Influence of high hydrostatic pressure on energetic structure and electron-lattice coupling of transition metal and rare earth related centers in solids

We present the results of the photoluminescence of the crystals doped with transition metals or rare earth ions obtained under high hydrostatic pressure up to 300 kbar applied in diamond anvil cells (DAC). We have focused on Al₂O₃, YAlO₃ LLGG and YAG garnets and LiNbO₃, and LiTaO₃ perovskites doped...

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Veröffentlicht in:Semiconductor Physics Quantum Electronics & Optoelectronics
Datum:2004
Hauptverfasser: Grinberg, M., Barzowska, J., Gryk, W.
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Sprache:English
Veröffentlicht: Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України 2004
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Zitieren:Influence of high hydrostatic pressure on energetic structure and electron-lattice coupling of transition metal and rare earth related centers in solids / M. Grinberg, J. Barzowska, W. Gryk // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2004. — Т. 7, № 2. — С. 180-184. — Бібліогр.: 30 назв. — англ.

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spelling Grinberg, M.
Barzowska, J.
Gryk, W.
2017-05-29T05:34:12Z
2017-05-29T05:34:12Z
2004
Influence of high hydrostatic pressure on energetic structure and electron-lattice coupling of transition metal and rare earth related centers in solids / M. Grinberg, J. Barzowska, W. Gryk // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2004. — Т. 7, № 2. — С. 180-184. — Бібліогр.: 30 назв. — англ.
1560-8034
PACS: 61.72.Ss, 78.60.-b
https://nasplib.isofts.kiev.ua/handle/123456789/118171
We present the results of the photoluminescence of the crystals doped with transition metals or rare earth ions obtained under high hydrostatic pressure up to 300 kbar applied in diamond anvil cells (DAC). We have focused on Al₂O₃, YAlO₃ LLGG and YAG garnets and LiNbO₃, and LiTaO₃ perovskites doped with Cr³⁺, Ti³⁺ and Ce³⁺. We have observed the pressure induced red shift of the df emission in the case of materials doped with Ce and blue shift of the ⁴T₂⁴A₂ and ²E²T₂ emission in the case of materials doped with Cr³⁺ and Ti³⁺, respectively. Considering our experimental data we have calculated the local compresibilities of the materials and found that almost in all cases this quantity is smaller than compressibility of the bulk.
This work was supported bу Polish State Committee for Scientific Researches bу Grant No 2PО3 ВО57 23.
en
Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
Semiconductor Physics Quantum Electronics & Optoelectronics
Influence of high hydrostatic pressure on energetic structure and electron-lattice coupling of transition metal and rare earth related centers in solids
Article
published earlier
institution Digital Library of Periodicals of National Academy of Sciences of Ukraine
collection DSpace DC
title Influence of high hydrostatic pressure on energetic structure and electron-lattice coupling of transition metal and rare earth related centers in solids
spellingShingle Influence of high hydrostatic pressure on energetic structure and electron-lattice coupling of transition metal and rare earth related centers in solids
Grinberg, M.
Barzowska, J.
Gryk, W.
title_short Influence of high hydrostatic pressure on energetic structure and electron-lattice coupling of transition metal and rare earth related centers in solids
title_full Influence of high hydrostatic pressure on energetic structure and electron-lattice coupling of transition metal and rare earth related centers in solids
title_fullStr Influence of high hydrostatic pressure on energetic structure and electron-lattice coupling of transition metal and rare earth related centers in solids
title_full_unstemmed Influence of high hydrostatic pressure on energetic structure and electron-lattice coupling of transition metal and rare earth related centers in solids
title_sort influence of high hydrostatic pressure on energetic structure and electron-lattice coupling of transition metal and rare earth related centers in solids
author Grinberg, M.
Barzowska, J.
Gryk, W.
author_facet Grinberg, M.
Barzowska, J.
