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Investigation on effect of LiCl doping on optical properties of L-arginine acetate single crystal
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ScienceDirect Materials Today: Proceedings 4 (2017) 9491–9495
www.materialstoday.com/proceedings
ICEMS 2016
Investigation on effect of LiCl doping on optical properties of Larginine acetate single crystal Gajanan G. Muleya, *, Prakash S. Ambhoreb, Anil B. Gambhirec a
Department of Physics, Sant Gadge Baba Amravati University, Amravati-444 602 (MS) India b SMD High school, Hingoli-431 513 (MS) India c Department of Chemistry, Shri Anand College, Pathardi, Ahmednagar-414 102 (MS) India
Abstract In the present study, L-arginine acetate (LAA) crystals with various level of LiCl doping were grown by low temperature solution growth method at a constant temperature. The effect of lithium chloride (LC) doping on the linear optical and second harmonic generation (SHG) properties of LAA crystal has been studied. The X-ray diffraction study has been performed to confirm the crystal structure of grown crystals. The enhancement in the optical transparency in doped crystals has been attested by ultraviolet-visible-infrared spectroscopic study. The photoluminescence studies have also been presented. The Kurtz - Perry test confirmed the increase in SHG efficiency of LAA crystal after addition of LC. © 2017 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of International Conference on Recent Trends in Engineering and Material Sciences (ICEMS-2016). Keywords: crystal growth; L-arginine acetate; second harmonic generation; x-ray diffraction
1. Introduction The organic, inorganic and semiorganic nonlinear optical crystals with outstanding properties seek large demand for frontier industrial applications [1-2]. Amino acids based crystals draw more interest of researchers owing to the chiral carbon atom and non-centrosymmetric molecular orientations which make them potential candidates for nonlinear optical applications. From the family of amino acid crystals the L-arginine acetate (LAA) crystal with
* Corresponding author. Tel.: +91-721-2662279 ext-269; fax: +91-721-2662135. E-mail address: [email protected], [email protected] 2214-7853 © 2017 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of International Conference on Recent Trends in Engineering and Material Sciences (ICEMS2016).
9492
Gajanan G. Muley, Prakash S. Ambhore, Anil B. Gambhire / Materials Today: Proceedings 4 (2017) 9491–9495
appealing optical and physical properties may serve as vital material for designing optoelectronics, telecommunication, photonics, optical parametric oscillators and electro-optic modulation device applications [3-5]. In recently reports many researchers have evaluated the impact of impurities (organic and inorganic) on the characteristic properties of LAA crystal. The influence of NaCl, KCl, glycine and urea on different properties of LAA crystal has been explored [6]. The influence of bivalent metallic additives Cu2+ and Mg2+ resulted to significant impact on photoconductivity and hardness of LAA crystals [7]. The literature evidences that metallic impurities play significant role in tuning the intrinsic properties of LAA crystal which are vital with perspective of engineering device manufacturing applications. In the present investigation, influence of different doping level of lithium chloride (LC) on structural, optical, SHG efficiency and photoluminescence properties of LAA crystal has been exclusively studied. 2. Experimental The LAA crystal material was synthesized by dissolving equimolar quantity of AR grade L-arginine and acetic acid in doubly distilled water. In order to dope LC in LAA crystal the supersaturated solution of LAA material was added by 2 and 4 mol% of LC in separate beakers. The pure and LC doped LAA materials were repetitively recrystallized to eliminate the impurities and achieve highly pure materials. The supersaturated solution of pure and LC doped LAA crystals was prepared and kept for slow solution evaporation in a constant temperature bath. The well grown single crystals were harvested and shown in Fig. 1.
Fig. 1. Photographs of (a) Pure LAA and (b) LAA2LC crystals.
3. Results and discussion 3.1. Powder X-ray diffraction (PXRD) analysis The PXRD pattern of pure and LC doped LAA crystals has been recorded as shown in Fig.2. The PXRD patterns of grown crystals have been analyzed using the Powder-X software and the evaluated cell parameters are discussed in table. 1. The analysis reveals that the grown crystals have been crystallized with monoclinic crystal symmetry and the doping of LC causes a shift in peak position of LAA crystal indicating the successful incorporation of LC in LAA crystal. The calculated cell parameters of LAA crystal are in good agreement with literature [4]. Table 1. XRD data. Crystal
Cell parameters (Å)
Volume (Å3)
Structure
LAA
a=9.258 b=5.197 c=13.307
583.055
Monoclinic
LAA2LC
a=9.277 b=5.188 c=13.291
582.591
Monoclinic
LAA4LC
a=9.251 b=5.186 c=13.237
578.343
Monoclinic
Intensity (au)
Gajanan G. Muley, Prakash S. Ambhore, Anil B. Gambhire / Materials Today: Proceedings 4 (2017) 9491–9495
9493
LAA4LC LAA2LC LAA 10
20
30
40
50
60
2θ (Degree)
70
Fig. 2. PXRD pattern of pure and doped LAA crystal.
