Table of Contents Author Guidelines Submit a Manuscript
International Journal of Optics
Volume 2012 (2012), Article ID 803797, 6 pages
http://dx.doi.org/10.1155/2012/803797
Research Article

Synthesis, Growth, and Electrical Transport Properties of Pure and -Doped Triglycine Sulphate Crystal

Department of Physics, Bangladesh University of Engineering and Technology, Dhaka 1000, Bangladesh

Received 31 October 2011; Revised 4 January 2012; Accepted 5 January 2012

Academic Editor: Dragomir Neshev

Copyright © 2012 Farhana Khanum and Jiban Podder. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

Pure triglycine sulphate (TGS) and LiSO4-doped TGS crystals were grown from aqueous solution by natural evaporation method. The grown crystals were characterized by UV-vis spectroscopy, electrical conductivity () measurement, dielectric studies, microhardness, and thermogravimetry/differential thermal analysis. Pure TGS and LiSO4-doped TGS crystals were found highly transparent and full faced. The direct current conductivity is found to increase with temperature as well as dopant concentrations. Curie temperature remains the same for pure and doped crystals, but dielectric constant and dielectric loss increase with dopant concentration. The Vicker’s microhardness of the LiSO4-doped TGS crystals along (001) face is found higher than that of pure TGS crystals. Etching studies illustrate the quality of the doped crystal. The experimental results evidence the suitability of the grown crystal for optoelectronic applications.

1. Introduction

Triglycine sulphate, (NH2CH2COOH)3 H2SO4, crystal is considered as one of the potential materials for its wide range of applications, namely, UV tunable laser, second harmonic generation, and pyroelectric infrared sensors due to its high pyroelectric coefficient, optical transmission, and reasonably low dielectric constant [14]. It is a hydrogen-bonded ferroelectric crystal having a typical second-order phase transition at Curie temperature of 49°C [57]. TGS has a major disadvantage that it depolarized by thermal, mechanical, and electrical means. In order to overcome this difficulty, several studies have been attempted with different organic and inorganic dopants to achieve effective internal bias to stabilize the domains and desired pyroelectric and ferroelectric properties of TGS crystals [813]. Alkali halides such as NaBr and KBr-doped TGS crystals were grown, and the effects of the dopant have been investigated [14, 15]. Metal ion dopants have been added to modify the properties of TGS crystal [16, 17]. In the literature, only limited information is available about the behavior of TGS doped with Lithium [18]. Lithium reacts with water easily and noticeably with less energy than other alkali metals. Li+1 ion has 90 pm ionic radius, so it can easily reside into the lattice site of the TGS crystal and it can modify the electrical, mechanical, thermal, and surface morphology of TGS crystals. In the present work, LiSO4 is used as a dopant to see its effect on the property of TGS crystal.

2. Experimental Methods

2.1. Synthesis and Crystal Growth

Analar Reagent (AR) grade glycine and concentrated sulphuric acid (H2SO4) were dissolved in deionized water in the molar ratio of 3 : 1, and the solution was heated at 50°C to obtain synthesized TGS salt. The synthesized salt was again dissolved in triple distilled water and then recrystallized by natural evaporation process. This process was repeated three times to improve the purity of the material. The seed crystals of pure TGS were prepared by natural evaporation method. Good quality and defect-free seed crystals were suspended with nylon thread within the solution of the beaker to grow bulk-size crystal. To obtain doped TGS crystal, 1 mole % LiSO4 was added to the saturated mother solution. Highly transparent and full-faced crystals were obtained within 4 weeks. The pure and LiSO4 doped TGS crystals are found colourless and shown in Figure 1.

fig1
Figure 1: (a) Pure TGS (b) 1 mole % LiSO4-doped TGS Crystal.

