEu2+ (20 nm),82 Y3xCexAl5O12 (22 nm),83 Ca12xCex-
LixAlSiN3 (33 nm),84 Sr3yCeyAlO4F (50 nm),85 etc. The values in the
above brackets show the redshift amplitude of emission peaks. In
addition, George et al. also observed that the different increase
variance for (La/Ce)–N bonds (0 o x r 3) with increasing Ce
content (for La(1)/Ce(1)–N and La(2)/Ce(2)–N bond lengths by 5%,
and by 21%, respectively) in La3xCexSi6N11 can contribute to an
increase in CFS. Therefore, they concluded that if multi-cation sites
existed, the increase in distortion of the bond length distribution of
different activator–anion bonds could also cause an increase in CFS
to generate redshift.53 Upon changing the doping level of activators,
the spectral tuning can also be realized by the crystal-site engineer-
ing approach, which involves the replacement of activator ions into
different cation sites owning to different coordination environments
and energy transfer of activator ions at different crystal sites.86,87
This section will be elaborately introduced in Section 3.5.
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Fig. 4 A schematic explanation of (a) the variation of the host lattice.
Green and gray spheres represent host cations and anion ligands, respec-
tively. Blue and red spheres are activator ions. The ionic radius is blue 4
green 4 red spheres. The replacement of green spheres by blue or red
spheres will increase or decrease the activator–anion bond length,
respectively. (b) The spectral red shift and blue shift mechanisms induced
by the variation of the crystal lattice. The increase of the activator–anion
bond length reduces crystal field splitting and the nephelauxetic effect,
resulting in the spectral blue shift. On the contrary, a spectral red shift will
appear.
In general, phosphors frequently involve in the substitution
of cations in the host lattice with activator ions (Ce3+ or Eu2+) to
produce luminescence, which easily results in a mismatch of
the crystal lattice due to different ion radii. These mismatches
lead to lattice expansion or contraction, which have a substan-
tial effect on CFS and thus further affect the energy difference
between the 5d and 4f states of Ce3+ or Eu2+ ions. A simple
model to illustrate the spectral tuning mechanism of phosphors
by controlling the doping level of Ce3+ or Eu2+ ions is shown in
Fig. 4. During the process of doping Ce3+ or Eu2+ ions into the
host lattice, if its ionic radii are smaller than that of host cations, a
lattice contraction will occur (Fig. 4a). Subsequently, the activator–
anion bond lengths will decrease and the interactions between
activator ions and anion ligands will strengthen (Fig. 4b), which
brings about a larger CFS and a stronger nephelauxetic effect of
5d energy levels of Ce3+ or Eu2+ ions. Finally, a red shift emission
can be observed in this system upon gradually increasing the
activator concentration, whereas a blue shift emission occurs
(Fig. 4b).
3.2 Cationic substitution
Cationic substitution is another common route to realize
spectral tuning of Ce3+ or Eu2+ doped phosphors by altering
their coordination environments. It is well known that there are
two kinds of cations in the host including host cations (Ch) and
cations in ionic complexes (Cic).49–51,71 For example, Y3+ ions
and Al3+ ions are Ch and Cic in Y3Al5O12, respectively. Both the
substitutions of Ch and Cic by other cations in the host can
affect the CFS and NE of Ce3+ or Eu2+ ions, inducing the change
in their energy difference between the lowest 5d energy level
and the ground state. To facilitate discussion here, the cationic
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substitutions in the host are classified into three kind patterns:
Ch substitution, Cic substitution and Ch–Cic substitution.
3.2.1 Host cation (Ch) substitution. For Ch substitution, a
large amount of cases such as Ce3+ or Eu2+ ion doped alkaline
earth metal silicates, aluminates, and (oxy)nitrides have been
investigated and reported, as shown in Table 1. It commonly
involves two mechanisms to explain spectral tuning: the average
lattice variation and the local lattice variation of the crystal
structure. On the basis of the average lattice variation of the
crystal structure, Denault et al. recently revealed a tunable
excitation and emission in SrxBa2xSiO4:Eu2+ by adjusting the
Sr/Ba ratio.54 With increasing Sr content, the excitation spectrum
exhibits a slight redshift (Fig. 5a), while the emission spectrum
shows a large redshift with a maximum emission wavelength of
574 nm (yellow-orange) for Sr2SiO4:Eu2+ and of 511 nm (green) for
Ba2SiO4:Eu2+ (Fig. 5b), increasing the Stokes shift. Because
Ba2SiO4 and Sr2SiO4 all can crystallize in the orthorhombic
b-K2SO4 structure, and the addition of Eu in Sr2SiO4 can’t change
this structure. Therefore, the intermediate compositions of the
SrxBa2xSiO4:Eu2+ phosphor maintain the same structure for all
Sr concentrations. The unit cell of SrxBa2xSiO4 contains two
cation sites, the 10-coordinate Wyckoff site 4c (Sr/Ba1) with a
larger polyhedral volume and the 9-coordinate Wyckoff site 4c
(Sr/Ba2) with a smaller polyhedral volume, as shown in Fig. 5c.
The comparison of the ionic radius for Sr2+, Ba2+, and Eu2+ in
Sr/Ba1 and Sr/Ba2 indicates possible site mixing of Sr2+ and Ba2+
in the intermediate compositions. Moreover, Eu2+ substitution
can occur on both sites. Fig. 5d shows that the unit cell para-
meters a, b, c and unit cell volume (V) present a linear decrease
following Vegard’s law with increasing Sr content, indicating the
formation of SrxBa2xSiO4:Eu2+ solid solution and a continuous
decrease in the Sr/Ba–O bond lengths. When Eu2+ ions enter into
Sr/Ba sites, the average Eu–O bond length also continuously
decreases and thus leads to an increasing CFS, generating red-
shift emission. Another reason to induce redshift emission is
more Eu2+ ions into the Sr/Ba1 sites with increasing Sr content,
which offers a larger nephelauxetic effect on the Eu2+ ions.
More interestingly, the thermal stability of SrxBa2xSiO4:Eu2+
phosphors were improved by changing the Sr/Ba ratio. Denault
et al. observed that the intermediate composition with 46% Sr
had the highest resistance to thermal quenching of lumines-
cence, remaining stable up to 413 K.54 The possible reason is that
the intermediate compositions possess optimal bonding that
creates a more rigid crystal structure compared to the end-
member compositions. Consequently, they concluded that this
result provides an impetus to the search for newly efficient
phosphor hosts that possess highly connected structures and
optimized bonding interactions. Based on the same mechanism,
Wu et al. reported a spectral blue shift from 553–590 nm (yellowish
orange light) to 440–470 nm (blue light) in Y1.98Ce0.02(Ca1ySry)F4S2
(0 r y r 1) when gradually replacing Ca2+ with Sr2+ (Fig. 5e),
which is related to the changed crystal field strength.43 Because the
above substitution leads to the expansion of the lattice volume due
to the larger Sr2+ ions, thus changing four Ce–S and four Ce–F
bonds to 286.94 and 262.41 pm within the internal YF4S5 poly-
hedra. The bond lengths of apical Ce–S, 284.63 and 284.71 pm are
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Fig. 5 (a) Excitation and (b) emission spectra collected at the maximum emission/excitation wavelength for each sample. (c) Crystal structure of
SrxBa2xSiO4 with SiO4 polyhedra shown as blue, O2 shown as orange, the Sr/Ba1 10-coordinate site shown as dark gray, and the Sr/Ba2 9-coordinate
site shown as light gray. (d) Refined unit cell parameters a, b, c, and V of (Sr,Ba)2SiO4:Eu2+ with increasing Sr content. (e) Excitation (monitored at
550–590 nm) and emission (lex = 440–470 nm) spectra of Y1.98Ce0.02(Ca1ySry)F4S2 (y = 0, 0.1, 0.25, 0.5, 0.75 and 1). The insets are the corresponding
photos taken under 365 nm excitation. (f) Schematic explanation of the spectral tuning mechanism based on the average lattice contraction of the crystal
structure. C1–3 represent host cations and the order of ionic radius is C3 o C1 o C2 (Reproduced with permission from ref. 43 and 54, copyright 2012,
2014, American Chemical Society, Royal Society of Chemistry.)

