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High pressure luminescence spectra of CaMoO4:Ln3+ (Ln=Pr, Tb)

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 2013 J. Phys.: Condens. Matter 25 105502 (http://iopscience.iop.org/0953-8984/25/10/105502) View the table of contents for this issue, or go to the journal homepage for more

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IOP PUBLISHING J. Phys.: Condens. Matter 25 (2013) 105502 (7pp)

JOURNAL OF PHYSICS: CONDENSED MATTER

doi:10.1088/0953-8984/25/10/105502

High pressure luminescence spectra of CaMoO4:Ln3+ (Ln = Pr, Tb)

S Mahlik1 , M Behrendt1 , M Grinberg1 , E Cavalli2 and M Bettinelli3
1

Institute of Experimental Physics, University of Gda nsk, Wita Stwosza 57, 80-952 Gda nsk, Poland Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Universit` a di Parma, Parma, Italy 3 Dipartimento di Biotecnologie, Universit` a di Verona and INSTM, UdR Verona, Verona, Italy
2

E-mail: doksma@univ.gda.pl (S Mahlik)

Received 28 July 2012, in nal form 8 November 2012 Published 6 February 2013 Online at stacks.iop.org/JPhysCM/25/105502 Abstract Photoluminescence spectra and luminescence kinetics of pure CaMoO4 and CaMoO4 doped with Ln3+ (Ln = Pr or Tb) are presented. The spectra were obtained at high hydrostatic pressure up to 240 kbar applied in a diamond anvil cell. At ambient pressure undoped and doped samples exhibit a broad band emission extending between 380 and 700 nm with a 3+ or maximum at 520 nm attributed to the MoO2 4 luminescence. CaMoO4 doped with Pr 3+ Tb additionally yields narrow emission lines related to ff transitions. The undoped CaMoO4 crystal was characterized by a strong MoO2 4 emission up to 240 kbar. In the cases of CaMoO4 :Pr3+ and CaMoO4 :Tb3+ , high hydrostatic pressure caused quenching of Pr3+ and Tb3+ emission, and this effect was accompanied by a strong shortening of the luminescence lifetime. In doped samples, CaMoO4 :Pr3+ and CaMoO4 :Tb3+ , quenching of the emission band attributed to MoO2 4 was also observed, and at pressure above 130 kbar this luminescence was totally quenched. The effects mentioned above were related to the inuence of the praseodymium (terbium) trapped exciton PTE (ITEimpurity trapped exciton) on the efciency of the Pr3+ (Tb3+ ) and MoO2 4 emissions.

1. Introduction
Calcium molybdate (CaMoO4 ) is a well known compound of the scheelite class that possesses an attractive luminescence and interesting structural properties. CaMoO4 is an important material due to its applications in solid state scintillators [1, 2], phosphors [35] and optical bers [6] and as a host lattice for solid state lasers [7, 8]. Undoped CaMoO4 has an excitation band in the near-UV region peaked about 300 nm assigned to the spin allowed 1 A1 1 T2 charge transfer (CT) transition in MoO2 4 [2, 9], in which an oxygen 2p electron goes into one of the empty molybdenum 5d orbitals. Since in CaMoO4 the valence band is formed by oxygen electronic orbitals and the conduction band is formed by molybdenum electronic orbitals, the CT transition can be considered as band-to-band host absorption with energy equal to the band gap Eg . Zhang et al [10] have calculated the value of the band gap energy of a pure CaMoO4 crystal using the linearized
0953-8984/13/105502+07$33.00 1

