Luminescence and excitation spectra due to inter- and intraconfigurational transitions of Er 3+ in...
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Luminescence and excitation spectra due to inter- and intraconfigurational transitions of Er 3+ in YAG:Er Aleksanyan Eduard a,b* , Harutunyan Vachagan b , Kostanyan Radik c , Feldbach Eduard a , Kirm Marco a , Liblik Peeter a , Makhov Vladimir a,d , Vielhauer Sebastian a a Institute of Physics, University of Tartu, 142 Riia Str., 51014 Tartu, Estonia b Yerevan Physics Institute, 2 Alikhanian Brothers Str., 0036 Yerevan, Armenia c Institute for Physical Research, Armenian National Academy of Sciences, 0203 Ashtarak-2, Armenia d Lebedev Physical Institute, 53 Leninskii Prospect, 119991 Moscow, Russia Abstract Inter-configurational 4f 10 5d ↔ 4f 11 transitions of the Er 3+ ion in the YAG host were studied under both VUV photon (using synchrotron radiation) and electron beam excitation. It was found that the lowest low-spin 5d level of the Er 3+ ion has a rather large energy gap to the next lower 4f 2 D(2) 5/2 crystal-field level, which results in a relatively low rate of non-radiative transitions from this 5d level leading to the appearance of weak spin-allowed 5d – 4f luminescence at low temperature. The lowest high-spin 5d level, from which spin-forbidden 5d – 4f radiative transitions could occur potentially, is situated only at ~500 cm -1 above the 4 D 1/2 level. Such close location allows fast depopulation of the 5d level resulting in the absence of spin-forbidden 5d – 4f luminescence and appearance of 4 D 1/2 4f – 4f luminescence. Experiment and samples Photoluminescence experiments were carried out at the SUPERLUMI station of HASYLAB at DESY using for excitation 3.75 – 20 eV synchrotron radiation from the DORIS storage ring [3,4]. The excitation spectra were recorded with an instrumental resolution of ~0.3 nm. Emission in UV/visible spectral range was analysed by using a 0.3 m Czerny-Turner monochromator-spectrograph equipped with a photomultiplier tube. VUV luminescence was recorded through a 0.5 m Pouey-type VUV monochromator equipped with a solar- blind photomultiplier tube. The spectral resolution of both monochromators was ~2 nm. Measured emission spectra were not corrected for the spectral response of the detection system. YAG:Er 3+ single crystal was grown by the Czochralski technique. The RE 3+ ions occupy in YAG the Y 3+ sites with D 2 point symmetry, and each site is coordinated to eight oxygens. The crystals were cleaved prior to the mounting onto a copper sample holder attached to a cold finger of a flow-type liquid helium cryostat. The orientation of crystallographic axes of the crystal was arbitrary with respect to polarization vector of exciting synchrotron radiation. All measurements were performed under ultrahigh vacuum conditions. Cathodoluminescence (CL) experiments were carried out with a special setup at the Institute of Physics, University of Tartu [5]. CL was detected in the region of 4 – 12 eV through a double vacuum-grating monochromator equipped with a photomultiplier tube. The CL spectra were measured in the temperature range of 5 – 420 K. The characteristics of the electron gun are: tuneable electron energy 1 – 30 keV and electron current 10 – 100 nA, a typical spot size ~0.5 mm 2 . Results and discussion Figures 1 and 2 show emission and excitation spectra of YAG:Er 3+ measured at 9 and 292 K, respectively. The excitation spectrum of 4 D 1/2 4f – 4f luminescence at 9 K shows an intense broad band with