almost the same in Y1.98Ce0.02SrF4S2 and Y1.98Ce0.02CaF4S2. In such
cases, the Ce3+ ion experiences a weaker crystal field splitting
due to the expansion of YF4S5 polyhedra in the Y1.98Ce0.02SrF4S2
system; therefore, it is reasonable to observe the blue-shifted
excitation and emission spectra. More evidence can be found
about spectral tuning and the improvement of thermal stability
based on the average lattice variation of the crystal structure in
(Sr2xBax)Ga2SiO7:Eu2+,88 (Sr1xCax)Si2O2N2:Eu2+,89 Sr4xMgxSi3-
O8Cl4:Eu2+,90 (Ba1xSrx)9Sc2Si6O24:Ce3+,Li+,91 A32xRECexNax(BO3)3
(A = Sr, Ca; RE = Y, La),92 a-(Y,Gd)FS:Ce3+,42 and (Sr1xyCax-
Bay)2Si5N8:Eu2+.93–95 A schematic explanation is shown in Fig. 5f.
Upon using a larger host cation (C2) to replace a smaller one (C1),
an average lattice expansion occurs, which brings out a linear
increase in the bond length of activator–anions followed by doping
of the activator ions (Ce3+ or Eu2+) into C1/C2 sites. This decreases
the interaction between activator ions and anion ligands, and
weaken the CFS strength and the nephelauxetic effect, and thus
shifts the maximum emission position to the shorter wavelength,
as shown by the (i) process in Fig. 5f. On the contrary, the redshift
emission will appear if the Ce3+ or Eu2+ ions enter the smaller
C3/C1 sites, as shown by the (ii) process in Fig. 5f. It is noted that
although a linear decrease/increase of the average activator–anion
distance appears, abnormal blueshift/redshift might be observed
in some systems, e.g., (Sr0.98xBaxEu0.02)Si2O2N2,96–100 Sr3xBax-
SiO5:Eu2+,101,102 (Ba1xSrx)Al2Si2O8:Eu2+,103 (Ca0.993xyMgxSry)9-
Y(PO4)7:Eu0.0072+,104 (Na1xCax)(Sc1xMgx)Si2O6:Eu2+,105 and
(Y,Gd,Lu)3Al5O12:Ce.106 The possible reason is that the local lattice
variation originating from the neighboring cation exerts a more
important effect on the luminescence properties of Ce3+ or Eu2+. For
instance, in the (Sr0.98xBaxEu0.02)Si2O2N2 system, a solid solution
was formed at x = 0–0.63 and a average lattice expansion could be
observed with the increase of Ba concentration due to a larger
ionic radius of Ba2+ than Sr2+.48 Based on the previous mechanism,
a blueshift of the maximum emission would be expected. However,
an abnormal redshift emission about 35 nm was observed with
increasing Ba content in the (Sr0.98xBaxEu0.02)Si2O2N2 (x = 0 to
0.63) system, as shown in Fig. 6a. The corresponding color
coordinates that moved from the green to the yellow region and
the corresponding digital photos (Fig. 6b) also verified this red-
shifted luminescence. Li et al. investigated the local fine structure
of (Sr0.98xBaxEu0.02)Si2O2N2 (x = 0 to 0.63) phosphors by the
extended X-ray absorption spectra (EXAFS) and found that there
is no a linear increase in the Sr/Ba–O distance, whereas the big
difference in end-member crystal structures (triclinic: P1 for
SrSi2O2N2 and orthorhombic: Pbcn for BaSi2O2N2).48 On the
contrary, the Sr–O and Sr–O/N bond lengths gradually decrease
with the increase in x in (Sr0.98xBaxEu0.02)Si2O2N2 (x = 0 to
0.63) series, as shown in Fig. 6c.
Because Eu2+ preferentially replace Sr2+ sites in (Sr0.98xBax-
Eu0.02)Si2O2N2 (x = 0 to 0.63) due to the isotypic structure of
EuSi2O2N2 and SrSi2O2N2, and the similar ionic radius of Eu2+
and Sr2+. Therefore, they proposed a possible mechanism for
the unexpected redshift emission based on the local lattice
variation,48 as shown in Fig. 6d: first, in a local structure, one
Eu2+ occupies one Sr2+ site in (Sr0.98xBaxEu0.02)Si2O2N2 (x = 0 to
0.63) series. The strain of the Ba–O bond increases when the
neighboring Sr2+ ion is replaced by one larger Ba2+ ion (i).
To release lattice strain, the Eu–O bond length decreases (i).
With the increase of Ba2+ content, other neighboring Sr2+ sites
are successively replaced by Ba2+ ions (ii and iii), thereby gradually

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increases the strength of the crystal field. As a result, the 5d

energy levels of Eu2+ are lowered, and the emission wavelength
is redshifted from 486 to 508 nm with Sr2+ content increasing.
Except for the main CFS effect, the nephelauxetic effect also
exerts an import effect on the resulting spectral shift. In fact,
the final luminescence spectra of many phosphor systems
are the complex results of several effects including the CFS
effect, the NE effect and so on. Sometimes, the CFS effect and
the NE effect play a conflicting role in spectral tuning, and the
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ultimate results depend on the bigger effect. For example, Jang

et al. observed that the emission spectra of (Sr1xBax)3SiO5:Eu2+
appeared to be first redshifted (x = 0–0.2) and then blue shifted
(x = 0.2–1.0) with the increasing x value from 0 to 1.0, as shown
in Fig. 7a.101 They thought that there exist the competitive CFS
effect and the NE effect in (Sr1xBax)3SiO5:Eu2+ systems. Upon
increasing the Ba content in (Sr1xBax)3SiO5:Eu2+, the former
enables the CFS effect of the 5d level of the Eu2+ ion to increase
in terms of the local lattice variation mechanism, while the
latter results in an reduced CFS effect due to the increased
Eu–O covalency. At x r 0.2, the crystal field splitting effect
dominates and thus appears to be redshifted (Fig. 7b).
However, after x Z 0.2, the NE effect surpasses the CFS
effect in (Sr1xBax)3SiO5:Eu2+, leading to a blue shift (Fig. 7b). In
addition, Xia et al. presented a double Ch substitution model
in (Na1xCax)(Sc1xMgx)Si2O6:0.03Eu2+, by which they can tune

Fig. 6 (a) Typical PL emission spectra of (Sr0.98xBaxEu0.02)Si2O2N2 (0 r

x r 0.63) phosphors with the increase of Ba contents (lex = 405 nm).
(b) The corresponding CIE color coordinate diagram of the above samples
and digital photos for x = 0, 0.30, 0.63 samples. (c) Extended X-ray
absorption spectra of (Sr0.98xBaxEu0.02)Si2O2N2 (x = 0 to 0.63) samples.
(d) Schematic explanation of the redshift luminescence mechanism in
(Sr0.98xBaxEu0.02)Si2O2N2 (0 r x r 0.63) series. (e) Dependence of
emission spectra of (Ca0.993xyMgxSry)9Y(PO4)7:Eu2+0.007 phosphors on
concentrations of Mg2+ and Sr2+ (Reproduced with permission from ref. 48
and 104, copyright 2011, 2014, American Chemical Society, Royal Society
of Chemistry.)

decreasing the Eu–O bond length. This result increases 5d-orbital

crystal field splitting of Eu2+ ions, causing a continuous redshift in
the emission spectra. Similar situation occurs in (Ca0.993xy-
MgxSry)9Y(PO4)7:Eu0.0072+ systems. There is a continuous blue-
shift emission from 486 to 435 nm with increasing Mg2+ content
(x r 0.5) and a redshift from 486 to 508 nm with increasing Sr2+
concentration (y r 0.5), as indicated in Fig. 6e.104 According to
the local lattice variation mechanism, the above phenomenon can
be explained as follows: when Ca2+ is substituted by a smaller
Mg2+ ion, the distance between Eu2+ and O2 becomes longer,
Fig. 7 (a) PL spectra of (Sr1xBax)3SiO5:Eu2+ samples with various Ba con-
resulting in smaller crystal field splitting, so that there is a
tent: x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0. (b) Schematic diagram of the energy
continuous blue-shift with the doped Mg2+ concentration. In band change of Eu2+ in (Sr1xBax)3SiO5:Eu2+ phosphors. D represents the
contrast, when Ca2+ is substituted with a larger Sr2+ ion, the crystal field splitting of the 5d level of the Eu2+ ion (Reproduced with
distance between Eu2+ and O2 becomes shorter, which in turn permission from ref. 101, copyright 2009, The Electrochemistry Society.)

