Research Journal of Chemistry and Environment

___________________________________ Vol.17 (7) July (2013) Res. J. Chem. Environ.

Thermal, Structural and Optical Analyses of Benzimidazole Single Crystal Grown with Organic Dopants for Nonlinear Optical Applications
Vijayan N.,1* Madhurambal G.,2 Bhagavannarayana G.1, Maurya K. K.1 and Mojumdar S. C.3, 4
1. CSIR-National Physical Laboratory, New Delhi, INDIA 2. Department of Chemistry, A.D.M. College for Women, Nagapattinam, INDIA 3. Department of Chemistry, University of Guelph, Guelph, ON, CANADA 4. Department of Chemical Technologies and Environment, Trenčín University of A, SLOVAKIA *scmojumdar@yahoo.com

Abstract Nowadays nonlinear optical (NLO) materials are gaining attention because of their numerous applications in the area of fibre optic communication and optical signal processing. In the present study, the nonlinear optical material of benzimidazole (BMZ) has been grown by slow evaporation solution growth technique using two different organic dopants (Urea and N-methyl urea) at different molar percentages. The effect of dopants on the growth and other physical properties has been analyzed by different instrumentation methods. The addition of urea and N-methyl urea (NMU) to the host material of benzimidazole has not changed the existing crystalline system, but there was a trivial variation in the lattice dimensions which is confirmed by powder X-ray diffraction analysis.
The crystalline perfection was analyzed by high resolution X-ray diffraction analysis. It was found that urea dopant enhances the crystalline perfection in comparison with the N-methyl urea, which is in tune with the scanning electron microscopic analysis. The thermal performance has been examined by TGDTA for all the doped specimens. Its relative second harmonic generation efficiency was evaluated by Kurtz powder technique and it was found that the doped specimens showed enhanced efficiency in comparison with the pure benzimidazole. Its optical properties have been examined by UV-VIS spectral analysis and found variations in the observed transmittance values were found.
Keywords: Single crystal, dopants, characterization methods, nonlinear optical material, second harmonic generation, TG, DTA.

The above said applications stimulated the materials scientists to search new model NLO material to satisfy the day-to-day technological requirements. In the present study, we have attempted to grow single crystals of benzimidazole by using urea and N-methyl urea as the dopants. Benzimidazole (BMZ-C7H6N2) is a fused, two ring conjugated system with six carbon atoms in one ring and five atoms in the other. The smaller ring has nitrogen atoms in the first and third positions. BMZ crystallizes in orthorhombic crystal system with space group Pna21 having lattice dimensions of a=13.504(3) Å, b=6.806(3) Å, c=6.939(3) Å. In our recent studies, the relative second harmonic generation (SHG) efficiency of BMZ was found to be 4.5 times than that of KDP and it is having relatively larger laser damage threshold4. The doped BMZ single crystals have been grown by slow evaporation solution growth technique using methanol as the solvent. The addition of dopants did not affect the existing crystal system, but led to enhance thermal stability, crystalline perfection, SHG efficiency and optical properties. Thermal, XRD, optical and spectral properties are very important properties of materials. Therefore, many authors have studied these properties of various materials.5-32

Material and Methods
The commercially purchased chemicals are of considerably variable quality, with purity lying in the range of 95-99 %. To improve the purity of the material, recrystallization is one of the easiest and inexpensive methods. In the present study, the commercially available benzimidazole, urea and NMU were dissolved in methanol and its purity was improved by repeated re-crystallization processes and the recrystallized salts were used as the charge material for preparing the saturated solution. The calculated amount of the host material of benzimidazole was prepared in four different beakers using 100 mL of methanol solution. The solubility of the pure benzimidazole was determined in three different solvents.33 Then the dopants of urea and NMU were added to the above mentioned solution in 0.5M% and 1M%, respectively. Then the solution was stirred well by using magnetic stirrer and the temperature was maintained slightly above the room temperature in order to complete the reaction process. (2)