the onset at ~6.3 eV, which is assigned to the edge of interconfigurational spin-allowed 4f – 5d transitions in Er 3+ . The intensity of 4 D 1/2 luminescence is strongly reduced at excitation photon energies above the edge of YAG host absorption at h 6.7 eV, where mainly 2 P 3/2 4f – 4f luminescence is observed (Fig. 2). In the case of the host absorption an effective host - Er 3+ ( 2 P 3/2 ) energy transfer takes place. The excitation spectrum of 2 P 3/2 4f – 4f luminescence also shows the band with the onset at ~6.3 eV, but in this case there are no drastic changes in the spectrum above the edge of the host absorption energy at h 6.7 eV, only small increase of intensity confirms the efficient energy transfer process from the host to 2 P 3/2 multiplet of Er 3+ . For comparison, the excitation spectrum of excitonic emission from “pure” YAG is also shown. However, in the CL spectrum of YAG:Er at 6 K both 2 P 3/2 and 4 D 1/2 4f – 4f luminescence is observed. In addition to narrow-line Er 3+ 4f – 4f luminescence the fast broadband emission at 6.2 eV has been detected under both VUV photon and electron beam excitation (Fig. 2). This emission was assigned to 4f 10 5d – 4f 11 interconfigurational spin-allowed transitions in the Er 3+ ion. The necessary condition for the observation of 5d – 4f radiative transitions in RE 3+ is the existence of large enough energy gap between the lowest 5d level and the closest lower-lying excited levels of 4f n configuration. Otherwise 5d – 4f luminescence will be completely quenched due to nonradiative transitions from the lowest RE 3+ 5d level to 4f levels. The position of the lowest low-spin 5d level of Er 3+ can be located in the middle between 6.2 eV emission band and first excitation band of 4f – 4f emission, i.e. at ~6.3 eV (50800 cm -1 ). From Er 3+ ion’s 4f energy level diagram [1] it is visible (see Fig. 3), that the lowest low-spin 5d level has a considerable energy gap (~1600 cm -1 ) to the next lower 4f 2 D(2) 5/2 crystal-field level (situated at ~49200 cm -1 ), which leads to the appearance of weak 5d – 4f luminescence. At higher temperatures nonradiative processes depopulate 5d level and no 5d – 4f luminescence can be detected. Estimations based on data from [2] show that the lowest high-spin 5d level of Er 3+ in YAG should be situated in the same energy range as crystal-field levels of the 2 L 15/2 multiplet term and only at ~500 cm -1 above the 4 D 1/2 level. Such an energetic location allows fast nonradiative depopulation channel of the 5d level, which results in complete absence of spin-forbidden 5d – 4f luminescence. In Fig. 4 the temperature dependence of Er 3+ 5d – 4f luminescence intensity is shown. At temperatures higher than 40 K the emission intensity is significantly reduced. This thermal quenching is due to circumstance that at higher temperatures mainly non-radiative depopulation of 5d level takes place, whereas at low temperatures radiative transitions clearly compete with non-radiative decay. However, after the strong decrease of intensity at T > 40 K the emission intensity does not reach zero value, and there is a plateau of intensity up to ~200 K after which the emission at 6.2 eV becomes completely quenched. As can be seen from Fig. 4, there is an anti-correlation between the temperature dependencies of 6.2 eV and 4.9 eV (STE) emissions. This effect is from a competition of two channels of energy branching between two processes: energy transfer to Er 3+ (with its excitation to 5d level) and thermally activated formation of