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the emission from yellow light (537 nm) to blue light (454 nm) with
the x value from 0 to 1, as shown in Fig. 8b.105 The tunable yellow-
blue emission in this system is related to the local variation of the
crystal structure. The crystal structure of NaScSi2O6 is isomorphous
with that of CaMgSi2O6, and the octahedral Mg site is occupied by
Sc and the Ca site is occupied by Na (Fig. 8a). Therefore, they can
form a complete series of solid-solutions. In this solid-solution,
the replacement of Mg2+ by Sc3+ is strongly accompanied by the
replacement of Ca2+ by Na+, to ensure the charge balance. The Na
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environment of the Eu2+ center leads to the spectrum with maxi-
mum emission in the yellow region, while the Ca environment
produce another emission center in the blue region. There is a
random distribution of these small NaSc units and CaMg units.
However, there are local clusters of NaSc and CaMg that would
result in two different Eu2+ sites with a difference in the covalency.
Therefore both bands (blue and yellow emission) are visible in the
solid solution. Moreover, the ratio of yellow emission to blue
emission varied with x values due to the different ratios of NaSc
local clusters to CaMg clusters, realizing a yellow-blue tunable
emission. In other words, Ch substitution is an effective route to
realize spectral tuning by the competition of CFS, NE and some
Fig. 8 (a) The polyhedral representation of the structure of the
(Na1xCax)(Sc1xMgx)Si2O6:Eu2+ solid-solution sample. (b) PL spectra (lex =
365 nm) of (Na1xCax)(Sc1xMgx)Si2O6:Eu2+ (x = 0–1) phosphors with different
x values, and the upper inset gives the digital images of some selected
phosphors under a 365 nm UV lamp. (Reproduced with permission from
ref. 105, copyright 2013, Nature Publishing Group.)
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other effects. Therefore, it is widely used in the modification of Ce3+
or Eu2+ activated phosphors for promoting their application in
WLED lighting and display areas.
3.2.2 Cations in ionic complex (Cic) substitution. As men-
tioned in the previous section, there are two kinds of cations in
most inorganic phosphor hosts: the host cation (Ch) and the
cation of ionic complexes (Cic).49–51,70 The role of Cic is to
connect anion ligands for forming stable frames of inorganic
crystals and cation vacancies. Ch and doping cations can
occupy these cation vacancies to form host materials and the
resulting phosphors, respectively. The common Ch in inorganic
phosphors contains alkali metal ions (Li+, Na+, and K+), alkaline
earth metal ions (Mg2+, Ca2+, Sr2+, and Ba2+), rare earth metal
ions (Y3+, Sc3+, La3+, Gd3+, and Lu3+) etc., and the usual Cic is
focused on the third and fifth main groups of the periodic
table, e.g. B3+, Al3+, Ga3+, Si4+, Ge4+, P5+ and so on. The Cic
substitution can be divided into the equivalent valence and
nonequivalent valence substitution based on the replacement
of Cic by metal ions in the same group and different main
groups, respectively. For example, Ga3+ - Al3+, and Ge4+ - Si4+
are equivalent valence replacements, while Si4+ - Al3+ is a
nonequivalent valence replacement. The spectral tuning
mechanism by two Cic substitutions can also change the local
coordination environments of activator ions, and thus influences
their energy difference between the lowest 5d state and the
ground state. The most representative examples are to tune the
luminescence spectra of garnet-structured phosphors by modify-
ing the composition of Al with Ga and Si.107 Ueda et al. reported
that the Ce3+ luminescence was blue-shifted with increasing Ga
content in (Ce0.005Y0.995)3Sc2Al3xGaxO12 (x = 0, 1, 2, 3), as shown
in Fig. 9a.108 In the photoluminescence excitation (PLE) spectra,
two excitation bands at approximately 340 nm and 430 nm were
attributed to transitions from the 4f level to the 5d1 and 5d2 levels
(5d1 and 5d2 are the lowest and the second lowest 5d levels),
respectively. When doping the larger Ga into the (Ce0.005Y0.995)3-
Sc2Al3xGaxO12 system, a linear increase of unit cell parameters
was observed (Fig. 9b), indicating the formation of solid solution.
With increasing lattice constants, the excitation energy of the
4f–5d1 peak shifts to higher energies and the 5d1–4f emission
peak also shifts to higher energies. However, the excitation
energy of the 4f–5d2 peak shifts to lower energies. Moreover,
the energy difference between the 5d1 and 5d2 levels decreased
with increasing lattice constants, as shown in Fig. 9c. The
decrease in the splitting energy between the 5d1 and 5d2 levels
shows that the crystal field strength becomes weaker with
increasing Ga content at the tetrahedral site. However, if the 5d
levels were modified by the nephelauxetic effect, both the 5d1 and
the 5d2 level would shift to lower or higher energies and would
maintain a constant splitting energy between the 5d1 and 5d2
level. Therefore, they concluded that the blue shift of the 5d1 level
with increasing Ga content at the tetrahedral site was caused
mainly by crystal field splitting not by the nephelauxetic effect.
Briefly, the substitution of smaller Al3+ ions by larger Ga3+ ions
enables the average crystal structure to expand and the rigidity
of the unit cell decreases, leading to a loosed environment
surrounding the Ce3+ ions. Accordingly, the crystal field splitting
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the local structure of phosphors. Recently, Shang et al. realized

the redshift emission in the Y3Al52xMgxSixO12:Ce3+ (41 nm)
and the Y3Al52xMgxGexO12:Ce3+ (19 nm) series by replacing
Al(1)3+–Al(2)3+ pairs with Mg2+–Si4+ and Mg2+–Ge4+ pairs, respec-
tively (Fig. 11a and b).111 In general, this should be mainly
assigned to the lattice distortion in local crystal structures. The
detailed mechanism can be explained as follows: the ionic radius
of Mg2+ with 6-fold coordinated O is larger than that of Al3+. When
the Al3+(1) site is occupied by the Mg2+ ion, the Mg2+–O2 bond
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length increases, while the adjacent Ce3+–O2 bond length (RCe–O)

decreases, resulting in the increase of the crystal field strength. So
the emission peak shifts to a longer wavelength. On the other
hand, the smaller Si4+ or Ge4+ ion substituted for Al(2)3+ would lead
to a longer RCe–O bond length and decrease the crystal field
strength around the Ce3+ ion, so that the emission spectra would
be blue-shifted. In the Y3Al52xMgxSixO12:Ce3+ and Y3Al52xMgxGex-
O12:Ce3+ solid solutions, Mg2+–Si4+/Ge4+ as ion pairs substituted for
Al(1)3+–Al(2)3+ are synchronously incorporated into the Y3Al5O12:Ce3+
host lattice. According to the crystal structure shown in Fig. 11c,
Fig. 9 (a) The photoluminescence excitation (PLE) and emission (PL) YO8 dodecahedra share the vertex with SiO4 tetrahedra, while YO8
spectra of the (Ce0.005Y0.995)3Sc2Al3xGaxO12 (x = 0, 1, 2, 3) (Ce:YSAGG) dodecahedra share the edge with MgO6 octahedra. The augmenta-
solid solutions. (b) Lattice constants of Ce:YSAGG. (c) Lattice constant tion of the crystal field strength arising from Mg2+ substitution
dependence of transition energies of the Ce3+ ions in Ce:YSAGG. (d) The
would dominate, namely, DE3 4 DE2 4 DE1, resulting in the
PL of Y2.9Ce0.1Al5xSixO12 as a function of x values. (Reproduced with
permission from ref. 108 and 109, copyright 2013, 2014, Elsevier.)
redshift emission in the above two phosphor systems. Moreover,
there is a larger redshift in the Mg2+–Si4+ systems than that in
Mg2+–Ge4+ systems.
of the 5d levels of Ce3+ ions in Ce:YSAGG decreased and induced
a blueshift of the emission spectra. Unfortunately, a decrease in
the rigidity of phosphors with increasing Ga or Si contents also
increased the nonradiative rate and decreased the distance
between the 5d1 level and the conduction band. The former
damaged the quantum yields of phosphors, and the latter
increased luminescence quenching. Therefore, the researchers
need to search for suitable composition to balance the various
luminescence performances of phosphors. Such phosphors
can produce the maximum effect in WLED lighting and display
applications. Based on a similar mechanism, Zhang et al. found a
blueshift in Y3yCeyAl5xSixO12 by the Si4+ - Al3+ nonequivalent
valence replacement, as shown in Fig. 9d.109 Jung et al. also
reported a tune emission from orange to red in CaAlxSi(73x)/4N3:Eu2+
phosphors by varying the Si/Al ratio, as shown in Fig. 10a.110 Fig. 10b
revealed that the emission spectrum of the representative
CaAl0.7Si1.225N3 sample could be deconvoluted into two Gaussian
components due to the presence of two Ca2+ sites (Ca1 and Ca2)
in the host. Moreover, the deconvoluted Gaussian components
of all non-stoichiometric CaAlxSi(73x)/4N3 phosphors depended
on their corresponding local environments, namely, the Al/Si
molar ratio around the Eu2+ activator. The high Al/Si ratio near
the Eu2+ activator abolished the high energy peak. Therefore, the
Eu2+ activator site in an Al-rich environment with a smaller
average Ca–N distance was assigned to the lower energy emission
peak due to the increased crystal field splitting and nephelauxetic
effect, while that in a Si-rich environment with a longer average
Fig. 10 (a) The emission spectra of CaAlxSi(73x)/4N3:Eu2+ phosphors
Ca–N distance was assigned to the higher energy emission peak. with x = 0.7–1.3 and images of each sample taken under an 365 nm UV
Except for the single substitution of Al3+ by Si4+, some researchers lamp. (b) Gaussian deconvolution of CaAl0.7Si1.225N3. (Reproduced with
exploited double substitution approaches to form the distortion of permission from ref. 110, copyright 2010, Optic Society of America.)