3.2. UV-Visible spectral analysis
Absorbance (au)
The transmittance involves the transition of electron to different energy states which evolves due to absorption of incident energy by optically active chromophores associated with the crystal. In present analysis the transmittance of grown crystals has been studied by recording the absorbance spectrum in the range of 200 to 1000 nm as shown in Fig. 3. The observation of spectrum discloses the transparent nature of grown crystals in entire visible region. It is noteworthy that the absorbance of 2 mol% LC doped LAA crystal is found significantly lower than pure LAA crystal. The absorbance spectrum also infers that the selective quantity of dopant plays key role in improving the optical properties of host material. The low absorbance, high transparency and lower cut-off wavelength of LC doped LAA crystal substantiates its prime utility in SHG and UV-tunable laser device applications [8]. LAA LAA2LC LAA4LC
3 2 1 0 200
400
600
800
1000
Wavelength (nm) Fig. 3. Absorbance spectra.
3.3. Kurtz-Perry test The SHG efficiency of pure and LC doped LAA crystals has been determined by following the method developed by Kurtz and Perry [9]. The crystal samples of pure and LC doped LAA crystal were grounded to microgranules of uniform size and tightly packed in a circular quartz cavity. The prepared samples were placed in a sample holder and illuminated by a Gaussian filtered beam of Nd:YAG laser (1064 nm, 10 Hz, 6 ns, 250 mW). The
Gajanan G. Muley, Prakash S. Ambhore, Anil B. Gambhire / Materials Today: Proceedings 4 (2017) 9491–9495
9494
green optical output offered by each sample was collected through the optical fiber which confirmed the prominent conversion of laser frequency to 532 nm. The recorded enhancement in output intensity of SHG signal is shown in Fig. 4 (a). The SHG efficiency of 2 and 4 mol% LC doped LAA crystal is 1.14 and 1.27 times greater than LAA material respectively. The enhanced delocalization of π-electron over donor-acceptor bonding network is the principle phenomenon resulting to high nonlinear response [10].
LAA LAA2LC LAA4LC
Intensity (au)
4 3 2 1 0
528 531 534
537 540
Wavelength (nm)
8
PL Intensity (au)
5
6
LAA LAA2C LAA4C
414 nm 417 nm
4 2 0
422 nm
400
450
500
550
Wavelength (nm)
600
Fig. 4. (a) SHG output intensity and (b) Photoluminescence spectra.
3.4. Photoluminescence studies The photoluminescence study is a promising tool to understand the intrinsic impurities associated with compounds through color centered emissions. The materials exhibiting color centered emissions have high demand in biomedical and medical applications [11]. The photoluminescence (PL) emission spectra of pure and LC doped LAA crystal has been examined in visible region of interest. The grown samples were photo excited with the wavelength of 347 nm and the emission spectrum of each sample was recorded in visible region at 420 nm (Fig. 4 (b)). The analysis reveals that the color centered emission of LAA crystal is higher at 422 nm corresponding to energy of 2.92 eV. The doping of LC facilitated significant change in emission intensity and marginal shift in peak emission wavelength of LAA crystal. The emission intensity enhances while the peak emission wavelength of LAA crystal shifts to lower value with reducing doping level of LC. The color centered emission of 2 and 4 mol% LC doped LAA crystal is at 414 nm (3 eV) and 417 nm (2.97 eV) respectively. All the grown crystals have indigo colored emission with LAA2LC crystal having maximum intensity. 4. Conclusions Optically transparent pure and LC (2 and 4 mol %) doped LAA crystals have been grown by slow evaporation solution technique. The PXRD analysis revealed the monoclinic structural symmetry of pure and LC doped LAA crystal. The incorporation of LC in LAA crystal favored slight change in cell parameters. The UV-visible studies confirmed the large enhancement in optical transparency of LAA crystal after addition of 2 mol% of LC vital for UV-tunable device applications. The Kurtz analysis established the enhancement in SHG efficiency of LC doped LAA crystals and the enhanced SHG efficiencies of 2 and 4 mol% LC doped LAA crystal are 1.14 and 1.27 times
