Journal of the European Ceramic Society 37 (2017) 4123–4128

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Journal of the European Ceramic Society

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Full Length Article

Annealing induced discoloration of transparent YAG ceramics using

divalent additives in solid-state reaction sintering
Tianyuan Zhou a,b,c , Le Zhang c,e,f,∗ , Farida A. Selim e , Rong Sun d , Chingping Wong f ,
Hao Chen c , Qitu Zhang a,b,∗∗
a
College of Materials Science and Engineering, Nanjing Tech University, Nanjing, 210009, PR China
b
Jiangsu Collaborative Innovation Center for Advanced Inorganic Function Composites, Nanjing Tech University, Nanjing, 210009, PR China
c
School of Physics and Electronics Engineering, Jiangsu Normal University, Xuzhou, 221116, PR China
d
Guangdong Provincial Key Laboratory of Materials for High Density Electronic Packaging, Shenzhen Institutes of Advanced Technology, Chinese Academy
of Sciences, Shenzhen, 518055, PR China
e
Center for Photochemical Sciences, Department of Physics and Astronomy, Bowling Green State University, Bowling Green, 43403, USA
f
School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, 30332, USA

a r t i c l e i n f o a b s t r a c t

Article history: Tetraethyl orthosilicate (TEOS) was commonly served as a sintering additive to promote the densification
Received 19 January 2017 of transparent Y3 Al5 O12 (YAG) ceramics. However, Si4+ that decomposed from TEOS would restrain the
Received in revised form 14 May 2017 conversion of dopants into a higher valence state (e.g., Cr3+ → Cr4+ ). In this study, by using divalent sinter-
Accepted 15 May 2017
ing additives (CaO and MgO), the colorless and highly transparent YAG ceramics (T = 84.6%, at 1064 nm)
Available online 22 May 2017
were obtained after vacuum sintering at 1840 ◦ C for 8 h and without subsequent annealing in air. An
absorption peak centered at ∼320 nm was observed before annealing, and it extended to ∼550 nm after
Keywords:
annealing at 1450 ◦ C for 10 h in air. A discoloration phenomenon occurred and more scattering centers
Transparent ceramics
Annealing
were observed with the formation of new [Mg/Ca2+ F+ ] color centers. Air annealing did not improve the
YAG optical quality of the as-fabricated YAG ceramics with divalent dopants as sintering additives, owing to
Sintering additives the formation of scattering centers.
Optical property © 2017 Elsevier Ltd. All rights reserved.

1. Introduction owing to its excellent physical and chemical properties, as well as

Solid state lasers are widely used in many fields such as med-
ical application, military, and scientific research, and there is an
urgent need to develop novel laser gain medium for the further
advancement of solid state lasers [1–3]. It is commonly recog-
nized that transparent ceramic material is a promising laser gain
medium for solid-state lasers, due to its relatively ease in fabrica-
tion and good uniformity as well the possibility of large size, which
is almost impossible with its single crystal counterpart [4,5]. With
the development of transparent ceramic technology, various kinds
of transparent ceramics for solid-state lasers have been developed
[6–12]. Among them, transparent yttrium aluminum garnet (YAG)
ceramic is the most widely adopted solid-state laser gain medium,
∗ Corresponding author at: School of Physics and Electronics Engineering, Jiangsu
Normal University, Xuzhou, 221116, PR China.
∗∗ Corresponding author at: College of Materials Science and Engineering, Nanjing
Tech University, Nanjing, 210009, PR China.
E-mail addresses: zhangle@jsnu.edu.cn (L. Zhang), ngdzqt@163.com (Q. Zhang).
its high transparency [13,14].
In order to fabricate transparent YAG ceramics with high opti-
cal quality, a fully dense and a pore-free microstructure must be
required, and tetraethyl orthosilicate (TEOS) is commonly served
as a sintering additive to promote the densification of YAG ceram-
ics [15,16]. Upon heating, TEOS decomposes into SiO2 which reacts
with YAG matrix according to the YAG-SiO2 phase diagram, to form
a liquid phase at ∼1400 ◦ C [17]. In this case, a liquid phase diffusion
mechanism is dominated during sintering, and the densification
rate of ceramics is accordingly accelerated. However, for some spe-
cific ion (e.g., Yb3+ or Cr4+ ) doped YAG ceramics, their conversion
into a higher valence states (such as Cr3+ → Cr4+ ) would dramati-
cally inhibited by TEOS (Si4+ ), which would have a negative effects
on their laser applications [7,18–20].
Even though researchers have taken efforts to investigate the
effect of reducing or eliminating silicon in YAG transparent ceram-
ics [21,22], only a handful of them have reported the development
of YAG ceramics with high transparency. In the present study, we
obtained high quality transparent YAG ceramics at a fixed amount
of divalent dopants as additives in solid state reaction sintering.

