Thermal, structural, magnetic and magneto-optical properties of dysprosium-doped phosphate glass

https://doi.org/10.1016/j.jnoncrysol.2019.119545Get rights and content

Highlights

  • The optical homogeneity of the glass shows a reduced content of bubbles striae and a remnant birefringence bellow 10 nm/cm.

  • The high hydrolytic resistance is due to Al2O3 which creates Al(OP)6 species, very resistant to hydrolytic attack.

  • FTIR and Raman spectra show the presence of Dy3+ ions, modifying the features of the specific vibration modes.

  • The magnetic measurements show a paramagnetic character, with an almost two orders of magnitude higher magnetic response.

  • The relative high transmission value of the doped sample at 600 nm results in Verdet constant being about −0.05 min/Oe/cm.

Abstract

The work is dedicated to the investigation of optical, structural, magnetic and magneto-optical properties of an aluminophosphate glass doped with Dy3+ ions, for specific applications as Faraday rotators in the visible spectral domain. The vitreous material belongs to the 16Li2O-8Al2O3-6BaO-60P2O5-10Dy2O3 system. Optical homogeneity measured by a polariscopic method, as well as by polarimetry and interferometry revealed an optical quality glass. Time dependent electrical conductance measurements have shown a high chemical strength of the glass. Optical absorption of the doped glass in the visible domain evidenced the specific absorption lines of dysprosium ions, whereas structural investigations made by FTIR and Raman spectroscopy put in evidence the vitreous network forming role of phosphorous pentoxide. Magnetic and magneto-optical measurements demonstrated paramagnetic features of the doped glass, as well as a Verdet constant of about −0.05 min/Oe/cm at 600 nm wavelength.

Introduction

In the last years, magneto-optical properties of glasses containing heavy ions, transition ions and rare-earth ions have been investigated due to their applications in optics and optoelectronics [[1], [2], [3]]. The influence of Bi+ ions and defects on silicate glass structures in the red and infrared luminescence was studied in dependence on the applied magnetic field and temperature [[4], [5], [6], [7]].

Very recently, magneto-optical materials based on Fe2O3/NiO spinel nanoparticles-doped PbO-Bi2O3-Ga2O3 [8] glass, on heavy metal oxide (PbO-Bi2O3)-containing borate [[9], [10], [11], [12]] or boro-phosphate glasses [13], or with addition of GeO2 [14] have been developed, as an alternative to conventional optical ones based on garnets and rare-earth-doped paramagnetic glasses [[15], [16], [17]]. Transition ions-containing glasses, such as Mn-doped SrO-P2O5 glass [18] or (CoFe2O4) silicate glass [19], have been studied in detail for their magnetic and magneto-optical properties [20,21]. Faraday rotators, such as TeO2–ZnO–Na2O–BaO glass fibers [22], 70TeO2–5×-10P2O5–10ZnO-5PbF2 (× = MgO, Bi2O3) glass [23] or other TeO2-based glass and fibers [[24], [25], [26], [27], [28], [29], [30], [31], [32]], constitute a new class of magneto-optical materials.

Chalcogenide glasses made of GeS2 Ga2S3 Sb2S3 and GeS2Ga2S3In2S3 [33] or GeS2-In2S3-PbI2 [34] systems are attractive as diamagnetic materials [35,36] with a large Verdet constant.

The most promising MO materials are based on rare-earth doped glass. Aluminoborosilicate glasses with high concentration of divalent europium ions showed large Faraday rotation angles in the visible range [37].

A recent study on magneto-optical, compositional, structural, optical and thermal properties of Tb-doped PbO-Bi2O3-B2O3 glass applied in magneto-optical sensing technology was reported [38]. The influence of Tb4+/Tb3+ equilibrium on diamagnetic/paramagnetic characteristics of the investigated glasses providing a positive, and a negative Verdet constant, respectively, was evidenced. This equilibrium is in dependence on glass basicity, melting temperature and Tb dopant amount. Thus, the higher the glass basicity is, the lower the melting temperature is, and hence a pronounced diamagnetic character of the glass is found. Among rare-earth ions, Tb3+ ion exhibits one of the highest magnetic moments and paramagnetic effects, being extensively used as dopant in silicate [39], phosphate [40], boro-germanate [41,42], rare-earth ions in lead-bismutate [43] boro-silico-germanate glasses [42,[44], [45], [46]] for its luminescence and magneto-optical properties. Since the linear birefringence increases with temperature while the magneto-optical effects decrease with temperature, these materials are suitable for application in environments with constant temperature, or if compensation measures for ambient temperature are required [47,48].

In the present paper, a high-level Dy3+doped Li2O-Al2O3-BaO-P2O5 glass was prepared and optical, structural, magnetic and magneto-optical characterization was performed based on the previous experience of the authors related to Dy3+/Tb3+/La3+ aluminophosphate vitreous systems applied as Faraday rotators and connected measurements [49,50]. The novelty of the paper consists in the wet non-conventional preparation method of the starting batch, that allows a higher chemical homogeneity both of the precursors and of the final vitreous material. On the other hand, an innovative phosphate glass composition having a high chemical stability, a reduced crystallization tendency and satisfactory thermal properties together with significant magnetic and magneto-optical properties was investigated.

Section snippets

Material and methods

A high content Dy-doped aluminophosphate glass was prepared by a non-conventional wet method processing of the starting reagents, followed by melting-stirring and annealing of the glass. The benefits of the wet non-conventional technique are presented in a recent work of the authors related to magneto-optical properties of Bi2O3 and PbO-doped aluminophosphate glasses [51], valid also for Dy2O3-doped glass in the present study.

The vitreous material belongs to the 16Li2O-8Al2O3-6BaO-60P2O5-10Dy2O3

Results

The optical homogeneity of the glass measured by polariscopic method evidenced: (a) striae on the lateral direction, birefringence 10.2 nm/cm; b) lack of striae on the measurement direction (birefringence 6.0 nm/cm); and (c) lack of striae on the opposite lateral direction (birefringence 4.0 nm/cm). Optical path difference performed by interferometric method revealed rough results within ±10 nm interval of error, taking into consideration the volume and surface defects distribution.

The density

Discussion

To obtain an appropriate glass sample to be used as a Faraday rotator, the areas without defects of the Dysingle bondV glass sample were selected so as to avoid the undesirable influence on the magneto-optical effect. In the case of the Dysingle bondV glass sample, the birefringence measured in the strains evidenced satisfactory values, of maximum 10 nm/cm on a lateral measurement direction, and <10 nm/cm on the measurement and opposite measurement direction.

The high level of Dy2O3 dopant amount results in an

Conclusions

An aluminophosphate glass doped by Dy3+ ion was prepared and optical, structural, magnetic and magneto-optical characterization was performed. The optical homogeneity of the glass indicated a reduced content of bubbles, striae and a remnant birefringence below 10 nm/cm. The glass has a relatively low thermal expansion coefficient, a high hydrolytic stability, and its viscosity decreases abruptly with temperature certifying the vitreous network forming ability of the investigated composition.

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 was supported by UEFISCDI (Executive Unity for Financing of Higher Education, Research and Innovation), project 186/2012 - Partnership Program, project 7-081/2013-M-ERA.NET Program, project 16N/2019, 18N/2019 and 21N/2019 - Core Program, project PN-III-P1-1.2-PCCDI-2017-0871 contract 47PCCDI/2018 and project PN-III-P1-1.2-PCCDI-2017-0619 contract 42PCCDI/2018, and by the Ministry of Research and Innovation through Program I - Development of the National R & D System, Subprogram 1.2 -

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