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Characterization of luminescence of samarium with phosphate compounds
Materials Today: Proceedings xxx (xxxx) xxx
Contents lists available at ScienceDirect
Materials Today: Proceedings journal homepage: www.elsevier.com/locate/matpr
Characterization of luminescence of samarium with phosphate compounds Sridhar Goud Arelli a,⇑, Anil Kumar a, S.J. Dhoble b a b
Department of Physics, OPJS University, Churu, Rajasthan, India Department of Physics, RTM Nagpur University, Nagpur 44001, Maharashtra, India
a r t i c l e
i n f o
Article history: Received 1 August 2019 Received in revised form 18 January 2020 Accepted 25 January 2020 Available online xxxx Keywords: Fluorescent Barium-phosphate-phosphorus Solid-state reaction Cathode-ray tube and fluorescence Lighting
a b s t r a c t Over the years, luminescence has been profoundly used for lighting purposes in lamp industries. The massive production of luminescence in Lamp industries is highly enhanced by use of LED phosphorus. Cathode rays, such as televisions, PC monitors, test equipment as well as fluorescent lighting profoundly make use of LED phosphorus for both white and colored luminescence. Luminescence in lamp industries can also be achieved through exposing Samarium, a rare earth element, to a phosphate compound. Usually, this is achieved by synthesizing Samarium (Sm3+) doped Ca6BaP4017 phosphorus through a conventional solid-state reaction method. The reaction leads to an emission of a spectrum consisting of three different peaks characterized by different intensity levels. Ó 2020 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of the scientific committee of the First International Conference on Recent Advances in Materials and Manufacturing 2019.
1. Introduction According to [1], LED phosphorus is an elemental product in a lamp industry for luminescence production. Over the years, phosphorus has been widely used for lighting purposes and has in recent years been employed for lighting purposes in cathode ray tubes and fluorescent lighting [2]. The Samarium is a element with atomic number 62 and configuration [xe]4f66s2, it was discovered by Paul-Emile in 1879, it was one of the abundant rare earth element. It has a Rhombohedra structure. Fresh Samarium has silver luster. The Samarium in the third oxidation state (Sm3+) is a potential activator for lighting industry, because it offers high luminescence efficiency due to narrow emission bands. The phosphors of Phosphate are a good luminescence materials because of thermal stabilities and physical properties at low temperature synthesis LED phosphorus can be used in producing multiple colors in a light generation such as white and blue lights. Moreover, luminescence in lamp industries can also be produced through synthesizing Samarium ions (Sm3+) doped phosphate ions (Ca6BaP4017) phosphorus through a conventional solid- state
⇑ Corresponding author.
reaction method. Exposing the phosphors formed from such a reaction to a UV or Blue lights can significantly result in multiple colors of light emission characterized by different intensities [3,4]. 2. Experimental materials i. ii. iii. iv. v.
Phosphors for optical and thermal measurements Fluorescent lamp Phosphors Samarium (Rare-Earth element) Barium Phosphate phosphorus (phosphate ions) UV and blue lights
3. Experimental methods and procedure Initiate a solid state reaction between Samarium ions with phosphate compound phosphorus through the following procedure. vi. vii. viii. ix.
To a clean glass container add five grams of solid Samarium Add five grams of solid Barium phosphate phosphorus Record the observations Expose the emitted light to a UV or blue light and record the observation
E-mail address: [email protected] (S.G. Arelli). https://doi.org/10.1016/j.matpr.2020.01.470 2214-7853/Ó 2020 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of the scientific committee of the First International Conference on Recent Advances in Materials and Manufacturing 2019.