Gryk, W.
publishDate 2004
language English
container_title Semiconductor Physics Quantum Electronics & Optoelectronics
publisher Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
format Article
description We present the results of the photoluminescence of the crystals doped with transition metals or rare earth ions obtained under high hydrostatic pressure up to 300 kbar applied in diamond anvil cells (DAC). We have focused on Al₂O₃, YAlO₃ LLGG and YAG garnets and LiNbO₃, and LiTaO₃ perovskites doped with Cr³⁺, Ti³⁺ and Ce³⁺. We have observed the pressure induced red shift of the df emission in the case of materials doped with Ce and blue shift of the ⁴T₂⁴A₂ and ²E²T₂ emission in the case of materials doped with Cr³⁺ and Ti³⁺, respectively. Considering our experimental data we have calculated the local compresibilities of the materials and found that almost in all cases this quantity is smaller than compressibility of the bulk.
issn 1560-8034
url https://nasplib.isofts.kiev.ua/handle/123456789/118171
citation_txt Influence of high hydrostatic pressure on energetic structure and electron-lattice coupling of transition metal and rare earth related centers in solids / M. Grinberg, J. Barzowska, W. Gryk // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2004. — Т. 7, № 2. — С. 180-184. — Бібліогр.: 30 назв. — англ.
work_keys_str_mv AT grinbergm influenceofhighhydrostaticpressureonenergeticstructureandelectronlatticecouplingoftransitionmetalandrareearthrelatedcentersinsolids
AT barzowskaj influenceofhighhydrostaticpressureonenergeticstructureandelectronlatticecouplingoftransitionmetalandrareearthrelatedcentersinsolids
AT grykw influenceofhighhydrostaticpressureonenergeticstructureandelectronlatticecouplingoftransitionmetalandrareearthrelatedcentersinsolids
first_indexed 2025-11-26T22:50:03Z
last_indexed 2025-11-26T22:50:03Z
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fulltext Semiconductor Physics, Quantum Electronics & Optoelectronics. 2004. V. 7, N 2. P. 180-184. © 2004, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine180 PACS: 61.72.Ss, 78.60.-b Influence of high hydrostatic pressure on energetic structure and electron-lattice coupling of transition metal and rare earth related centers in solids M. Grinberg*, J. Barzowska, W. Gryk Institute of Experimental Physics, University of Gdansk, Wita Stwosza 57, 80-952 Gdansk, Poland Abstract. We present the results of the photoluminescence of the crystals doped with transi- tion metals or rare earth ions obtained under high hydrostatic pressure up to 300 kbar ap- plied in diamond anvil cells (DAC). We have focused on Al2O3, YAlO3 LLGG and YAG garnets and LiNbO3, and LiTaO3 perovskites doped with Cr3+, Ti3+ and Ce3+. We have observed the pressure induced red shift of the d→f emission in the case of materials doped with Ce and blue shift of the 4T2→4A2 and 2E→2T2 emission in the case of materials doped with Cr3+ and Ti3+, respectively. Considering our experimental data we have calculated the local compresibilities of the materials and found that almost in all cases this quantity is smaller than compressibility of the bulk. Keywords: high pressure spectroscopy, Ce3+, Cr3+, Ti3+, garnets, perovskites, elastic proper- ties, electron -lattice coupling Paper received 09.03.04; accepted for publication 17.06.04. 1. Introduction Luminescent solid state materials comprised of insulat- ing host lattices (normally oxides, chlorides and fluo- rides) activated by rare earth and transition metal ions continue to be an active area of research. These materi- als are desirable for practical applications for several reasons including mechanical strength, durability, chemi- cal inertness, portability, frequent ease of chemical syn- thesis, and diversity of properties. All considered materi- als are characterized by the broad band gap (10 eV) [1]. The activity arises from the promise in areas such as solid state lasers, optical communications, scintillation, medi- cal