3. Results and Discussion

3.1. Optical Transmission Studies

The optical transmission spectra of the grown crystal were carried out in the range of 190 to 1100 nm covering the entire near-ultraviolet, visible, and near infrared region using SHIMADZU UV-160 Spectrometer to find the transmission range about the suitability of this grown crystal for optical applications. An optically polished 10 × 10 × 2 mm3 single crystal was used for this study. The transmission spectra are shown in Figure 2. The transmittance in the visible region is found nearly about 84% for pure TGS and ~94% for LiSO4-doped TGS crystal. A strong absorption and the UV cut off wavelength is found to be at 230 nm for both pure TGS and LiSO4-doped TGS crystal, and it reveals the good optical quality of the grown crystal. High transmission in the whole visible region for LiSO4-doped TGS crystal shows the suitability of this grown crystal for use of UV tunable laser and second harmonic generation (SHG) device applications. Using the formula , the band gap is calculated to be 5.404 eV, which is in good agreement with the reported literature [19].

803797.fig.002
Figure 2: UV-visible transmittance spectra for pure and LiSO4-doped TGS Crystals.
3.2. D.C. Electrical Conductivity

For D.C. electrical measurement, crystal samples were prepared in the form of thin plates of 2 mm thickness. The samples were elevated far from the seed portion to ensure the homogenicity and optical quality and free from any noticeable defects. The conducting silver paste is applied on the two opposite (001) faces of crystal samples. Two connecting leads were taken out from the two opposite faces using thin Cu wire. Temperature versus D.C. electrical conductivity () is shown in Figure 3. It is seen that, the DC electrical conductivity increases with increase in both the temperature and 1 mole % LiSO4 doping concentration, which is in good agreement with the reported literature [20]. The increase of conductivity with the increase in temperature observed for pure TGS and LiSO4-doped TGS crystals was due to the temperature dependence of the proton transport.

803797.fig.003
Figure 3: D.C. electrical conductivity for pure and LiSO4-doped TGS crystals.
3.3. Dielectric Studies

Crystal samples for dielectric studies were prepared in the similar way of DC electrical measurement. The dielectric constant of the pure TGS and LiSO4-doped TGS crystals was calculated as function of temperature at 1 kHz and shown in Figure 4. Curie point, Tc, (para-ferroelectric phase) was observed at 49°C for pure and LiSO4-doped TGS crystals. The dielectric constant is small at low temperature, but it increases with temperature and rises sharply up to the Tc.

803797.fig.004
Figure 4: Graph for dielectric constant versus temperature of pure TGS and LiSO4-doped TGS crystals.

Above Tc, the dielectric decreases suddenly and obeys Curie-Weiss law. The rapid increase of dielectric constant may be due to space charge polarization of thermally generated carriers. The Curie temperature of pure TGS and LiSO4-doped TGS remains the same. The increase in dielectric constant for LiSO4-doped TGS crystals may be due to incorporation of impurities into the TGS lattice [21]. The temperature dependence dielectric loss of pure TGS and LiSO4-doped TGS crystals is shown in Figure 5.

803797.fig.005
Figure 5: Graph for dielectric loss versus temperature of pure TGS and LiSO4-doped TGS crystals.

The dielectric loss for the LiSO4-doped TGS is higher than that of pure TGS crystal. The value of dielectric loss (tan ) at room temperature is low that the grown crystals are of high quality.

3.4. Vicker’s Microhardness Studies

The hardness of a material is related to its bond strength and crystallographic orientation. The important property of any device material is its mechanical strength, represented by its hardness. Vicker’s microhardness indentations were made on the (001) face of the pure TGS and LiSO4-doped TGS crystals at room temperature with the load ranging from 10 g to 100 g. The indentation time was kept as 6 sec for all the loads. Vicker’s microhardness number, , was calculated using the following equation: where P is the applied load in kg, d is the diagonal length of indentation impression in millimeter, and 1.8544 is a constant of a geometrical factor for the diamond pyramid. From Figure 6, it is seen that the hardness value of LiSO4-doped TGS crystal is higher than the hardness of the pure TGS crystal. Maximum hardness number is found at 50 g. LiSO4-doped TGS crystal is found to be much harder than pure TGS crystal thus confirmed the greater crystalline perfection.