Please cite this article as: S. G. Arelli, Anil Kumar and S. J. Dhoble, Characterization of luminescence of samarium with phosphate compounds, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.01.470
2
S.G. Arelli et al. / Materials Today: Proceedings xxx (xxxx) xxx
4. Results and discussion Samarium ions (Sm3+-) doped Ca6BaP4017 phosphorus exposed into a convectional solid-state reaction method results to the production of Ca6BaP4017: Sm3+ as shown below [5,6]
Sm3þ - + Ca6 BaP4 017 phosphorus ! Ca6 BaP4 017 : Sm3þ phosphors The Ca6BaP4017: Sm3+ phosphors are responsible for the emission of the light observed during the reaction shown above. When the Ca6BaP4017: Sm3+ phosphors resulting from the reaction are brought close to a Ultra-Violet and blue light, a spectrum of emission peaks of different intensities are observed [7]. When the phosphors are further exposed to Ultra-Violet based WLEDs, a redorange light is emitted. In their solid state form, Samarium ions react with Ca6BaP4017 phosphorus to form Ca6BaP4017: Sm3+ phosphors [8] which are responsible for luminescence produced during the reaction. Ca6BaP4017: Sm3+ phosphors emit different colors of light when brought near a UV light. According to [9], the same phenomenon is observed when Ca6BaP4017: Sm3+ phosphors a blue light as shown in the characteristic figures below the lowest excited 4f55d(Eg) level above the another excited 4f6 level (5D0) level, the 4f5-5d1 excited electronic configuration association with the 5Dj levels of the 4f ground configuration The clear radiation line at 683 nm assign to zero-phonon line of (4f55d)-(4f6) transition. Another emission lines of major wavelength nm, 697 nm and 693 nm, have a vibronic origin according to [11] and correspond to the ZPL minus the frequency of modes 355, 250 and 210 cm1, respectively. For the configuration 5D0-7FJ (J = 6.0). The emission lines at 793,761,748,730, 720 and 708 nm are assigned and the 365, 452, 467, 485 and 494 nm lines on the excitation spectrum to the 4f6-4f5 transitions, respectively. 5. Characteristic figure During a solid-state chemical reaction of Sm3+ doped Ca6BaP4017, luminescence intensity increases with an increase in
Fig. 1. Various doping concentrations of Sm2+.
Fig. 2. Luminescence spectra of Sm2+.
doping concentrations. However, at higher concentrations, the doping concentration is reduced for the Samarium ions to avoid concentration quenching effect [10]. When the Ca6BaP4017: Sm3+ phosphors (which are formed from the reaction between Sm3+ and Ca6BaP4017 phosphorus in a solid-state reaction method), are exposed to UV and blue lights, a spectrum, with multiple light peaks are formed (Figs. 1 and 2). From the above Fig. 2. It was observed that (a) The excited spectrum observed at 682 nm (black curve) at 6 k temperature (b) Excited spectra observed at 485 nm (Red curve) at 100 k temperature (c) Excited spectra observed at 485 nm 9blue curve) at 6 k temperature respectively.
Fig. 3. Luminescence spectra of Sm3+.
Please cite this article as: S. G. Arelli, Anil Kumar and S. J. Dhoble, Characterization of luminescence of samarium with phosphate compounds, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.01.470
3
S.G. Arelli et al. / Materials Today: Proceedings xxx (xxxx) xxx Table 1 The most convenient conditions for steady - state measurements of Sm2+ and Sm3+. kexc [nm] 485 442 399
ION 2+
Sm Sm3+ Sm3+:
Emission line (s) [nm)
Transition (s)
kem [nm]
Excitation line (s)
683, 699, 730, 761, 793: 598, 607, 614 560: 596, 606 644, 653
5
682 614 606
365, 452, 467, 485, 494 442, 466, 479, 490 363, 378, 399, 442
From the above Fig. 3. It was observed that (a) Excitation spectra observed at kem. = 596 nm (red curve) at 300 k temperature (b) Excitation spectra observed at 606 nm (blue curve) at 300 k temperature (c) Emission spectrum measured for kexc. = 399 nm (black curve) at 300 k temperature The most efficient Sm3+ luminescence is usually measured for Kexc. = 399–401 nm [12]. The luminescence spectra of crystal (Fig. 3) have seemed similar to those presented by [13]. Besides the emission of Sm3+: 560 nm (4G5/2-6H5/2), 599 and 606 nm (4G5/2-6H7/2) and 644 and 653 nm (4G5/2-6H9/2) and Sm2+ at 683 nm (4f55d-4f6) were observed as well (Table 1). The most convenient conditions for steady-state measurements of Sm2+ and Sm3+ ions; excitation and emission lines and electronic transitions.