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Fig. 11 The photoluminescence emission spectra of (a) Y3Al52xMgxSixO12:Ce3+ (x = 0–2) and (b) Y3Al52xMgxGexO12:Ce3+ (x = 0–1.6) with the excitation
monitoring wavelengths of 456 nm. (c) The crystal structure of Y3Al5O12 and the schematic illustrates the replacement of Al(1)3+–Al(2)3+ pairs by
Mg2+–Si(Ge)4+ pairs. (Reproduced with permission from ref. 111, copyright 2014, American Chemical Society.)
3.2.3 Ch–Cic substitution. Since both Ch and Cic substitutions
can distort the microenvironments of the local structure surroun-
ding Ce3+ or Eu2+ ions in phosphor compounds, namely, by
changing their CFS and NE effects, the simultaneous Ch–Cic
substitutions are predicted to possibly further intensify the
above effects and thus have been developed to tune the lumi-
nescence properties of phosphors recently.112,113 Considering a
charge balance in phosphors that is used to reduce nonradia-
tive transitions, the Ch–Cic substitutions mainly contained the
following several types: (1) A+ + C3+ 2 2B2+ or B12+ + B22+, (2) A+
+ D4+ 2 B2+ + C3+, (3) B2+ + D4+ 2 2C3+ or C13+ + C23+, (4) B2+ +
E5+ 2 C3+ + D4+, (5) B2+ + D4+ 2 A+ + D5+ 2 2C3+ or C13+ +
C23+, as shown in Fig. 12; The above 5 types are the predictable
Ch–Cic substitution types; ‘‘2’’ means that the substitution not
only can be executed from left to right but also can be
substituted from right to left; A, B, C, D, and E in these
inorganic phosphors generally represent the alkali metal, the
alkali earth metal, the IIIA and IIIB metal, the IVA metal, the VA
metal elements in the periodic table, respectively, for example,
A are Li, Na, and K; B are Mg, Ca, Sr, and Ba; C are Sc, Y, La, Gd,
Lu or B, Al, Ga, and In; D are Si and Ge; E are P, Mo, and W. B1
and B2 are different alkali earth metal elements, while C1 and
C2 are different IIIA and IIIB metal elements. In addition, there is a
basic requirement that phosphor compounds should form a
solid-solution or a single phase after Ch–Cic substitution. Wang
et al. systematically investigated spectral tuning properties and
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thermal quenching behaviour based on the (2) and (3) Ch–Cic
substitution types that substituted Li+/Si4+ for Ca2+/Al3+ (Li series)
and La3+/Al3+ for Ca2+/Si4+ (La series) in the CaAlSiN3:Eu2+ lattice.50
Linear shifts in the lattice parameters in both series with increas-
ing x, as plotted in Fig. 13a, which demonstrates the formation of
solid solutions in both materials. The sum of the cation radii of
the CaAlSiN3 parent structure is smaller than that of the La lattice,
but larger than that of the Li lattice. Therefore, the lattice
expansion with x in the La series occurs, while a lattice contrac-
tion in the Li series is observed. The maximum emission peak in
the La series shifts to the shorter wavelength region with x due to
a decrease in the CFS of 5d orbitals caused by lattice expansion
(Fig. 13bi). However, an unexpected broadening of the emission
peak in the shorter wavelength region with increasing x instead
of shifting to the longer wavelength region appears despite the
lattice contraction in the Li series (Fig. 13bii), which is signi-
ficantly correlated with the local structural change of activators.
In addition, with increasing x values in the two systems, the
thermal quenching of the La series increased while the thermal
quenching of the Li series decreased, as depicted in Fig. 13c.
Wang et al. proposed a possible mechanism that the accom-
modation of the Eu2+ activator is controlled by variable neighboring
cations to elucidate the variations in the photoluminescence and
quenching behaviour in both series. Schematic models for the
neighboring-cation induced effect are shown in Fig. 13d. This
model explains the site occupation of Eu2+ activators in both series,
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Fig. 12 (left) Schematic illustration of the Ch–Cic substitutions in Ce3+ or Eu2+ activated phosphors. (right) The typical types of Ch–Cic substitutions.
(5) are the predictable types. ‘‘2’’ means that the substitution can be executed from left to right or from right to left; A, B, C, D, and E in these inorganic
phosphors generally represent the alkali metal, the alkali earth metal, the IIIA and IIIB metal, the IVA metal, the VA metal elements in the periodic table,
respectively. B1 and B2 are different alkali earth metal elements, while C1 and C2 are different IIIA and IIIB metal elements. The blue and green spheres are
Ch, the red and yellow are Cic, and the gray spheres are anion ligands.
Fig. 13 (a) Relative changes in the lattice parameters with x in (Ca1xLax)-
(Al1+xSi1x)N3:Eu (La series) and (Ca1xLix)(Al1xSi1+x)N3:Eu (Li series). (b) PLE
and PL spectra of (i): La series and (ii): Li series (lex = 460 nm). The arrows
present the energy shift for the emission spectra of the La series and the
relative intensity change for the Li series with increasing x. The PL spectra
of the Li series are decomposed into two Gaussian peaks from different
Eu2+ environments. (c) Thermal quenching behavior for La series and
Li series. (d) Local coordination of CaAlSiN3, La and Li series lattices. The
dashed line represents the longer and looser bonds. The broad solid line
represents the shorter and tenser bonds. (Reproduced with permission
from ref. 50, copyright 2013, American Chemical Society.)
as presented in Fig. 13dii and diii. Since the bonding distance of
the nitride and Ca2+ that connects with the La3+ and AlSi7+ pair
becomes longer due to the neighboring-cation induced effect.
When Eu2+ activator is introduced, it would preferably be accom-
modated at the looser Ca2+ site to minimize the lattice strain in
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view of the larger ion size of Eu2+ than Ca2+, thereby providing
a weak covalent coordination environment for Eu2+. A reverse
argument can predict the accommodation of Eu2+ ions in the Li
series. Therefore, the Eu2+ activator is controlled to locate at the
relatively loose outer Ca2+ site, which is connected to the nitride
with Li+ and SiSi8+ pair branches, namely, the Si-rich site. The
Eu2+ activators in both series locate at the relatively loose site for
minimizing the lattice strain. Thus, the photoluminescence in the
La series is expected to blueshift because there is a progressive
decrease in the covalency and crystal field strength with x. By
contrast, the nitrides connecting with excess Si4+ neighbors in the
Li series possess a smaller nephelauxetic effect than that connecting
with Si4+/Al3+-equivalent neighbors for Eu2+ ions. This result creates
the other high-energy emission as fitted in Fig. 13bii. In general, a
remote control effect that guides Eu2+ activators into different
Ca2+ sites is proposed for neighboring-cation substitution when
the Si4+/Al3+ ratio varies with the valence of the Mn+ (n = 1–3) cation.
According to the remote control effect, the Eu2+ activators are
surrounded by nitride anions that neighboring with M3+-
dominant and Si4+/Al3+-equivalent coordination when M is a
trivalent. However, when M is a monovalent, the Eu2+ ions
will be surrounded by nitride anions neighboring with M+-
dominant and Si-rich coordination.50 This mechanism not only
can reveal the underlying mechanisms in optical changes by
adjusting the cation/anion composition of phosphors but also
can efficiently tune optical properties, especially thermal stability.
Therefore, it could be general to luminescent materials that are
sensitive to valence variation in local environments. Other types of
simultaneous Ch–Cic substitutions such as La1x0.025Ce0.025Sr2+x-
Al1xSixO5 (x = 0–0.975) and (Ca1xCex)6Ba(P1xSix)4O17 (x =
0–0.07) have been reported to tune spectral positions or improve
emission intensity.112,113 The above results obviously confirm that
the Ch–Cic substitutions based on the variation of the local
environment of activators can efficiently tune the luminescence
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properties of phosphors, and thus could be greatly developed.
Moreover, on the basis of the summarized (1)–(4) types of
Ch–Cic substitution, some new Ch–Cic substitution such as
B2+ + D4+ 2 A+ + D5+ 2 2C3+ or C13+ + C23+, as shown by (5)
in Fig. 12, can be predicted. This can help improve the
application of phosphors in WLED lighting and display areas.
However, the underlying luminescence mechanisms in many
Ch–Cic substituted systems are still unclear, and need to be
further investigated and explored.
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Ca3Sc2Si3O12:Ce3+ resulting in a great enhancement in the
longer wavelength (610 nm) side of the typical green band,
correspondingly leading to the change of luminescent colors
from green to yellow-orange, as shown in Fig. 14a.116 This is
assigned to the presence of N3 around Ce3+ ions in Ca3Sc2-
Si3O126xN4x:Ce3+ (x = 0–0.8) systems. Because N3 can offer
the stronger nephelauxetic effect on Ce3+ than O2, the incor-
poration of N3 anions leads to a decrease in the energy
difference between the lowest 5d excited state and the ground

state of Ce3+ ions, which promotes a redshift emission.

3.3 Anionic substitution However, a decreased emission intensity of the representative
In inorganic phosphor compounds, the first coordination layer Ca2.97Sc2Si3O126xN4x:0.03Ce3+ phosphor was also observed
of host cations and activator ions consists of various anions, with the increase of x values in the inset of Fig. 14a. The
and the interaction of activator ions with anions directly influ- possible explanation is that the substitution of O2 by N3 in
ences the energy difference between 5d levels and the ground Ca3Sc2Si3O126xN4x generates oxygen vacancy defects, resulting
state, which is described by the nephelauxetic effect.58–69 in the enhancement of the non-radiative transition host, and
Commonly, the nephelauxetic effect is linked to the covalency thus quenches the luminescence. Based on the similar mechanism,
of the crystal.59 As the degree of covalency between the activator Setlur et al. realized a distinct low-energy Ce3+ absorption and
ion and the surrounding anions increases, the stronger inter- emission bands in Ce3+ doped RE3Al5O12:Ce3+ (RE = Lu3+, Y3+,
action causes the energy difference between the lowest 5d state or Tb3+) garnet phosphors through the introduction of N3 into
and the ground state of activator ions to decrease. Thus the
covalency of the crystal is related to the electronegativity of
anions and the cation—anion distance. For the same cation,
the higher negative charge and the smaller ionic radius of the
coordinated anion usually lead to the stronger covalency
between the cation and the anion. Thus, the nephelauxetic effect
(centroid shift) in the descending order is selenides 4 sulphides 4
nitrides 4 oxides 4 fluorides, namely, Se2 4 S2 4 N3 4
O2 4 F. Typically, Ce3+ or Eu2+ doped sulfide and nitride
phosphors have a longer emission wavelength than oxide phos-
phors and commonly give yellow-to-red emission.41–47,93,95 If the
activator ions were surrounded by anion groups, the higher
charge density on the anion groups would exert the stronger
nephelauxetic effect on activator ions. The charge density of some
common anion groups is oxides 4 aluminates 4 silicates 4
borates 4 phosphates.71 On the other hand, the interaction
between the molecular orbitals of neighboring anions causes
the 5d orbitals of the activator ion to hybridize, creating bonding
orbitals at lower energies and antibonding orbitals at higher
energies. With the increase of the degree of covalency, both the
bonding and antibonding orbitals move to lower energies, which
causes a red shift. Thus a blue shift occurs with a decrease in the
degree of covalency. In addition, the coordination geometry also
affects the nephelauxetic effect and further changes the crystal
field splitting of Ce3+ or Eu2+ 5d levels. By comparing five different
coordination geometries, Dorenbos determined that octahedral
coordination generates the largest crystal field splitting, followed
by cubic coordination and dodecahedral coordination, and the
smallest crystal field splitting originates from tricapped trigonal
prisms and cuboctahedral coordination.1,71 In general, the varia-
tion of anion coordination circumstances around Ce3+ or Eu2+
ions, namely, anionic substitution, can affect the optical properties
Fig. 14 (a) PL spectra and relative intensity (inset) for Ca2.97Sc2-
of phosphors due to the change in crystal field splitting strength
Si3O126xN4x:0.03Ce3+ (x = 0–0.8). (b) Excitation and emission spectra of
and the nephelauxetic effect. One of the most commonly used Sr1.984Si(N,O)4:0.016Eu2+ (0.7 o z o 1.2). Green lines are two Gaussian
anion substitutions is to change the N/O ratio of phosphor fitting components. (Reproduced with permission from ref. 116 and 118,
compounds.114,115 Recently, Liu et al. introduced N3 into copyright 2011, 2013, Royal Society of Chemistry.)