Gajanan G. Muley, Prakash S. Ambhore, Anil B. Gambhire / Materials Today: Proceedings 4 (2017) 9491–9495
9495
greater than LAA crystal material. The grown crystals show fluorescent nature with color centered emission in indigo region. Acknowledgements This work was supported by a grant from Science and Engineering Research Board (SERB), New Delhi under EEOES scheme (SB/EMEQ-328/2013). References [1] M. Anis, G.G. Muley, G. Rabbani, M.D. Shirsat, S.S. Hussaini, Mater. Technol.: Advc. Perform. Mater. 30 (2015) 129-133 [2] M. Anis, G.G. Muley, M.D. Shirsat, S.S. Hussaini, Mater. Res. Innovat. 19 (2015) 338-344 [3] Tanusri Pal, Tanusree Kar, Mater. Chem. Phys. 91 (2005) 343-347 [4] M. Meena, C.K. Mahadevan, Mater. Lett. 62 (2008) 3742-3744. [5] M. Meena, C.K. Mahadevan, Arch. Appl. Sci. Res. 2 (2010) 185-199. [6] M. Gulam Mohamed, M. Vimalan, J.G.M. Jesudurai, J. Madhavan, P. Sagayaraj, Cryst. Res. Technol. 42 (2007) 948-954 [7] N. Kanagathara, G. Anbalagan, N.G. Renganathan, Int. J. Chem. Res. 1 (2011) 11-15 [8] Mohd Anis, R.N. Shaikh, M.D. Shirsat, S.S. Hussaini, Opt. Laser Technol. 60 (2014) 124-129 [9] S.K. Kurtz, T.T. Perry, J. Appl. Phys. 39 (1968) 3798-3813 [10] Mohd Anis, S.S. Hussaini, A. Hakeem, M.D. Shirsat, G.G. Muley, Optik 127 (2016) 2137-2142 [11] Mohd Anis, Muley G.G., Shirsat M.D., Hussaini S.S., Cryst. Res. Technol., 50 (2015) 372-378.
ScienceDirect Materials Today: Proceedings 4 (2017) 9491–9495
www.materialstoday.com/proceedings
ICEMS 2016
Investigation on effect of LiCl doping on optical properties of Larginine acetate single crystal Gajanan G. Muleya, *, Prakash S. Ambhoreb, Anil B. Gambhirec a
Department of Physics, Sant Gadge Baba Amravati University, Amravati-444 602 (MS) India b SMD High school, Hingoli-431 513 (MS) India c Department of Chemistry, Shri Anand College, Pathardi, Ahmednagar-414 102 (MS) India
Abstract In the present study, L-arginine acetate (LAA) crystals with various level of LiCl doping were grown by low temperature solution growth method at a constant temperature. The effect of lithium chloride (LC) doping on the linear optical and second harmonic generation (SHG) properties of LAA crystal has been studied. The X-ray diffraction study has been performed to confirm the crystal structure of grown crystals. The enhancement in the optical transparency in doped crystals has been attested by ultraviolet-visible-infrared spectroscopic study. The photoluminescence studies have also been presented. The Kurtz - Perry test confirmed the increase in SHG efficiency of LAA crystal after addition of LC. © 2017 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of International Conference on Recent Trends in Engineering and Material Sciences (ICEMS-2016). Keywords: crystal growth; L-arginine acetate; second harmonic generation; x-ray diffraction
1. Introduction The organic, inorganic and semiorganic nonlinear optical crystals with outstanding properties seek large demand for frontier industrial applications [1-2]. Amino acids based crystals draw more interest of researchers owing to the chiral carbon atom and non-centrosymmetric molecular orientations which make them potential candidates for nonlinear optical applications. From the family of amino acid crystals the L-arginine acetate (LAA) crystal with
* Corresponding author. Tel.: +91-721-2662279 ext-269; fax: +91-721-2662135. E-mail address: [email protected], [email protected] 2214-7853 © 2017 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of International Conference on Recent Trends in Engineering and Material Sciences (ICEMS2016).