procedures, imaging, displays, flow cytometry, ho- lography, and remote sensing [2�3]. Transition metals and rare earth ions contribute to the energetic structure of the system via localized states with energies inside the forbidden gap of the host materi- als. These states are occupied by the electrons from the unfilled internal electronic shells 3dn (1 ≤ n ≤ 10) in the case of transition metals and 4fn or 4fn�15d1(1 ≤ n ≤ 14) in the case of rare earths. Although 3d and 5d electrons are localized at the transition ion, they extend enough to interact with the nearest neighbor host ions. As a result, the energetic structure of transition metals and rare earths is different in different hosts. The sensitivity of the energetic structure of transition ions on the host caused our interests in high pressure spectroscopy of these systems. The high hydrostatic pres- sure applied in the diamond anvil cell (DAC) diminishes the distance between the ion and ligands. As a conse- quence, the influence of ligands on localized electrons is stronger. High pressure spectroscopy has been exten- sively applied for the investigation of 3d�3d optical tran- sitions in transition metal ions in solids [4�5]. One can find the review of earlier works on this topic in [4]. The author of this paper has used high pressure spectroscopy for characterization of Cr3+ ions in LiNbO3, LiTaO3 crystals [6�9] and garnet crystals [10] as well as glasses [11]. In recent years, high pressure has been used for investigation of the emission related to 4fn�15d1→4fn tran- sitions [12�14]. In this contribution, we summarize our investigations on high pressure spectroscopy of Ti3+, Ce3+ and Cr3+ ions in various materials. M. Grinberg et al.: Influence of high hydrostatic pressure on energetic structure � 181SQO, 7(2), 2004 2. Experimental results 2.1 High pressure spectroscopy of Ti3+ and Ce3+ The simplest energetic structure have the Ti3+ and Ce3+ ions. It is determined by singe electron that occupies the terms belonging to the 3d1 electronic configuration and 4f1or 5d1 electronic configurations in the case of Ti3+ and Ce3+, respectively. We have investigated Ti doped Al2O3 and YAlO3 crystals. In both materials Ti3+ substitutes Al3+ ion in octahedral coordination of the six O2� ligands. According to the crystal field theory [15], the 3d1 state is splitted into the 2E and 2T2 states, energies of which are given by: DqEE 6)( 2 = (1) DqTE 4)( 2 2 −= (2) Crystal field strength parameter depends on the cen- tral ion-ligand distance according to relation naDq −∝ where exponent and depends on the nature of ligands. We have investigated the Ce3+ ions incorporated in the Y3Al5O12 and Gd3Sc2Al3O12. In these hosts the Ce3+ ions occupy the dodecahedrally coordinated Y3+ and Gd3+ positions, respectively. In both cases the ground electronic configurations 4f1 splits due to strong spin- orbit interaction into the 2F7/2 ground state and 2F5/2 excited state. It is assumed further that electron in these state is well screened from interaction with the ligands. The excited electronic configuration that is 5d1 interacts with the lattice in the same way as the 3d1, thus for dodecahedrally coordinated system the 5d1 splits into the 2E and 2T2 states that energies are given by: DqEE 3 16 )(2 −= (3) DqTE 9 32 )( 2 2 = (4) The energetic structure of these two systems is pre- sented in Fig. 1,a and b. Actually, the energy of the low- est state of the 5d1 electronic configuration of the Ce3+ ion in lattice is diminished by the quantity of depression energy Edepr [16]: cendepr EDqE +−= 3 16 (5) where Ecen is the centroid shift related to changes in the ligands polarization that accompanies 4f1�5d1 transition. One considers that nQ Dq 1 ∝ (6) and ' 1 ncen Q E ∝ (7) In the standard crystal field model [17], n = 5, whe- reas according to the ligands polarization model [18], n' = 6. According to the Fig. 1 a and b, one expects that pres- sure induces a blue shift of the emission of the Ti3+ and a red shift of the emission of the Ce3+. Actually such shifts have been observed. Typical emission spectra are pre- sented in Fig. 2,a and b. One can see that the spectral lineshape almost does not depend on pressure. One no- tices that maxima of the emission bands shift linearly with pressure. Thus, one can describe these shifts by re- spective pressure coefficients. Table 1 contains data ob- tained for Ce3+ and Ti3+ ions. Here the pressure shifts of the absorption maxima of the lowest absorption band for some materials are presented. 