6. Conclusion As discussed above, LED phosphorus is a fundamental requirement in a lamp industry for luminescence production. Phosphorus has been widely used in multiple applications such as in cathode ray tubes and fluorescence lighting. Lamp industries can also produce luminescence by Synthesizing Samarium ions (Sm3+) doped phosphate ions (CaBaP4017) phosphorus through a convectional solid state reaction method. Such a reaction leads to the formation of Ca6BaP4017: Sm3+ phosphors which are responsible for luminescence production. When a UV and a blue light are brought near the Ca6BaP4017: Sm3+ phosphors, a spectrum of three different peaks is
7
D0- FJ (J = 0, 1, 2, 3, 4) G5/2 -6H7/2 G5/2-6H5/2 4 G5/2-6H7/2 4 G5/2-6H9/2 4 4
observed. However, the intensity between the peaks vary from each other.
References [1] C.H. Chiang, Y.C. Fang, H.Y. Lin, S.Y. Chu, Photo luminescence properties and thermal stability of samarium-doped barium phosphate phosphors, Ceram. Int. 43 (5) (2016) 4353–4356. [2] H. Li, X. Gong, Y. Chen, J. Huang, Y. Lin, Z. Luo, Y. Huang, Luminescence properties of phosphate phosphors Ba3Gd1 x (PO4) 3: xSm3+, J. Rare Earths 36 (5) (2018) 456–460. [3] W. Ying, T. Abudouwufu, T. Yusufu, H.E. Jiuyang, A. Sidike, Photoluminescence properties and energy transfer of a single-phased white-emitting NaAlSiO4: Ce3+, Sm3+ phosphor, J. Rare Earths 35 (9) (2017) 850–856. [4] V.R. Prasad, S. Damodaraiah, S. Babu, Y.C. Ratnakaram, Structural, optical and luminescence properties of Sm3+ and Eu3+ doped calcium borophosphate phosphors for reddish-orange and red emitting light applications, J. Lumin. 187 (2017) 360–367. [5] M. Shoaib, G. Rooh, R. Rajaramakrishna, N. Chanthima, H.J. Kim, S. Tuscharoen, J. Kaewkhao, Physical and luminescence properties of samarium doped oxide and oxyfluoride phosphate glasses, Mater. Chem. Phys. (2019). [6] Y.K. Sharma, S.S.L. Surana, R.K. Singh, Spectroscopic investigations and luminescence spectra of Sm3+ doped soda lime silicate glasses, J. Rare Earths 27 (5) (2009) 773–780. [7] X. Haiping, L. Qiongfei, J. Zhang, Q. Zhang, 2 lm mid-infrared optical spectra of Tm3+-doped germanium gallate glasses, J. Rare Earths 27 (5) (2009) 781–785. [8] Z. Xia, D. Chen, Synthesis and luminescence properties of BaMoO4: Sm3+ phosphors, J. Am. Ceram. Soc. 93 (5) (2010) 1397–1401. [9] X. Lin, X. Xia, X. Fan, Synthesis and luminescence properties of a novel red SrMoO4: Sm3+, R+ phosphor, Solid State Sci. 13 (3) (2011) 579–583. [10] Y.C. Li, Y.H. Chang, Y.F. Lin, Y.S. Chang, Y.J. Lin, Synthesis and luminescent properties of Ln3+ (Eu3+, Sm3+, Dy3+)-doped lanthanum aluminium germanate LaAlGe2O7 phosphors, J. Alloy. Compd. 439 (1–2) (2009) 367–375. [11] M.M. Elcombe, A.W. Pryor, Lattice dynamics of calcium fluorite, J. Phys. C 3 (1970) 492. [12] S. Bodył, M. Czaja, Z. Mazurak, Optical properties of Pr3+, Sm3+ and Er3+ ions in apatite and phosphate glasses, Phys. Proceedia 2 (2) (2009) 515–525. [13] S. Aierken, I. Kusachi, N. Yamashita, Natural fluorite emitting yellow fluorescence under UV light, Phys. Chem. Miner. 30 (2003) 478–485.