9492
Gajanan G. Muley, Prakash S. Ambhore, Anil B. Gambhire / Materials Today: Proceedings 4 (2017) 9491–9495
appealing optical and physical properties may serve as vital material for designing optoelectronics, telecommunication, photonics, optical parametric oscillators and electro-optic modulation device applications [3-5]. In recently reports many researchers have evaluated the impact of impurities (organic and inorganic) on the characteristic properties of LAA crystal. The influence of NaCl, KCl, glycine and urea on different properties of LAA crystal has been explored [6]. The influence of bivalent metallic additives Cu2+ and Mg2+ resulted to significant impact on photoconductivity and hardness of LAA crystals [7]. The literature evidences that metallic impurities play significant role in tuning the intrinsic properties of LAA crystal which are vital with perspective of engineering device manufacturing applications. In the present investigation, influence of different doping level of lithium chloride (LC) on structural, optical, SHG efficiency and photoluminescence properties of LAA crystal has been exclusively studied. 2. Experimental The LAA crystal material was synthesized by dissolving equimolar quantity of AR grade L-arginine and acetic acid in doubly distilled water. In order to dope LC in LAA crystal the supersaturated solution of LAA material was added by 2 and 4 mol% of LC in separate beakers. The pure and LC doped LAA materials were repetitively recrystallized to eliminate the impurities and achieve highly pure materials. The supersaturated solution of pure and LC doped LAA crystals was prepared and kept for slow solution evaporation in a constant temperature bath. The well grown single crystals were harvested and shown in Fig. 1.
Fig. 1. Photographs of (a) Pure LAA and (b) LAA2LC crystals.
3. Results and discussion 3.1. Powder X-ray diffraction (PXRD) analysis The PXRD pattern of pure and LC doped LAA crystals has been recorded as shown in Fig.2. The PXRD patterns of grown crystals have been analyzed using the Powder-X software and the evaluated cell parameters are discussed in table. 1. The analysis reveals that the grown crystals have been crystallized with monoclinic crystal symmetry and the doping of LC causes a shift in peak position of LAA crystal indicating the successful incorporation of LC in LAA crystal. The calculated cell parameters of LAA crystal are in good agreement with literature [4]. Table 1. XRD data. Crystal
Cell parameters (Å)
Volume (Å3)
Structure
LAA
a=9.258 b=5.197 c=13.307
583.055
Monoclinic
LAA2LC
a=9.277 b=5.188 c=13.291
582.591
Monoclinic
LAA4LC
a=9.251 b=5.186 c=13.237
578.343
Monoclinic
Intensity (au)
Gajanan G. Muley, Prakash S. Ambhore, Anil B. Gambhire / Materials Today: Proceedings 4 (2017) 9491–9495
9493
LAA4LC LAA2LC LAA 10
20
30
40
50
60
2θ (Degree)
70
Fig. 2. PXRD pattern of pure and doped LAA crystal.
3.2. UV-Visible spectral analysis
Absorbance (au)
The transmittance involves the transition of electron to different energy states which evolves due to absorption of incident energy by optically active chromophores associated with the crystal. In present analysis the transmittance of grown crystals has been studied by recording the absorbance spectrum in the range of 200 to 1000 nm as shown in Fig. 3. The observation of spectrum discloses the transparent nature of grown crystals in entire visible region. It is noteworthy that the absorbance of 2 mol% LC doped LAA crystal is found significantly lower than pure LAA crystal. The absorbance spectrum also infers that the selective quantity of dopant plays key role in improving the optical properties of host material. The low absorbance, high transparency and lower cut-off wavelength of LC doped LAA crystal substantiates its prime utility in SHG and UV-tunable laser device applications [8]. LAA LAA2LC LAA4LC
3 2 1 0 200
400
600
800
1000
Wavelength (nm) Fig. 3. Absorbance spectra.
3.3. Kurtz-Perry test The SHG efficiency of pure and LC doped LAA crystals has been determined by following the method developed by Kurtz and Perry [9]. The crystal samples of pure and LC doped LAA crystal were grounded to microgranules of uniform size and tightly packed in a circular quartz cavity. The prepared samples were placed in a sample holder and illuminated by a Gaussian filtered beam of Nd:YAG laser (1064 nm, 10 Hz, 6 ns, 250 mW). The
Gajanan G. Muley, Prakash S. Ambhore, Anil B. Gambhire / Materials Today: Proceedings 4 (2017) 9491–9495
9494
green optical output offered by each sample was collected through the optical fiber which confirmed the prominent conversion of laser frequency to 532 nm. The recorded enhancement in output intensity of SHG signal is shown in Fig. 4 (a). The SHG efficiency of 2 and 4 mol% LC doped LAA crystal is 1.14 and 1.27 times greater than LAA material respectively. The enhanced delocalization of π-electron over donor-acceptor bonding network is the principle phenomenon resulting to high nonlinear response [10].