augmented plane-wave method and obtained 3.41 eV. The experimentally measured values are slightly higher and the optical band gap has been found to be equal to 4.22 eV [11] or 4.5 eV [9, 12]. After excitation through the CT band the CaMoO4 yields a broadband luminescence in the range 400700 nm with a peak maximum around 520 nm assigned to the spin forbidden 3 T1,2 1 A1 transition in the MoO2 4 complex [2, 10]. Despite the fact that these materials have been thoroughly studied for more than 50 years, the electronic structure and spectral properties of CaMoO4 still constitute an open research topic [9, 13, 14]. The internal energetic structure of the 4fn electronic conguration of Ln3+ ions in the lattice is approximately the same as that of the free ion and does not depend strongly on the host, since the unlled 4fn electronic conguration is separated from the inuence of the electric eld of the host ions by the lled electronic shell 5s2 5p6 . Since d electrons are much more extended than f, the energy of the lowest state
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of the 4fn1 5d electronic conguration of the Ln3+ ion in the lattice is diminished with respect to the free ion by the quantity of centroid shift and crystal eld splitting [15]. The relative energy of the ground state of the given Ln3+ with respect to valence and conduction band edges is different in different lattices and depends on the ionligand distance R [1618]. Pr3+ has electronic conguration 4f2 , where the ground state is the 3 H4 and the excited emitting states are the 1 D2 with energy at about 17 000 cm1 and 3 P0 with energy equal to about 20 500 cm1 . Tb3+ has similar energetic structure but shifted to higher energies (4f8 electronic conguration). In the case of Tb3+ the ground state is the 7 F6 and the excited emitting states are the 5 D4 with energy at about 20 500 cm1 and a mixture of the 5 D3 and 5 L10 with energy equal approximately to 26 000 cm1 . According to the diagram proposed by Dorenbos [15, 19, 20], the energies of the ground states of Pr3+ and Tb3+ with respect to the band edges are the same in the given host. Specically, in molybdates and tungstates the ground state of Pr3+ is located in the forbidden bandgap close to the conduction band. In this case, the energy that is needed for ionization of Pr3+ (Tb3+ ), creation of Pr4+ (Tb4+ ) and the electron in the conduction band [Pr4+ (Tb4+ ) + ecb ] is a little bit smaller than Eg . Actually, Pr4+ (Tb4+ ) attracts the conduction band electron by the Coulomb potential, that creates a bound state considered as an impurity trapped exciton (ITE) [17, 21, 22] state, also called an intervalence charge transfer (IVCT) state [18, 12]. The ITE state corresponds to an Ln3+ that has captured a hole forming Ln4+ and an electron bound by the Coulomb potential of the impurity. In the case of CaMoO4 :Pr3+ and CaMoO4 :Tb3+ the ITE energy is comparable to the energies of the excited states of Pr3+ and Tb3+ (this is evidenced specically for CaMoO4 :Pr3+ [9, 21]). Applying high hydrostatic pressure, one compresses the materials and diminishes the distance between the Ln3+ and the ligands. One expects that such compression should cause an increase of the energies of the localized states of the ground electronic conguration 4fn of the Ln3+ ion with respect to the conduction band edge [1618]. As at ambient pressure the rst excited states of Pr3+ and Tb3+ are below the conduction band, high pressure can cause their degeneration. As a result, pressure induced luminescence quenching should be observed. In this paper, detailed spectroscopic investigations including photoluminescence, time-resolved spectroscopy and luminescence kinetics spectra of crystals of pure CaMoO4 and doped with Tb3+ and Pr3+ ions are presented. To analyze the energetic structure of the system and the origins of the individual luminescence features, experiments under high hydrostatic pressures were performed. Pressure dependences of Raman spectra of CaMoO4 are analyzed in the context of pressure induced phase transition. Previous studies of the Raman spectra under high pressure [23, 24] of pure CaMoO4 showed a phase transition from tetragonal (scheelite) to monoclinic (fergusonite) phase at a pressure of about 80 kbar. The results obtained in this paper are compared and discussed in the context of our earlier published results on the CaMoO4 crystal doped with Pr3+ [21].
2