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phosphor hosts.117 In addition, changing the nephelauxetic effect
in some common phosphors by designing anionic substitution
could obtain unusual luminescence properties. For example, by
increasing the N/O ratio of the host, Zhao et al. obtained novel
red-emitting Sr2SiNzO41.5z:Eu2+ (0.7 o z o 1.2) phosphors with
the maximum emission wavelength at 617 nm (Fig. 14b), which
has a obvious redshift than that of Sr2SiO4:Eu2+ phosphors
(530–560 nm).118 This might originate from the formation of
new Eu2+–N sites in Sr2SiNzO41.5z:Eu2+ (0.7 o z o 1.2) systems.
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Since the nephelauxetic effect of N3 is larger than O2, it leads
to an enhanced covalency between Eu2+ and anions, finally
resulting in redshift emission. Generally, the increase of the
N/O ratio will enable the excitation and emission spectra of
phosphors to shift the lower energy position, while a reverse
change will generate blue-shifted luminescence. Of course, in
addition to changing the N/O ratio, other anionic substitutions
with different electronegativities can also designed to tune the
luminescence spectra of phosphors. Xia et al. reported an asym-
metric blue emission band from 420 nm to 550 nm with a peak
at 442 nm in Ba5SiO4Cl6:Eu2+ under UV light excitation.119 Eu2+
ions in Ba5SiO4Cl6 formed two emission centers, namely Eu(1)
and Eu(2), with maxima at 442 and 470 nm, respectively.
Moreover, Eu(1) centers act as the main luminescent centers
in the Ba5SiO4Cl6:Eu2+ phosphor. By replacing Cl by F, the
emission peaks of Ba5SiO4(FxCl6x):Eu2+ (x = 1, 3, 4, 6) phos-
phors presented a green emission band from 450 nm to 575 nm
with centers at 503 nm. Because the emission band on the long
wavelength side of the Ba5SiO4Cl6:Eu2+ phosphor was centered
at 470 nm, with a full width at half maximum (FWHM) of
50.5 nm, while the main emission band of the Ba5SiO4(FxCl6x):Eu2+
(x = 1, 3, 4, 6) phosphor was centered at 503 nm, with a FWHM
of 48.5 nm. It indicates that the two emissions belong to the
same luminescent center, which should be the Eu(2) centers.
Therefore, the spectral red shift from 442 nm to 503 nm in
Ba5SiO4(FxCl6x):Eu2+ systems should be attributed to two
reasons. The one is that the addition of F ions generates the
strong polarization effect, which promotes the preferred occupa-
tion of the loose environment of the Eu(2) sites, generating an
intense green emission.119 The other reason is that the F element
has a larger electronegativity than the Cl element, while the F ion
has a smaller ionic radius than Cl. The introduction of F ions
increases the crystal field strength and covalency of Eu2+ ions,
generating a red shift from 470 nm to 503 nm at Eu(2) sites. Except
for single anion substitution, some anion group substitution,
for example, substituting SiO44 by PO43 in apatite-structured
phosphor systems can also tune the luminescence properties
of phosphors and improve their luminescence performance.120
In summary, anionic substitution can realize an efficient and
controllable adjustment of the optical properties of phosphors,
which has enlarged the phosphor family used in the pc-WLEDs,
and improved their luminescence performances.
3.4 Cationic–anionic substitution
Because cationic–anionic (C–A) substitution can efficiently and
systematically control the local structures of inorganic com-
pounds to some extent, it has been extensively used to adjust
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the physical properties of functional materials that are sensitive
to the coordination environment and the valence change at specific
sites such as magnetic, electrical and mechanics properties.49,50
Recently, it has also been extended to tune the luminescence
properties of Ce3+ or Eu2+ ion activated phosphors.49 The simulta-
neous C–A substitutions can controllably change the crystal field
splitting and nephelauxetic effects around Ce3+ or Eu2+ ions, and
thus can realize a controllable adjustment of spectra and thermal
quenching behaviour of phosphors. Based on the electrically
neutral principle in compounds, the C–A substitutions are generally
classified into the following types: (1) C3+ + Y2 2 D4+ + Z3
(Al3+ + O2 2 Si4+ + N3), (2) D4+ + Y2 2 C3+ + X (Si4+ + O2 2
Al3+ + F), (3) C3+ + U4 2 B2+ + C3 (Y3+ + C4 2 Sr2+ + N3), (4)
D4+ + U4 2 C3+ + Z3 (Si4+ + C4 2 Al3+ + N3), (5) D4+ + Y2 2
E5+ + Z3 2 C3+ + X (Si4+ + O2 2 P5+ + N3 2 Al3+ + F), and
(6) E5+ + Y2 2 D4+ + X (P5+ + N3 2 Si4+ + F), as shown in
Fig. 15. The expressions in brackets are representative C–A
substitution examples. The (5) and (6) substitution types are the
predictable Ch–Cag substitution types. ‘‘2’’ means that the sub-
stitution can be substituted from left to right or from right to left.
B, C, D, and E in these inorganic phosphors generally represent
some of the alkali earth metal, the IIIA,B metal, the IVA metal, the
VA metal elements in the periodic table, respectively, for example,
B are Mg, Ca, Sr, and Ba; C are Sc, Y, La, Gd, Lu or Al, Ga, and In;
D are Si and Ge; E is P. X, Y, Z, and U are F, O, N and C elements,
respectively. Similarly, the solid-solution should be formed after
C–A substitution in phosphor compounds. These C–A substitu-
tions will be illustrated through some representative examples as
follows.
Many oxides and nitrides, particularly silicon nitride-based
materials with good thermal stabilities, such as M2Si5N8 and
MSi2O2N2 (M = Ca, Sr, Ba), CaAlSiN3, and SiAlON, are useful
phosphor hosts.34,36,49,50,121,122 When doping Ce3+ or Eu2+ ions
into silicon nitride-based materials, it generates excellent
yellow to red emission under the excitation of UV or blue light.
Therefore, they are widely combined with a blue light-emitting
diode to emit white light for everyday applications. Sometimes,
in order to satisfy the diverse WLED lighting requirements
(for example, different correlated color temperatures and color
rendering indices), the shape, FWHM and position of lumines-
cence spectra need to be tuned. Chen et al. showed that the size-
mismatch between the host and doping cations based on the
substitution of Si4+–N3 pairs by Al3+–O2 pairs can systematically
tune photoluminescent shifts in M1.95Eu0.05Si5xAlxN8xOx, leading
to a red shift when the M = Ba and Sr host cations are larger than
the Eu2+ dopant (Fig. 16a and 17b), but a blue shift when the
M = Ca host cations are smaller than the Eu2+ dopant (Fig. 16c).49
In addition, the size-mismatch tuning of thermal quenching was
also observed. A local anion clustering mechanism in which Eu2+
gained excess N coordination in the M = Ba and Sr structures, but
excess O coordination in the Ca analogues, was proposed for
explaining these mismatch effects, as shown in Fig. 16d. The local
structure of Ca1.95Eu0.05Si4AlN7O (top), where Eu2+ is bigger than
the Ca2+ ions and lattice strain are minimized by clustering oxide
anions around Eu2+ cations (and hence more nitrides around Ca2+
ions), resulting in a blue shift emission. Ba1.95Eu0.05Si4AlN7O
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Fig. 15 (left) Schematic illustration of the cation–anion (C–A) substitutions in Ce3+ or Eu2+ activated phosphors. (right) (1)–(4) are the typical types of
C–A substitutions. (5) and (6) are the predictable types. ‘‘2’’ means that the substitution can be executed from left to right or from right to left; C, D, and E
in these inorganic phosphors generally represent some of the IIIA,B, IVA and VA metal elements in the periodic table, respectively. The blue and green
spheres are cations in anion groups; the red and gray spheres are anion ligands.

