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

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

0167-577X/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 7 - 5 7 7 X ( 0 2 ) 0 0 6 8 0 - 8
 Y.Y. Lin et al. / Materials Letters 56 (2002) 10741077 1075

large high-quality crystals is still difficult due to unfa- have suitable solubility and positive temperature coef-
vorable growth properties. On the other hand, along the ficients in ethanol, and so we have selected ethanol as
line of so-called molecular engineering procedure, the solvent in our studies.
some better properties of growth and optics may be Urea crystals exhibit a needle-like shape whose
expected in derivatives and mixed systems of urea growth axis is along the c-direction and have a large
[9,10]. Taking advantage of previous experience in aspect ratio. In the case of mixed systems, the growth
the growth of urea crystals, we have tested the crystal- habit has completely got changed and results in
lization and SHG efficiency of mixed systems of urea growth in all three axes. Also the hygroscopic nature
meta nitro benzoic acid (mNBA) and L-malic acid. 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. Experimental procedure
2.2. Crystal growth
2.1. Solubility and crystal habits
Slow cooling technique by self-seeding method
Urea belongs to the tetragonal crystal system was employed for the growth of mixed systems of
(space group P421m). It is soluble in water, alcohol urea and mNBA and L-malic acid in all regions from
and other organic solvents over a wide range of 10% urea to 100% urea. In the present study, synthe-
solubility with quite large temperature coefficients. sized salt of urea and mixed systems of various
This makes it possible to grow urea crystals from combinations was recrystallized before preparing
solution by the temperature reduction method. In saturated solution for product quality. The crystals
water, urea has a very large solubility that is unfav- were grown from 48 jC to room temperature. The
orable for growing high-quality crystals. In ethanol, crystals of 2  1.5  0.8 cm are harvested from the
the solubility is too low for the growth of large mother solution in 10 days. The growth of urea and its
crystals. But the mixed systems of urea mNBA and mixed systems like most organic materials is problem-
urea L-malic acid show a reasonable solubility curve. atic owing to its polar electrical characteristics, which
The solubility studies show that the mixed systems enhance the interaction between growth surfaces and

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).
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 different compositions of urea and the parent materials
usually show very strong anisotropic growth habits. were carried out using Kurtz method [11]. The sche-
matic of the experimental setup is shown in Fig. 1.
2.3. SHG measurements It consists of a Nd:YAG passively Q-switched laser
of wavelength 1064 nm whose beam falls focused
The SHG measurements of both the two compo- onto a thin section of the material powder contained in
nent systems urea mNBA and urea L-malic acid of 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 1077

used are 3 AJ pulse energy, 3.5 kW peak power, 8.62 urea compositions. Crystal growth and powder SHG
kHz repetition rate, and 860 ps pulse width. The SHG measurements are carried out for all the combination
efficiency plots of the two-component systems urea of crystals. All the combinations show the second-
mNBA and urea L-malic acid are shown in Fig. 2 and harmonic generation with 1064 nm laser light, except
Fig. 3 which shows a SHG efficiency variation with that the SHG signal from the 50:50 combination
composition variation. 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
3. Results and discussion SHG efficiency. We also found that the addition of
mNBA and L-malic acid changes the hygroscopic
Synthesis of these mixed systems of urea mNBA nature and the morphology of urea making the urea
and urea L-malic acid systems with different compo- system easier for crystal growth and possible for
sitions of urea varying from 10% to 100% was done several applications.
by the mixing of both the parent materials by recrys-
tallization method using ethanol as solvent. The
synthesized material was used for subsequent growth.
Acknowledgements
Crystals of optical quality and large size have been
grown. The grown crystals were of rectangular mor-
This work is supported by National Science
phology with well-defined growth faces. Also the
Council under contracts NSC 90-2736-L-007-001
crystals were nonhygroscopic.
and NSC 90-2811-E-007-005. The authors appreciate
The SHG variation of urea mNBA is due to the
technical supports from S.T. Lin, Chih-Wei Liou,
interaction of acceptor and donor groups. The inter-
Yuan-Yau Lin, U.C. Liang and R.Y. Tu.
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 References
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4. Conclusion

We have synthesized two-component urea mNBA

systems and urea L-malic acid systems with different