2. Experiment
CaMoO4 (CMO) single crystals nominally doped with 0.5 mol% Pr3+ or Tb3+ were grown by the ux growth method using Na2 MoO4 as a solvent in the 13501600 C temperature range. Details of sample preparation are described in previous papers [25, 12]. CMO crystallizes in a tetragonal scheelite structure with space group I 41 /a, and the and c = 11.430 A [26]. unit cell parameters are a = 5.226 A 3 + 3 + 2 + The Pr (or Tb ) ions occupy the Ca sites with eightfold oxygen coordination (distorted dodecahedron, actual point group S4 ). Luminescence excitation spectra were recorded using a Horiba spectrouorometer model FluoroMax-4P TCSPC equipped with a 150 W xenon lamp as an excitation source. The uorescence intensity was measured after passing through a monochromator using a model R928 Hamamatsu photomultiplier tube (side on). Raman spectra were obtained by an integrated confocal micro-Raman system with a LabRam Aramis (Horiba Jobin Yvon) 460 mm spectrometer equipped with a confocal microscope. The excitation source was a diode pumped solid state (DPSS) laser emitting green light at 532 nm with 50 mW power. High resolution steady state luminescence spectra was obtained using a system consisting of a PGS2 spectrometer working as a monochromator and a model R943-2 Hamamatsu photomultiplier working in the photon counting regime. The luminescence was excited with HeCd and diode lasers with the wavelength of 325 nm and 473 nm respectively. The experimental setup for luminescence kinetics [27] consists of a laser system as the excitation source, which consists of a PL 2143A/SS laser and a PG 401/SH parametric optical generator, that generates 30 ps laser pulses, with frequency 10 Hz. The detection part consists of a 2501S spectrograph (Bruker Optics) and a Hamamatsu model C4334-01 streak camera. High hydrostatic pressure was applied in a Merrill Bassett type diamond anvil cell (DAC) [28] with a poly(dimethylsiloxane) oil as a pressure-transmitting medium. The luminescence of a ruby crystal was used for the estimation of pressure.

3. Results and discussion

The room temperature luminescence excitation spectra and emission spectra measured upon 325 nm excitation of CaMoO4 , CaMoO4 :Pr3+ and CaMoO4 :Tb3+ crystals are presented in gures 1(a)(f). Luminescence excitation spectra and emission spectra of pure CaMoO4 are presented in gures 1(a) and (b), respectively, those of the CaMoO4 :Pr3+ are presented in gures 1(c) and (d), respectively, and those of the CaMoO4 :Tb3+ are presented in gures 1(e) and (f), respectively. Luminescence excitation spectra were monitored at 520 nm for pure CaMoO4 , at 489 nm for CaMoO4 :Pr3+ and at 544 nm for CaMoO4 :Tb3+ . The optical properties measured at room temperature are in agreement with previous literature [2931, 9, 12]. The emission spectrum

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Figure 1. Room temperature excitation spectra and emission spectra of pure CaMoO4 (a and b, respectively), CaMoO4 :Pr3+ (c and d, respectively) and CaMoO4 :Tb3+ , (e and f, respectively). Luminescence spectra were excited at 325 nm. Luminescence excitation spectra were monitored at 520 nm for pure CaMoO4 , at 489 nm for CaMoO4 :Pr3+ and at 544 nm for CaMoO4 :Tb3+ .

of pure crystal CaMoO4 presented in gure 1(b) consists of a broadband luminescence extending across the region 400700 nm and was assigned to the spin forbidden 3 T1,2 1 A transition in the MoO2 complex [9, 31]. The excitation 1 4 spectrum of the CaMoO4 measured in ambient conditions was obtained by monitoring the emission of MoO2 4 at 520 nm and is shown in gure 1(a). The spectrum consists of a strong broad band peaked at around 300 nm that can be attributed to group. charge transfer (CT) transition in the MoO2 4 Upon excitation at 325 nm the luminescence spectra of CaMoO4 :Pr3+ (gure 2(d)) are dominated by two strong emission lines peaked at 489 nm and 651 nm related to