2.2. High pressure spectroscopy of Cr3+ Cr3+ ion occupies usually octahedrally coordinated sites. Energetic structure of the lowest states of the Cr3+ system is presented is presented in Fig. 1,c. One can see that depending on the crystal field strength the firs excited state is the 4T2 or 2E. In the low field systems, the 4T2 state has lower energy than the 2E state and Cr3+ exhibits broad band emission related to the 4T2 → 4A2 transi- tion. In the high field case, the 2E state is lower in energy and sharp, structured (R-lines) emission relate to 2E → → 4A2 transition is observed. Energy of the 4T2 state with respect of the ground state is equal to 10Dq. Thus similarly like in the case of Ti3+ in the case of the Cr3+ system one expects pressure induced blue shift of the 4T2 4A2 emission band. Luminescence spectra of the LiTaO3:Cr3+ obtained for different pressure are pre- sented in Fig. 2,c. In Table 1, the pressure blue shift of 4T2 → 4A2 emission band in various crystals doped with Cr3+ are summerized. Fig. 1. Energetic structure of the Ti3+ ion in octahedral position (a), Ce3+ In dodecahedral position (b) and Cr3+ in the octahe- dral position (c). For the Cr3+ only the 4A2, 4T2 and 2E states are presented. a 3d 5d E E10Dq 80/9Dq 4f T T T E 10Dq A F F 1 1 1 2 2 2 2 2 2 2 2 2 2 2 4 4 5/2 7/2 b c 182 SQO, 7(2), 2004 M. Grinberg et al.: Influence of high hydrostatic pressure on energetic structure � 3. Discussion One considers that pressure causes an increase of crystal field according to relation B K nDq dp da a nDq dp dDq 3 1 =−= , (8) where B is the bulk moduli of material. The dimensionless coefficient K 0 0 da da a a K = , (9) where a0 and a is the lattice constant and central ion- ligand distance, respectively, describes the way in which the macroscopic effect of pressure modifies the local en- vironment of the central ion. K = 1, K < 1 and K > 1 means that the compression of the ion-ligand system is the same, smaller and larger than compression of the bulk lattice. Since, in the excited state, the system is characterized by another distribution of electron charge than that in the ground state, after excitation the lattices ions shift a little to adapt to the new charge distribution. As a result, lattice relaxes and total energy of the system diminishes. The situation is described by configurational coordinate diagram presented in Fig. 3. The energy of lattice rela- xation ωhS may also depend on pressure. Thus, one ob- tains dp dS dp dE dp dE emabs ωh 2+= . (10) In the case of the Ti3+ and Cr3+ systems, one can re- late the pressure changes of the absorption peak to the pressure changes of the crystal filed strength by B nK Dq dp dDq dp dEabs 3 1010 == . (11) Usually it is difficult to measure pressure dependence of the absorption spectrum. Therefore, instead of absorp- tion we use the emission. Neglecting the dependence of the lattice relaxation energy on pressure, one obtains: B nK Dq dp dDq dp dEem 3 1010 == . (12) In the case of Ce3+, one can consider the relation: B nK E dp dE depr abs 3 −≈ , (13) that is valid under condition that exponents (in relations (6) and (7)) are very similar; 'nn ≈ . Relations (11) and (13) allows to calculate quantity nK. Than assuming that the exponent value is known, one can calculate the local compressibility K. The results of calculations are listed in Table 1. One can see that almost in all the cases quan- tity nK is significantly smaller than 5. The exception is YAlO3:Ti3+ system. Table. 