803797.fig.006
Figure 6: Variation of load versus Vicker’s microhardness number ().
3.5. Thermal Analysis

TG-DTA of pure TGS and LiSO4-doped TGS crystals was carried out between 35°C and 600°C at a heating rate 10°C/min in nitrogen atmosphere. The endothermic peak in DTA at 246.4°C for pure TGS and 238.0°C for LiSO4-doped TGS are shown in Figure 7. TG curve shows that there is a sharp weight loss at 232°C for pure TGS and 228°C for LiSO4-doped TGS crystals. The change in decomposition temperature is owing to incorporation of Li+1 ion impurities into the lattice.

fig7
Figure 7: (a) TG/DTA for pure TGS. (b) TG/DTA for 1 mole % LiSO4-doped TGS.
3.6. Etching Studies

The etching studies reveal the structural perfection and growth features of grown single crystals. The (001) face of pure TGS and LiSO4-doped TGS crystals were subjected to etching with water at room temperature. The surface of pure TGS and LiSO4-doped TGS crystals were completely immersed for 10 s in the water etchant for etching. The features were analyzed using a Magnus MLX microscope shown in Figure 8. It was observed that the identical pyramidal-shaped etch pits were observed more in pure TGS than LiSO4-doped TGS. The etch pits density is 6.1 × 103 cm−2 for pure TGS and 1.25 × 103 cm−2 for LiSO4-doped TGS crystal. Less number of etch pits shows that the quality of the LiSO4-doped TGS crystals is better than pure TGS crystal.

fig8
Figure 8: (a) Pure TGS (b) 1 mole % LiSO4-doped TGS crystal.

4. Conclusions

The good quality of pure TGS and LiSO4-doped TGS crystals was grown by natural evaporation method. The UV-visible spectra showed that the transmittance of LiSO4-doped TGS is more than pure TGS crystal. DC conductivity increases with temperature and also with LiSO4 concentration, which proves the incorporation of the dopant into the lattice sites. The Curie temperature, Tc, of pure and LiSO4-doped TGS crystals remain the same. The Vicker’s microhardness studies show that the (001) plane of LiSO4-doped TGS crystal has higher hardness than the pure TGS crystal. Melting point is reduced due to LiSO4 as observed by TG-DTA analyses. Etch pits decrease with dopant concentration, which proves that the quality of doped crystal is getting better than pure crystal by the minimization of dislocations and defects. The high optical transparency, thermal stability, low dielectric constant, and microhardness properties exhibit the optical quality and suitability of the as-grown TGS crystal doped with LiSO4 for SHG and optoelectronic device applications.