Introduction
In the recent past, organic nonlinear optical materials are gaining attention due to their efficient second harmonic generation and tailor made flexibility. They are very much useful in the filed of fibre optic communication, optical data storage and frequency doubling applications.1-3
*Author for Correspondence

solvent molecules (methanol) which were entrapped within the crystal during growth. It is due to faster growth rate and leads to internal boundaries in the specimen.34 The well-collimated and monochromated MoKα1 beam obtained from the three monochromator Si crystals set in dispersive (+. The half widths as well as the peak separation are within a minute of arc which shows the crystal quality is reasonably good. Fig. Due to dispersive configuration. The calculated lattice parameters are given in table 1.4 Fig. These types of behavior deteriorate the quality of the specimen.5M% urea added BMZ. The harvested single crystals are shown in fig.-. It is worth to mention here that the addition of 1M% of urea enhances the growth rate but reduces the crystalline perfection. As seen in the fig. 3b shows DC recorded for (002) diffracting planes.5M% of urea added BMZ specimen. The obtained two-theta values were used to calculate the lattice dimensions of the respective compounds by using PROZKI software package (APPLEMAN programme). The additional peaks. though the lattice constant of the monochromator crystal(s) and the specimen are different. These observations show that NMU doping enhances the (3) Then. 3c. These multi-peaks indicate that the specimen contain many structural internal low angle grain boundaries. 3d shows the diffraction curve which contains multiple peaks in an angular range of ~ 1000 arc sec. After a span of 12 days.+) configuration. which are 7 and 37 arc sec away from the main peak. The formation of very low angle boundaries due to dopants (1M% of NMU) suggests that at higher dopant concentrations. the crystal matrix could not accommodate them. The FWHM of the main peak is 40 arc sec. Results and Discussion Powder X-ray diffraction analysis: The urea and NMU added BMZ single crystal was crushed into fine powder and the crushed material was subjected to powder X-ray diffraction analysis. Chem. The slight broadening of the DC is due to the inclusion of dopants in the crystalline matrix.-) configuration has been used as the exploring X-ray beam. The peak intensity of this curve is very high as compared to that of SEST grown BMZ crystal which also shows better crystalline perfection similar to fig. Addition of dopants enhances the growth rate and reduces the defects as compared to the pure BMZ crystal. the unwanted dispersion broadening in the diffraction curve of the specimen crystal is insignificant.-. No such line defects were observed in the SEM of the 0. The specimen crystal is aligned in the (+. The half widths of the main peak and the peaks due to very low angle boundaries are 95. At the same time NMU added crystals were harvested after a time span of 20-22 days and it was found that the dopant of urea enhanced the rate of growth as well as the crystalline quality of the specimens which is later confirmed by high resolution X-ray diffraction analysis. There are five main peaks whose FWHM values are in the range of several arc min. Then the beakers were housed in a constant temperature bath (CTB) with a setting temperature of 34 C and the complete growth process was carefully examined. J. Evaluation of crystalline perfection by HRXRD : In the present analysis. This may be due to the addition of dopants in the host material. Similar observation was also found from the HRXRD. Environ. urea added single crystals were grown in the bottom of the beaker with natural facets. The harvested single crystals have been subjected to different characterization analyses. The surface of the specimen is quite smooth. The smoothness of the surface indicates betterment of the specimen as compared to urea added specimen.Research Journal of Chemistry and Environment ___________________________________ Vol.-. The analysis was carried on a powder X-ray diffractometer at a scanning speed of 1 /minute.33 But there is a slight variation in the lattice dimensions due to the inclusion of Urea and NMU in the host material interstitials. the prepared solution was filtered using a filter paper and then covered using a thick plastic sheet in order to avoid fast evaporation. The size of the crystal is also reasonably good. From the measurement we found that the addition of dopants did not affect the existing crystal system. 2 (a-d). The very low angle boundary obtained for this solution grown specimen may be attributed to the segregation of .17 (7) July (2013) Res. The half widths of the main peak and the peak due to very low angle boundary are 23 and 19 arc secs respectively. 3b due to the inclusion of NMU dopants. The solid line in the figure is the convoluted curve of three peaks shown with dotted lines. The schematic line representation is given in our earlier reports. Fig. It can be seen that the surface roughness of the 1M% of urea added BMZ crystal is more comparable to that 0. 18 and 25 arc sec respectively. the crystalline perfection of the pure and doped specimens of BMZ was characterized by HRXRD on multicrystal X-ray diffractometer developed at NPL. indicate that the specimen contains two very low angle boundaries whose tilt angles are 7 and 37 arc sec. 1 (a-d). The recorded XRD patterns are shown in the fig. Surface analysis by SEM: The surface features of the specimen can be easily examined by scanning electron microscopy and the surface defects. the DC is having a single peak having the FWHM of 26 arc sec. From the micrograph we have observed that the specimen contains line defects on the surface. growth spirals can be easily identified. From the growth experiments we observed that NMU added solutions take more time to form a single crystal and that yielded a good quality specimen. 3a shows that the diffraction curve (DC) contains one additional peak at an angular separation of 46 arc sec from the main peak. The additional peak shows that the specimen contains one very low angle boundary.