http://dx.doi.org/10.1016/j.jeurceramsoc.2017.05.030
0955-2219/© 2017 Elsevier Ltd. All rights reserved.
4124 T. Zhou et al. / Journal of the European Ceramic Society 37 (2017) 4123–4128
The densification process, as well as the microstructure proper-
ties of the as-prepared ceramics, were investigated. However, it is
expected that the vacancy formation mechanism would inevitably
take place, if divalent ions substitute the original cations in YAG
lattice. For this reason, we fabricated vacuum sintered ceramics
with and without air annealing, in order to investigate the effect
of vacancy mechanism on the optical properties of YAG ceramics.
Considering all of these above, the theoretical and experimental
support to achieving high valence state doping in YAG transparent
ceramics was provided in the present study.
2. Materials and experimental details
2.1. Fabrication of YAG transparent ceramics
Commercially available ␣- Al2 O3 (99.999% purity, Sumitomo
Chemicals, Tokyo, Japan) and Y2 O3 (99.99%, Alfa Aesar, Ward Hill,
America) were selected as the raw materials, they were weighted
precisely using an analytical balance to form Y3 Al5 O12 . Divalent
dopants CaO (99.999% purity, Alfa Aesar, Ward Hill, America) and
MgO (99.999% purity, Alfa Aesar, Ward Hill, America) powders were
adopted as sintering additives. All the powders that applied in this
work were ultra-high purity powders, and their impurity content
(e.g. Si and Fe) were less than 15 ppm. In this work, the molar ratio
of Ca and Mg were 0.04 mol% and 0.16 mol% according to Al3+ con-
tent, respectively, which was based on our optimized experimental
results [23].
These powder mixtures were mixed with anhydrous alcohol in
a nylon ball milling jar, and then ball milled for 12 h using agate
balls (>99.9 purity) with a diameter of 5 mm to obtain powders
with uniform size distribution. During our process, a planetary ball
milling method was adopted, and the mass ratio of powder: milling
medium was 1: 2. The milled slurry was dried in an oven at 55 ◦ C
for 1 day and then sieved through a 100 mesh screen. The sieved
powders were then uniaxially pressed at 20 MPa in a stainless steel
mold with a diameter of 16 mm, followed by cold isostatic pressed
(CIPed) at 200 MPa to obtain green bodies with a relative density
of ∼56%. The CIPed pellets were calcined in a muffle furnace at
800 ◦ C for 4 h in air to remove the volatile organic residues, and
then vacuum sintered between 1540 ◦ C to 1780 ◦ C for 4 h to check
their microstructure evolution during vacuum sintering. The CIPed
pellets were also sintered at 1840 ◦ C for 8 h to evaluate the optical
qualities of the fabricated ceramics. The sintering process was car-
ried out using a tungsten mesh heated vacuum furnace (KZG-110F,
Shanghai Chenrong Electrical Furnace Co., Ltd., Shanghai, China)
under 10−4 Pa. The applied heating rate and the cooling rate was
3 ◦ C/min and 10 ◦ C/min, respectively. Air annealing was carried out
at 1450 ◦ C for 10 h to further expect to improve their optical qual-
ities after vacuum sintering. Finally, all samples were grinded and
mirror polished on both surfaces using diamond slurry, and the
thicknesses of all samples after mirror polishing were kept at 3 mm.
2.2. Characterizations
Densities of the sintered ceramics were evaluated by the
