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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, Trenn 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) , b=6.806(3) , c=6.939(3) . 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

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solvent molecules (methanol) which were entrapped within the crystal during growth. Fig. 3b shows DC recorded for (002) diffracting planes. The FWHM of the main peak is 40 arc sec. The slight broadening of the DC is due to the inclusion of dopants in the crystalline matrix. As seen in the fig. 3c, the DC is having a single peak having the FWHM of 26 arc sec. 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. 3b due to the inclusion of NMU dopants. Fig. 3d shows the diffraction curve which contains multiple peaks in an angular range of ~ 1000 arc sec. There are five main peaks whose FWHM values are in the range of several arc min. These multi-peaks indicate that the specimen contain many structural internal low angle grain boundaries. It is worth to mention here that the addition of 1M% of urea enhances the growth rate but reduces the crystalline perfection. The solid line in the figure is the convoluted curve of three peaks shown with dotted lines. The additional peaks, which are 7 and 37 arc sec away from the main peak, indicate that the specimen contains two very low angle boundaries whose tilt angles are 7 and 37 arc sec. The half widths of the main peak and the peaks due to very low angle boundaries are 95, 18 and 25 arc sec respectively. 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. Surface analysis by SEM: The surface features of the specimen can be easily examined by scanning electron microscopy and the surface defects, growth spirals can be easily identified. From the micrograph we have observed that the specimen contains line defects on the surface. These types of behavior deteriorate the quality of the specimen. No such line defects were observed in the SEM of the 0.5M% of urea added BMZ specimen. This may be due to the addition of dopants in the host material. Addition of dopants enhances the growth rate and reduces the defects as compared to the pure BMZ crystal. 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. The smoothness of the surface indicates betterment of the specimen as compared to urea added specimen. The size of the crystal is also reasonably good. It can be seen that the surface roughness of the 1M% of urea added BMZ crystal is more comparable to that 0.5M% urea added BMZ. Similar observation was also found from the HRXRD. It is due to faster growth rate and leads to internal boundaries in the specimen. The surface of the specimen is quite smooth. These observations show that NMU doping enhances the (3)

Then, the prepared solution was filtered using a filter paper and then covered using a thick plastic sheet in order to avoid fast evaporation. 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. After a span of 12 days, urea added single crystals were grown in the bottom of the beaker with natural facets. 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. The harvested single crystals are shown in fig. 1 (a-d). The harvested single crystals have been subjected to different characterization analyses.

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. The analysis was carried on a powder X-ray diffractometer at a scanning speed of 1 /minute. The obtained two-theta values were used to calculate the lattice dimensions of the respective compounds by using PROZKI software package (APPLEMAN programme). The recorded XRD patterns are shown in the fig. 2 (a-d). From the measurement we found that the addition of dopants did not affect the existing crystal system.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 calculated lattice parameters are given in table 1. Evaluation of crystalline perfection by HRXRD : In the present analysis, the crystalline perfection of the pure and doped specimens of BMZ was characterized by HRXRD on multicrystal X-ray diffractometer developed at NPL.34 The well-collimated and monochromated MoK1 beam obtained from the three monochromator Si crystals set in dispersive (+,-,-) configuration has been used as the exploring X-ray beam. The specimen crystal is aligned in the (+,-,-,+) configuration. Due to dispersive configuration, though the lattice constant of the monochromator crystal(s) and the specimen are different, the unwanted dispersion broadening in the diffraction curve of the specimen crystal is insignificant. The schematic line representation is given in our earlier reports.4 Fig. 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. The half widths of the main peak and the peak due to very low angle boundary are 23 and 19 arc secs respectively. The half widths as well as the peak separation are within a minute of arc which shows the crystal quality is reasonably good. The very low angle boundary obtained for this solution grown specimen may be attributed to the segregation of

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benzimidazole single crystals.

