Structural and Electronic Characterization of Molybdenum-Phosphate Glasses by X-Ray Absorption at the Molybdenum K-absorption Edge

Poirier G.1 and Ottoboni F.S1

1 Universidade

Federal de Alfenas - Alfenas MG Brazil

INTRODUCTION

Phosphate glasses belong to a special group of optical glasses of technological interest. Their specic properties include larger thermal expansion coefcient, smaller liquid viscosity and softening temperatures than silicate glasses. Another important feature of these glasses is their ability to incorporate large amounts of transition metal without reduction of glass forming ability. The incorporation of transition metals in phosphate glasses is known to improve several physico-chemical properties like chemical resistance against atmospheric moisture[1] as well as thermal stability against devitrication[2]. Besides that, these modied phosphate glasses were intensively investigated for their electronic and ionic conductivities as well as their specic optical absorption properties in the visible and near infrared[3]. Particularly, tungsten phosphate glasses with high WO3 concentrations were intensively investigated for their optical properties such as upconversion phenomena when doped with Tm3+ [4] or two-photon non linear optical absorption[5]. In addition, a new volumetric photochromic effect was observed in samples with high levels of WO3 incorporation under exposure to visible laser[6]. Since chemical properties of tungsten and molybdenum are very similar in condensed matter, MoO3 based glasses should exhibit such interesting optical properties. These glasses are already known for their high ionic and electronic properties but optical applications are limited by their poor transparency in the visible and near infrared which is commonly attributed to reduced Mo5+ species due to oxygen vacancies in the glass network[7]. However, we suggested in a recent study which was submitted for publication that a suitable control of glass synthesis parameters can considerably improve the transparency in this spectral range. Structural investigations in the binary system NaPO3 MoO3 already explained the strong dependence of Tg with composition to the structural changes in the covalent network with MoO3 addition. Particularly, some compositions form phosphate tetrahedral Q3 units which increase the degree of polymerization[8]. As a result, a remarkably stable glass structure is formed, whose Tg is greatly increased and which resists recrystallization under thermal analysis heating conditions. For higher MoO3 -concentrated samples, the glass transition temperatures decrease again and the glass stability is lower since intense crystallization peaks are observed again by thermal analysis. This thermal behaviour of most concentrated samples was directly correlated with isolated phosphate tetrahedral units connected to Mo as well as clusters of MoO6 identied by Mo-O-Mo bonding. In this work, vitreous samLNLS 2007 Activity Report 1

ples prepared in the binary system NaPO3 MoO3 were characterized by X-Ray absorption spectroscopy (XANES) at the Mo-K absorption edge to investigate both coordination and oxidation number of Mo in these glasses.
EXPERIMENT

Vitreous samples in the binary system (100-x) NaPO3 xMoO3 labeled NMox with x varying from 10 to 50% were prepared by conventional melt-quenching with melting in a platinum crucible at 1000 C for 60 minutes to ensure homogenization and ning and quenching in a brass mold preheated at a temperature around 20 C below Tg. Sample MoKLN of composition: 60MoO3 20K2 O 10Li2 O 10Na2 O was prepared in the same conditions. In a second step, sample NMo30 was prepared by another route for comparison: the batch was kept at 1000 C for 60 minutes and then slowly cooled at 1 C/min to room temperature (sample NMo30-SQ). It was observed that this sample is transparent in the visible whereas the same composition prepared by the classical melt-quenching method (sample NMo30-1000) exhibits a strong absorption in the visible. All XANES spectra were collected in transmission mode, at room temperature, at the LNLS D04B-XAS beam line. X-ray absorption spectra were collected around the Mo (20000 eV) K edge. Each spectrum corresponded to an average over 3 independent scans. The spectra were energy calibrated by simultaneous measurement of the transmission spectrum of Mo foil, where the energy of the rst inection point for the reference sample absorption edge, E0, was dened as 20000 eV.
RESULTS AND DISCUSSION