Archimedes method. Microstructural investigation of the as-
prepared ceramics was carried out by a scanning electron
microscope (SEM; JSM- 6510, JEOL, Kariya, Japan) and an optical
transmission microscope (Axio Scope. A1, Carl Zeiss, Oberkochen,
Germany). A UV–VIS-NIR spectrophotometer (Lambda 950, Perkin
Elmer, Waltham, MA, America) was used to measure the in-line
transmittance of the mirror polished YAG ceramics with a scan-
ning range from 1500 nm to 200 nm. The measurements were
carried out at room temperature with a standard, dual light beam
Fig. 1. Sintering trajectory for YAG ceramics sintered between 1540 ◦ C and 1780 ◦ C
for 4 h.
arrangement with adjustable slit width, and the scanning speed
was 600 nm/min.
3. Results and discussion
Fig. 1 shows the average grain sizes and the relative densi-
ties of YAG ceramics vacuum sintered between 1540 ◦ C to 1780 ◦ C
for 4 h. The average grain sizes were confirmed by calculating the
average grain diameters of at least 200 grains obtained from the
SEM images. It could be seen that both the average grain sizes and
the relative densities of the ceramics increased with the increase
of sintering temperature. At the beginning, the relative densi-
ties of ceramics increased quickly when the sintering temperature
was lower than 1660 ◦ C, but changed slightly if further increase
the sintering temperature. The grain growth of ceramics domi-
nated at temperatures higher than 1620 ◦ C. Besides, the average
grain size was only 3.6 ␮m, even though the sintering temperature
was reached up to 1780 ◦ C. Accordingly, it was clear that divalent
dopants could effectively inhibit the grain growth of YAG ceramic
during sintering.
In a previous study, G. L. Messing et al. [24] investigated the rela-
tionship between grain growth and densification in SiO2 doped YAG
ceramics. They found that the activation energies for densification
and grain growth were 235 kJ/mol and 946 kJ/mol, respectively,
and they suggested that the difference in the activation energy is
responsible for the fine microstructure of their as-fabricated ceram-
ics. In the current study, the average grain size was only 3.6 ␮m,
after the ceramics were sintered at 1780 ◦ C for 4 h. Therefore, the
activation energy difference between grain growth and densifi-
cation in the divalent dopant system is one possible reason with
respect to the inhibition of grain growth while promoting the den-
sification of YAG ceramics. Besides, a portion of divalent dopants
were segregated at grain boundaries as solutes, which could result
in a drag on grain boundaries of YAG during sintering. In this case,
the grain boundary mobility of YAG ceramics was decreased owing
to solute drag effect, and discontinuous grain growth was conse-
quently inhibited [25].
The fracture surfaces of YAG ceramics sintered between 1580 ◦ C
and 1780 ◦ C for 4 h are shown in Fig. 2. Obviously, the pore volume
of ceramics decreased with the increase of sintering temperature.
At a sintering temperature of 1580 ◦ C, a large amount of residual
pores could be observed, and their morphologies were character-
ized by both continuous and isolated pores (Fig. 2(a)), indicating
that the sample was at its intermediate stage of sintering. When the