internal transitions in the Pr3+ ion: 3 P0 3 H4 and 3 P0 3 F , respectively. The weaker lines peaked between 590 and 2 645 nm are related to the 1 D2 3 H4 and 3 P0 3 H6 transitions. Lines located at 559 nm and 534 nm are attributed to the transitions from 3 P0 and 3 P1 to the 3 H5 state, respectively [30]. The weak broadband emission in the region from 700 to 400 nm is related to the host emission. The excitation spectrum of the luminescence monitored at 489 nm related to the 3 P0 3 H4 transition is presented in gure 1(c). The spectrum consists of a broad band peaking at about 320 nm that can be attributed to overlapping host absorption (CT transition) and the photoionization process of the Pr3+ ion: Pr3+ Pr4+ + e in the conduction band. The excitation spectrum of the CaMoO4 :Tb3+ luminescence monitored at 544 nm corresponding to the 5 D4 7 F6 transition in Tb3+ is presented by the curve in gure 1(e). The spectrum consists of a broad band peaking at about 320 nm that can be attributed (similarly to the case of CaMoO4 :Pr3+ ) to host absorption and photoionization of the Tb3+ ion. The weak lines from 350 to 400 nm are associated with the ff transitions from the ground state to excited states (5 DJ ) of the Tb3+ ion. In gure 1(f) luminescence spectra of CaMoO4 :Tb3+ are presented. The sharp peaks at 488 nm, 544 nm, 583 nm, 618 nm and 652 nm are associated with the transitions 5 D4 7 F6 , 5 D4 7 F5 , 5 D4 7 F4 , 5 D4 7 F and 5 D 7 F of Tb3+ , respectively. The host related 3 4 2 broadband emission from 400 to 700 nm is also observed, but is much weaker than the emission of Tb3+ due to energy transfer from the free electrons and holes in the host to Tb3+ ions. We can consider two pathways of excitation energy transfer from the host to the Ln3+ ions. The rst process is the direct nonradiative transfer from the excited lattice to the lanthanide that leaves the lanthanide ion in one of the excited states. The second pathway takes place through an intermediate state such as the ITE [17, 22] state, also called

Figure 2. (a) Raman spectra of CaMoO4 at different pressures. (b) Pressure dependence of the Raman mode frequencies of the scheelite and fergusonite phase structures in CaMoO4 .
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Figure 3. (a) Room temperature luminescence spectra of pure CaMoO4 obtained at different pressures. (b) Luminescence decay proles at different pressures for luminescence monitored in the region between 480 and 520 nm.

the intervalence charge transfer state (IVCT) [18, 12] in the case of Pr3+ and Tb3+ . One notices that the emission from the higher excited state 5 D3 of Tb3+ , which should be observed in the region 380470 nm, is absent from CaMoO4 :Tb3+ . The 5 D3 state is depopulated by an autoionization process to the conduction band or by the ITE state. In the next step the ITE 5 D4 nonradiative transition yields the emission of Tb3+ originating from the 5 D4 state. Raman spectra of CaMoO4 taken at different pressures up to 160 kbar are presented in gure 2(a). In gure 2(b) the pressure dependences of the phonon energies are plotted. Vibrational modes characteristic of the scheelite phase in the tetrahedral structure were observed. The modes are labeled referring to the Raman-active internal modes, 1 (Ag ), 3 (Bg ), 3 (Eg ), 4 (Eg ), 4 (Bg ), 2 (Bg ), 2 (Ag ), R (Bg ) and R (Eg ), and external modes, T (Bg Eg Eg ), of the tetrahedral MoO4 system. Measured energies at ambient pressure are in agreement with results obtained by Longo et al [32] and Phuruangrat et al [33]. Splitting of the modes of Eg symmetry (with energies 1 = 145 and 3 = 797 cm1 at ambient pressure) into two components at pressures above 40 kbar can be associated with phase transition from scheelite to fergusonite at pressure between 40 and 90 kbar [23, 24]. Room temperature luminescence spectra of pure CaMoO4 crystal obtained at different pressures are presented in gure 3(a). Tyner and Drickamer [34] observed a blueshift of the lattice luminescence of CaMoO4 in the pressure range up to 100 kbar and estimated the shift rate as equal to 11.5 cm1 /kbar accompanied by an increase of the decay time from 16 to 26 us at ambient pressure and 100 kbar respectively. In our case the blueshift of the emission band of the MoO2 4 complex was estimated to be equal to 7.8 cm1 /kbar below 80 kbar and approximately
4