References

  1. R. B. Lal and A. K. Batra, “Growth and properties of triglycine sulfate (TGS) crystals: review,” Ferroelectrics, vol. 142, pp. 51–82, 1993. View at Google Scholar
  2. H. P. Beerman, “Improvement in the pyroelectric infrared radiation detector,” vol. 2, pp. 123–128. View at Google Scholar · View at Scopus
  3. S. Kielich, “Nonlinear optical and electro-optical properties of dielectrics and ferroelectrics,” Ferroelectrics, vol. 4, no. 4, pp. 257–282, 1973. View at Google Scholar
  4. G. Dolino, J. Lajzerowicz, and M. Vallade, “Second-harmonic light scattering by domains in ferroelectric triglycine sulfate,” Physical Review B, vol. 2, no. 6, pp. 2194–2200, 1970. View at Publisher · View at Google Scholar · View at Scopus
  5. M. E. Lines and A. M. Glass, Principles and Application of Ferroelectric and Related Materials, Oxford University Press, Oxford, UK, 1977.
  6. Landolt-Bornstein, Crystal and Solid State Physics, New series, Group III, vol. 3, Springer, New York, NY, USA, 1969.
  7. S. Hoshino, Y. Okaya, and R. Pepinsky, “Crystal structure of the ferroelectric phase of (glycine)3·H2SO4,” Physical Review, vol. 115, no. 2, pp. 323–330, 1959. View at Publisher · View at Google Scholar · View at Scopus
  8. V. N. Shut, I. F. Kashevich, and S. R. Syrtsov, “Ferroelectric properties of triglycine sulfate crystals with a nonuniform distribution of chromium impurities,” Physics of the Solid State, vol. 50, no. 1, pp. 118–121, 2008. View at Publisher · View at Google Scholar · View at Scopus
  9. P. Selvarajan, A. T. H. Sivadhas, T. H. Freeda, and C. K. Mahadevan, “Growth, XRD and dielectric properties of triglycine sulfo-phosphate (TGSP) crystals added with magnesium sulfate,” Physica B, vol. 403, pp. 4205–4208, 2008. View at Google Scholar
  10. X. Sun, M. Wang, Q. W. Pan, W. Shi, and C. S. Fang, “Study on the growth and properties of guanidine doped triglycine sulfate crystal,” Crystal Research and Technology, vol. 34, no. 10, pp. 1251–1254, 1999. View at Publisher · View at Google Scholar · View at Scopus
  11. K. Biedrzycki, “Energy distribution of electron emission from L-α alanine doped TGS single crystals,” Solid State Communications, vol. 118, no. 3, pp. 141–144, 2001. View at Publisher · View at Google Scholar · View at Scopus
  12. G. Su, Y. He, H. Yao, Z. Shi, and Q. Wu, “New pyroelectric crystal L-lysine-doped TGS (LLTGS),” Journal of Crystal Growth, vol. 209, no. 1, pp. 220–222, 2000. View at Publisher · View at Google Scholar · View at Scopus
  13. S. Aravazhi, R. Jayavel, and C. Subramanian, “Growth and characterization of benzophenone and urea doped triglycine sulphate crystals,” Ferroelectrics, vol. 200, no. 1–4, pp. 279–286, 1997. View at Google Scholar
  14. N. T. Shanthi, P. Selvarajan, and C. K. Mahadevan, “Studies on Triglycine Sulfate (TGS) crystals doped with sodium bromide NaBr grown by solution method,” Indian Journal of Science and Technology, vol. 3, pp. 49–52, 2009. View at Google Scholar
  15. F. Khanum and J. Podder, “Structural and optical properties of triglycine sulfate single crystals doped with potassium bromide,” Journal of Crystallization Process and Technology, vol. 1, no. 2, pp. 26–31, 2011. View at Google Scholar
  16. M. A. Gaffar and A. Abu El-Fadl, “Effect of doping and irradiation on optical parameters of triglycine sulphate single crystals,” Crystal Research and Technology, vol. 34, no. 7, pp. 915–923, 1999. View at Publisher · View at Google Scholar · View at Scopus
  17. F. Khanum and J. Podder, “Crystallization and characterization of triglycine sulfate (TGS) crystal doped with NiSO4,” Journal of Crystallization Process and Technology, vol. 1, no. 3, pp. 15–22, 2011. View at Google Scholar
  18. C. S. Fang, Y. Xi, A. S. Bhalla, and L. E. Cross, “Growth and properties of manganese and lithium doped TGS crystals,” Materials Research Bulletin, vol. 18, no. 9, pp. 1095–1100, 1983. View at Google Scholar · View at Scopus
  19. K. Balasubramanian and P. Selvarajan, “Studies on growth, XRD and various properties of triglycine sulfate (TGS) crystals doped with copper sulphate,” Recent Research in Science and Technology, vol. 2, pp. 6–13, 2010. View at Google Scholar
  20. C. K. Mahadevan, “DC electrical conductivity measurements on KCl and KNO3-added MgSO4·7H2O single crystals,” Physica B, vol. 403, no. 1, pp. 57–60, 2008. View at Publisher · View at Google Scholar · View at Scopus
  21. M. Banan, R. B. Lal, and A. Batra, “Modified triglycine sulphate (TGS) single crystals for pyroelectric infrared detector applications,” Journal of Materials Science, vol. 27, no. 9, pp. 2291–2297, 1992. View at Publisher · View at Google Scholar · View at Scopus