Materials Science and Engineering B 122 (2005) 9499

Structure and properties of rare earth-doped lead borate glasses

W.A. Pisarski a, , T. Goryczka a , B. Wodecka-Du b , M. Po ska b , J. Pisarska c s n
c

University of Silesia, Institute of Materials Science, Bankowa 12, 40-007 Katowice, Poland z University of Silesia, Department of Materials Science, Sniena 2, 41-200 Sosnowiec, Poland Silesian University of Technology, Department of Materials Science, Krasi skiego 8, 40-019 Katowice, Poland n
b

Received 21 May 2004; received in revised form 5 May 2005; accepted 7 May 2005

Abstract Inuence of rare earth oxide (Nd2 O3 , Er2 O3 ) addition on structure and glass properties has been investigated in PbOB2 O3 Al2 O3 WO3 system. With an increasing of rare earth concentration, intensity of OH band drastically decreases and IR transparency is slightly shifted to the longer wavelengths. The ErBO3 crystalline phase has been identied basing on X-ray diffraction analysis. In opposite to the neodymium oxide, the erbium oxide plays the role as glass-modier and inuences on BO3 BO4 conversion, what was stated by infrared spectroscopy. 2005 Elsevier B.V. All rights reserved.
Keywords: Lead borate glasses; Rare earth ions; Structure; Infrared spectroscopy

1. Introduction Since the past several years, borate glasses have attracted much attention because of their electrochemical and optical applications, namely as solid-state batteries, optical waveguides and luminescent materials. Several previous works on borate glasses are devoted to studying the structure, magnetic and electrical properties [15]. The glassy materials, which consist of heaviest metal oxides, such as lead, are more promising for photonics and optoelectronics. Dependently on a kind of bond: ionic or covalent between lead and oxide, PbO plays the role as a modier or a glass former. It is a function of PbO/B2 O3 ratio in the glass. In order to stabilize glass network, many of elements have been added to the base matrix. It has been very well known that iron [6], vanadyl [7], BaO [8], titanium dioxide [9] and copper [10] addition affect structure and glass properties in PbOB2 O3 system. Lead borate glasses are an optically transparent from the visible to the near-infrared range, forming over a wide compositional region of PbO concentration and creating an excellent host to incorporate trivalent rare earth ions. Moreover, optical glasses with their extreme difference between the masses of the lead and the boron atom are favorable for spec

troscopic studies. Thus, such properties of lead borate glasses, containing Nd3+ , Sm3+ , Dy3+ [11] and Ho3+ [12] ions, have been extensively studied. However, a little information is available on structure and properties of the multicomponent lead borate glasses containing rare earth ions. It has been stated, that increasing of heavy metal oxide causes increasing of thermal stability whereas the maximal phonon energy of the host decreases. In consequence, larger quantum efciencies of rare earth excited states are expected due to smaller multiphonon decay rates and larger radiative transition probabilities. From this point of view, structure and properties of the undoped and rare earth doped lead borate glasses with higher PbO content have been analyzed in presented paper. The studies have been limited to Nd3+ and Er3+ ions as a representative elements, which are different in ionic radii. Moreover, Nd3+ and Er3+ ions are the most important rare earth ions investigated in different host matrices due to their 4 F3/2 4 I11/2 (1.06 m) and 4 I13/2 4 I15/2 (1.55 m) laser transitions, especially, demanded for application in near-infrared optoelectronics.

2. Experimental Series of lead borate glasses (in wt.%): (73.5 x)PbO 18.5B2 O3 5Al2 O3 3WO3 xLn2 O3 (Ln = Nd, Er) were pre-

Corresponding author. E-mail address: wpisarsk@us.edu.pl (W.A. Pisarski).

0921-5107/$ see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.mseb.2005.05.002

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pared by mixing and melting of appropriate amounts of lead oxide, boron oxide, aluminum oxide, tungsten oxide and rare earth oxide of high purity (99.99%, Aldrich Chemical Co.). Reagents were mixed homogeneously together in an agate ball mill for 2 h in the composition. In doped samples, the PbO was partially substituted by neodymium or erbium ions in various concentrations (x = 15 wt.%). Then they were melted at 900 C, quenched and annealed below Tg in order to eliminate the internal stresses. Each glass was divided into two parts. From the rst part a slice 1 mm in thickness was cut and polished for optical properties measurement. In aim to conrm glassy nature, second part was subjected to X-ray diffraction (XRD) analysis. The X-ray diffraction analysis was carried out using INEL diffractometer with Cu K 1 radiation. The diffractometer is equipped with curved position sensitive detector CPS 120 which allows for data collection in 2 range: 0120 . The IR transmission spectra in the frequency region 4004000 cm1 were stored on BIORAD spectrometer using the KBr pellet disc technique.