surface smoothness as well as the bulk crystalline perfection as no boundaries were observed in these specimens but for urea doping, it is not the same. Assessment of thermal behavior: In order to know the thermal stability of the grown specimen, the powder form of the relevant specimen is subjected to TG-DTA analysis. Fig. 4a shows the thermal behavior of the 0.5% M of urea added BMZ specimen. The melting point of the specimen is shifted to the higher temperature of 176 C which is 4 C more than that of the pure specimen. Fig. 4b shows the 1M% of urea added BMZ specimen. The endothermic peak gives the melting point at 178 C which is 6 C more than that of the pure specimen. After analyzing the effect of urea dopants on the BMZ single crystal, it is interesting to conclude that the dopants enhance the thermal stability of the compound. The adjacent figs. 4d and 4e depict the thermal behavior of 0.5M and 1 M% NMU added BMZ. Similar to that of urea as seen above, NMU also enhances the thermal stability as the melting point increases up to 8 C at a concentration of 1M%. Measurement of SHG efficiency: The nonlinear optical conversion efficiency has been carried out using the Kurtz and Perry35 technique at the Indian Institute of Science, Bangalore. It is an important and popular tool to evaluate the conversion efficiency of a NLO material. A Q-switched Nd:YAG laser operating at the fundamental wavelength 1064 nm, generating about 1.3 mJ and pulse of width 8 ns was used for the present experimental study. 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. The light emitted by the sample was detected by a photodiode detector integrated with oscilloscope assembly. When the laser was passed through these specimens, second harmonic signal of 532 nm is generated and it was confirmed by the emission of green light. To estimate the relative SHG efficiency with respect to KDP, microcrystalline powder (with same particle size as that of the specimen i.e. 120-125 m) of KDP was used. The observed values are given in table 2. UV-VIS spectral analysis: The optically polished single crystal of pure and doped benzimidazole having the thickness of 1.5 mm was subjected to Shimadzu UV-1061 UV-VIS spectrophotometer in the wavelength range of 200 800 nm. The recorded spectrum is shown in fig. 5. From the figure, we can understand that the title compound is transmitting the entire incident light and there is no absorption in the whole visible region of the spectrum. At 280 nm a sharp fall of transmittance to zero was observed indicating a single transition in the near UV region of Benzimidazole. The nearly sharp fall in transmittance at 280 nm suggests nearly similar distribution of energies among all molecules of Benzimidazole single crystal33. 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. Even though NMU added specimens were taking more time for the growth but the crystalline perfection is good in comparison with the urea added dopants. Its crystal system, lattice dimensions and functional groups were determined by powder-XRD and FTIR analyses. Its crystalline perfection has been evaluated by HRXRD. Surface micro morphological analysis has been carried out using SEM. Relative SHG efficiencies have been measured and urea doping in BMZ crystals leads to enhance the SHG efficiency as compared to that of NMU.

Acknowledgement
The authors are very much thankful to Director, NPL for his constant encouragement and support in carrying out these studies. The authors are also thankful to Dr. S. K. Halder and Dr. S. K. Dhawan for providing the powder XRD thermal characterization facilities.

References
1. Badan J., Hierle R., Perigand A., Zyss J., Williams ed., Nonlinear Optical Properties of Organic Molecules and Polymeric Materials, Am. Chem. Society, Washington, DC, (1993) 2. Aggarwal M.D., Stephens J., Batra A.K. and Lal R.B., Bulk crystal growth and characterization of semiorganic Nonlinear optical materials, J. Opt. Adv. Mat., 5, 555-62 (2003) 3. Melo F.E.A., Moreira S.G.C., Chaves A.S., Guedes I., Freire P.T.C. and Mendes F.J., Temperature-uniaxial pressure phase diagram of KH2PO4, Phys. Rev. B, 59, 3276-9 (1999) 4. Vijayan N., Bhagavannarayana G., Kanagasekaran T., Ramesh Babu R., Gopalakrishnan R. and Ramasamy P., Crystallization of benzimidazole by solution growth method and its characterization, Cryst. Res. Tech., 41, 784-9 (2006) 5. Chowdhury B. and John M.E., Thermal Evaluation of bioengineered cotton, Thermochimica Acta, 313, 43-53 (1998) 6. Mojumdar S.C., Sain M., Prasad R.C., Sun L. and Venart J.E.S., Thermoanalytical Techniques and their Applications from Medicine to Construction Part I, J Therm Anal Calorim., 90, 65362 (2007) 7. Tian F., Sun L., Mojumdar S.C., Venart J.E.S. and Prasad R.C., Absolute Measurement of Thermal Conductivity of Poly (acrylic acid) by Transient Hot Wire Technique, J Therm Anal Calorim, 104, 82329 (2011) 8. Chowdhury B. and Mojumdar S.C., Aspects of thermal conductivity relative to heat flow, Technique, J Therm Anal Calorim., 81, 17982 (2005)