Fig. 17 (a) Excitation and (b) emission spectra of Sr2.975Ce0.025Al1x-

SixO4+xF1x (SASF:Ce3+; x = 0–1). Sr1 and Sr2 polyhedra looking down
the [100] direction are shown to the right of (a); the upper two polyhedra
are from the Sr3AlO4F (SAF) structure and the lower two are from the
Fig. 16 Normalized excitation and emission spectra of M1.95Eu0.05-
Sr3SiO5 (SSO) structure. Light gray, black, orange, and green spheres
Si5xAlxN8xOx:M = (a) Ca, (b) Sr, (c) Ba. The emission spectra are decom-
represent Sr1, Sr2, O, and F atoms, respectively. (c) VUV emission spectra
posed into Gaussian contributions. The arrows illustrate the energy shift
(lex = 254 nm) and dependence of the CIE chromaticity coordinates on
and the change in relative intensity of the spectra with increasing x.
varying z values in Ca11.9Al14zSizO32+zF2z:Eu0.1 (z = 0–0.5). The inset
(d) Schematic local anion distributions driven by the cation size-
shows the schematic variation of the activator site driven by Si4+–O2
mismatch in M1.95Eu0.05Si5xAlxN8xOx phosphors. (e) Emission spectra
incorporation and the irradiated phosphor images of each composition.
of Y2.91Ce0.09Al5xSixO12xNx for x = 0, 0.10, 0.20; (g) emission spectra
(Reproduced with permission from ref. 136 and 139, copyright 2011, 2012,
of Y2.94Ce0.06Al(5x)SixO(12x)Nx for x = 0.2–0.3. (Reproduced with
American Chemical Society, Wiley.)
permission from ref. 49, 117 and 123, copyright 2008, 2012, American
Chemical Society, Wiley.)

redshift was observed in Sr1.95Eu0.05Si5xAlxN8xOx. They found

(bottom), where Eu2+ is smaller than the Ba2+ ions, tends to
be coordinated by nitride, while the introduced oxide anions
preferentially coordinate Ba2+. Since N3 ions can induce a
stronger nephelauxetic effect than O2 ions, Ba1.95Eu0.05-
Si5xAlxN8xOx presents a redshift emission with x. A similar
that the size-mismatch effect originated from the substitution of
Si4+–N3 pairs by Al3+–O2 pairs in M1.95Eu0.05Si5xAlxN8xOx
materials could also be used to tune photoluminescence in some
phosphors having (oxo)nitridosilicate frameworks such as a- and
b-SiAlONs and the MSi2O2N2 (M = Ca, Sr, and Ba) family. There-
fore, this mechanism was predicted to be general to oxynitride

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materials and would be useful in tuning optical and other properties
that are sensitive to local coordination environments. A reverse
substitution of Al3+–O2 by Si4+–N3 was also reported in
Y3Al5O12:Ce3+ garnet phosphors by Setlur and Michalik et al.,
respectively, and they obtained a similar redshift phenomenon by
this reverse substitution, as described in Fig. 16e and f.117,123 This
is assigned to the occurrence of N3 in their local coordination
of Ce3+ ions. In view of the larger covalency of Ce–N than that of
Ce–O, indicating the stronger nephelauxetic effect surrounding
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the Ce3+ ions compared to typical garnets. It is noted that there is
also a stronger luminescence quenching in these systems versus
typical Ce3+ ions in garnets. This might result from the damage
due to the rigidity of the Y3Al5O12:Ce3+ lattice due to the size-
mismatch between Al3+–O2 pairs and Si4+–N3 pairs. In general,
the substitution between Al3+–O2 pairs and Si4+–N3 pairs in
phosphors can change the local environment around the activator
ions, and thus realize a controllable tuning of luminescence
properties of phosphors. By the above substitutions, some promising
phosphor systems including Si–N doped BaMgAl10O17:Eu2+,124
Ba(Si,Al)5(O,N)8:Eu2+,125 Sr5Al5+xSi21xN35xO2+x:Eu2+ (x E 0),126
Sr2Al2xSi1+xO7xNx,127 Mval+
m/val+Si12(m+n)Alm+nOnN16n (M = Mg, Ca,
and Lu (0.5 r m r 2.0, 1 r n r 1.8),128 La1xCexAl(Si6zAlz)-
(N10zOz) (z B 1),129 and a-SiAlON series,130–135 have been modified
or developed.
Another common C–A substitution type is D4+ + Y2 2 C3+ +