3. Results and discussion Fig. 1 shows X-ray diffraction patterns, registered at room temperature, for the studied PBAW:Ln glasses, where Ln = Nd, Er. Undoped PBAW glass matrix as well as that

Fig. 1. X-ray diffraction patterns of lead borate glasses.

one containing 1% Nd and 5% Nd reveal typical characteristic pattern for amorphous materialtwo broaden diffraction lines (Fig. 1ac). Despite of amorphous component, several diffraction lines observed for sample containing erbium prove the presence of additional polycrystalline phase (Fig. 1d and e). Comparing X-ray diffraction pattern for both Er doped samples it can visible that the diffraction lines show the same position but they are different in intensities. Phase identication reveals, that crystalline peaks can be related to the ErBO3 phase (PDF-2 card no. 74-1935). For the sample with 1% Er, the correlation between experimental results and pattern (Fig. 1f) was very high in the meaning of peak position and its intensity. However, for the sample containing 5% Er there were signicant discrepancy in the intensity, which could originated from the other atoms distribution in the unit cell. It has been very well known that the crystal structure of the rare earth orthoborates can be related to the three polymorphs of CaCO3 : aragonite, vaterite or calcite [13]. The borate materials are characterized by trigonal BO3 and tetrahedral BO4 groups, which can occur as isolated or condensed fundamental building blocks, including chains, rings, layers and cyclic or non-cyclic [B3 O9 ]9 units. The B3 O9 -ring can be connected to the next B3 O9 -ring via trigonal BO3 unit forming a six-membered ring or via two common corners forming a four-membered ring [14]. The erbium ions are situated between the layers. Moreover, applying high pressure or high temperature can cause layers rebuilding from the non-cyclic [B3 O9 ]9 -anions containing one trigonal BO3 and two tetrahedral BO4 groups, what in consequence leads to structural transformationto the ErBO3 polymorph. From the other hand, the inuence of Er concentration on the local structure was observed for InF3 -based glasses [15] where dependently on erbium concentration increase completely different phases were formed. In aim to clarifying differences in the diffraction line intensities, for sample containing 5% Er, additionally texture measurement were carried out and structure of ErBO3 was analyzed by meaning of the Ritveld method. Registered pole gures revealed presence of the 0 0 1 ber texture component. In the Rietveld analysis, the amorphous component was treated as a background and after cutting off only peaks represented crystalline phase were taken into consideration. The vaterite model of the unit cell was a base for a theoretical X-ray diffraction pattern calculation. Considering texture presence the theoretical X-ray diffraction pattern was tted to the experimental one with relatively good reliability factors: Rp = 4.5%, Rwp = 6.0%. It proves that the increasing of erbium concentration do not inuence on the polymorphic ErBO3 structure formation. However, erbium increase causes change in the heat capacity, what leads to lowering of a cooling speed and in consequence causes oriented ErBO3 grains growing. XRD results are also consistent with the optical measurements. Similar inuence of the rare earth concentration on structural behavior of lead borate glasses has been observed by infrared spectroscopy.

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Fig. 2. IR transmission spectra of lead borate glasses in 14004000 cm1 region.

Fig. 3. IR edges of lead borate glasses.

