J Mater Sci

Energy
E N E R G Y Mmaterials
ATERIALS

High refractive index coating of phosphor-in-glass

for enhanced light extraction efficiency of white LEDs
Xujia Xu1, Hong Li1,* , Yong Zhuo1, Ruixin Li1, Peijing Tian1, Dehua Xiong1, and Mingxiang Chen2

1
State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, China
2
School of Mechanical Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China

Received: 30 March 2017 ABSTRACT

Accepted: 13 September 2017
Ó Springer Science+Business
Media, LLC 2017
The coating of phosphor-in-glass with high refractive index was successfully
fabricated for enhanced light extraction efficiency of white LEDs through a
multilayer screen-printing and low-temperature sintering procedure. The effects
of sintering temperature on the B2O3–SiO2–ZnO glass coating and YAG:Ce
phosphor concentration on the phosphor-in-glass coating were investigated.
The B2O3–SiO2–ZnO glass matrix possesses low glass transition temperature
and appropriate thermal expansion coefficient. With the addition of La2O3 and
WO3, high refractive index of 1.82 at 460 nm is acquired. The amorphous glass
coating, sintered at 600 °C, yields an optimized transmittance of 50%. Further-
more, negligible thermal degradation is observed in the phosphor-in-glass
coating, and the emission peak under the 460-nm excitation is at *540 nm.
When increasing the concentration of phosphor, luminous efficacy and corre-
lated color temperature are both improved, but color rendering index is dete-
riorated. As the refractive index increases, the light extraction efficiency of white
LEDs is enhanced due to the reason that the match of refractive index between
the glass matrix and the phosphor decreases the total internal reflection at the
interface.

Introduction chips with cerium-doped yttrium aluminum garnet

Owing to the advantages such as higher luminous
efficiency, lower energy consumption, and longer
operation lifetime, white light-emitting diodes (w-
LEDs) are one of the major achievements in semi-
conductor technology, compared to traditional
incandescent, fluorescent, and high-pressure gas
discharge-based lamps [1–3]. Recently, commercial
w-LEDs are manufactured by integrating blue LED
(YAG:Ce) yellow phosphor in organics for the rea-
sons of simple fabrication, cost-efficiency, and well-
developed maturing process [4–6]; nevertheless,
w-LEDs are adversely affected by weak thermal
property of organics, which directly contacts the
chips and reduces the lifetime because of accumu-
lated heat from the chips [7–9]. In addition, the
refractive index of the organics is *1.5, which is
lower than that of the YAG:Ce phosphor (1.83). As a

