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Energy Transfer Kinetics and Luminescence in Nd3+/Yb3+Co-Doped Lead-Borate Glasses at 800 nm Excitation

Received: 24 April 2024    Accepted: 16 May 2024    Published: 30 May 2024
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Abstract

Nd3+ and Nd3+/Yb3+ ion-doped lead-borate glasses were created. For the thermal studies of sample such as glass transition temperature, crystallization temperature and, melting temperature Tm, differential scanning calorimetry (DSC) is done. The X-ray diffraction is used to justify the glassy nature of the samples. UV-VIS-IR of the prepared samples is carried for the studies of absorption bands available in Nd3+ and Nd3+/Yb3+ ion-doped lead-borate glasses. For the studies of fluorescence spectra and energy transfer mechanism the samples were excited at 800nm and spectra is recorded. The Nd3+ glasses exhibited strong NIR emission at 1mol% concentration at 903, 1068, and 1348 nm upon pumping at 800 nm. These transitions were labelled as 4F3/24I9/2, 4F3/24I11/2, and 4F3/24I13/2. Interpretation is given to the effects of multiphonon, cross-relaxation, and OH- group on Nd3+ emission that causes photoluminescence quenching above 1.0mol% Nd3+. Through the co-doping of Nd3+ ion (1mol%) and Yb3+ ion (1mol%) concentrations, the sensitising impact of Nd3+ emission on Yb3+ luminescence is examined. The significant spectrum of Yb3+ absorption and Nd3+ emission, photoluminescence characteristics, has supported the likelihood of energy-transfer (ET) between these ions. The findings show that the Neodymium ion (4F3/2)→ytterbium ion (4F5/2) energy-transfer process is of a non-radiative type controlled by phonon-assisted electric dipole-dipole interaction.

Published in Journal of Photonic Materials and Technology (Volume 10, Issue 1)
DOI 10.11648/j.jmpt.20241001.11
Page(s) 1-6
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This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.