Fig. 2 shows infrared spectra of lead borate glasses undoped and doped with rare earth ions in 40001400 cm1 ranges. The IR spectrum of an undoped PBAW sample exhibits two characteristic H2 O (OH stretching vibration) bands. The rst broad and asymmetric band 1 appears with its maximum at about 3445 cm1 (2.9 m). The second smaller band 2 is located near 1640 cm1 (6.1 m) and usually indicates the water incorporation before glass devitrication. Addition of rare earth ions (1% Nd and 1% Er) unexpectedly decreases the OH content. For higher rare earth concentration these bands are completely invisible. In order to compare intensity ratio of OH band, measurement were carried out for the samples with the same thickness because absorption intensity of the OH band increases with the sample thickness increasing [16]. Besides that, the same processing conditions were certainly remained during glass preparation. It is known, that processing condition inuences intensity of OH band [17]. The OH absorption increases the optical attenuation and decreases quantum efciency of the rare earth excited levels, as well as leads to the luminescence quenching, which results in reduction of potential application such as ultra-low loss bers and a luminescent material. Therefore, a great effort has been conveyed toward the synthesis of high quality glass with minimum OH content. Fig. 3 presents IR edge of lead borate glasses. The IR cut-off dened as the intersection between the zero base line and the extrapolation of the IR edge increases from 7.2 m for the undoped PBAW sample up to 7.3 and 7.45 m for Nd:PBAW and Er:PBAW glasses, respectively. Addition of rare earth ions to the base glass slightly increases IR trans-

mission (above 75%) and shifts IR transparency to the region with longer wavelengths. Fig. 4 presents absorption spectrum of the undoped PBAW sample, where the edge is located near 400 nm. Inset shows inuence of rare earth (Nd, Er) ions on the edge location observed in the visible region. This dependence was analyzed only for the samples, which contained from 0.5 up to 5% of rare earth. Above 5% addition of the rare earth oxide, luminescence quenching is observed due to the LnLn interaction,

Fig. 4. Absorption spectrum of an undoped lead borate glass. Inset shows shift of absorption edge observed for Nd (2) and Er (3) doped samples in comparison to undoped sample (1).

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which is useless from the point of view of their optical application. It has been stated in optical materials like glasses [18] and other disordered systems [19] containing rare earth ions. The results obtained from absorption spectra are in a good agreement with infrared measurements, which prove the same direction of edge shift. Additionally, the absorption bands connected with ff transitions of rare earth ions were observed for samples containing Nd3+ and Er3+ ions, respectively. Inuence of the rare earth oxides on the edge location in lead borate glasses is similar to that one observed for various PbO concentration [20]. The edge is shifted from the visible to the UV region with decreasing PbO content. Considering that fact, absorption bands connected with rare earth transitions will not be located on the tail of absorption edge. Also, obtaining of higher efcient excitation is possible by level pumping of lanthanides. Unfortunately, radiative transition probabilities decreases with decreasing of heavy element (Pb) concentration. From this point of view, the proper choise of PbO concentration in glass composition is a compromise between light transparency in UVvis region and radiative parameters. The infrared spectra of lead borate glasses with the ionic Pb O bonding showed that characteristic bands, which corresponds to Pb O vibrations, are located in 100190 cm1 range [21]. Increasing of PbO content (covalent Pb O bonding) shifts them to 250400 cm1 range. Bands above 400 cm1 are correlated with vibrations of borate network. Fig. 5 shows normalized IR spectra of investigated glasses in the range of 1400400 cm1 . Normalization procedure was applied before spectral analysis. The bands have been assigned based on literature data [2224]. The IR spectra in 4001400 cm1 region consist of four characteristic group of bands (IIV). The rst group of bands (I) has been identied as B O B and Pb O B bending vibration as well as borate rings deformation (400650 cm1 ). Due to the BO3 bending, the second group of bands (II) occurs at 650700 cm1 . The third group of bands (III) is associated with B O stretching vibration of tetrahedral BO4 group (8501050 cm1 ). The antisymmetric stretching mode causes that bands are centered at about 1050 cm1 , whereas the symmetric stretching frequency is located in the 850900 cm1 region [22]. The fourth group of bands (IV) centered at about 1300 cm1 is due to the antysymmetric B O stretching vibration of the trigonal BO3 group. It is noted that borate glasses can not be viewed as a simple network constructed only from BO3 triangles and/or BO4 tetrahedra [25,26]. Studies, where different experimental techniques were applied, have demonstrated that multicomponent and complex borate glasses consist of relatively large structural units, such as boroxol, pentaborate, triborate, diborate and metaborate groups with bridging or non-bridging oxygen (NBO) ions. Lead oxide is incorporated in the borate network as [PbO4/2 ]2 . It results in the creation of three and four coordinated boron as well as in the occurrence of band in the 640 cm1 region, which is attributed to a Pb O B bending [27]. Addition of Al2 O3 in the lead borate glasses