X and the representative example is the double substitution
of Si4+–O2 by Al3+–F. According to this strategy, Seshadri’
group have made much effort to modify and develop newly
oxyfluoride-based pc-WLED phosphors recently.136–138 The
replacement of Al3+ by Si4+ and of F by O2 not only compensate
charge, but also more importantly change the local environment
of the lattice. For example, in the Sr2.975Ce0.025Al1xSixO4+xF1x
(SASF:Ce3+) system, abnormal spectral tuning were obtained by
substituting Si4+–O2 by Al3+–F across the solid solution series
of Sr3AlO4F (SAF) and Sr3SiO5 (SSO) (Fig. 17a and b).136 A
conventional d-orbital splitting model predicts a blueshift in
the excitation and emission spectra as x increases in SASF:Ce3+,
based on the increasing average Sr–O/F distance. However, with
the increasing x value in SASF:Ce3+, the emission peak positions
gradually move toward longer wavelengths, in the range from
474 nm for SAF:Ce3+ (x = 0) to 537 nm for SSO:Ce3+ (x = 1.0)
(Fig. 17b). The modified SASF:Ce3+ phosphors have wider emission
peaks than SAF:Ce3+, which allows SASF:Ce3+ phosphors to provide
a higher color rendering properties when incorporated into an
LED chip. The emission red-shift is partially attributed to increas-
ing distortion of the Ce3+ sites, which causes an increased crystal
field splitting. Other contributions originate from the increasing
nephelauxetic effect offered by O2 than F in the lattice (different
Sr sites) as x increases. Note that there is a non-monotonic increase
of the excitation wavelength maximum with varying x. The above
inconsistency in the shift of excitation and emission wavelengths
with x should be attributed to the increasingly anisotropic of the
coordination around both Sr sites, as shown in Fig. 17a. In
addition, the modified Sr2.975Ce0.025Al1xSixO4+xF1x phosphors
had a high quantum efficiency of 85% at room temperature, close
to that of commercial YAG:Ce3+, which may be due to the optimal
Chem. Soc. Rev.
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bonding of Ce3+ ions in the structure. Unfortunately, SASF:Ce3+
have a more serious thermal quenching for luminescence, where
the maximum PL intensity of the x = 0.5 sample can only retain
55% of the initial value at 170 1C with respect to the 64% of
commercial YAG:Ce3+. This serious thermal quenching arises from
softer phonon modes associated with fluorine atoms in the host.
However, the SSO:Ce3+ (x = 1.0) phosphor had improved thermal
quenching properties compared to the x = 0.7 or x = 0.9 materials.
Disordering of Al3+/Si4+ and F/O2 provides an alternate quench-
ing path in the host lattice which outweighs the effect of softer
phonon modes of F. On the basis of the same substitution type,
Liu’s group developed an new approach that can tune the valency
of Eu by controlling the size of the activator site in phosphors for
designing phosphors used in pc-WLEDs.139 They have revealed
that by replacing Al3+–F by the appreciate dopant Si4+–O2,
the valence state of Eu3+ can be tuned to Eu2+ in Ca12Al14z-
SizO32+zF2z:Eu (z = 0–0.5, CASOF:Eu) phosphors due to the
enlargement of the activator site, which leads to a rise in broad-
band emission at 440 nm of Eu2+ (Fig. 17c). Moreover, the
emission intensity of Eu2+ and Eu3+ alternatively increases and
decreases with z. The chromaticity coordinates of CASOF:Eu
phosphors could be tuned from (0.6101, 0.3513) for z = 0 to
(0.1629, 0.0649) for z = 0.5, as shown in Fig. 17d, suggesting their
potential for use in WLEDs. They thought that this approach could
not only be limited to present materials but could be general to
other related systems, which may lead to more opportunities
for developing novel phosphors for WLEDs. As mentioned in
SASF:Ce3+, double substitutions of cations and anions may
optimize the Ce3+ ions bonding with the surrounding anion
ligands, improving the quantum efficiency of phosphors. Similar
work was reported by Shi et al. and Xie et al. on the (SiC)x–
(AlN)1x:Eu2+ solid-solution phosphors by replacing Al3+–N3 by
Si4+–C4.140,141 The (SiC)x–(AlN)1x:Eu2+ (x = 0–1) phosphor shows
broad absorption bands in the 250–425 nm range, and bright
blue emissions peaking at 470 nm, which has a more high color
purity (0.135 and 0.167) for the x = 0.5 sample than that of the
AlN:Eu2+ sample.140 Interestingly, the luminescence intensity
increases with the SiC content and reaches its maximum at
x = 0.20.140 The reason is that the formation of (SiC)x–(AlN)1x
solid solution promotes the doping of Eu2+ ions into Al sites
of the host. Moreover, the composition-optimized (SiC)0.20–
(AlN)0.80:0.006Eu2+ phosphor shows a small thermal quenching
effect than AlN:Eu2+. This is because the incorporation of SiC into
the AlN host increases the rigidity of the crystal lattice.
Generally, the (1), (2) and (4) C–A substitutions only involve
the substitutions between the Cic and anion ligands. In fact, the
C–A substitution could also occur between the Ch and anion
ligands. Huang et al. have confirmed this situation in the
Sr1xY0.98+xCe0.02Si4N7xCx (x = 0–1) system, in which Sr2+–
N3 was successfully substituted by Y3+–C4. By this substitution,
the emission peak of Sr1xY0.98+xCe0.02Si4N7xCx phosphors can
be widely and controllably tuned from blue light to yellow light
with the increase of Y3+–C4 content; blue for x = 0–0.07, blue-
green for x = 0.1, green for x = 0.2–0.6, yellow-green for x = 0.7 and
yellow for x = 0.8 and 1.0 samples, as shown in Fig. 18a.51
However, the overall trend of increasing thermal quenching
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behaviour with increasing x is surprising, as the progressive
replacement of Sr2+ and N3 by Y3+ and C4 was expected to
introduce more covalency into the materials and hence
increase lattice rigidity and the quenching barrier height. They
proposed a dominant neighboring-cation effect to explain this
color-tunable emission and the thermal quenching luminescence.
The local structures around Ce3+ activator ions when occupying
Y3+ sites in the x = 0 and x = 1 materials are shown in Fig. 18b and
c, respectively. Briefly, the Sr2+/Y3+ substitution in the second
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coordination sphere has a strong effect on the coordination of
Ce3+. The degree of covalency in the Ce–N bonding is controlled
by the bonding of the nitride with other neighbors. Sr2+ ions form
more strong ionic bonds with N3, and so the Ce–N covalency is
enhanced, whereas Y–N bonds are more covalent, and so the
Ce–N covalency is reduced. Thus the Ce–N bonds become less
covalent as the second-neighbor Sr2+ ions around Ce3+ are gradu-
ally replaced by Y3+, namely, the nephelauxetic effect continuously
decreases. This results in a progressive increase of the thermal
quenching luminescence of phosphors. While the redshift of
emission can be explained, the neighboring-cation effect of
replacing Sr2+ by Y3+ is suppressed by the overall effect of the
lattice contraction (a larger crystal field splitting).
According to the previous discussion, it obviously indicates
that the C–A substitutions can efficiently tune the optical pro-
perties of pc-WLED phosphors including the spectral position,
Fig. 18 (a) Excitation and emission spectra of Sr1xY0.98+xCe0.02Si4N7xCx
samples. The representation of the local first- and second-coordination
around Ce3+ activator ions occupying Y3+ sites in Sr1xY0.98+xCe0.02-
Si4N7xCx phosphors for (c) x = 0 and (d) x = 1. (Reproduced with
permission from ref. 51, copyright 2013, Wiley.)
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shape, quantum efficiency, thermal quenching behaviour and
so on through controlling the local structure around activator
ions. Therefore, modifying the current Pc-WLED phosphors or
developing newly efficient phosphors for application in WLEDs
by this strategy is necessary. Furthermore, some newly C–A
substitution types such as (5) and (6) in Fig. 15 (right) can be
predicted to realize spectral tuning based on a similar principle
to that in (1)–(4) types. Schnick and coworkers have developed a
series of oxonitridophosphate (MgSrP3N5O2, CaMg2P6O3N10,
SrP3N5O, Ba3P6O6N8, (Ca, Sr, Ba)P2N4, etc.) recently, which offer
more phosphor host materials and also offer a possibility to
tune their luminescence properties by the Si4+ + O2 2 P5+ +
N3 2 Al3+ + F and P5+ + N3 2 Si4+ + F substitutions.142–148
Thus, more highly efficient phosphors might be developed for
WLED applications. Certainly, the above-mentioned several
types in Section 3.4 do not contain all C–A substitution types
due to the limitation of classification conditions. For example,
in the (KSrPO4)1x(Ba,Sr)2SiO4)x system, it exhibits tunable
emission from blue to green for (KSrPO4)1x(Ba2SiO4)x (Fig. 19a)
and from blue to yellow for (KSrPO4)1x(Sr2SiO4)x (Fig. 19b) by
substituting of K+–Sr2+ by 2Ba2+/2Sr2+ and of PO43 groups by
SiO44 groups simultaneously.149 Both emission peaks of Eu2+
have a redshift as x increases due to the increasing crystal field
effect and an anomalous occupation at some cation sites with the
bigger nephelauxetic effect.
3.5 Crystal-site engineering approach
It is known that the activator ions randomly occupy the cation
sites in the phosphor host according to the balance of the ionic
radius and valency. Nevertheless, there is still some strategies
to change the sites of activator ions in the phosphor matrix
when multi-cation sites are available, including the control of
the doping level of activator ions, cationic substitution and so
on, which is called the crystal-site engineering approach.86,87
By these crystal-site engineering approaches, one can expect
spectral tuning of phosphors owning to different coordination
environments and energy transfer of activator ions between
different crystal sites.150–153 According to the cationic substitution
approach, Daicho et al. reported a yellow-emitting (Ca1xySrxEuy)7-
(SiO3)6Cl2 (Cl_MS:Eu2+) with high luminescence efficiency.150 The
as-prepared Cl_MS:Eu2+ can be efficiently excited by UV light or blue
light, exhibiting a broad emission from 475 nm to 725 nm with the
maximum emission at 580 nm under the excitation of 400 nm UV
light, as shown in Fig. 20a. This broad emission band is attributed
to two different Eu2+-occupied sites, the M(2) and M(3) sites in
Fig. 20c and d, respectively. Moreover, they found that the dominant
wavelength was linearly red-shifted with the increase of the Ca/Sr
ratio (Fig. 20b), namely, the emission color of could be tuned by
varying the Ca/Sr atomic ratio. The reason can be explained as
follows: the increase of the Ca/Sr ratio drives more Eu2+ ions into the
M(3) sites; then, anisotropic lattice contraction occurred along the
a axis and this contraction induced substantial deformation of
the M(3) site; finally, such deformation strengthened the crystal-
field splitting, and the 580 nm luminescence band was red-
shifted.150 By the doping level control, Liang’s group has successfully
tuned the photoluminescence properties of many phosphor systems
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Fig. 19 Photoluminescence emission spectra of Eu2+-activated (a)
(KSrPO4)1x(Ba2SiO4)x and (b) (KSrPO4)1x(Sr2SiO4)x at various x values
under 380 nm excitation. The insets are photos showing colors of
the corresponding samples, which were taken with a 380 nm emitting
UV-LED. (Reproduced with permission from ref. 149, copyright 2013, Wiley.)
such as Ca3La3(1x)Ce3x(BO3)5, La2CaB10O19:Ce3+, Sr3yCeyAlO4F and
so on. For example, in the Ca3La3(1x)Ce3x(BO3)5 system, Liu et al.
reported spectral tuning from UV light to blue-green light.151 Fig. 20f
show the normalized emission spectra upon excitation of the Ce(1)3+
site at 311 nm in the wavelength range of 340–550 nm. It is shown
that the emission from Ce(2)3+ gradually increases with the
increase of the x value, whereas the emission from Ce(1)3+
decreases regularly. Meanwhile, emission intensity from
Ce(2)3+ always keeps increasing when excitation is on the
Ce(2)3+ site at 368 nm (Fig. 20g). This might be attributed to
the different occupancy probability between Ce(1)3+ and Ce(2)3+
and the energy transfer from Ce(1)3+ to Ce(2)3+. The Ce3+ ions
occupy two sites in the above systems, Ce(1)3+ for the 10-fold
coordination La3+ site and Ce(2)3+ for the 8-fold coordination
Ca2+ site, and the occupations of both the Ce(1)3+ site and the
Ce(2)3+ site increase with the total doping concentration. Before
the occurrence of concentration-quenching, both the emission
of the Ce(1)3+ site and the Ce(2)3+ site will regularly increase.
The lowest 5d absorption band for the Ce(2)3+ site (at about
370 nm) has obvious overlap with the emission bands from the
Ce(1)3+ site, which results in the Ce(2)3+ ions absorbing the
emission from the Ce(1)3+ site efficiently. As a consequence, an
effective resonance-type energy transfer may occur from Ce(1)3+
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to Ce(2)3+. This energy transfer will quench the emission of Ce(1)3+
and strengthen the emission of Ce(2)3+. Certainly, different nephel-
auxetic effects under different sites also generate an obvious
influence on the resulting luminescence of Ce3+ and Eu2+ ions.
Through the doping level control, Sato et al. reported a novel deep-
red light (B650 nm) emission, when doped a large amount of Eu2+
ions in Ca2xEuxSiO4 phosphors, as shown in Fig. 20e. This should
be attributed to the substitution of Eu2+ ions in the small Ca sites
that possessed strong interactions between Eu2+ and O2.86 Chen’s
group found that this approach is available in sulfide-based
phosphor systems.41–43 For example, the b-YFS lattice consists of
two distinct coordination polyhedra. The Y(1) site in the YS6
polyhedron has a stronger bond covalency than the Y(2) site in
the YS2F6 polyhedron. This suggests that the green emission at
around 495 nm originates from the substitution of Ce3+ ions for
Y3+ ions in the Y(2) site whereas the yellow component at around
547 nm is the emission of Ce3+ in the Y(1) site. By increasing the
Ce3+ doping concentration from 1% to 5% in the b-YFS:Ce3+
system, the emission colors of phosphors were adjusted from
green light (495 nm) to yellow light (540 nm).41 This should be
attributed to energy transfers between two different Ce3+ emission
centers with increasing Ce3+ concentration. A simple model to
illustrate the spectral tuning mechanism of Ce3+ or Eu2+ ion doped
phosphors by the crystal-site engineering approach is shown in
Fig. 21. Commonly, when doping Ce3+ or Eu2+ ions into the host
that have several cation sites, it preferentially enter into a part of
cation sites at a low doping concentration, while other sites are
subsequently seized with increasing the doping content. Because of
different coordination environments in different crystal sites that
result in a difference in CFS and the nephelauxetic effect, the
corresponding shapes and positions of emission spectra are
different. Moreover, the energy transfer easily occur between
different luminescent centers with gradually enhancing the
concentration of activator ions in this host, which also leads
to spectral shift of phosphors. It is noted that although the
crystal-site engineering approach is an efficient route to tune
the spectra of rare earth ion activated pc-WLED phosphors,
the tunable range for spectra strongly depends on different
cation-coordination environments that contain a sophisticated
complex of crystal field splitting, the nephelauxetic effect and
so on. Sometimes, it is difficult to realize a continuous and
controllable luminescence adjustment for Ce3+ or Eu2+-acti-
vated phosphors. Moreover, this spectral tuning approach
commonly needs a high level of cationic substitution or a
doping level, which easily sacrifices the emission intensity
and thermal stability of phosphors. That is because that an
excessive doping level may result in the concentration quenching
effect and self-absorption.85 Accordingly, the reasonable doping
level should be employed to give simultaneous consideration of
luminescence efficiency, thermal stability and emission position
desired by WLEDs’ requirements.
3.6 Mixing of the nanophase
Commonly, phosphors used in WLEDs should retain a single
phase in order to achieve excellent luminescence efficiency
and thermal stability. This single phase is a macroscopical
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Fig. 20 (a) Emission (dotted curves) and excitation spectra (solid curves) of (Ca0.37Sr0.53Eu0.10)7(SiO3)6Cl2 (Cl_MS:Eu2+) phosphors. The inset shows its
IQE and absorption (Ab) values. (b) Dominant wavelengths of luminescence as a function of the Ca fraction in Cl_MS:Eu2+. (c) and (d) are the coordination
geometries of the M(2) and M(3) sites. Pink and orange spheres represent oxide and chloride ions, respectively. (e) Emission spectra of Ca2xEuxSiO4 with
x = 0.2, 0.4, 0.6, and 0.8. Inset: Photographs of these samples under 365 nm UV light. The emission spectra of Ca3La3(1x)Ce3x(BO3)5 with different x
values at RT: (f) lex = 311 nm and (g) lex = 368 nm. (Reproduced with the permission from ref. 86, 150 and 151, copyright 2012, 2014, American Chemical
Society, Nature Publishing Group, Wiley.)

