H E 5 a JOURNAL OF Eos LUMINESCENCE ELSEVIER Jouenal of Luminescence 72-74 (1997) 188-187 MnO}~ NIR luminescence in Ba,Si L.C. Ferracin*, M.R. Davolos"*, L.A.O. Nunes? “nsttato de Quimica, UNESP, 143801-970, Araraguara, SP. Bra stata de Fisica, USP, 1860-970, Sio Carls, SP. B Abstract BaSiO.: MnO luminescence is reported and compared to similar host lattices based on POS, VO3~ and AsO2”, where Mn®* substitutes for PS", V5" or As**, The observed energy position of MnO2- *E state in SiOE> is in accordance with interelectronic repulsion caused by Mn°*-O bond length, At 77 K the 'E splitting is 119 m=", which is inagreement with 18°, the average deviation of O- M—O angles from the regular tetrahedron, These values are adjusted to Cs point symmetry. The vibronic-structure spectra evidenced a progression with a frequency assigned to the v.(E) bending mode of MnO} Keywords: Ma® 1. Introduction Recently, 3d?-doped materials emitting light in the near infrared (NIR) have attracted much atten- tion because of their possible applications as laser materials [1, 2]. Manganese (+5) a 34? ion is sta- bilized in tetraoxo coordination [3] and can pres- ent NIR emission in the 1.0-1.5 um region [4-6]. This emission is due to the 'E (T, notation) excited state that is independent of the crystalline field. In several host lattices based on POY, VOL” and AsOI”, Mn®* substitutes for P**, V5" or As® [4-8]. In these cases there are straight correlations between the MnO” tetrahedral distortion angle and the 'E emitting-state splitting [8] and also between the Mn-O distance and the 'E energy position [4]. Sit" replaced by Mn‘ in Y3SiOs “Corresponding author. Fax: 55162227932; e-mail davolosiaiq.unesp.br. (0022-2313/97/$17.00 €) 1997 Elsevier Sc PL $0022-2313(96)00224-4 jarium orthosilicate; NIR luminescence presented a 'E splitting lower than that expected and the authors suggested to study other silicates [9]. Then it is interesting to study the 'E spectral properties in a SiO$~ group in different silicate host lattices where the Mn-O distances are not far from the Si-O ones. The purpose of this work is to investigate the 'E state splitting in Mn‘*-doped SiO}” and to account for the vibronic structure. The chosen host lattice was BaxSiO., 2. Experimental The polycrystalline powder silicate samples were obtained by a solid-state technique using BaCO,, and SiO, at 900°C with static air atmosphere for 30h, The doped sample was then obtained by adding MnCO) yielding Ba,SiO.:MnO3~ 2.at The charge compensation was inferred by subtra tion of barium resulting in a barium vacaney yee BLY. Al rights reserved186 LC. Ferracin etal The powders were characterized by XRD and IR vibrational spectroscopy elsewhere. NIR lumines- cence was excited by a 488nm Coherent Innova 400 Ar laser. The emission was dispersed by a Jarrell-Ash 3 monochromator and the signal detected by an N,(l) cooled germanium detector of Judson Infrared. The measurements were taken at room and liquid-nitrogen temperatures. 3. Results and discuss on The host lattice does not present NIR lumines- cence. The Ba,SiO,:MnO3~ exhibits the lumines- cence spectra shown in Fig. 1. We observe the “EA, emission line and the vibronic structure. At Ny(l) temperature the "E +A, emission pre- sents a doublet due to "E excited state splitting (AE =119cm~'), In BaySiO, with Pmen space group, the angles O-Mn-O are different from the regular tetrahedral one [10]. The Ty-distortion (6) or average deviation from T, angle [3] gives 1.8) and it can be compared with others from different host lattices. The splitting and Ty-distortion values are perfectly adjusted to Cs symmetry when compared with barium and strontium apatites where splittings of 67 and 148 em~' were observed for 1.6° and 1.9° Ty-distortion values, respectively [8]. The energy position of the "E can be analyzed by the baricenter registered at room-temperature spec- trum. In this condition, the 'E + 3A emission baricenter is 8355 cm™'. This value is expected considering the interelectronic repulsion caused by the Mn-O distances in SiO$ (1.632 A) [10]. The average M-O bond length in Ca,PO,Clis 1.541 A and in Ca,VO,C1 is 1.707 A, and the 'E positions are 8526 and 8159 cm~. respectively [4] To assign vibrational structure, the Iow- and room-temperature spectra were analyzed. The band positions and their assignment for the 77 K spectrum are shown in Table I. The vibronic struc- ture of the 77K spectrum showed a progression with a frequency assigned to the v,(E) bending mode of MnO§", indicating a dynamic Jahn-Teller effect. Other vibrational energies can be assigned to the v,(A,) mode of MnO3” and some shoulders to lattice modes, Journal of Luminescence 72-74 (1997) 185-187 INTENSITY (arbitrary units) 77K 300 K fears! 9500 9000 8500 8000 7500 ‘WAVENUMBER (crt) Fig. 1. Emission spectra of Ba,SiO, Mn, and 300 K, Table 1 Assignment of NIR luminescence at 77K Band Interval from Assignment position 4 BU "Ay (6336-1 (6237) fem™")fem~p 5356 0 =119 ta star 8237 u9 0 tarsal 3025 3 wi} 7921 a5 aE) 7145 on = 2va(E) (306) 7600 637 2(E) G19) 7535 a1 WA or 7535 702 4 (62)+20(6) (20) 7430 807 wAD Finally, Mn** is a very good probe also in sili- cate systems. NIR luminescence of Mn‘* in Ba,SiO, shows strictly host lattice microsymmetry characteristics Acknowledgements Financial support by CNPq and FAPESP is, gratefully acknowledged. L.C.F. thanks for CNPq scholarship.LC. Ferracin etal. / Jounal of Luminescence 72-74 (1997) 188-187 187 References (1] T. Brunold, M. Herren, U. Oetliker, H.U. Gilde, U. Kesper, C. Albrecht and D. Reinen, J. Lumin. 60861 (1994) 138. [2] A. Bellet, R. Borromei and L. Oleari Inorg. Chem. Acta 235 (1995) 349, [3] H. Lachwa and D. Reinen, Inorg. Chem. 28 (1989) 1044 [4] 4A. Capobianco, G. Cormier . M. Bettineli, R. Moncorge and H, Manaa, J. Lumin, $4 (1992) 1 [5] M. Herren, H.U. Guide, Albrecht and D. Reinen, Chem, Phys. Lett 183 (1991) 98, [6] M. Herren, T. Riedener, H.U. Giidel, C. Albrecht, U. Kaschuba and D. Reinen, J. Lumin. 53 (1992) 452, [7] LD. Merkle, A. Pinto, HLR. Verdin and B. Melntosh, Appl. Phys. Lett. 61 (1992) 2386. [8] U. Oetiker, M. Herren, H.U. Giidel, U. Kesper, C. Albrecht and D. Reinen, J. Chem. Phys. 190 (1994) 8656, [9] U. Hommerich, H. Eilers, WM. Yen and H.R. Verdin, Chem. Phys. Lett. 213 (1993) 163, [10] E. Tillmanns and H.P. Grobe, Cryst. Struct. Comm, 3 (1974) 599.