1. Spectroscopic data and calculated parameters for transition metal and rare earth ions in different materials Material Edepr, Eem, dEem/dp, Eabs, dEabs/dp, B, nK [16] cm�1 cm�1/kbar cm�1 cm�1/kbar kbar cm�1 YAG:Ce3+ 27570 19100±100 �12.5±0.7 21750±100 �12.5 0.7 1870 [19] 2.85 * [14] 17560±100 �11.8 0.7 �8.3 0.5 GSAG:Ce3+ 2 7000 17340±100 �7.5 0.5 22320±100 �15.2 0.7 1916** 2.67 15250±100 13 2[20] LLGG:Cr3+ 11700 [20] 5.40 [5] 15033[20,21] 8.4 3 [24] 1330[22,23] 3.45 (3.88) Al2O3:Cr3+ 14790 *** 5.93 [5] 17950 50[24] 6.96 [5] 2420 [25] 3.41 (3.71) Al2O3:Ti3+ 13670 [5] 20590 [5] 8.52 [5] 2420 [25] 2.98 12450 [5] 19.6 [26] 17690 [5] YAlO3:Ti3+ 16330 [26] 13.5 22880 [26] 2004 [27] 5.44 13.5[9] 20400 [26] LiNbO3:Cr3+ 10800 15000 1058 [28] 2.85 (3.31) LiTaO3:Cr3+ 11020 15820 1057 [28] 2.7 (3.22) YAG:Cr3+ 16500 [29] 9****[29] 1870 [19] 3.06 * These data were calculated under assumption that pressure absorption and emission pressure coefficients are the same. ** The calculated here bulk moduli were taken from [30] *** These data were calculated from the values of the absorption maximum and electron-lattice coupling energy ωhS in accordance with the following relation ωhSEE absem 2−= ****The pressure shift was calculated from the analysis of R line lifetime dependence on pressure M. Grinberg et al.: Influence of high hydrostatic pressure on energetic structure � 183SQO, 7(2), 2004 4. Conclusions We have discussed the dependence of d-d and d-f transi- tion energies in the case of Ti3+, Cr3+ and Ce3+ on the high hydrostatic pressure. Using the crystal field ap- proach, we have related the pressure rates energy of the respective emission and absorption bands on comp- ressibility (elastic moduli) of the material. In all the cases, apart of YAlO3:Ti3+, we have found that the compres- sibility of the dopant local environment is almost two times less than the compressibility of bulk materials. In the exceptional case, this local compressibility and the bulk one possess practically the same value. Acknowledgements This work was supported by Polish State Committee for Scientific Researches by Grant No 2P03 B057 23. References 1. T. Kano in Phosphor Handbook, ed. S. Shionoya and W.M. Yen CRC Press, Boca Raton 1999. 2. G. Randolph // Laser Focus World, 31, pp. 121-122 (1995). 3. M.J. Padgett, F.G. Colville. M.H. Dunn // IEEE J Quant. Electr., pp. 2979-2985 (1994). 4. K.L. Bray // Topics in Current Chemistry, 213, pp. 1-94, Springer Verlang, Berlin Heidelberg, (2001). 5 S. Garsia-Revilla, F. Rodriguez, R. Valiente, M. Pollnau // J. Phys. Condens. Matter, 14, pp. 447-459 (2002). 6 Y.R. Shen, K. L. Bray, M. Grinberg, I. Sokólska // Phys Rev. B., 61, pp. 14263-14266 (2000). 7. A. Kaminska, A. Suchocki, J. Garcia-Sole, F. Jaque, L. Ariz- mendi, M. Grinberg // J. Lumin., 87-89, pp. 571-573 (2000). Fig. 2. Room temperature emission spectra of the YAlO3:Ti3+ (a), YAG: Ce3+ (b) and LiTaO3:Cr3+ (c) systems obtained at different pressures applied in diamond anvil cell. 14000 16000 18000 20000 22000 a 181 kbar 170 kbar 151 kbar 129 kbar 103 kbar 83 kbar 58 kbar 28 kbar AP Energy, cm Energy, cm Energy, cm �1 �1 �1 15000 20000 b 98 kbar 74 kbar 66 kbar 40 kbar 1 atm 10000 12000 14000 84 kbar 74 kbar 69 kbar 60 kbar 49 kbar arb c Fig. 3. Configurational coordinate model of the system strongly interacting with lattice. S • S • w w E ab s E 0 E lum Assuming that the exponent is n ≈ 5, the local compres- sibility in the vicinity of the dopant ion is significantly smaller than the bulk compressibility, K< 1. 184 SQO, 7(2), 2004 M. Grinberg et al.: Influence of high hydrostatic pressure on energetic structure � 8. A. Kaminska, A. Suchocki, L. Arizmendi, D. Callejo, E. Dieguez, J. Garcia Sole and F. Jaque, M. Grinberg // Phys Rev B., 62, pp. 10802-10811 (2000). 9. M. Grinberg, J. Barzowska, Y.R. 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