Optical Materials 23 (2003) 357362

www.elsevier.com/locate/optmat

Growth and properties of K2Al2B2O7 crystal

Chengqian Zhang a,b,c,*, Jiyang Wang a, Xiufeng Cheng a, Xiaobo Hu a,c
,
Huaidong Jiang a,c, Yaogang Liu a,b, Chuangtian Chen b
a
State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, PR China
b
Beijing Center for Crystal Research & Development, Chinese Academy of Sciences, Beijing 100080, PR China
c
Laboratory of Solid State Microstructure, Nanjing University, Nanjing 210008, PR China

Abstract

The ux systems for the growth of crystalline K2 Al2 B2 O7 (KABO) are discussed. KABO can be grown from both
KF and NaF ux by a top-seeded growth method. It is easier to grow the crystal in NaF ux than to do so in KF ux.
Seed directions inuence the quality and morphology of the KABO crystal. The average thermal expansion coecients
are experimentally determined to be 8:4
106 /K, 1:65
105 /K along a-axis and c-axis, respectively. The specic heat
was measured over a range of temperature 30295 C, which is double that of crystalline BBO. Some other data on the
chemical and physical properties of KABO are also presented.
2003 Published by Elsevier Science B.V.

PACS: 42.65.kg; 42.70.Nq; 81.10.)h; 61.66.Fn

Keywords: Top seeded solution growth; Borates; Nonlinear optic materials

1. Introduction 1990s, a series of DUV NLO crystals, such as

Nonlinear optical (NLO) crystals are key ma-
terials in harmonic generation and optical para-
metric oscillation processes for solid-state lasers
[1]. Before 1975, all the NLO crystals were based
on PO, IO and NbO bonds. In 1975, the dis-
covery of KB5 O8 4H2 O [2], and after that the dis-
covery of the high-performance crystals BBO [3]
and LBO [4], brought attention to the borate
compounds for new NLO crystals, especially for
deep ultra-violet (DUV) NLO crystals [5,6]. In
* ering the toxicity of beryllium, aluminum was used
Corresponding author. Address: Beijing Center for Crystal
Research & Development, Chinese Academy of Sciences, P.O.
Box 2711, Beijing, 100080, PR China. Tel.: +86-10-62588302.
E-mail address: chqzhang@cl.cryo.ac.cn (C. Zhang).
KBe2 BO3 F2 (KBBF), Sr2 Be2 B2 O7 (SBBO),
Ba2 Be2 B2 O7 (TBO), BaAl2 B2 O7 (BABO) and
K2 Al2 B2 O7 (KABO), were discovered [7]. KBBF
[8] possesses excellent linear and nonlinear prop-
erties. Its UV cut-o edge is about 155 nm, which
is the shortest in all the reported NLO materials at
present. However, it is hard to grow to large sized
crystals of this material because of its layer struc-
ture [9]. In order to form chemical bonds between
layers in the KBBF structure, uoride was re-
placed by oxygen. Thus the new compounds SBBO
[10] and TBO [11] were synthesized, in which the
layers were connected by oxygen atoms. Consid-
instead of beryllium, which led to the discovery of
BABO and KABO. KABO was rst reported in
1998 [12,13]. It belongs to the space group P321.

0925-3467/03/$ - see front matter 2003 Published by Elsevier Science B.V.

doi:10.1016/S0925-3467(02)00318-X
358 C. Zhang et al. / Optical Materials 23 (2003) 357362

Its cell parameters are a 0:8558002 nm and

c 0:8455763 nm [14]. It possesses a similar
structure to KBBF. Its transparency range lies
between 180 and 3600 nm, and its SHG coecient
d 0:47 pm/v. It may be a promising candidate
for the FOTH and FITH for Nd:YAG lasers [15].
Hu et al. [1618] reported on the growth process of
KABO using the K2 CO3 B2 O3 system as a ux.
However, it is hard to grow high quality crystals
because of the layer growth habit. The problems
associated with the layer growth habit were avoi-
ded and the crystal quality and size were greatly
improved on the present work. Large sized, high
optical quality KABO crystals were successfully
grown in our laboratory using NaF as a ux
[19,20]. In this paper, the choice of ux, the growth
procedure in NaF ux, and the eects of seed
orientations on the crystal quality are reported and
Fig. 1. Photos of KABO with a spontaneous nucleation
discussed. Some chemical, physical and thermal method in NaF.
properties of the crystal are also reported.
with an appropriate ratio of K2 CO3 and B2 O3 (the
preferable ratio is K2 CO3 :B2 O3 1:1.52.0). The
2. Growth of KABO crystals latter seems suitable for KABO growth. But fur-
ther growth experiments indicate that inclusions
2.1. Flux selection with a spontaneous nucleation are often found in the crystals grown with this ux,
method and the transparency of the crystal is poor. The
layer growth habit is clearly observed in the
Successful growth of a new crystal with the ux growth process. We can conclude that it is hard to
method depends to a large extent on whether an grow large-sized high optical quality crystals using
appropriate ux can be found. For this reason, a self-ux. Finally KF and NaF were investigated
eorts have been made to search for the best ux as possible new uxes. Triangular crystals can
for the growth of KABO crystals. easily crystallize to a size of 35 mm spontaneously
KABO can be synthesized by the following re- when the temperature is decreased at a rate of
action: 30 C/h between 850 and 600 C both in KF and
K2 CO3 Al2 O3 B2 O3 K2 Al2 B2 O7 CO2 " NaF (Fig. 1). The main crystal growth results with
dierent uxes are shown in Table 1. According to
K2 CO3 , Al2 O3 and B2 O3 are the constituents of the results shown in Table 1, both KF and NaF
KABO, the possible self-uxes may be K2 CO3 , can be used as a ux to grow KABO crystals. We
B2 O3 and K2 CO3 B2 O3 . Al2 O3 and its complexes chose NaF ux because of its low volatility.
are not considered because of its high melting
point. Experiments were performed using a spon- 2.2. Top-seeded growth of KABO
taneous nucleation method for investigating the
ux. Results show that B2 O3 ux is unsuitable due KABO crystals were grown using a top-seeded
to the high viscosity of the solution, while using slow cooling technique with a resistance furnace.
K2 CO3 as a ux leads to a high saturation tem- The temperature was controlled by a Shimaden
perature and the solution rapidly volatilized. The FP21 controller, and crystal rotation was provided
complex ux K2 CO3 B2 O3 was investigated, and by DC-controller with a programmable reversible
the viscosity and volatility problems are overcome crystal rotation unit.
 C. Zhang et al. / Optical Materials 23 (2003) 357362 359