4d and 4e depict the thermal behavior of 0. At 280 nm a sharp fall of transmittance to zero was observed indicating a single transition in the near UV region of Benzimidazole. Temperature-uniaxial pressure phase diagram of KH2PO4. Similar to that of urea as seen above. The input laser beam was passed through an IR reflector and then directed on the microcrystalline powdered sample of doped BMZ packed in a capillary tube. 313. The observed values are given in table 2..E. 81. Bangalore.5 mm was subjected to Shimadzu UV-1061 UV-VIS spectrophotometer in the wavelength range of 200 – 800 nm. Guedes I.. There are no noticeable changes in the pure and doped (4) Conclusion Doped benzimidazole single crystals (with urea and NMU) have been grown by conventional solution growth method and it was found that growth period was varied depending on the percentage of dopants.. 4b shows the 1M% of urea added BMZ specimen. S. Aspects of thermal conductivity relative to heat flow. and John M. The authors are also thankful to Dr. 104. DC. The endothermic peak gives the melting point at 178 °C which is 6 °C more than that of the pure specimen. Kanagasekaran T. (1993) 2. 784-9 (2006) 5. Zyss J. and Lal R. Chem. Washington. Acknowledgement The authors are very much thankful to Director. Res..T. It is an important and popular tool to evaluate the conversion efficiency of a NLO material... 120-125 m) of KDP was used. Dhawan for providing the powder XRD thermal characterization facilities. Mat.Research Journal of Chemistry and Environment ___________________________________ Vol. References 1. Chaves A. J Therm Anal Calorim. it is not the same. Aggarwal M.. Moreira S.J. 179–82 (2005) . After analyzing the effect of urea dopants on the BMZ single crystal. J Therm Anal Calorim.. Gopalakrishnan R. surface smoothness as well as the bulk crystalline perfection as no boundaries were observed in these specimens but for urea doping. Perigand A. Thermochimica Acta.. 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1: Images of the grown single crystal of BMZ (a) (b) (c) (d) (a) (b) (c) (5) . Environ. Fig. Chem.17 (7) July (2013) Res. J.Research Journal of Chemistry and Environment ___________________________________ Vol.

3: HRXRD patterns for the (a) (b) (c) (d) (6) .17 (7) July (2013) Res. 2: Powder X-ray diffraction patterns of (a) (b) (c) (d) Fig. Environ. Chem. (d) Fig. J.Research Journal of Chemistry and Environment ___________________________________ Vol.

Chem. J. Environ.17 (7) July (2013) Res. 4: TG-DTA curves of (a) (b) (c) (d) (7) . (a) (b) (c) (d) Fig.Research Journal of Chemistry and Environment ___________________________________ Vol.

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