Fig. 5. Normalized infrared spectra of lead borate glasses in 4001400 cm1 region.

modies the network structural units causing a conversion from the BO3 units to the BO4 ones [23,24]. It can be clearly draw from Fig. 5 that incorporation of Nd ions to the PbOB2 O3 Al2 O3 WO3 glassy system does not change IR spectrum. In contrast to the undoped PBAW sample and the Nd-doped sample, concentration of 1% Er ions results in occurrence a new band located at 872 cm1 (referred as * in Fig. 5). This band is shifted to 859 cm1 by increasing of Er content and can be attributed to the boroxol rings similarly to that one, which was observed for Ho ions in borate glasses [3], or Er O B bending identied as deformation mode of BO3 vibration in lanthanide borates [28]. Taking into account results from X-ray diffraction measurements, where ErBO3 phase was identied, the second possibility is more probable. However, the most important information is that band intensities are changed for samples containing erbium in contrast to Nd-doped ones. It is evidently shown, that relative intensity of the group of peaks at 8501050 cm1 region due to the stretching vibrations of BO4 units decreases in comparison to the intensity of group of peaks at 650700 cm1 region related to the BO3 units with increasing of Er concentration. This effect has

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not been found in Nd-doped samples. It indicates, that 5% Er ions addition to the lead borate glasses causes partially conversion from BO4 to BO3 groups. This phenomenon, so called back conversion, has been observed for rare earthdoped borate glasses with high lead oxide content [2931]. Direction of borate group conversion depends on PbO concentration. Addition of small amounts of PbO to the borate matrix converts BO3 to BO4 units. For high PbO concentration, a back conversion from BO4 to BO3 appears. Similar effect is also observed for broad infrared band in 12001400 cm1 region, which consists of two absorption lines at 1210 and 1320 cm1 . Thus, intensity of the peak at 1310 cm1 decreases whereas intensity of the peak at 1210 cm1 increases with increasing of erbium concentration. From the relative peak areas of BO3 and BO4 units at 650700 and 8501050 cm1 region, respectively, the fraction of three- and four-fold coordinated boron can be estimated as follows: NBO3 = A3 , A3 + A 4 NBO4 = A4 A3 + A 4 (1)

The back conversion from BO4 to BO3 units has been observed with increasing Er2 O3 content. In contrary to that, this phenomenon has not been found with infrared spectroscopy as a function of Nd2 O3 concentration. Both Nd2 O3 and Er2 O3 glass components decrease intensity of OH absorption band and slightly shift IR transparency in direction to the range of longer wavelengths.

Acknowledgment This work was supported by the Polish Committee for Scientic Research (KBN) under Grant No. 4 T08D 017 25.

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values of A3 and A4 denote an area of BO3 and BO4 group, respectively. The peaks should be separated by a Gaussian deconvolution before calculation of both borate fractions. The deconvolution procedure and the analysis of the infrared bands have been described in details and discussed for borate systems elsewhere [3234]. Preliminary calculations indicate, that the A3 /A4 value is changed from 0.32 to 1.27 with increasing of Er concentration, whereas this ratio is nearly the same (A3 /A4 = 0.31) for low and high concentrated Nddoped samples. However, this problem will be discussed in separate work. The structural changes proved by the infrared spectroscopy measurements together with X-ray diffraction analysis suggest that erbium ions play role as a modier in lead borate glasses in opposite to the neodymium ions.

4. Conclusions Lead borate glasses containing rare earth ions have been studied by XRD and IR methods. Rare earth plays the role not only as an optically active ion. Addition of rare earth ions selectively inuences on the structure and properties of the multicomponent lead borate glasses. The local structure of lead borate system consists of connected trigonal units together with tetrahedral one. However, degree of both BO3 and BO4 units depends on rare earth occurrence and its concentration in glass composition. Any signicant changes of structure have been observed in the glass with Nd2 O3 addition to the base matrix when compare to the undoped sample. However, addition of Nd2 O3 improves the glass stability and enhances the resistance to crystallization, while the addition of Er2 O3 increases the tendency towards crystallization.

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