Address correspondence to E-mail: lh_648@whut.edu.cn

DOI 10.1007/s10853-017-1571-y

result, more than half of the light emitted from
phosphor undergoes total internal reflection, leading
to a degradation of light extraction efficiency [10, 11].
To overcome these drawbacks, inorganic lumines-
cence materials with enhanced heat resistance have
been considered as new color converters [12, 13].
Among them, phosphor-in-glass (PiG), synthesized
by co-sintering of a mixture of glass powder and
phosphor at proper temperature, is considered
[14, 15]. Besides simple fabrication process, the
properties of PiG can be easily modified by varying
mixing ratio of glass powder and phosphor. In our
previous work, P2O5–ZnO–B2O3 and SiO2–B2O3–PbO
glasses were investigated to utilize as the glass matrix
for PiG fabrication [16, 17]. Although the P2O5–ZnO–
B2O3 glasses show excellent thermal property, the
luminous efficacy is limited due to low optical
transmittance. In addition, the SiO2–B2O3–PbO glas-
ses have good stability, but the sintered temperature
is so high that the luminescence properties of phos-
phor are eliminated. Some literature proposes the use
of high boron-containing glasses [18–20]. The sin-
tered temperature of high boron- and high silicon-
containing glasses is about 600 and 750 °C, respec-
tively. Compared to that of high silicon-containing
glasses, the sintered temperature of high boron-con-
taining glasses is much lower due to weaker network
structure. Furthermore, the refractive index of glass
can be simply modified by adding ions of large
polarizability, such as PbO, La2O3, TeO2, and WO3
[21–23].
In this paper, a lead-free glass of B2O3–SiO2–ZnO
(BSZ) was chosen as the glass matrix for PiG fabri-
cation. High refractive index can be obtained by
adding La2O3 and WO3. The coating was synthesized
by stacking multiple layers using multilayer screen
printing [24–26]. The width and thickness of coating
can be easily tuned with this novel technique. The
effects of sintering temperature on the BSZ glass
coating and YAG:Ce phosphor concentration on the
PiG coating were investigated. The results indicate
Table 1 The nominal compositions and thermo-physical properties of the BSZ glass
Sample B2O3 SiO2 ZnO Li2O
(mol%) (mol%) (mol%) (mol%)
BSZ glass 23–26 10–12 33–36 5–8
J Mater Sci
that the PiG coating has unique advantages for
package of w-LEDs.
Experimental
Preparation of BSZ glass matrix
SiO2, B2O3, ZnO, Li2O, La2O3, and WO3 are the
components of the BSZ glass. The nominal composi-
tions of the glass matrix are listed in Table 1. The
glass matrix was fabricated via high-temperature
solid-state reaction. The analytical reagent silicon
dioxide (SiO2, 96%), boric acid (H3BO3, 99.5%), zinc
oxide (ZnO, 99%), lithium carbonate (Li2CO3, 98%),
lanthanum oxide (La2O3, 99.99%), and tungsten oxide
(WO3, 99%) were used as raw materials. Each batch
was thoroughly mixed. The reaction mixture was first
calcined at 300 °C for 1 h and then at 1250 °C for 1 h
in a high-purity alumina crucible. After that, the
homogeneous melt was cast in a preheated steel plate
after melting, followed by annealing for 1 h at 400 °C,
and slowly cooled down to room temperature in a
muffle furnace. Finally, the glass bulk was kept in a
desiccator.
Synthesis of BSZ glass coating and PiG
coating
The prepared glass bulk was ground into powder
and sifted out through 500-mesh sieve. The binder
(ethyl cellulose) was dissolved thoroughly in the
solvent of alpha-terpineol and diethylene glycol
monobutyl ether at 80 °C. The glass powder was
stirred homogeneously in the prepared solvent to
obtain the glass paste. After that, the glass paste was
printed on the glass substrate by multilayer screen
printing and the coating was dried at 150 °C to
volatilize the solvent. Finally, the BSZ glass coating
was sintered at different temperatures (575, 600, 625,
650, and 700 °C) in the air. To fabricate PiG coating,
BSZ glass powder was mixed with different
La2O3 WO3 Tg (°C) Tf (°C) Tc (°C) a (910-7
(mol%) (mol%) K-1)
12 12 410 535 584 81
J Mater Sci
phosphor concentrations (30, 35, 40, 45, and 50 wt %).
The PiG coating was sintered at 600 °C.
The process of multilayer screen printing is illus-
trated in Fig. 1. The screen is made of nylon with 200
mesh. The pattern of screen is rectangle with the same
size of glass substrate. First, the glass paste was put on
the un-patterned area of screen. Then, the squeegee
was moved. The mesh of screen is larger than the size
of powder, so the glass paste can be transferred to the
glass substrate through the patterned area. After that,
the coating was dried at 150 °C until the organic sol-
vent volatilized. The second layer was printed on the
first layer following the same procedure. Finally, the
multilayer coating was fabricated.
Characterizations
Differential scanning calorimetry (DSC) was used to
measure the glass transition temperature (Tg) and the
Figure 1 Schematic diagram of multilayer screen printing.
a Printing the first layer. b Drying and organic solvent is out.
c Printing the second layer and more.
crystallization temperature (Tc) by simultaneous
thermal analysis (STA449F3, Netzsch, Germany). The
coefficient of thermal expansion (CTE) and the
dilatation softening temperature (Tf) of glass were
measured by dilatometry using a thermomechanical
analyzer (DIL402C, Netzsch, Germany). The refrac-
tive index of glass was measured using polished
glass bulk by spectroscopic ellipsometry (M-2000 V,
J.A.Woollam, America). The visible transmittance of
glass coating was measured by UV/VIS spectropho-
tometer (Lambda 35, PerkinElmer, America). The
crystallization behavior of glass coating was mea-
sured by D/MX-IIIA XRD system (D8 Advance,
Brooke AXS, Germany) with Cu Ka radiation
(k = 0.15406 nm). The surface and cross-sectional
microstructures were investigated using a field
emission scanning electron microscope (FE-SEM,
Ultra Plus, Zeiss, German) equipped with energy-
dispersive spectrometer (EDS). The excitation pho-
toluminescence (PLE) and photoluminescence (PL)
spectra were measured using a spectrometer (FP-
6500, Jasco, Japan) with a 500-W xenon discharge
lamp as the excitation source in the visible range.
Commission Internationale de l’Eclairage (CIE)
chromaticity color coordinates, color rendering index
(CRI), correlated color temperature (CCT), luminous
efficacy, and electroluminescence spectra of PiG
coating packaged w-LEDs modules were measured
in an integrating sphere (HAAS-2000, Everfine,
China) with the diameter of 50 cm at the driving
current of 700 mA.
Results and discussion
BSZ glass matrix
Thermo-physical properties
The thermo-physical properties of the glass matrix
are summarized in Table 1. DSC thermogram is
shown in Fig. 2a. Tg is determined as the onset of the
change of the thermal capacity in the glass transition
region, which is 410 °C [27]. It is mainly attributed to
the low reticulation of glass structure with principal
component of B2O3. Moreover, the strong La–O and
W–O bonds lead to the growth in the network con-
nectivity [28, 29]. The exothermic peak is represented
as Tc, due to the crystallization of glass. Tc is about
50 °C higher than that of crystallization analysis in
 J Mater Sci