Please cite this article as: S. G. Arelli, Anil Kumar and S. J. Dhoble, Characterization of luminescence of samarium with phosphate compounds, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.01.470
Contents lists available at ScienceDirect
Materials Today: Proceedings journal homepage: www.elsevier.com/locate/matpr
Characterization of luminescence of samarium with phosphate compounds Sridhar Goud Arelli a,⇑, Anil Kumar a, S.J. Dhoble b a b
Department of Physics, OPJS University, Churu, Rajasthan, India Department of Physics, RTM Nagpur University, Nagpur 44001, Maharashtra, India
a r t i c l e
i n f o
Article history: Received 1 August 2019 Received in revised form 18 January 2020 Accepted 25 January 2020 Available online xxxx Keywords: Fluorescent Barium-phosphate-phosphorus Solid-state reaction Cathode-ray tube and fluorescence Lighting
a b s t r a c t Over the years, luminescence has been profoundly used for lighting purposes in lamp industries. The massive production of luminescence in Lamp industries is highly enhanced by use of LED phosphorus. Cathode rays, such as televisions, PC monitors, test equipment as well as fluorescent lighting profoundly make use of LED phosphorus for both white and colored luminescence. Luminescence in lamp industries can also be achieved through exposing Samarium, a rare earth element, to a phosphate compound. Usually, this is achieved by synthesizing Samarium (Sm3+) doped Ca6BaP4017 phosphorus through a conventional solid-state reaction method. The reaction leads to an emission of a spectrum consisting of three different peaks characterized by different intensity levels. Ó 2020 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of the scientific committee of the First International Conference on Recent Advances in Materials and Manufacturing 2019.
1. Introduction According to [1], LED phosphorus is an elemental product in a lamp industry for luminescence production. Over the years, phosphorus has been widely used for lighting purposes and has in recent years been employed for lighting purposes in cathode ray tubes and fluorescent lighting [2]. The Samarium is a element with atomic number 62 and configuration [xe]4f66s2, it was discovered by Paul-Emile in 1879, it was one of the abundant rare earth element. It has a Rhombohedra structure. Fresh Samarium has silver luster. The Samarium in the third oxidation state (Sm3+) is a potential activator for lighting industry, because it offers high luminescence efficiency due to narrow emission bands. The phosphors of Phosphate are a good luminescence materials because of thermal stabilities and physical properties at low temperature synthesis LED phosphorus can be used in producing multiple colors in a light generation such as white and blue lights. Moreover, luminescence in lamp industries can also be produced through synthesizing Samarium ions (Sm3+) doped phosphate ions (Ca6BaP4017) phosphorus through a conventional solid- state
⇑ Corresponding author.
reaction method. Exposing the phosphors formed from such a reaction to a UV or Blue lights can significantly result in multiple colors of light emission characterized by different intensities [3,4]. 2. Experimental materials i. ii. iii. iv. v.
Phosphors for optical and thermal measurements Fluorescent lamp Phosphors Samarium (Rare-Earth element) Barium Phosphate phosphorus (phosphate ions) UV and blue lights
3. Experimental methods and procedure Initiate a solid state reaction between Samarium ions with phosphate compound phosphorus through the following procedure. vi. vii. viii. ix.
To a clean glass container add five grams of solid Samarium Add five grams of solid Barium phosphate phosphorus Record the observations Expose the emitted light to a UV or blue light and record the observation
E-mail address: [email protected] (S.G. Arelli). https://doi.org/10.1016/j.matpr.2020.01.470 2214-7853/Ó 2020 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of the scientific committee of the First International Conference on Recent Advances in Materials and Manufacturing 2019.