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Fig. 1: Images of the grown single crystal of BMZ (a) (b) (c) (d)

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Fig. 2: Powder X-ray diffraction patterns of (a) (b) (c) (d)

Fig. 3: HRXRD patterns for the (a) (b) (c) (d)

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Fig. 4: TG-DTA curves of (a) (b) (c) (d)

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Fig. 5: Absorbance spectra of ??

Table 1 Calculated lattice dimensions of pure and doped BMZ crystal

Name of the specimen Pure BMZ 0.5M% urea 1M% urea 0.5M% NMU 1M% NMU

a/ 6.9393 6.8655 6.9662 6.9692 6.9703

b/ 6.8063 6.9765 6.8561 6.8477 6.8503

c/ 13.5043 13.4647 13.5303 13.5502 13.5603

Volume/3 637.8210 644.9209 646.2201 646.6560 647.4859

Table 2 Determined SHG efficiency of pure and doped BMZ single crystal

Sample name KDP Pure BMZ 0.5M% urea 1M% urea 0.5M% NMU 1M% NMU
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Relative SHG efficiency/mV 7 32 168 188 69 22

10. Mojumdar S.C., Raki L., Mathis N., Schimdt K. and Lang S., Synthesis, Thermal Conductivity, TG/DTA, AFM, FTIR, 29 Si and 13 C NMR Studies of Calcium Silicate HydratePolymer Nanocomposite Materials, J Therm Anal Calorim., 85, 11924 (2006)

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24. Mojumdar S.C., Thermoanalytical and IR spectroscopy investigation of Mg(II) complexes with heterocyclic ligands, J Therm Anal Calorim, 64, 629-36 (2001) 25. Gonsalves L.R., Mojumdar S.C. and Verenkar V.M.S., Synthesis and Characterisation of Co0.8Zn0.2Fe2O4 Nanoparticles, J Therm Anal Calorim., 104, 869-73 (2011) 26. Raileanu M., Todan L., Crisan M., Braileanu A., Rusu A., Bradu C., Carpov A. and Zaharescu M., Sol-Gel Materials with Pesticide Delivery Properties, J Environ Protect, 1, 302-13 (2010) 27. LizaK. P., Murarova A. and Mojumdar S.C., Heat transfer through a textile layer composed of hollow fibres, J Therm Anal Calorim., 108, 851-7 (2012) 28. Mojumdar S.C., imon P. and Krutokov A., [1] Benzofuro [3,2-c] pyridine: synthesis and coordination reactions, J Therm Anal Calorim., 96, 1039 (2009) 29. Moricov K., Jna E., Plko A. and Mojumdar S.C., Thermal Stability of Li2O - SiO2 - TiO2 Gels Evaluated by the Induction Period of Crystallization, J Therm Anal Calorim., 100, 817-20 (2010) 30. Mojumdar S.C., Miklovic J., Krutosikova A., Valigura D. and Stewart J.M., Furopyridines and furopyridine-Ni(II) complexes Synthesis, thermal and spectral characterization, J Therm Anal Calorim., 81, 211 5 (2005) 31. Vasudevan G., AnbuSrinivasan P., Madhurambal G. and Mojumdar S.C., Thermal analysis, effect of dopants, spectral characterisation and growth aspects of KAP crystals, J. Therm. Anal. Calorim., 96, 99102 (2009) 32. Murrov A., Physiology of Clothing, Mens Thermal Regulation. Vlkna a Textil, 8(1), 48-9 (2001) 33. Vijayan N., Ramesh Babu R., Gopalakrishnan R. and Ramasamy P., Harrison WTA. Growth and characterization of benzimidazole single crystals: a nonlinear optical material, J. Crystal Growth, 262, 490-98 (2004) 34. Lal K. and Bhagavannarayana G., A high-resolution diffuse X-ray scattering study of defects in dislocation-free silicon crystals grown by the float-zone method and comparison with Czochralski-grown crystals, J. Appl. Cryst., 22, 209-15 (1989) . 35. Vijayan N., Bhagavannarayana G., Budakoti G.C., Kumar B., Upadhyaya V. and Das S., Optical, dielectric and surface studies on solution grown benzimidazole single crystals, Mat. Lett., 62, 1252-4 (2008) 36. Kurtz S.K. and Perry T.T., A Powder Technique for the Evaluation of Nonlinear Optical Materials, J. Appl. Phys., 39, 3798-3813 (1968). (Received 28th March 2013, accepted 10th May 2013)