thermo-physical properties of the BSZ glass meet the

requirements of low melting temperature and
appropriate expansion coefficient.

Refractive index

The measured and fitting dispersion curves of the

BSZ glass are plotted in Fig. 3. The Cauchy disper-
sion formula was used to fit the measured refractive
index by the polarization principle. In Fig. 3, it is
shown that refractive index of the glass matrix at
460 nm is *1.82, which is similar to that of the
YAG:Ce phosphor (1.83). The light efficiency loss by
total internal reflection at the interface is closely
related to the difference of refractive index between
the glass matrix and the phosphor [34, 35]. To achieve
higher refractive index than that of most of the nor-
mal glass (1.5–1.6), La2O3 and WO3 are added. On the
one hand, the refractive index of glass is strongly
related to the electronic polarizability of ions. La2O3
and WO3 are the modifiers of the glass network,
which leads to the formation of non-bridging oxy-
gens. Since the molar polarizability of non-bridging
oxygens is higher than that of bridging oxygens, the
molar polarizability is larger [36–38]. On the other
hand, molecular weights of W6? and La3? are larger
than that of other ions in the glass matrix, leading to
the increase in molecular weight of unit volume. As a
result, the structure of glass network remains impact
[36, 39, 40]. Therefore, the refractive index increases.
Figure 2 a DSC thermogram and b dilatometric curve of the
BSZ glass.

Fig. 5 because of hysteresis effect of the instrument

[30]. The linear dilation response of the glass is pre-
sented in Fig. 2b. The slope (a) of the delta L/L0 in the
dilatometric curve is denoted as CTE [31, 32]. CTE of
the glass matrix and the soda–lime–silicate glass
substrate are 81 9 10-7 and 90 9 10-7 K-1, respec-
tively. The difference on CTE between the glass
matrix and the glass substrate should not be more
than 10 9 10-7 K-1 to obtain crack-free interface
without tensile of compressive stress. Tg is also
illustrated in the dilatometric curve, which is deter-
mined from the change in the slope of the elongation
versus temperature plot [33]. However, Tg is rarely
crucial from the dilatometric curve due to lack of
suitable samples prepared by free cooling in the air
[29]. Tf, corresponding to the maximum value on the
expansion trace, is 535 °C. The results show that the Figure 3 Measured dispersion curve and fitting curve of the
measured refractive index of the BSZ glass.
J Mater Sci

BSZ glass coating

Transmittance

The BSZ glass was printed on the glass substrate and

then sintered at various temperatures (575, 600, 625,
and 650 °C). To increase the transmittance, the sin-
tered temperature must be controlled properly to
minimize the residual porosity and the associated
light scattering [41, 42]. The UV/VIS transmission
spectra are plotted in Fig. 4. The photographs are also
shown in the inset of Fig. 4. The BSZ glass shows
good flow performance and is tightly printed on the
glass substrate at the sintered temperature higher
than 575 °C. In Fig. 4, the glass coating sintered at
600 °C shows the best transmittance of 50% in the
visible region. Lower transmittance is showed at a Figure 5 XRD curves of BSZ glass coatings sintered at various
lower sintered temperature for the insufficient den- temperatures (575, 600, 625, 650, and 700 °C).
sification, so scattering is mostly responsible for the
limited transmittance. It should be noted that the Crystallization
transmittance decreases when the sintered tempera-
The crystallization of glass coatings sintered at vari-
ture is higher than 600 °C. The crystalline peaks are
ous temperatures (575, 600, 625, 650, and 700 °C) was
clearly observed in Fig. 5, so reduced transparency
investigated. The XRD patterns are depicted in Fig. 5.
may be attributed to the formation of microcrystalline
The glass coating sintered at the temperatures lower
phases. The PiG coating transmits blue and yellow
than 600 °C is amorphous. After the heat treatment
light from the chips and the phosphor, respectively.
above 600 °C, the sample is crystallized due to the
The loss of light is minimized for higher transmit-
appearance of some sharp lines. The standard pat-
tance and thus enhances the luminous efficacy of
terns of Li2W5O16 (JCPDS 28-0600) and LaBO3 (JCPDS
w-LEDs [43]. Therefore, the optimized sintered tem-
12-0762) are shown, and most of the diffraction peaks
perature is 600 °C.
are well indexed. The main crystalline phase at
625 °C is identical with Li2W5O16 phase. When sin-
tered at 650 °C, some weak peaks of LaBO3 phase
also appear. It indicates that the main crystalline
phases of the glass coating sintered at higher tem-
perature are Li2W5O16 and LaBO3.

