1.53 μm luminescent properties and energy transfer processes of Er3+/Yb3+ co-doped bismuth germanate glass laser material
Introduction
The development of Er3+/Yb3+ co-doped bismuth glass at 1.5 μm has been gaining continuous interest because of the extensive applications of such lasers in environmental detection, space communications, infrared countermeasures, and guidance [[1], [2], [3], [4], [5]]. Er3+ ion is an idea candidate for 1.5 μm near-infrared (NIR) laser emission because of the Er3+: 4I13/2 → 4I15/2 transition and the 4I15/2 → 4I11/2 transition can pump by commercialization of 980 nm solid-state laser diode (LD). However, Er3+ ion has low utilization of pump light because of the weak absorption near 980 nm, and will cause up-conversion luminescence [6,7]. Yb3+ ion, a two-energy level system, there is no up-conversion luminescence effect and concentration quenching effect, exhibit not only a large absorption cross-section but also a broad absorption band near 980 nm. The pump efficiency of 980 nm LD can be improved by co-doping Yb3+ ions in Er3+-doped materials as sensitizer [8].
In 2017, K. Linganna et al. reported a longer lifetime of Er3+/Yb3+ co-doped fluorophosphate glasses, studied effect of Yb3+ concentration on Judd-Ofelt parameters and spectroscopic properties, the optimum Er3+/Yb3+ concentration ratio was found to be 3:4. The high concentration of Yb ions improves the energy transfer, which in turn reduces the quenching of Er emission [9]. And in 2019, J. J. Leal et al. reported the effect of TiO2 on the thermal and optical properties of Er3+/Yb3+ co-doped tellurite glasses, results show that the glass transition temperature and thermal stability increases with the addition of TiO2. Meanwhile, by introducing TiO2, the maximum sensor sensitivity is increases by 32% [10]. The choice of host glass plays an important role in realizing good 1.5 μm emission properties. Until now, 1.5 μm band emission of Er3+/Yb3+ co-doped non-oxide, silicate, germanate and tellurite, glasses have been widely reported [[11], [12], [13], [14]]. Non-oxide glasses including fluoride glass and chalcogenide glass have low phonon energy (the maximum phonon energy is about 580 cm−1 and 350 cm−1) [15,16], wide infrared transparent range and good transmittance However, the poor chemical stability, low mechanical properties, and poor thermal stabilities make the fabrication of laser glassed difficult so that limit the development of non-oxide glasses [16,17]. The silicate glass has a relatively mature preparation process and strong structural strength. But the high phonon energy (about 1100 cm−1) and relatively low rare-earth ion solubility make silicate glass has low gain performance [18,19]. Tellurite glass has relatively high rare-earth ion solubility, but Er3+ ion has an obvious up-conversion luminescence phenomenon in tellurite glass. Meanwhile, the poor thermal stabilities of tellurite glass also caused the difficulties for the further processing [[20], [21], [22]]. On the one hand, germanate glass has high refractive index, and good spectral properties in IR band. On the other hand, the melting point and viscosity of germanate glass are relatively high, which is easy to produce bubble streaks, and it is difficult to remove the hydroxyl groups in the glass. Bismuth germanate glass is an ideal host glass matrix, which has the advantages of both bismuth and germanate glass (good chemical stability, good infrared transmittance, lower phonon energy and higher refractive index) [23,24]. Therefore, this work selects bismuth germanate glass as the matrix glass material.
In this work, the thermal and spectral properties of Er3+/Yb3+ co-doped 40Bi2O3-30GeO2-15Ga2O3-15Na2O glass were investigated systematically, the influence of different Er3+/Yb3+ ion doping concentration on 1.53 μm luminous intensity was studied. Finally, the high gain laser glass material which spectral quality factor (χ = Ω4/Ω6) is 2.236, gain bandwidth can reach 189.651 × 10−21 nm cm2 was obtained. The maximum stimulated gain coefficient at 1530 nm was 4.6 cm−1. And the up-conversion luminescence and energy transfer mechanism of Er3+/Yb3+ co-doped glass were studied. The above research results show that the Er3+/Yb3+ co-doped bismuth germanate glass is an ideal gain medium material for 1.53 μm laser.
Section snippets
Experiment
Er3+/Yb3+ co-doped bismuthate glasses with molar composition of 40Bi2O3-30GeO2-15Ga2O3-15Na2O-0.5Er2O3-xYb2O3 (where x = 0.25, 0.5, 0.75, 1.0 and 1.5, named as BGGN1-5) and the Yb3+ single doped glass with 1 mol% named as BGGN0 were prepared by melt-quenching method. Accurately weighted 20 g batch were fully mixed and move into platinum crucible and melted in electronic furnace in a temperature of 1200 °C. Thereafter, the melt was poured into a preheated stainless-steel mold, and then were
Thermal stability and Raman spectrum
Thermal stability is an important property for laser glasses. The thermal stability of host glass is often characterized by three temperature parameters, the glass transition temperature Tg, the crystallization onset temperature Tx, the difference ΔT = Tx - Tg. Generally, the ΔT of the glass sample should be larger than 100 °C to indicate the good glass formation ability or glass thermal stability. Fig. 1 shows the DSC curve of the BGGN4, the Tg and Tx are 432 °C, 553 °C, and ΔT is 121 °C,
Conclusion
Er3+/Yb3+ co-doped 40Bi2O3-30GeO2-15Ga2O3-15Na2O laser glasses were prepared by melt-quenching method, and the thermal stability and spectral characteristics of the glasses were analyzed. The results show that the prepared bismuth germanate glass has good thermal stability (ΔT is 121 °C) and low phonon energy (750 cm−1). According to the J-O theory, the intensity parameters Ω2,4,6 of BGGN4 (Er3+/Yb3+ = 0.5%:1.0%) glass were calculated, and the spectral quality factor (χ = Ω4/Ω6) is 2.236, which
Author statement
Fang Tan has made substantial contributions to the conception or design of the work included the acquisition, analysis, and interpretation of date for the work. Pengfei Xu has drafted the work or revised it critically for important intellectual content. Dechun Zhou has approved the final version to be published. Lili Wang and Qiang Yang have finished the samples testing and data processing. Xiangyang Song and Kexuan Han have completed the samples preparation. The above contents have been
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgements
This work is supported by “Thirteen Five-Year Plan” Science and Technology Project of Education Department (NO. JJKH20200565KJ), Department of Science and Technology of Jilin Province (No. 20200401053GX), Research of Jilin Provincial Science and Technology Agency (NO.20200201023JC).
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