Please cite this article as: S. G. Arelli, Anil Kumar and S. J. Dhoble, Characterization of luminescence of samarium with phosphate compounds, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.01.470
2
S.G. Arelli et al. / Materials Today: Proceedings xxx (xxxx) xxx
4. Results and discussion Samarium ions (Sm3+-) doped Ca6BaP4017 phosphorus exposed into a convectional solid-state reaction method results to the production of Ca6BaP4017: Sm3+ as shown below [5,6]
Sm3þ - + Ca6 BaP4 017 phosphorus ! Ca6 BaP4 017 : Sm3þ phosphors The Ca6BaP4017: Sm3+ phosphors are responsible for the emission of the light observed during the reaction shown above. When the Ca6BaP4017: Sm3+ phosphors resulting from the reaction are brought close to a Ultra-Violet and blue light, a spectrum of emission peaks of different intensities are observed [7]. When the phosphors are further exposed to Ultra-Violet based WLEDs, a redorange light is emitted. In their solid state form, Samarium ions react with Ca6BaP4017 phosphorus to form Ca6BaP4017: Sm3+ phosphors [8] which are responsible for luminescence produced during the reaction. Ca6BaP4017: Sm3+ phosphors emit different colors of light when brought near a UV light. According to [9], the same phenomenon is observed when Ca6BaP4017: Sm3+ phosphors a blue light as shown in the characteristic figures below the lowest excited 4f55d(Eg) level above the another excited 4f6 level (5D0) level, the 4f5-5d1 excited electronic configuration association with the 5Dj levels of the 4f ground configuration The clear radiation line at 683 nm assign to zero-phonon line of (4f55d)-(4f6) transition. Another emission lines of major wavelength nm, 697 nm and 693 nm, have a vibronic origin according to [11] and correspond to the ZPL minus the frequency of modes 355, 250 and 210 cm1, respectively. For the configuration 5D0-7FJ (J = 6.0). The emission lines at 793,761,748,730, 720 and 708 nm are assigned and the 365, 452, 467, 485 and 494 nm lines on the excitation spectrum to the 4f6-4f5 transitions, respectively. 5. Characteristic figure During a solid-state chemical reaction of Sm3+ doped Ca6BaP4017, luminescence intensity increases with an increase in
Fig. 1. Various doping concentrations of Sm2+.
Fig. 2. Luminescence spectra of Sm2+.
doping concentrations. However, at higher concentrations, the doping concentration is reduced for the Samarium ions to avoid concentration quenching effect [10]. When the Ca6BaP4017: Sm3+ phosphors (which are formed from the reaction between Sm3+ and Ca6BaP4017 phosphorus in a solid-state reaction method), are exposed to UV and blue lights, a spectrum, with multiple light peaks are formed (Figs. 1 and 2). From the above Fig. 2. It was observed that (a) The excited spectrum observed at 682 nm (black curve) at 6 k temperature (b) Excited spectra observed at 485 nm (Red curve) at 100 k temperature (c) Excited spectra observed at 485 nm 9blue curve) at 6 k temperature respectively.
Fig. 3. Luminescence spectra of Sm3+.
Please cite this article as: S. G. Arelli, Anil Kumar and S. J. Dhoble, Characterization of luminescence of samarium with phosphate compounds, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.01.470
3
S.G. Arelli et al. / Materials Today: Proceedings xxx (xxxx) xxx Table 1 The most convenient conditions for steady - state measurements of Sm2+ and Sm3+. kexc [nm] 485 442 399
ION 2+
Sm Sm3+ Sm3+:
Emission line (s) [nm)
Transition (s)
kem [nm]
Excitation line (s)
683, 699, 730, 761, 793: 598, 607, 614 560: 596, 606 644, 653
5
682 614 606
365, 452, 467, 485, 494 442, 466, 479, 490 363, 378, 399, 442
From the above Fig. 3. It was observed that (a) Excitation spectra observed at kem. = 596 nm (red curve) at 300 k temperature (b) Excitation spectra observed at 606 nm (blue curve) at 300 k temperature (c) Emission spectrum measured for kexc. = 399 nm (black curve) at 300 k temperature The most efficient Sm3+ luminescence is usually measured for Kexc. = 399–401 nm [12]. The luminescence spectra of crystal (Fig. 3) have seemed similar to those presented by [13]. Besides the emission of Sm3+: 560 nm (4G5/2-6H5/2), 599 and 606 nm (4G5/2-6H7/2) and 644 and 653 nm (4G5/2-6H9/2) and Sm2+ at 683 nm (4f55d-4f6) were observed as well (Table 1). The most convenient conditions for steady-state measurements of Sm2+ and Sm3+ ions; excitation and emission lines and electronic transitions.