PiG coating

Luminescence properties

The photoluminescence excitation (PLE) and photo-

Figure 4 UV/VIS transmission spectra of the glass coatings
sintered at various temperatures (575, 600, 625, and 650 °C). The
inset shows the photographs of the glass coatings.
luminescence (PL) spectra of PiG coatings with vari-
ous phosphor concentrations (30, 35, 40, 45, and 50
wt%) are plotted in Fig. 6a. There are two broad
excitation bands peaked at 340 and 460 nm in the
PLE spectra (kem = 540 nm), which are ascribed to
the transitions of Ce3? from the 4f ground states to
the 5d states [44–46]. In Fig. 6b, the 4f electron con-
figuration has two ground states of 2F5/2 and 2F7/2.
The 5d electron configuration has five states of lower-

Figure 6 a PLE (kem = 540 nm) and PL(kem = 540 nm)spectra
of the PiG coatings with various phosphor concentrations (30, 35,
40, 45, and 50 wt%) sintered at 600 °C. b The energy level of
Ce3? in YAG.
lying doublet Eg and upper-lying triplet T2g, owing to
the tetragonal symmetry of dodecahedral yttrium site
in YAG. The well-known bands correspond to the
spilt levels of Eg [47, 48]. The PL spectra were mea-
sured (kex = 460 nm). When excited by the blue light
of 460 nm, Ce3? raises from the 4f level to higher 5d
level and feeds afterward to the lower 2D(5d) excited
states. The broad asymmetric band with a peak at
540 nm is the sum of two 5d ? 4f transitions [49–51].
It indicates that the PiG coating can absorb blue
emission from the chips and transmit yellow light.
In Fig. 6a, the peak locations remain unchanged
because the energy level transition is not affected by
phosphor concentration. The peak intensity with 40
wt% phosphor is the strongest, which is mainly
influenced by two factors, the activator concentration
and the defects [52]. As the phosphor concentration
J Mater Sci
rises to 40 wt%, the concentration of YAG crystalline
phase and activator increases, leading to enhanced
intensity. When the phosphor concentration is higher
than 40 wt%, the defects play the main role, influ-
encing the absorption, reflection, and scattering of
light. As the phosphor concentration goes up, the
increase in defects results in the reduced absorption
and enhanced consumption of excited light.
Performances of w-LEDs based on PiG coating
The performances of w-LEDs based on PiG coatings
with various phosphor concentrations (30, 35, 40, 45,
and 50 wt %) were evaluated. The corresponding
photometric and CIE chromaticity coordinates are
listed in Table 2. With increasing phosphor concen-
tration, luminous efficacy and CCT are improved, but
CRI is deteriorated. CIE chromaticity coordinates and
electroluminescence (EL) spectra are illustrated in
Fig. 7. In Fig. 7a, the chromaticity coordinates of
w-LEDs strongly depend on the phosphor concen-
tration. The CIE coordinates (0.3297, 0.3351) of
w-LEDs with 50 wt% phosphor get close to the ideal
white light (0.33, 0.33) [53], indicating that the white
light emission can be achieved by controlling of
phosphor concentration. In Fig. 7b, the EL spectra
exhibit blue and yellow emission bands, yielding
white light emission. The suitable phosphor concen-
tration is 50 wt%.
The corresponding photometric and CIE chro-
maticity coordinates of w-LEDs based on the PiG
coatings with different refractive index glass matrices
(1.82, 1.72, and 1.62) are listed in Table 3. On the
bases for equal Ra, luminous efficacy of w-LEDs with
different refractive index coatings (1.62, 1.72, and
1.82) is 58.85, 59.33, and 65.21 lm W-1, respectively. It
shows that the light extraction efficiency enhances as
the refractive index increases. The EL spectra are
presented in Fig. 8. The intensity of yellow light
increases with increasing refractive index. The
enhanced luminous efficacy is ascribed to the
refractive index match between the glass matrix and
the phosphor. The wavelength of light from the chips
is 460 nm. Therefore, the refractive index of glass
matrix is matching with that of phosphor at the
wavelength 460 nm. The difference of refractive
index causes light to be reflected at the interface; thus,
the light efficiency loss through total internal reflec-
tion between the two media increases [54–56].
Therefore, high refractive index of the glass
J Mater Sci