3.6 cm1 /kbar above 80 kbar. In gure 3(b) the decay proles of the CaMoO4 luminescence at room temperature for different pressures are presented. For all pressures the decays are single exponential and the decay constant increases from 20 s at ambient pressure to 29.5 s at 65 kbar. Above 85 kbar the lifetime reduces and reaches a value of 1.82 s at 287 kbar. The increase of energy of the host luminescence with increasing pressure can be attributed to a pressure induced increase of the energetic distance between bonding and antibonding states of the MoO4 complex (increase of the bandgap energy Eg ). This is correlated to an increase of the lifetime. The reason why the luminescence lifetime decreases and with increasing pressure for pressures above 85 kbar and the luminescence is quenched at pressures above 200 kbar is probably related to many effects. Tentatively, one can consider creation of nonradiative recombination centers (lattice defects) and similar effects. Luminescence spectra of CaMoO:Tb3+ obtained under excitation at 325 nm for various pressures are shown in gure 4(a). Apart from typical lines related to the ff Tb3+ emission, the weak broad band originating from MoO2 4 is observed. The results show that, when the pressure increases, the intensity of the emission from the 5 D4 state decreases. At pressure above 98 kbar the Tb3+ emission is quenched and only weak host emission is observed. One notices that the intensity of the host emission also decreases with increasing pressure, but with a slower rate. Diminishing of the luminescence intensity is accompanied by shortening of the luminescence decay (see gures 4(b) and (c), where the decay proles are presented). In gure 4(b) the decay proles of the MoO2 4 luminescence in CaMoO:Tb3+ are presented for different pressures. Decay becomes faster when pressure increases.

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Figure 4. (a) Luminescence spectra of CaMoO4 :Tb3+ obtained at different pressures. Luminescence decay proles under different pressures for luminescence monitored at 540555 nm, that corresponds to the 5 D4 7 F5 emission Tb3+ (b), and 526507 nm, that corresponds to the MoO2 4 emission (c).

Since the decay is not single exponential, we estimated the average decay constant av using the formula av = tI (t) dt I (t) dt (1)

where I corresponds to the emission intensity. This average decay constant is equal to 7.6 s at ambient pressure and is equal to 0.98 s at 105 kbar. For pressure above 105 kbar emission is too weak and the decay prole measurements become impossible. One notices that when pressure increases the decay proles progressively deviate from the single to multi-exponential behavior. This fact and the shortening of the decay of the lattice emission show a change in the mechanism of excitation energy transfer from the lattice to the Tb3+ ions. Figure 4(c) shows decay proles of the luminescence related to the 5 D4 7 F6 transition in CaMoO4 :Tb3+ . Decays are exponential and the lifetime slowly decreases from 468 s to 429 s at ambient pressure and 51 kbar, respectively. Above 51 kbar the decay time rapidly decreases when the pressure increases. In our previous paper [21], the dependence of the Pr3+ luminescence on high hydrostatic pressure in CaMoO:Pr3+ was presented. We summarize these results in gure 5, where the relation between the intensity of emission from the 3 P0 and from the MoO2 4 to the intensity of the emission from 1 the D2 state as a function of pressure is presented. The intensity of luminescence from the MoO2 4 groups and from the upper excited state of Pr3+ 3 P0 decreases as the pressure increases, and both emissions vanish for pressure higher than
5

Figure 5. Relative intensity of emissions in CaMoO4 :Pr3+ crystal.

110 kbar. The intensity of the emission related to the 1 D2 3 H transition rises when the pressure increases and at 45 kbar 4 dominates the spectrum. For pressure greater than 100 kbar, the intensity of the emission from the 1 D2 state decreases with increasing pressure and vanishes above 127 kbar. For pressure higher than 127 kbar, no emission from CaMoO:Pr3+ is observed. The decays of the luminescence originating from the 3 P state in CaMoO :Pr3+ are almost exponential and the 0 4 decay constant decreases from 380 ns for ambient pressure to 17 ns for 60 kbar. Above 60 kbar the emission intensity is too weak to allow a meaningful analysis of the decay. The decays related to the spin forbidden 1 D2 3 H4 transition are