sintering temperature reached 1620 ◦ C, the pore volume as well as
the pore size of the ceramics dramatically decreased, and the mor-
 T. Zhou et al. / Journal of the European Ceramic Society 37 (2017) 4123–4128
Fig. 2. SEM micrographs of the fracture surfaces of samples sintered at (a) 1580 ◦ C, (b) 1620 ◦ C, (c) 1660 ◦ C, (d) 1700 ◦ C, (e) 1740 ◦ C, (f) 1780 ◦ C for 4 h.
phology of pores was transformed into isolated pores (Fig. 2(b)).
Then, the sample reached its final sintering stage. Residual pores
could hardly be detected when the sintering temperature was
increased to 1660 ◦ C or higher. The average grain size of ceramic
dramatically increased when the further increase in sintering tem-
peratures (Fig. 2(c–f)).
Fig. 3 shows the SEM micrographs of the thermally etched sur-
face and fracture surface of the ceramics vacuum sintered at 1840 ◦ C
for 8 h, and the etching process was carried out at 1450 ◦ C for 2 h
in air. It could be clearly seen that the sample exhibited a fully
dense microstructure, and there was no pores or secondary phase
observed. The average grain size of the ceramics after sintering was
5.3 ␮m, and its fracture mode was mainly characterized as trans-
granular mold.
The photograph and the in-line transmission spectra of vac-
uum sintered samples with and without air annealing are shown
in Fig. 4. The vacuum sintered sample before air annealing was
highly transparent, and the words behind it could be clearly rec-
ognized by the naked eyes. The air-annealed sample was slightly
hazy (especially at its central part), indicating a decrease in its trans-
parency. In addition, a discoloration phenomenon occurred in the
air-annealed sample, indicating that a new light absorption band
was formed. The transmittance of the sample at 1064 nm before
annealing was as high as 84.6%; it nearly reached the theoretical
limit of YAG. More importantly, the average grain size at this trans-
mission was only 5.3 ␮m (see Fig. 3). It was much smaller than that
of previously reported vacuum sintered YAG ceramics using TEOS
4125
as sintering additive at the same transmission [26–28], even though
a moderate amount of TEOS could also inhibit the grain growth
of YAG ceramics according to Maître’s report [29]. Consequently,
the results presented here indicate that adopting divalent dopants
as sintering additive is an effective approach for the inhibition of
grain growth while promoting the transmission of YAG transparent
ceramic. The transmittance of the sample after air annealing was
not as high as that of the sample without annealing, and the absorp-
tion band in the UV–visible region extended to ∼550 nm, resulting
in the discoloration of sample.
Generally, pressure induced oxygen vacancies associated with
free electrons are easily generated during vacuum sintering accord-
ing to Eq. (1), owing to the oxygen partial pressure difference
between the ceramic interior and the chamber of vacuum furnace.
As is depicted in Fig. 5 (a), these pressure induced oxygen vacancies
were unstable. As a result, the F color centers were formed when
free electrons were captured by these oxygen vacancies according
to Eq. (2) and (3), which were quite unanimously considered as the
cause of absorption and in the near UV region [30] (peak at 320 nm
in Fig. 4):
1
OO = VO + O2 ↑ +2e (1)
2
 