Copyright

Copyright © The Author(s), 2024. Published by Science Publishing Group

Keywords

Lead-Borate Glasses, Multiphonon Relaxation, Cross Relaxation

1. Introduction
Research on the optical characteristics of solid-state materials containing single and dual combinations of di- and trivalent lanthalide ions has made it possible to gain a thorough understanding of the energy transfer process. Novel pumping strategies were developed in tandem through the evolution of laser diodes (LDs) in solid-state lasers to provide improved lasing process at lower threshold frequency, hence fostering novel opto-electronic features. Neodymium (Nd3+) and ytterbium (Yb3+) are two opposing ions among the rare earths. Since the development of Nd3+-based optical lasers, the Nd3+ ion with 4F3 configuration which has a 7F0 ground and a 5D0 lower excited state has been the most studied active centers in relation to lanthanides doped lasers, regardless of the host's crystalline or amorphous nature .
Neodymium (Nd3+) lasers have a four-level system that may operate in a continuous or pulsed mode. For instance, Nd3+: YAG crystals exhibit a strong and focused emission at/around 1μm (1.064μm), whereas glasses containing Nd3+ exhibit emission between 1.054 and 1.056μm . Additionally, it displays near-ultra voilet laser line at 514.5 nm and near-NIR laser transitions at 0.92 μm and 1.34 μm . Furthermore, Nd3+ ions may efficiently absorb solar energy in the 582 nm absorption band at (4I9/24G5/2+ 2G7/2). Due of undesirable effects similar to multi-phonon with cross-relaxation, Nd3+ is more susceptible to luminescence quenching when there are more exciting levels with greater absorption probability. But the Yb3+ ion, which has a special pumping level scheme made up of two manifolds 2F5/2 for the excited state and 2F7/2 for the ground state is also a possible laser active ion. In addition to NIR tunability and mode-locking operation, non-radiative losses such as OH− group effects, cross-relaxation, and multi-phonon relaxations have significantly less of an impact on the Yb3+ ion. Longer lived excited states also have higher energy storage efficiency . For up-and down-conversion experiments, Neodymium ions and ytterbium ions are commonly co-doped as sensitizers to various near-infrared emitting activators such as praseodymium, erbium, holmium, and thulium ions. Neodymium and ytterbium ions were supposed to co-dope in the NABFBS host glass based on this situation. The integration of Neodymium ions and ytterbium ionsinto a host matrix with low phonon strength can open up new potential for the growth of ultra short pulsed lasers with superior efficiency and better lasing properties for advanced applications. Effective solar energy incorporation for tunable lasers and solar concentrators is ensured by the non-radiative energy transfer from Nd3+ to Yb3+, which emits light at 2F5/2 and 2F7/2 brightness levels, fitting well with the silicon solar cell energy-gap (9182cm−1). Pr3+-doped fibre amplifiers may also be pumped using the Neodymium/ytterbium ionscoupled system (Nd/Yb: YAG laser) at or around 1330 nm (1G43H5) . The Forster-Dexter theory states that the host matrix doped with lanthanide ion(s) that show small emission intensities because of deprived excited energy absorption or a reduce in luminescence intensity because of absorption quenching from non-radiative relaxations is meant to dope in addition to another lanthanide ion (called a donor or sensitizer) to the original doped ion (called an activator or acceptor). Luminance characteristics are increased when the excitation energy is first absorbed by the sensitizer/donor and then transferred to the activator/acceptor through a non-radiative energytransfer mechanism or by releasing radiation that are then reabsorbed by the acceptor centers . Energy transfer between optically active ions improves the properties of photoluminescence, such as absorbance, luminescence intensity, life-times, and quantum efficiencies.
The host glass substrate powered by luminescent active (lanthanide metal) ions for laser and display operations should be a crucial component to enhance optical and luminescence-related features.
In order to address this, we suggested creating borosilicate glass based on oxy fluoride that contains bismuth oxide, aluminum, and sodium oxide as modifiers and intermediates in the glass matrix. A special and unusual benefit exists for host glasses that combine components of fluoride and oxide over those that just contain fluoride or oxide. While the low-phonon energy fluorides lower non-radiative decay losses and boost the rare earths' quantum efficiency, the oxides offer mechanical strength, chemical resistance, and thermal stability.
Lead borate glasses exhibit increased optical non-linearity as a result of Pb2+ ions in glass matrices with a high polarizability . Such substances are appealing for use in triggered Raman amplifiers, waveguides, and other optical switches.
Here, we primarily focus on examining the energy-transfer mechanism that occur while co-doping neodymium ions and ytterbium ionsin a lead borate glass matrix. Based on optical and luminescence patterns, the Nd3+ ion concentration was first optimized in this technique to 1mol%. Afterwards, Yb3+ was co-doped in various concentrations with the glass that had an optimized concentration of 1mol% Nd3+.
2. Experimental Methods (Glass Sample Preparation)
The glass system of following batch composition
1.60B2O3-30PbO-10Na2O (reference glass)-PBN
2. 59%B2O3-30%PbO-10%Na2O-1.0%Nd2O3}-PBNN
3. 58%B2O3-30%PbO-10%Na2O-1.0%Nd2O3-1.0%Yb2O3-PBNNY
were prepared by employing the classical melt-quench method. Reagent-grade chemicals B2O3, PbO, Na2O, Yb2O3 and Nd2O3of Otto Chemie Pvt Ltd, were used. Separately weighed in 12g batch each and mixed thoroughly and powdered finely with agate mortar and pestle in open atmosphere. The precursor chemicals were ground until a homogeneous mix was obtained. The finely ground mixture, each batch weighing 12g is separately taken in an alumina crucible covered with the lid and heated in an electric muffle furnace for about 80 minutes at 910°C. To guarantee homogeneity, the mixture is physically agitated until a liquid without bubbles forms. Subsequently, the melts were poured into stainless steel pellet moulds to be cooled. In order to eliminate internal thermal stress, glass samples that had been quenched and measured about 0.8 cm in diameter and 0.3 cm in thickness were annealed for two hours at 350°C, the glass transition temperature. Ultimately, these glass samples were collected for further analysis.
3. Characterization
3.1. X-Ray Diffraction Spectra
X-Ray Diffractogram for the undoped and doped specimens were carried on a Rigaku Smart Lab 9kW x-ray diffractometer, plot obtained (Figure 1) is quit flat else a wide hump near 28°, implies the the samples are glassy in nature.
Figure 1. X-Ray diffraction plots of PBN, PBNN and PBNNY glasses.
3.2. Differential Scanning Calorimetry
The Differential Scanning Calorimetry (DSC) measurements were simultaneously carried out by TA instruments, USA, Q10) at a heating rate of 10°C/min, the DSC plots were carried in r the temperature range 100°C - 550°Cas shown in figure 2. For the prepared samples glass transition temperature Tg is observed near of 330°C, crystallization temperature Tc near 370°C and, Melting temperature Tm were found around 450°C.
Figure 2. DSC plots of PBN, PBNN and PBNNY glasses.
4. Optical Analysis
4.1. Absorption Spectra
The absorption spectra of neodymium ions doped alone and in combination with ytterbium ions doped, PBNN and PBNNY glasses are shown in Figure 3(a) and Figure 3(b) correspondingly. A sequence of bands ranging from the lower lying 4I9/2 state to 4D3/2,11/2 (362 nm), 2P1/2 (430 nm), 2G9/2, 4G11/2 (470 nm), 4K13/2 (510 nm), 4G9/2 (524 nm), 4G5/2, 2G7/2(582 nm), 4H11/2(624 nm), 4F9/2 (680 nm), 4F7/2, 4S3/2 (746 nm), 4F5/2, 4H9/2 (803 nm), 4F3/2 (875 nm), and 4I15/2 (1720 nm) were visible in the Nd3+ absorption spectrum. Nd3+/Yb3+ co-doped glass's absorption spectra revealed a distinct band at 980 nm that was linked to the Yb3+: 2F7/22F5/2 transition in addition to the Nd3+ absorption bands.
Figure 3. (a) Absorption spectra of PBNN glass. (b) Absorption spectra of PBNNY glass.
4.2. Fluorescence Spectra and Energy Transfer Mechanism
Figure 4 illustrate how, when pumped to 800 nm, the normal state Nd3+ ions absorb a photon to the 4F5/2 and 2H9/2 levels. They then relax to the 4F3/2 level by a non-emission relaxation mechanism, and luminescence starts at this 4F3/2 level. The 2F7/2 to 2F5/2 emission of Yb3+ in Nd3+/Yb3+ PBNN and PBNNY glasses is caused by two effective Nd3+→Yb3+energy transfer processes, which may be divided into two main forms: (4F3/24I9/2, 2F7/22F5/2) and (4F3/24I11/2, 2F7/22F5/2). Ultimately, the emission at 1020 nm is caused by the 2F5/22F7/2 transition.
Figure 4. Fluorescence mechanismfor Nd3+ and Yb3+. at 800 nm excitation in PBNN and PBNNY glasses.
Figure 5. Luminescence Spectra ofPBNN and PBNNY glassesat 800 nm excitation.
Luminescence spectra of lead-borate glasses doped with 1mol% Nd3+ and co-doped with 1mol% Nd3+1mol% Yb3+ under 800nm pumping are displayed in Figure 5. Three primary emission spectra at 885nm, 1056nm, and 1325nm are caused by the Nd3+ ion's 4F3/2 to4I9/2, 4F3/2to 4I11/2, and 4F3/2 to 4I13/2 transitions. Under a laser stimulation at 800 nm, the typical near-infrared emission 2F7/2 to 2F5/2 transition of Yb3+ with peaks at 980 and 1020 nm is detected in the Neodymium/Ytterbium ions co-doped lead-borate glasses.
5. Conclusions
Conventional melt-quench method is used to create the Neodymium/Ytterbium ions co-doped lead-borate glasses. It is possible to acquire the spectroscopic characteristics of the samples pumped by 800 nm LD. This work describes the mechanism of energy transfer from Neodymium to Ytterbium ions and obtains a large energy transfer microparameter and high transfer efficiency between Neodymium and Ytterbiumions. According to the current research, glass co-doped at 1020 nm with 1.0 mol% Nd2O3 and 1.0 mol% Yb2O3 should be a great choice for Yb3+ fibre laser systems that use Nd3+ as a multiple pump guide source.
Abbreviations