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Figure 6. Effective decay constant characterized luminescence of undoped CaMoO4 crystal and CaMoO4 :Ln3+ (Ln = Pr, Tb) versus pressure.

multi-exponential and become shorter for higher pressure. The average lifetime of the 1 D2 3 H4 luminescence calculated according to relation (1) is approximately equal to 8.7 s at ambient pressure and is less than 3.9 s at 127 kbar. One notices the changes of the decay are not so strong as in the case of the 3 P0 3 F2 transition. The decays originating from the 5 D4 state in CaMoO4 :Tb3+ also decrease when pressure increases and at pressure above 98 kbar the emission from Tb3+ is totally quenched. These results are summarized in gure 6, where all obtained decay times of pure CaMoO4 and CaMoO4 :Ln3+ (Ln = Pr, Tb) versus pressure are collected. The intensities of the selected transitions in the case of CaMoO4 , CaMoO4 :Tb3+ and CaMoO4 :Pr3+ are represented by squares, triangles and circles, respectively. One notices that a similar effect of quenching of Pr3+ and Tb3+ emission under high pressure has been observed earlier in oxide lattices [3537] and has been related to nonradiative depopulation of these states via a Pr3+ (Tb3+ ) trapped exciton. The decay times of the band emission originating from the MoO2 complex for samples doped with both Pr3+ 4 3 + and Tb decrease similarly and quite fast when pressure increases, while in the case of undoped CaMoO4 the MoO2 4 emission lifetime is much more stable and decreases slightly when pressure increases (squares in gure 6). It is interesting to notice that quenching of the MoO2 4 emission accompanied by shortening of the lifetime in the doped CaMoO4 samples takes place approximately for the same pressure when impurity related emission from the 5 D4 state for Tb3+ and the 3 P0 state for Pr3+ is quenched.

Raman spectra of undoped CaMoO4 have been measured as a function of pressure and a phase transition from scheelite to fergusonite evidenced in the pressure range 4090 kbar. The pressure dependence of the luminescence from the impurities is strongly affected by the presence of an ITE state, that selectively quenches the emission from excited levels when pressure increases. The energetic distance between the ITE state and the ground state of the impurity decreases with increasing pressure, that is in good agreement with currently accepted models for ITE (or IVCT). The ITE causes oxidation of the excited lanthanide impurity when its energy is higher than the energy of the ITE. The intrinsic luminescence of the MoO2 4 group appears to be quenched by the presence of the impurity, through energy transfer processes from MoO2 4 to ITE and then to lanthanide ions. When the pressure increases, the energy of the MoO2 4 luminescence increases as the result of a pressure induced increase in energetic distance between bonding and antibonding states of the MoO4 complex. One considers that at ambient pressure the excited states of the system, the lowest excited state of MoO2 4 complex and ITE have approximately the same energy. When the pressure increases the energy of the excited state of MoO2 4 increases with respect to the energy of the ITE and excitation energy transfer from MoO2 4 to the ITE becomes more effective. As a result, at high pressure in doped crystals the intrinsic MoO2 4 luminescence is more effectively quenched by pressure than in the pure crystal. The results on spectroscopy of CaMoO4 crystals undoped and doped with Tb3+ or Pr3+ ions obtained at high hydrostatic pressure presented in this study clearly evidence that the formation of ITEs cannot be neglected when the optical spectroscopy of new hosts activated with lanthanide ions such as Ce3+ , Pr3+ and Tb3+ is considered and investigated. The ITEs can have a signicant impact on the performance of these materials as phosphors.

Acknowledgments
This paper has been supported by the Polish Ministry of Science and Higher Education by a grant active in years 20122014 and by Polish National Center for Research and Development grant NR 15 002906.

References
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4. Conclusions
We have presented new data concerning the optical spectroscopy under high pressure of CaMoO4 undoped and doped with Pr3+ or Tb3+ , extending previous investigations carried out on CaMoO4 :Pr3+ [21]. Final conclusions can be summarized as follows.

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