VO + e = VO F+ (2)
VO + 2e = VX (3)
O (F)
4126 T. Zhou et al. / Journal of the European Ceramic Society 37 (2017) 4123–4128
Fig. 3. SEM micrographs of thermally etched surface (a) and fracture surface (b) of the YAG sample sintered at 1840 ◦ C for 8 h in vacuum.
In fact, YAG material was firstly discovered in the 1950s and
has been proved as an end member of a continuous solid-solution
between Y3 Al5 O12 and Mn3 Al2 Si3 O12 [31], and subsequent works
showed that Ca could be totally substituted for Mn to form
Ca3 Al2 Si3 O12 , owing to the small ionic radius difference between
Mn2+ (0.96 Å) and Ca2+ (1.12 Å) [32–34]. Similar to Mn2+ ion, Y3+
has an ionic radius of 1.019 Å that is coordinated by 8 O2− ions
to form a dodecahedron structure in YAG lattice. This means Ca2+
is ready to substitute Y3+ to form a discontinuous solid solution,
owing to the charge difference between Ca2+ and Y3+ . Also, it has
been proved that Mg2+ substitutes the octahedral Al3+ in YAG lat-
tice [19,25]. By introducing divalent dopants, a portion of divalent
ions could substitute the original cations in YAG lattice to generate
oxygen vacancies (named divalent ion induced oxygen vacancy),
which were given by Eqs. (4) and (5) [35]:
2CaO + 2YY + OO = 2Ca’Y + VO· · + Y2 O3
2MgO + 2AlAl + OO = 2Mg’Al + VO· · + Al2 O3
With respect to YAG transparent ceramics, the more oxygen
vacancies that have been generated, the harder to generate addi-
tional oxygen vacancies during sintering, because of the dynamic
equilibrium of [VO· · ] concentration. This implies that the presence of
divalent ion induced oxygen vacancy would no doubt suppress the
generation of pressure induced oxygen vacancy. Therefore, even
though Ca2+ and Mg2+ dopant did not directly affect the PO2 accord-
ing to the Eq. (4) and (5), the presence of Ca2+ and Mg2+ would
reduce the concentration of pressure induced oxygen vacancy (not
the total amount of [VO· · ]) indirectly, and thus driven the equilib-
rium (1) to the left. Consequently, the internal oxygen pressure
of ceramics was thus affected. For the charge compensation pur-
pose, divalent ion induced oxygen vacancies are stable, and it was
much harder for them to capture free electrons to form color cen-
ters compared with the pressure induced vacancies. In this case, the
amount of F-centers decreased by introducing divalent dopants.
However, the formation of pressure induced color centers could
not be completely prevented by divalent ions, leading to the resid-
ual absorption at the UV–vis region centered at ∼320 nm shown in
Fig. 4. Besides, HIP treatment has been proved to be an effective
way to further eliminate such absorption [36].
It has been quantitatively proved by Kuklja et al. that Si4+ incor-
poration in YAG lattice is associated with the formation of cation
vacancy and the antisite Si.Al defect according to this reaction [37]:
5 1 · 1 1
2SiO2 + Al + YY = SiAl + V’’’ + Y3 Al5 O12
6 Al 2 3 Y 6
In this case, the presence of cation vacancies V’”
Y would likely
to accelerate the intrinsic thermal defects generation like Frenkel
defect pair under high temperature, which would make oxygen
ions in YAG lattice unstable. Compared with divalent ion doping,
which would suppress the generation of pressure induced oxygen
(4)
(5)
Fig. 4. A photograph and in-line transmission spectra of vacuum sintered samples
before and after annealing.
vacancy, Si4+ doping would generate more pressure induced oxy-
gen vacancies V..O under high temperature and vacuum atmosphere,
see Fig. 5 (b).
It is noteworthy to see that the color of the sample without air
annealing was almost colorless. Zhang et al. [38] fabricated YAG
transparent ceramics using TEOS as sintering additive, and the sam-
ple after vacuum sintering was grey, which was inconsistent with
the current study where divalent additives was used in the sinter-
ing process. They regarded the gray tint was originated from the
color centers generated during vacuum sintering. In fact, it was
not the case. As known, even though Si4+ could promote the for-
mation of additional pressure induced oxygen vacancies (and the
amount of F-centers increased as well) as mentioned, a grey tint
required a uniform lowering of transmission (over the whole VIS
region). It could not come from the advancement into VIS of color
center bands. Such bands, when advancing, produce first various
chromatic colors and then black. According to Zhang’s report, air
annealing eliminated the cause of grey, as shown by the general
rise of transmission in VIS region. However, simultaneously the
absorption edge shifted in a bathochrome sense. This could not hap-
pen under air annealing, if this process reduced the color centers
concentration, supposing centers were presented in as-fired spec-
(6) imens. Therefore, air annealing affected other factors (e.g. Si0 , W0
impurities) which were the real causes of grey color, which was fur-
ther confirmed by Adam’ results [39]. Consequently, the colorless
of ceramics in our work was more likely owing to the high purity
of starting powders, but not the reduced amount of color centers.
Fig. 6 is the optical transmission photo of the central part of
the vacuum sintered samples before and after annealing observed
 T. Zhou et al. / Journal of the European Ceramic Society 37 (2017) 4123–4128 4127

