November 2002

Materials Letters 56 (2002) 1074 1077

www.elsevier.com/locate/matlet

Crystal growth of two-component new novel organic NLO crystals

Y.Y. Lin a, N.P. Rajesh a, P. Santhana Raghavan a, P. Ramasamy b, Y.C. Huang a,*
a
Department of Electrical Engineering, National Tsing Hua University, 30043 Hsinchu, Taiwan, Peoples Republic of China
b
Crystal Growth Centre, Anna University, Chennai 600 025, India
Received 28 January 2002; accepted 13 February 2002

Abstract

Urea is an excellent nonlinear optical (NLO) medium. However, growth of large high-quality crystals for practical use still
remains a challenge due to its unfavorable growth properties. Improved crystalline and optical quality could be expected in
mixed systems. This work presents the synthesis, growth and second-harmonic-generation (SHG) studies of two-component
new organic NLO systems, urea meta nitro benzoic acid (mNBA) and urea L-malic acid. The material property of urea seems
to be modified by the addition of mNBA and L-malic acid. The SHG efficiency was measured by Kurtz powder method
showing variation with composition variation.
D 2002 Elsevier Science B.V. All rights reserved.

Keywords: Nonlinear optical; Powder SHG; Organic NLO material; mNBA

1. Introduction such applications require materials with very large

Organic crystals have been extensively studied due
to their nonlinear optical (NLO) coefficients being
often larger than those of inorganic materials. Many
new organic crystals have been found based on the
predictive molecular engineering approach and have
been shown to have potential applications in nonlinear
optics. Some interest has been shown in the search for
ultraviolet laser materials [1]. Recently, there is con-
siderable interest in the synthesis of new materials
with large second-order optical nonlinearities because
of their potential use in applications including tele-
communications, optical computing, optical data stor-
age, and optical information processing [2 6]. Many
*
Corresponding author. Tel.: +886-3-571-5131x4121; fax:
+886-3-575-2061.
E-mail address: ychuang@ee.nthu.edu.tw (Y.C. Huang).
macroscopic second-order susceptibilities which are
usually constituted from molecules with large molec-
ular first hyperpolarizability and oriented in a non-
centrosymmetric arrangement.
Urea is one of the organic crystals that have been put
to practical uses [7,8]. It has larger nonlinear optical
coefficients, a high degree of birefringence, and rela-
tively high laser damage threshold. Since urea trans-
parency range extends to 200 nm in the short
wavelength limit, it is one of the most promising
materials for nonlinear optical applications in UV.
The powder second-harmonic generation (SHG) of
urea is 2.5 times that of ADP and the d14 nonlinear
coefficient is 2.5 F 0.2 times that of d36 of ADP or
about 1.40 pm/V. The d36 NLO coefficient value of
urea is 1.30 pm/V at 1.06 Am. The damage threshold of
urea is 3  109 W cm 2 at 532 nm and 5  109 W
cm 2 at 1.064 Am for 10 ns pulse. However, growth of

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 Y.Y. Lin et al. / Materials Letters 56 (2002) 10741077
large high-quality crystals is still difficult due to unfa-
vorable growth properties. On the other hand, along the
line of so-called molecular engineering procedure,
some better properties of growth and optics may be
expected in derivatives and mixed systems of urea
[9,10]. Taking advantage of previous experience in
the growth of urea crystals, we have tested the crystal-
lization and SHG efficiency of mixed systems of urea
meta nitro benzoic acid (mNBA) and L-malic acid.
2. Experimental procedure
2.1. Solubility and crystal habits
Urea belongs to the tetragonal crystal system
(space group P421m). It is soluble in water, alcohol
and other organic solvents over a wide range of
solubility with quite large temperature coefficients.
This makes it possible to grow urea crystals from
solution by the temperature reduction method. In
water, urea has a very large solubility that is unfav-
orable for growing high-quality crystals. In ethanol,
the solubility is too low for the growth of large
crystals. But the mixed systems of urea mNBA and
urea L-malic acid show a reasonable solubility curve.
The solubility studies show that the mixed systems
Fig. 1. Schematic of the SHG setup. A passively Q-switched Nd:YAG laser generates 1064 nm laser pulses at 3.5 kW peak power and 8.62 kHz
repetition rate. The powder sample emits the SHG of the 1064 nm laser, which is detected by a photomultiplier tube (PMT).
1075
have suitable solubility and positive temperature coef-
ficients in ethanol, and so we have selected ethanol as
the solvent in our studies.
Urea crystals exhibit a needle-like shape whose
growth axis is along the c-direction and have a large
aspect ratio. In the case of mixed systems, the growth
habit has completely got changed and results in
growth in all three axes. Also the hygroscopic nature
of urea was not seen in the case of two-component
systems. This is an added advantage for the growth of
mixed systems for useful applications.
2.2. Crystal growth
Slow cooling technique by self-seeding method
was employed for the growth of mixed systems of
urea and mNBA and L-malic acid in all regions from
10% urea to 100% urea. In the present study, synthe-
sized salt of urea and mixed systems of various
combinations was recrystallized before preparing
saturated solution for product quality. The crystals
were grown from 48 jC to room temperature. The
crystals of 2  1.5  0.8 cm are harvested from the
mother solution in 10 days. The growth of urea and its
mixed systems like most organic materials is problem-
atic owing to its polar electrical characteristics, which
enhance the interaction between growth surfaces and
1076 Y.Y. Lin et al. / Materials Letters 56 (2002) 10741077