XANES spectra of vitreous samples and crystalline references MoO3 and Na2 MoO4 are shown in Figure 1. The pre-edge feature observed for reference Na2 MoO4 is due to the electronic transition 1s(Mo) 4d (Mo) + 2 p(O) which is dipole-allowed for tetrahedral symmetry but forbidden for octahedral symmetry (inversion center). As expected, the pre-edge feature is observed for Na2 MoO4 where Mo is known to be tetrahedral and for sample MoKLN. On the other hand, XANES spectra of crystalline MoO3 and vitreous samples in the binary system NaPO3 MoO3 dont exhibit this feature suggesting that Mo atoms are six-fold coordinated in these materials. Increasing MoO3 concentration in these glasses results in a stronger absorption in the visible and consequently darker samples. In addition, it was alBrazilian Synchrotron Light Laboratory

FIG. 1: XANES spectra of crystalline references and vitreous samples at the Mo-K edge

FIG. 2: XANES spectra of samples NMo50, NMo30-1000, NMo30SQ and NMo10

ready shown that a control of synthesis parameters can result in transparent glasses. Particularly, slow cooling of the melt at 1 C/min from the melting temperature promotes the obtaining of more transparent glasses and it has been suggested that lower melting temperatures shift the redox equilibrium to the formation of oxidized species (Mo6+ ). Since the position of the inexion point of X-Ray absorption edges is strongly related with the oxidation state of the absorber, XANES spectra of samples NMo10, NMo30-1000, NMo30-SQ and NMo50 were compared in Figure 2. A careful observation of the edge position in energy suggests that the inexion point is progressively shifted to higher energy from NMo50 to NMo30-SQ. This result is in agreement with the hypothesis of reduced Mo species in dark samples (NMo50) and oxidized Mo species in transparent samples (NMo30-SQ). However, the value of the maximum shift in energy is smaller than 1 eV and the resolution of the beam line at this energy (20000 eV) is estimated to be about 2 eV. For that reason, such investigations must be realized at energies where the resolution is higher such as L-edges. These results are presented in another work in this activity report.
CONCLUSION

dination number of Mo but is limited in resolution to identify oxidation state changes.

ACKNOWLEDGEMENTS

The authors wish to thank the National Laboratory of Synchrotron Radiation for measurements at the D04B-XAS beam line and FAPEMIG for nancial support.

X-Ray absorption spectroscopy (XANES) at the Mo-K edge was used to characterize glass samples in the binary system NaPO3 MoO3 and was useful to investigate the coorLNLS 2007 Activity Report 2

[1] Al-Hawery, A. S. J. Phys. Chem. Solids, 1997, 58, 1325. [2] Boudlich, D.; Bih, L.; El Hassane Archidi, M.; Haddad, M.; Yacoui, A.; Nadiri, A.; Elouadi, B. J. Am. Ceram. Soc., 2002, 85, 623. [3] Chiodelli, G.; Magistris, A.; Villa, M.; Bjorkstam, J. J. NonCryst. Solids, 1982, 51, 143. [4] Poirier, G.; Messaddeq, Y.; Ribeiro, S. J. L.; Poulain, M. J. NonCryst. Solids, 2005, 351, 293. [5] Poirier, G.; de Arajo, C. B.; Messaddeq, Y.; Ribeiro S. J. L.; Poulain, M. J.Appl.Phys., 2002, 91, 10221. [6] Poirier, G.; Nalin, M.; Messaddeq, Y.; Ribeiro, S. J. L. Brazilian Pending Patent PI 0502711-0 (2005). [7] Parke, S.; Watson, A. I. Phys. Chem. Glasses, 1969, 10, 37. [8] S. Santagneli, C.C. de Arajo, W. Strojek, H. Eckert, G. Poirier, S.J.L. Ribeiro and Y. Messaddeq, J.Phys.Chem.B 2007, 111, 10109-10117.

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