statistical analysis of phosphor compounds. Therefore, this

Fig. 21 A schematic illustration of the red shift and blue shift mechanisms
induced by occupying different crystal sites. Green and gray spheres
represent host cations and anion ligands, respectively. H1n are cation
sites with different sizes. The size is H1 4 H2 4 Hn. The crystal field splitting
strength of activator ions in H1n sites are H1 o H2 o Hn. A spectral red
shift will appear when activator ions entering into cation sites from H1 to
Hn. On the contrary, a spectral blue shift will appear. The energy transfers
of activator ions among the H1n sites also contribute to a spectral
red shift.
result can’t guarantee a single phase or a single crystal in all
regions of phosphor compounds. Actually, phosphor powders
commonly consist of polycrystalline particles, which may result
in some mixing of the nanophase in the local region, which
means mixing of different crystal phases in the nano-domain
region. While these mixings of the nanophase in the local
crystal structure of phosphors offer a possibility for spectral
tuning.48,51 For example, Li et al. reported tunable emission
in (Sr0.98xBaxEu0.02)Si2O2N2 systems by the mixing of nano-
phases.21 Fig. 22a and b show the typical PL emission spectra
of (Sr0.98xBaxEu0.02)Si2O2N2 phosphors at x = 0.65 to 0.77 and
x = 0.78 to 0.98, respectively. Obviously, there are two emission
bands with centers at 494 nm and 565 nm in (Sr0.98xBaxEu0.02)-
Si2O2N2 (x = 0.78 to 0.98) series, which respectively originate
from the Ba0.98Eu0.02Si2O2N2 phase and the (Sr0.63Ba0.35Eu0.02)-
Si2O2N2 phase. Similarly, the two emission bands with centers
at 494 nm and 565 nm in the (Sr0.98xBaxEu0.02)Si2O2N2 (x = 0.65 to
0.77) series are attributed to the (Sr0.30Ba0.68Eu0.02)Si2O2N2
phase and the (Sr0.63Ba0.35Eu0.02)Si2O2N2 phase, respectively.
Moreover, the relative emission intensity of two emission bands
in the above two series can be adjusted by the Sr/Ba ratio,
namely, the relative content of two phases in the local region,
which generates a single-host white light emission. This result
can be further confirmed by HRTEM results, as shown in
Fig. 22c, which shows a domain structure of (Sr0.30Ba0.68Eu0.02)-
Si2O2N2. The d-spacings of two domains are marked. For the
top domain, A = 2.91 Å, B = 5.14 Å, and the interplanar angle is
76.51. For the bottom domain, C = 2.94 Å, D = 3.53 Å, and the

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Fig. 22 Typical PL emission spectra of (Sr0.98xBaxEu0.02)Si2O2N2 samples:
(a) x = 0.65 to 0.77 and (b) x = 0.78 to 0.98. The relative emission intensities
at 470, 494, and 565 nm as functions of x are shown as insets in (c) and (d).
Black dotted lines in parts (c) and (d) show Gaussian fitting curves of x = 0.73
and x = 0.93 samples, respectively. (c) Typical HRTEM image of
(Sr0.30Ba0.68Eu0.02)Si2O2N2 showing a domain structure. (d) HRTEM image
of the Sr1xY0.98+xCe0.02Si4N7xCx sample, showing multidomain nanostruc-
tures in the two-phase x = 0.4 sample. (Reproduced with permission from
ref. 48 and 51, copyright 2013, American Chemical Society, Wiley.)
interplanar angle is 110.01. The A and B originate from the
Ba0.98Eu0.02Si2O2N2 phase, while C and D are identified as the
(Sr0.63Ba0.35Eu0.02)Si2O2N2 phase. Similar spectral tuning was
reported by mixing of nanophases in the local structure in
Sr1xY0.98+xCe0.02Si4N7xCx (Fig. 18a and 22d) and (Na1xCax)-
(Sc1xMgx)Si2O6:Eu2+ systems (Fig. 8).51,105 In general, the mix-
ing of nanophase in LED phosphor compounds can be used to
tune spectra. However, this approach is closely related to the
synthesis conditions such as calcination temperature, calcina-
tion time, synthesis procedure, the use of flux, which make it
has bad controllability. Moreover, it also easily suffers from
reduced thermal stability and efficiency. In terms of real
applicability (stable emission color, temperature stable, high
quantum efficiency,. . .) of phosphors in WLEDs, it needs to be
further investigated and optimized.
4. Summary and outlook
Currently, white LED technology is becoming more and more
mature with the development of modern science and technology.
Except for the wide use in various outdoor lighting and display
backlight areas, pc-WLEDs have gradually entered into home
lighting, which will bring enormous energy saving and environ-
mental protection. In order to meet the needs of different lighting
and display, and further enhance the luminescence performances
of pc-WLED devices, namely, avoiding phosphor conversion to be
the performance-limiting factor in pc-WLEDs devices, significant
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effort has been made to improve and develop highly efficient
pc-WLED phosphors. The 5d - 4f transitions of rare-earth ions
(i.e., Eu2+ and Ce3+) depends greatly on the surrounding environ-
ments including symmetry, coordination, covalence, bond length,
site size, and crystal field strength in which they reside, making it
possible to tune the excitation and emission wavelength over a
wide range by varying the composition and local crystal structure.
In this review, we have given several approaches to realize the
spectral tuning of pc-WLED phosphors based on local structural
variation of phosphor host lattices, including doping level control,
cationic substitution, anionic substitution, cationic–anionic sub-
stitution, the crystal-site engineering approach, and mixing of
nanophases. The spectral tuning based on the above approaches
can improve the luminescence performance of pc-WLED phos-
phors such as improving the luminous efficiency, optimizing the
color rendering properties, achieving the desired color tempera-
ture, enhancing the color gamut and so on. Moreover, by the
variation of local crystal structure, one can also expect to improve
the thermal stability of phosphors due to the optimization of
lattice rigidity. Although spectral tuning originating from local
structural variation of phosphor hosts can effectively improve the
luminescence performances of pc-WLED phosphors, the under-
lying luminescence mechanisms in many systems are unclear due
to the complex effects of crystal field splitting, the nephelauxetic
effect, the Stokes shift, the distortion of the host lattice and so on.
Therefore, there is no a general law to be suitable for all phosphor
systems at current, and more concerns should be focused on
exploring the structured-related luminescence mechanisms.
On the other hand, some non-rare-earth-based luminescent
materials like semiconducting quantum dots,154–159 Mn4+-
activated red-emitting materials (aluminates, silicates, fluoro-
silicate, fluorotitanate)160–168 and defect-related luminescent
materials show excellent luminescence properties under n-UV
and blue light excitation. For example, defect-related lumines-
cent materials can also emit white light by controlling the
concentration of the defect and reaction conditions.169 This
kind of luminescent material has been greatly accelerated to
develop due to the advantages of non-toxic, environment
friendly and cheap. Newly modified Mn4+-activated red-emitting
materials such as (Na,K)2(Si,Ge,Ti)F6:Mn4+ and Ba(Si,Ge)F6:Mn4+
prepared by modified soft chemical methods show high lumines-
cence efficiency and low thermal quenching under blue light
excitation, which are efficient red-emitting phosphors for the
WLED backlight source.79 Therefore, these non-rare-earth-based
phosphors should also be actively explored to open the door to
novel WLED lighting and display applications. Finally, the search
for new host materials for the efficient doping of rare-earth
ions (i.e., Eu2+, Ce3+) is also a huge challenge. Some methods
for exploration and discovery of novel pc-WLED phosphors,
especially, (oxy)nitride phosphors, including the single crystal
growth method (by Schinick’s group),36,170–173 the single-particle-
diagnosis approach (by Xie and Hirosaki’s group),174,175 the
heuristics optimization based solid state combinatorial chemistry
method (by Sohn’s group)176,177 and so on should be concerned
and encouraged, which might readily be scaled up for industrial
WLED applications. In summary, photoluminescence tuning by
This journal is © The Royal Society of Chemistry 2015

Chem Soc Rev
compositional optimization based on the variation of the local
crystal structure can be realized, which can improve the lumines-
cence performance of rare earth ion activated phosphors in
pc-WLED devices. However, a large number of novel pc-WLED
phosphors and emerging methods for host materials are still in
the research stage, and need to be further optimized and
improved for practical WLED applications. Therefore, there is
a long way in achieving the goal, and much effort is needed by
scientists and industrialists.
Published on 30 September 2015. Downloaded by University of Tasmania on 30/09/2015 10:15:45.
Acknowledgements
This project is financially supported by National Basic Research
Program of China (Grants No. 2010CB327704), the National
Natural Science Foundation of China (Grants No. NSFC
21301162, 60977013, 91433110, U1301242, 21221061) and the
Fundamental Research Founds for National University, China
University of Geosciences (Wuhan) (Grant No. CUG130402,
CUG130614, CUG130624, CUG120864, GBL31510).
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