Table 1
Crystal growth results in dierent uxes
Flux system Results of crystal growth
K2 CO3 Melted at high temperature and volatilized rapidly; unsuitable for the growth of KABO crystals
B2 O3 The viscosity of the solution is high; unfavorable for the growth of KABO crystals
K2 CO3 B2 O3 The viscosity and melting temperature become lower. The ux may be used to grow KABO if the
phase region is determined
KF The viscosity and melting temperature is low. The layer growth habit of the crystal is avoided. It can
be used to grow KABO crystal, but great care should be taken to control nucleation because of
volatility problems
NaF The viscosity and melting temperature are suitable. The layer growth habit of the crystal is avoided,
and the volatility of the solution is low. It is a favorable ux for growing high optical quality KABO
crystals

The charge was prepared from a stoichiometric
mixture of K2 CO3 , Al2 O3 and B2 O3 with a mole
ratio of KABO:NaF 35% in accordance with
the solubility curve (Fig. 2).
The KABO compound was synthesized in situ
when the solution formed. The raw materials of
K2 CO3 , B2 O3 and NaF were mixed and ground in
an agate mortar. It was added to a platinum cru-
cible with dimensions of 60
90 mm. The cru-
cible was put into the furnace and the temperature
was increased to 700 C at a rate of 20 C/h, and
then kept at steady temperature for 4 h in order to
melt the raw materials slowly and avoid ejection of
the powered raw materials from the crucible due to
the vigorous evolution of CO2 in the reaction of
carbonates and boron oxide. When the reaction
nished and a transparent solution formed, the
Al2 O3 was added and the temperature was in-
creased quickly to 950 C. After that the solution
was stirred for 24 h with a platinum stirrer in order
10
concentration (g KABO/g NaF)
to mix it completely. The saturation point was
repeatedly tested with seeds. It is very important to
test the saturation point accurately in the process
of crystal growth. The saturation point was usually
determined to be in the range of 790800 C for
KABO in NaF in our experiments. A high quality
seed was introduced above at a temperature 15 C
higher than the saturation point. Then the tem-
perature was lowered to the saturation point in 30
min in order to melt the surface of the seed crystal.
The temperature was kept at the saturation point
for 24 h and then decreased at a rate lying in the
range 0.10.25 C/d for about 30 days. The grown
crystal was pulled out the surface of the solution.
The temperature of the solution was decreased to
350 C at a rate of 20 C/h in order to prevent the
cracks in the crystals, the crystal was then cooled
to room temperature in the furnace as it reached
room temperature after being turn o. Various
orientations of seeds were investigated for the
growth of large-sized crystals. Crystals grown with
seeds along the [0 0 1], [1 0 0] and [1 1 0] directions
are shown in Fig. 3.