LAA LAA2LC LAA4LC
Intensity (au)
4 3 2 1 0
528 531 534
537 540
Wavelength (nm)
8
PL Intensity (au)
5
6
LAA LAA2C LAA4C
414 nm 417 nm
4 2 0
422 nm
400
450
500
550
Wavelength (nm)
600
Fig. 4. (a) SHG output intensity and (b) Photoluminescence spectra.
3.4. Photoluminescence studies The photoluminescence study is a promising tool to understand the intrinsic impurities associated with compounds through color centered emissions. The materials exhibiting color centered emissions have high demand in biomedical and medical applications [11]. The photoluminescence (PL) emission spectra of pure and LC doped LAA crystal has been examined in visible region of interest. The grown samples were photo excited with the wavelength of 347 nm and the emission spectrum of each sample was recorded in visible region at 420 nm (Fig. 4 (b)). The analysis reveals that the color centered emission of LAA crystal is higher at 422 nm corresponding to energy of 2.92 eV. The doping of LC facilitated significant change in emission intensity and marginal shift in peak emission wavelength of LAA crystal. The emission intensity enhances while the peak emission wavelength of LAA crystal shifts to lower value with reducing doping level of LC. The color centered emission of 2 and 4 mol% LC doped LAA crystal is at 414 nm (3 eV) and 417 nm (2.97 eV) respectively. All the grown crystals have indigo colored emission with LAA2LC crystal having maximum intensity. 4. Conclusions Optically transparent pure and LC (2 and 4 mol %) doped LAA crystals have been grown by slow evaporation solution technique. The PXRD analysis revealed the monoclinic structural symmetry of pure and LC doped LAA crystal. The incorporation of LC in LAA crystal favored slight change in cell parameters. The UV-visible studies confirmed the large enhancement in optical transparency of LAA crystal after addition of 2 mol% of LC vital for UV-tunable device applications. The Kurtz analysis established the enhancement in SHG efficiency of LC doped LAA crystals and the enhanced SHG efficiencies of 2 and 4 mol% LC doped LAA crystal are 1.14 and 1.27 times
Gajanan G. Muley, Prakash S. Ambhore, Anil B. Gambhire / Materials Today: Proceedings 4 (2017) 9491–9495
9495
greater than LAA crystal material. The grown crystals show fluorescent nature with color centered emission in indigo region. Acknowledgements This work was supported by a grant from Science and Engineering Research Board (SERB), New Delhi under EEOES scheme (SB/EMEQ-328/2013). References [1] M. Anis, G.G. Muley, G. Rabbani, M.D. Shirsat, S.S. Hussaini, Mater. Technol.: Advc. Perform. Mater. 30 (2015) 129-133 [2] M. Anis, G.G. Muley, M.D. Shirsat, S.S. Hussaini, Mater. Res. Innovat. 19 (2015) 338-344 [3] Tanusri Pal, Tanusree Kar, Mater. Chem. Phys. 91 (2005) 343-347 [4] M. Meena, C.K. Mahadevan, Mater. Lett. 62 (2008) 3742-3744. [5] M. Meena, C.K. Mahadevan, Arch. Appl. Sci. Res. 2 (2010) 185-199. [6] M. Gulam Mohamed, M. Vimalan, J.G.M. Jesudurai, J. Madhavan, P. Sagayaraj, Cryst. Res. Technol. 42 (2007) 948-954 [7] N. Kanagathara, G. Anbalagan, N.G. Renganathan, Int. J. Chem. Res. 1 (2011) 11-15 [8] Mohd Anis, R.N. Shaikh, M.D. Shirsat, S.S. Hussaini, Opt. Laser Technol. 60 (2014) 124-129 [9] S.K. Kurtz, T.T. Perry, J. Appl. Phys. 39 (1968) 3798-3813 [10] Mohd Anis, S.S. Hussaini, A. Hakeem, M.D. Shirsat, G.G. Muley, Optik 127 (2016) 2137-2142 [11] Mohd Anis, Muley G.G., Shirsat M.D., Hussaini S.S., Cryst. Res. Technol., 50 (2015) 372-378.