ET

Energy-Transfer

UV-VIS-IR

Ultraviolet-Visible-Infrared

Acknowledgments
Authors acknowledging Research India limited for their support for the absorption and luminescence characterization.
Conflicts of Interest
The authors declare no conflicts of interest.
References
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    Bairagi, R., Ansari, G. F., Lone, M. Y., Sharma, S. K. (2024). Energy Transfer Kinetics and Luminescence in Nd3+/Yb3+Co-Doped Lead-Borate Glasses at 800 nm Excitation. Journal of Photonic Materials and Technology, 10(1), 1-6. https://doi.org/10.11648/j.jmpt.20241001.11

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    Bairagi, R.; Ansari, G. F.; Lone, M. Y.; Sharma, S. K. Energy Transfer Kinetics and Luminescence in Nd3+/Yb3+Co-Doped Lead-Borate Glasses at 800 nm Excitation. J. Photonic Mater. Technol. 2024, 10(1), 1-6. doi: 10.11648/j.jmpt.20241001.11

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    AMA Style

    Bairagi R, Ansari GF, Lone MY, Sharma SK. Energy Transfer Kinetics and Luminescence in Nd3+/Yb3+Co-Doped Lead-Borate Glasses at 800 nm Excitation. J Photonic Mater Technol. 2024;10(1):1-6. doi: 10.11648/j.jmpt.20241001.11