9 With a [0 0 1] seed, a crystal about 5 mm thick

8
was grown (Fig. 3(a)), and the planes f0 0 1g,
f1 0 0g and f1 1 0g were presented as its appearance
7
faces. Six sector boundaries were observed clearly.
6
The f0 0 1g face grows slower than other faces. So
5 f0 0 1g shows a large face. To improve the growth
4 rate of the f0 0 1g face or to control the growth
3 rate of the other two faces is the main problem for
780 800 820 840 860 880 900 920
the growth of large sized bulk crystals. The crystal
0 may be grown thicker with a pulling method.
temperature ( C)
However, perhaps by changing the temperature
Fig. 2. Solubility of KABO in NaF. eld of the furnace one could also obtain the same
360 C. Zhang et al. / Optical Materials 23 (2003) 357362
Fig. 3. Photos of KABO with (a) [0 0 1], (b) [1 0 0], (c) [1 1 0]
seeds.
result. Crystals grown with [0 0 1] seeds are unfa-
vorable for the device fabrication because of the
sector boundaries. If we grow the crystal with
[1 0 0] seeds, the mass transfer process of the so-
lution can improve greatly due to the stirring of
the crystal that is not unlike using a stirrer. The
growth rate of the f0 0 1g face was also improved.
Large crystals were grown successfully. The size
along [0 0 1] direction reached 15 mm and the layer
growth habit was avoided (Fig. 3(b)). Unfortu-
nately, the quality of the crystals is poor. Macro-
scopic bulk defects such as cracks and inclusions
of ux can be observed by eye. Mosaic crystals
were usually formed on the f0 0 1g face. Aniso-
tropic growth was found along the direction of its
diad axis, which is parallel to the bottom of the
crucible. All of these unfavorable factors are
overcome by using a [1 1 0] seed. The diad axis is
along the [1 1 0] direction, which is perpendicular
to bottom of the crucible when a [1 1 0] seed is
used. So the problems caused by anisotropic
growth when the crystal grows with a [1 0 0] seed
were solved. After 30 day runs, high quality
KABO crystals with sizes of 50
20
17 mm3
and a weight of 30 g were successfully produced
with [1 1 0] seeds (Fig. 3(c)).
3. Physical, chemical and thermal properties of
KABO
The physical and chemical properties of KABO
crystal were measured. The crystal is not hygro-
scopic. It cannot be dissolved in water, but it can
be dissolved in acids such as HCl, HNO3 and
H3 PO4 at room temperature. Its hardness is mea-
sured to be 5.5 and 6.5 at f1 0 0g and f0 0 1g face,
respectively, similar to that of KTP crystal. So it is
easy to be cut and polished for the fabrication of
optical devices. Its density is measured to be 2.47
g/cm3 using a buoyancy method. A dierential
thermal analyzer made by Perkin Elmer was used
to measure its melting point. The experiment was
carried out in a N2 atmosphere with a current rate
of 40 cc/min. The sample was powdered KABO
ground with a transparent single crystal and the
weight was 12 mg. The temperature was increased
from room temperature to 1200 C at a rate of 10
C/min. The melting point was determined to be
1109.7 C. No phase changes were observed in the
temperature range from room temperature to its
melting point.
A thermomechanical analyzer made by Perkin
Elmer and a dierential scanning calorimeter equip-
ment (Dsc 822e ) made by Mettler-Toledo Instru-
ments (Shanghai) Ltd. were used to measure the
thermal expansion coecients and specic heat,
respectively. The sample for the thermal expansion
measurements was an oriented crystal polished on
all six faces. Its dimensions are X
Y
Z
4:38 mm
4:06 mm
3:28 mm. The experiment
was carried out at over temperature range of 25
300 C with a scan rate of 5 C/min. The weight of
the single crystal powder for specic heat mea-
surements was 15.82 mg. The measurement range
covers 30295 C.
Fig. 4 shows the thermal expansion curve along
the X , Y and Z-direction. The thermal expansion is
linear and no abnormality is observed within the
measured temperature range. When the sample
was heated, it showed only thermal expansion and
no thermal contraction occurred. The average
linear thermal expansion coecients from 25 to
300 C are calculated to be 8:4
106 , 7:3
106 ,
and 16:5
106 /C along the X , Y and Z-direction,
respectively. Because the crystal belongs to the
trigonal system, the thermal expansion coeent
along the Y -axis is not independent, and it can be
calculated from that of the X -direction. The cal-
culated result is in agreement with the measured
result. Obvious anisotropic thermal expansions are
 C. Zhang et al. / Optical Materials 23 (2003) 357362
Fig. 4. Thermal expansion of KABO along the X , Y and
Z-direction.
observed along the X and Z-axes, which is im-
portant for crystal growth and laser applications.
Cracks on the f0 0 1g face may be explained by
anisotropic thermal expansion.
The specic heat is one of the important factors
that inuence the damage threshold of crystals.
The higher the specic heat is, the higher the
damage threshold of the crystal is in pulsed laser
operation. The specic heat is measured to be
1.0084 and 1.39 J/g C at temperatures of 47.6 and
294.6 C, respectively (Fig. 5), which is more than
double than the average value for BBO crystals.
The specic heat increases approximately linearly
in the experimental temperature range. This result
implies that KABO will be better than BBO for
resisting photo damage and photorefractvie dam-
age.
Fig. 5. The specic heat of KABO vs temperature.
361
4. Conclusion
Single crystalline KABO can be grown using
both KF and NaF ux by a top-seeded growth
method. It is easier to grow the crystal in NaF ux
than to do so in KF ux. Seed directions inuence
the quality and morphology of the KABO crystal.
It is favorable to choose a [1 1 0] seed for the
growth of KABO. The thermal expansion coe-
cients are experimentally determined to be 8:4

106 , 16:5
106 /C along the a and c-axis, re-
spectively. The specic heat is more than double
that of BBO crystals.
Acknowledgements
This work was supported by a grant for state
key program of China and visiting scholar pro-
gram of Chinese Ministry of Education.
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