Fig. 2. SHG measurements for the mixed systems of urea mNBA systems. For the 50:50 combinations, the compensation of the donor and
acceptor group is very intense and results in poor SHG efficiency.

molecules of solvent and solute. For that reason, they
usually show very strong anisotropic growth habits.
2.3. SHG measurements
The SHG measurements of both the two compo-
nent systems urea mNBA and urea L-malic acid of
different compositions of urea and the parent materials
were carried out using Kurtz method [11]. The sche-
matic of the experimental setup is shown in Fig. 1.
It consists of a Nd:YAG passively Q-switched laser
of wavelength 1064 nm whose beam falls focused
onto a thin section of the material powder contained in
a 3-mm cuvette. The specifications of the laser we

Fig. 3. SHG efficiency of urea L-malic acid system for different compositions.
 Y.Y. Lin et al. / Materials Letters 56 (2002) 10741077
used are 3 AJ pulse energy, 3.5 kW peak power, 8.62
kHz repetition rate, and 860 ps pulse width. The SHG
efficiency plots of the two-component systems urea
mNBA and urea L-malic acid are shown in Fig. 2 and
Fig. 3 which shows a SHG efficiency variation with
composition variation.
3. Results and discussion
Synthesis of these mixed systems of urea mNBA
and urea L-malic acid systems with different compo-
sitions of urea varying from 10% to 100% was done
by the mixing of both the parent materials by recrys-
tallization method using ethanol as solvent. The
synthesized material was used for subsequent growth.
Crystals of optical quality and large size have been
grown. The grown crystals were of rectangular mor-
phology with well-defined growth faces. Also the
crystals were nonhygroscopic.
The SHG variation of urea mNBA is due to the
interaction of acceptor and donor groups. The inter-
action between the NH2 group (which is a donor) and
the COOH and NO2 group (which are acceptors)
results in the SHG efficiency variation. For the
50:50 combinations, the compensation of donor and
acceptor group is very intense and results in poor
SHG efficiency. For the other compositions, the
electron donor and acceptor interaction is very weak
and so shows higher SHG efficiency when compared
to urea. To check the interaction of electron donor and
acceptor groups, mixed systems of urea benzoic acid
systems (without the NO2 group) were carried out. In
this case, the SHG efficiency is much higher than the
mixed systems of urea mNBA but plagued by diffi-
culties in growth.
In the case of the new compound urea L-malic
acid system, it crystallizes in noncentrosymmetric
space group due to a chiral character of malic acid.
The SHG variation with different composition of
malic acid may be attributed to difference in non-
centrosymmetric properties.
4. Conclusion
We have synthesized two-component urea mNBA
systems and urea L-malic acid systems with different
1077
urea compositions. Crystal growth and powder SHG
measurements are carried out for all the combination
of crystals. All the combinations show the second-
harmonic generation with 1064 nm laser light, except
that the SHG signal from the 50:50 combination
urea mNBA was too weak to measure. For the
50:50 combinations, the compensation of the donor
and acceptor group is very intense and results in poor
SHG efficiency. We also found that the addition of
mNBA and L-malic acid changes the hygroscopic
nature and the morphology of urea making the urea
system easier for crystal growth and possible for
several applications.
Acknowledgements
This work is supported by National Science
Council under contracts NSC 90-2736-L-007-001
and NSC 90-2811-E-007-005. The authors appreciate
technical supports from S.T. Lin, Chih-Wei Liou,
Yuan-Yau Lin, U.C. Liang and R.Y. Tu.
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