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  • @article{10.11648/j.jmpt.20241001.11,
      author = {Renuka Bairagi and Ghizal Firdous Ansari and Mohd Yaseen Lone and Sandeep Kumar Sharma},
      title = {Energy Transfer Kinetics and Luminescence in Nd3+/Yb3+Co-Doped Lead-Borate Glasses at 800 nm Excitation
    },
      journal = {Journal of Photonic Materials and Technology},
      volume = {10},
      number = {1},
      pages = {1-6},
      doi = {10.11648/j.jmpt.20241001.11},
      url = {https://doi.org/10.11648/j.jmpt.20241001.11},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.jmpt.20241001.11},
      abstract = {Nd3+ and Nd3+/Yb3+ ion-doped lead-borate glasses were created. For the thermal studies of sample such as glass transition temperature, crystallization temperature and, melting temperature Tm, differential scanning calorimetry (DSC) is done. The X-ray diffraction is used to justify the glassy nature of the samples. UV-VIS-IR of the prepared samples is carried for the studies of absorption bands available in Nd3+ and Nd3+/Yb3+ ion-doped lead-borate glasses. For the studies of fluorescence spectra and energy transfer mechanism the samples were excited at 800nm and spectra is recorded. The Nd3+ glasses exhibited strong NIR emission at 1mol% concentration at 903, 1068, and 1348 nm upon pumping at 800 nm. These transitions were labelled as 4F3/2→4I9/2, 4F3/2→4I11/2, and 4F3/2→4I13/2. Interpretation is given to the effects of multiphonon, cross-relaxation, and OH- group on Nd3+ emission that causes photoluminescence quenching above 1.0mol% Nd3+. Through the co-doping of Nd3+ ion (1mol%) and Yb3+ ion (1mol%) concentrations, the sensitising impact of Nd3+ emission on Yb3+ luminescence is examined. The significant spectrum of Yb3+ absorption and Nd3+ emission, photoluminescence characteristics, has supported the likelihood of energy-transfer (ET) between these ions. The findings show that the Neodymium ion (4F3/2)→ytterbium ion (4F5/2) energy-transfer process is of a non-radiative type controlled by phonon-assisted electric dipole-dipole interaction.
    },
     year = {2024}
    }
    

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  • TY  - JOUR
    T1  - Energy Transfer Kinetics and Luminescence in Nd3+/Yb3+Co-Doped Lead-Borate Glasses at 800 nm Excitation
    
    AU  - Renuka Bairagi
    AU  - Ghizal Firdous Ansari
    AU  - Mohd Yaseen Lone
    AU  - Sandeep Kumar Sharma
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    PY  - 2024
    N1  - https://doi.org/10.11648/j.jmpt.20241001.11
    DO  - 10.11648/j.jmpt.20241001.11
    T2  - Journal of Photonic Materials and Technology
    JF  - Journal of Photonic Materials and Technology
    JO  - Journal of Photonic Materials and Technology
    SP  - 1
    EP  - 6
    PB  - Science Publishing Group
    SN  - 2469-8431
    UR  - https://doi.org/10.11648/j.jmpt.20241001.11
    AB  - Nd3+ and Nd3+/Yb3+ ion-doped lead-borate glasses were created. For the thermal studies of sample such as glass transition temperature, crystallization temperature and, melting temperature Tm, differential scanning calorimetry (DSC) is done. The X-ray diffraction is used to justify the glassy nature of the samples. UV-VIS-IR of the prepared samples is carried for the studies of absorption bands available in Nd3+ and Nd3+/Yb3+ ion-doped lead-borate glasses. For the studies of fluorescence spectra and energy transfer mechanism the samples were excited at 800nm and spectra is recorded. The Nd3+ glasses exhibited strong NIR emission at 1mol% concentration at 903, 1068, and 1348 nm upon pumping at 800 nm. These transitions were labelled as 4F3/2→4I9/2, 4F3/2→4I11/2, and 4F3/2→4I13/2. Interpretation is given to the effects of multiphonon, cross-relaxation, and OH- group on Nd3+ emission that causes photoluminescence quenching above 1.0mol% Nd3+. Through the co-doping of Nd3+ ion (1mol%) and Yb3+ ion (1mol%) concentrations, the sensitising impact of Nd3+ emission on Yb3+ luminescence is examined. The significant spectrum of Yb3+ absorption and Nd3+ emission, photoluminescence characteristics, has supported the likelihood of energy-transfer (ET) between these ions. The findings show that the Neodymium ion (4F3/2)→ytterbium ion (4F5/2) energy-transfer process is of a non-radiative type controlled by phonon-assisted electric dipole-dipole interaction.
    
    VL  - 10
    IS  - 1
    ER  - 

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Author Information
  • Department of Physics, Madhyanchal Professional University, Bhopal, India

  • Department of Physics, Madhyanchal Professional University, Bhopal, India

  • Department of Physics, Madhyanchal Professional University, Bhopal, India

  • Department of Physics, Govt. Art’s and Commerce College Majhauli, Sidhi, India