6. Conclusion As discussed above, LED phosphorus is a fundamental requirement in a lamp industry for luminescence production. Phosphorus has been widely used in multiple applications such as in cathode ray tubes and fluorescence lighting. Lamp industries can also produce luminescence by Synthesizing Samarium ions (Sm3+) doped phosphate ions (CaBaP4017) phosphorus through a convectional solid state reaction method. Such a reaction leads to the formation of Ca6BaP4017: Sm3+ phosphors which are responsible for luminescence production. When a UV and a blue light are brought near the Ca6BaP4017: Sm3+ phosphors, a spectrum of three different peaks is
7
D0- FJ (J = 0, 1, 2, 3, 4) G5/2 -6H7/2 G5/2-6H5/2 4 G5/2-6H7/2 4 G5/2-6H9/2 4 4
observed. However, the intensity between the peaks vary from each other.
References [1] C.H. Chiang, Y.C. Fang, H.Y. Lin, S.Y. Chu, Photo luminescence properties and thermal stability of samarium-doped barium phosphate phosphors, Ceram. Int. 43 (5) (2016) 4353–4356. [2] H. Li, X. Gong, Y. Chen, J. Huang, Y. Lin, Z. Luo, Y. Huang, Luminescence properties of phosphate phosphors Ba3Gd1 x (PO4) 3: xSm3+, J. Rare Earths 36 (5) (2018) 456–460. [3] W. Ying, T. Abudouwufu, T. Yusufu, H.E. Jiuyang, A. Sidike, Photoluminescence properties and energy transfer of a single-phased white-emitting NaAlSiO4: Ce3+, Sm3+ phosphor, J. Rare Earths 35 (9) (2017) 850–856. [4] V.R. Prasad, S. Damodaraiah, S. Babu, Y.C. Ratnakaram, Structural, optical and luminescence properties of Sm3+ and Eu3+ doped calcium borophosphate phosphors for reddish-orange and red emitting light applications, J. Lumin. 187 (2017) 360–367. [5] M. Shoaib, G. Rooh, R. Rajaramakrishna, N. Chanthima, H.J. Kim, S. Tuscharoen, J. Kaewkhao, Physical and luminescence properties of samarium doped oxide and oxyfluoride phosphate glasses, Mater. Chem. Phys. (2019). [6] Y.K. Sharma, S.S.L. Surana, R.K. Singh, Spectroscopic investigations and luminescence spectra of Sm3+ doped soda lime silicate glasses, J. Rare Earths 27 (5) (2009) 773–780. [7] X. Haiping, L. Qiongfei, J. Zhang, Q. Zhang, 2 lm mid-infrared optical spectra of Tm3+-doped germanium gallate glasses, J. Rare Earths 27 (5) (2009) 781–785. [8] Z. Xia, D. Chen, Synthesis and luminescence properties of BaMoO4: Sm3+ phosphors, J. Am. Ceram. Soc. 93 (5) (2010) 1397–1401. [9] X. Lin, X. Xia, X. Fan, Synthesis and luminescence properties of a novel red SrMoO4: Sm3+, R+ phosphor, Solid State Sci. 13 (3) (2011) 579–583. [10] Y.C. Li, Y.H. Chang, Y.F. Lin, Y.S. Chang, Y.J. Lin, Synthesis and luminescent properties of Ln3+ (Eu3+, Sm3+, Dy3+)-doped lanthanum aluminium germanate LaAlGe2O7 phosphors, J. Alloy. Compd. 439 (1–2) (2009) 367–375. [11] M.M. Elcombe, A.W. Pryor, Lattice dynamics of calcium fluorite, J. Phys. C 3 (1970) 492. [12] S. Bodył, M. Czaja, Z. Mazurak, Optical properties of Pr3+, Sm3+ and Er3+ ions in apatite and phosphate glasses, Phys. Proceedia 2 (2) (2009) 515–525. [13] S. Aierken, I. Kusachi, N. Yamashita, Natural fluorite emitting yellow fluorescence under UV light, Phys. Chem. Miner. 30 (2003) 478–485.
Please cite this article as: S. G. Arelli, Anil Kumar and S. J. Dhoble, Characterization of luminescence of samarium with phosphate compounds, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.01.470