11. Chowdhury B. and Orehotsky J., Scope of electron transport studies by thermally stimulated discharge current measurement, J. Therm Anal Calorim., 73, 53-57 (2003) 12. Mojumdar S.C. and Raki L., Preparation, thermal, spectral and microscopic studies of calcium silicate hydrate-poly (acrylic acid) nanocomposite materials, J Therm Anal Calorim., 85, 99 105 (2006) 13. LizaK.P., Legerska J., MilitkyJ. and Mojumdar S.C., Thermal transport characteristics of polypropylene fiber-based knitted fabrics, J Therm Anal Calorim., 108, 837-41 (2012) 14. Porob R.A., Khan S.Z., Mojumdar S.C. and Verenkar V.M.S., Synthesis T.G., SDC and infrared spectral study of NiMn2(C4H4O4)3 6N2H4 A precursor for NiMn2O4 nanoparticles, J Therm Anal Calorim., 86, 605 08 (2006) 15. Mojumdar S.C., Varshney K.G. and Agrawal A., Hybrid fibrous ion exchange materials, Past, present and future, Res. J. Chem. Environ., 10(1), 89 103 (2006) 16. Doval M., Palou M. and Mojumdar S.C., Hydration behaviour of C2S and C2AS nanomaterials, synthesized by sol-gel method, J Therm Anal Calorim., 86, 595 9 (2006) 17. Mojumdar S.C., Moresoli C., Simon L.C. and Legge R.L., Edible Wheat Gluten (WG) Protein Films: Preparation, Thermal, Mechanical and Spectral Properties, J Therm Anal Calorim., 104, 929-36 (2011) 18. Varshney G., Agrawal A. and Mojumdar S.C., Pyridine based cerium (IV) phosphate hybrid fibrous ion exchanger, Synthesis, characterization and thermal behavior, J. Therm Anal Calorim., 90, 731 4 (2007) 19. Mojumdar S.C., Melnik M. and Jona E., Thermal and spectral properties of Mg(II) and Cu(II) complexes with heterocyclic N-donor ligands, J Anal Appl Pyrolysis., 53, 149 60 (2000) 20. Moner P., Vosejpkov K., Koudelka L. and Bene L., Thermal studies of ZnOB2O3P2O5TeO2 glasses, J Therm Anal Calorim., 107, 1129-35 (2012) 21. Mojumdar S.C., Thermal Properties, Environmental Deterioration and Applications of Macro-Defect-Free Cements, Res. J. Chem. Environ., 9(1), 23-27 (2005) 22. Rejitha K.S. and Mathew S., Investigations on the thermal behavior of hexaamminenickel(II) sulphate using TG-MS and TR-XRD, Glob J Anal Chem., 1(1), 100-108 (2010) 23. Pajtov M., Ondruov D., Jna E., Mojumdar S.C., alkov S., Bazylkov T. and Gregor M., Spectral and thermal characteristics of copper(II) carboxylates with fatty acid chains and their benzothiazole adducts, J Therm Anal Calorim., 100, 769-77 (2010)

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