Table 2 Detail performances

of w-LEDs based on the PiG Sample Luminous efficacy (lm W-1) CIE coordinate Ra CCT (K)
coatings with various
S0 (30 wt%) 55.04 (0.2826, 0.256) 81.2 12727
phosphor concentrations under
S1 (35 wt%) 56.43 (0.2901, 0.2688) 80.7 10084
700-mA current (30, 35, 40,
S2 (40 wt%) 58.90 (0.298, 0.2821) 79.7 8445
45, and 50 wt%)
S3 (45 wt%) 63.32 (0.3189, 0.3173) 75.6 6241
S4 (50 wt%) 65.21 (0.3297, 0.3351) 73.4 5626

Figure 7 a CIE color

coordinates and b normalized
EL spectra of w-LEDs based
on the PiG coatings with
various phosphor
concentrations (30, 35, 40, 45,
and 50 wt %).

Table 3 Detail performances

of w-LEDs based on the PiG Sample Luminous efficacy (lm W-1) CIE coordinate Ra CCT (K)
coatings with different
S (1.82) 65.21 (0.3297, 0.3351) 73.4 5626
refractive index glass matrices
B (1.72) 59.33 (0.306, 0.3057) 74.3 6861
C (1.62) 58.85 (0.3116, 0.3051) 73.3 6798
The samples S, B, and C are 1.82, 1.72, and 1.62 refractive index coatings with 50 wt% phosphor,
respectively

comparable to that of the phosphor results in low

light scattering loss and high light extraction
efficiency.

Morphology and composition analysis

To investigate the morphology of PiG coating, the

Figure 8 The normalized EL spectra for the w-LEDs based on
the PiG coatings with different refractive index glass matrices
(1.62, 1.72, and 1.82).
surface and the cross-sectional micrographs are
shown. In Fig. 9a, the surface of the coating is rough
and the average thickness is about 20 lm. In Fig. 9b,
the phosphor is well distributed in the glass matrix
without significant corrosion. In addition, few inter-
facial phases are observed, suggesting that there is a
negligible interaction. To distinguish the glass matrix
and the phosphor, the energy-dispersive spectra
(EDS) are exhibited in Fig. 9d. Y/Al/O and Zn/O/
La/W elements are detected in different spots of
Fig. 9c, showing their characteristic compositions.

Figure 9 FE-SEM images of PiG coating with 50 wt% phosphor sintered at 600 °C. a The sectional image, b the surface image, c the
surface images in higher magnification, and d the composition analysis results of each phase.
There is no other composition, indicating that no
noticeable chemical reactions occur. The results
demonstrate that low erosion of phosphor happens
during the melting process; thus, its original lumi-
nescence property is retained [57].
Conclusions
In summary, the coating of phosphor-in-glass was
fabricated by a multilayer screen-printing and low-
temperature sintering procedure. The high refractive
index glass matrix for improvement on light extrac-
tion efficiency of w-LEDs was obtained with the
addition of La2O3 and WO3. The refractive index of
glass matrix at 460 nm (1.82) is similar to that of the
YAG:Ce phosphor (1.83). The optimized sintering
temperature is 600 °C from the analysis of XRD and
transmittance. The average thickness of the PiG
coating is 20 lm and the phosphor is well distributed
in the glass matrix. Under excitation by blue light at
J Mater Sci
460 nm, the emission peak of the PiG coating is
at *540 nm. With increasing phosphor concentra-
tion, the intensity of spectra increases first and then
decreases. When the phosphor concentration rises
from 30 to 50 wt%, luminous efficacy increases from
55.04 to 65.21 lm W-1, CCT decreases from 12727 to
5626 K, and CRI decreases from 81.2 to 73.4. The
white light can be achieved with 50 wt% phosphor.
As the refractive index increases from 1.62 to 1.82,
luminous efficacy increases from 58.85 to
65.21 lm W-1. The research indicates that the PiG
coating has potential to replace the organics in
applications of w-LEDs.
Acknowledgements
This work was supported by the National Natural
Science Foundation of China (51372179), the Hubei
Province Foreign Science and Technology Project
J Mater Sci
(2016AHB027), and the Science and Technology
Planning Project of Hubei Province (2014BAA136).
Compliance with ethical standards
Conflict of interest There is no conflict of interest.
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