Fig. 5. Schematic diagram of substitution process in YAG lattice by (a) divalent ion, (b) tetravalent ion during vacuum sintering.

Fig. 6. Optical transmission micrographs of vacuum sintered YAG samples and (a) before annealing, (b) annealed at 1450 ◦ C for 10 h in air.

under open polarizers. From Fig. 6 (a), it is evident that the vacuum 6
3+
sintered sample without air annealing exhibited a homogeneous Absorption of Fe ions
Residual absorption (cm )

and a pore-free structure after vacuum sintered at 1840 ◦ C for 8 h

-1

5
in vacuum, indicating its excellent optical quality. On the contrary,
optically inhomogeneous scattering centers could be observed
Absorption caused by
4
from the depth direction of the air annealed sample (Fig. 6 (b)), lead-
ing to the decrease of its transparency at the non-absorption band. Scatting loss and
3 Scatting loss
Therefore, it is clear that annealing under high temperature and color centers
oxygen enriched atmosphere has a negative effect on the optical
quality of YAG ceramics using divalent dopants as sintering addi- 2
tives. One possible reason is that under high temperature annealing
treatment, residual small nanopores or vacancy clusters are dif- 1
fused and then combined into big ones, even though they could
not be observed from the sample without air annealing, thanks to 0
their homogeneous distribution, small sizes, and loss of activity. 200 400 600 800 1000
In order to further investigate the discoloration phenomenon Wavelength (nm)
of the annealed sample, we made a comparison of the absorp-
Fig. 7. Absorption property of the sample vacuum sintered and then air annealed
tion properties of the vacuum sintered samples with and without
at 1450 ◦ C for 10 h in air.
annealing (i.e., the absorption coefficient of the sample after air
annealing minus that of before annealing). In Fig. 7, the residual
absorption from 550 to 1000 nm was caused by scattering cen- ions. As a result, a F+ color center was generated when a divalent
ters. Notably, a strong absorption band centered at ∼255 nm could ion induced oxygen vacancy lost one electron. Although Ca2+ and
be observed, corresponding to the absorption of oxidized trivalent Mg2+ were truly Ca,Y and Mg,Al , respectively, and charge compen-
Fe3+ ion [39,40], owing to Y2 O3 raw powder (rare earth) was hard sation is required, if they substitute the Y3+ or Al3+ cations in YAG
to purify. Besides that, another wide absorption band extended to lattice to promote charge balance. As a result, these F+ color centers
∼550 nm could also be observed. Lu et al. [36] observed the same were ready to combine with the nearby Ca2+ or Mg2+ that substi-
phenomenon in Yb doped YAG ceramics only using MgO as the tuted Y3+ or Al3+ sites to form new types of color centers [Mg2+ F+ ] or
sintering additive. One explanation is that the pressure induced [Ca2+ F+ ] in a form of trivalent, in order to compensate charge imbal-
oxygen vacancies are compensated by oxygen under high temper- ance when divalent dopants substitute the original cations in YAG
ature and oxygen enriched annealing atmosphere, and divalent ion lattice, leading to the discoloration of the sample after air anneal-
induced oxygen vacancies could not be eliminated by an annealing ing. In addition, color centers are acted as a kind of defect, and they
process, thanks to the stable charge state of the applied divalent would diffuse and couple with each other under high temperature
4128 T. Zhou et al. / Journal of the European Ceramic Society 37 (2017) 4123–4128
annealing treatment to form more complex color center systems
(thermally induced transition), which is also possible with respect
to the discoloration of air-annealed sample. Finally, the color cen-
ters that introduced by divalent ions in YAG ceramics, as well as
their influence on the lasing properties of rare-earth doped YAG
ceramics will be interesting, and deserve further investigation.
4. Conclusions
Without TEOS doping, YAG ceramics could also be sintered to
fully transparent and fine grained microstructure with a colorless
appearance. High quality ceramics (84.6% @ 1064 nm) with an aver-
age grain size of only 5.3 ␮m was obtained, after vacuum sintered
the sample at 1840 ◦ C for 8 h at the doping amount of CaO and MgO
of 0.04 mol% and 0.16 mol% according to Al3+ content. Discoloration
phenomenon along with a decrease in transmission occurred, and
scattering centers could be clearly observed by the optical trans-
mission micrograph, after annealed the vacuum sintered sample at
1450 ◦ C for 10 h in air. This was because the light scattering centers
and new [Mg2+ F+ ] and [Ca2+ F+ ] or more complex color centers were
formed under high temperature and oxygen enriched atmosphere.
Therefore, this study suggests that air annealing is not an effec-
tive way to further enhance the optical quality of YAG transparent
ceramic in the case of divalent dopants as sintering additives.
Acknowledgements
The authors acknowledge the generous financial support from
Priority Academic Program Development of Jiangsu Higher Edu-
cation Institutions (PAPD), Guangdong Provincial Key Laboratory
(2014B030301014), Research and Innovation Program for College
Graduates of Jiangsu Province (KYZZ16 0231), and National Natural
Science Foundation of China (51402133, 51202111, 11274144).
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