STEs. Such anti-correlated behavior confirms also that excitonic mechanism of the energy transfer from the host to Er 3+ does not lead to the excitation of Er 3+ ions to 5d level. Conclusion Fast UV luminescence at 6.2 eV has been detected at low temperature from Er 3+ doped YAG under both photon and electron beam excitation. This luminescence was assigned to 5d – 4f spin-allowed radiative transitions in Er 3+ . Under the YAG host absorption the 2 P 3/2 4f – 4f luminescence of Er 3+ is efficiently excited whereas under the Er 3+ 4f – 5d excitation the radiative transitions from the 4f 4 D 1/2 level dominate in the emission spectrum. Figure 2. Excitation spectra of the 4 D 1/2 and 2 P 3/2 4f – 4f luminescence from YAG:Er 3+ and of intrinsic emission from “pure” YAG. Temperature is 9 K. For comparison d – f emission spectra (VUV range) under both photon and electron (CL at 5.6 K) excitation is also shown. Figure 1. Emission spectrum of YAG:Er 3+ crystal in UV/visible spectral range upon Er 3+ 4f – 5d (6.67 eV, black line) at 9 K and host absorption (7.5 eV, red line) at 292 K excitation. References [1] R. Wegh, Ph.D. Thesis, Utrecht University, Netherlands, 1999. [2] P. Dorenbos, J. Lumin. 91 (2000) 91, 155. [3] G. Zimmerer, Nucl. Instr. Meth. A 308 (1991) 178. [4] G. Zimmerer, Radiation Measurements 42 (2007) 859. [5] E. Feldbach, A. Kotlov, I. Kudryavtseva, P. Liblik, A. Lushchik, A. Maaroos, I. Martinson, V.Nagirnyi, E. Vasil’chenko, Nucl. Instr. Meth. B 250 (2006) 156. 200 300 400 500 600 700 4 I 15/2 4 I 15/2 4 I 11/2 4 I 13/2 2 P 3/2 2 H 11/2 4 F 3/2 4 F 5/2 4 F 7/2 4 F 9/2 4 I 13/2 4 I 11/2 4 I 9/2 T =292 K h ex = 7 .5 e V h ex = 6 .7 e V T =9 K YA G :E r 3+ In te n sity W a ve le n g th (n m ) 4 D 1/2 4 S 3/2 6 7 8 h ex =6.7 eV em =404 nm (E r 3+ : 2 P 3/2 4 I 13/2 ) In te n sity P h o to n e n e rg y (eV ) YA G :E r 3+ T =9 K em =317.4 nm (E r 3+ : 4 D 1/2 4 F 9/2 ) T = 5 .6 K CL x50 YAG "p u re " h em =4.7 eV (S TE ) Figure 3. Energy level diagram illustrating the relative positions of 4f and 5d levels of Er 3+ in YAG. Solid arrows mark radiative decay and dashed arrows non-radiative transitions. 44 48 52 56 2 L 1 5/2 4f 11 2 I 13/2 4 D 1/2 2 D (2) 5/2 2 H (1) 11 /2 2 F (2) 7/2 2 D (2) 3/2 4f 10 5d E n e rg y (1 0 3 cm -1 ) LS HS 0 50 100 150 200 250 300 h em = 6 .2 e V h em = 4.9 e V Lum in e sce n ce in te n sity T em p era ture (K ) Figure 4. Temperature dependencies of Er 3+ 5d – 4f luminescence (6.2 eV) and STE emission (4.9 eV) from YAG:Er 3+ crystal under excitation with 5 keV electron beam. Acknowledgements This work has been supported by by the European Community under Contract RII3-CT-2004-506008 (IA-SFS) (VUV studies), and by the Estonian Science Foundation (grant 6538). E. Aleksanyan gratefully acknowledges a PhD fellowship by SA Archimedes.
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Transcript of Luminescence and excitation spectra due to inter- and intraconfigurational transitions of Er 3+ in...
Luminescence and excitation spectra due to inter- and intraconfigurational transitions of
Er3+ in YAG:Er
Aleksanyan Eduarda,b*, Harutunyan Vachaganb, Kostanyan Radikc, Feldbach Eduarda, Kirm Marcoa, Liblik Peetera, Makhov Vladimira,d, Vielhauer Sebastiana
aInstitute of Physics, University of Tartu, 142 Riia Str., 51014 Tartu, EstoniabYerevan Physics Institute, 2 Alikhanian Brothers Str., 0036 Yerevan, ArmeniacInstitute for Physical Research, Armenian National Academy of Sciences, 0203 Ashtarak-2, ArmeniadLebedev Physical Institute, 53 Leninskii Prospect, 119991 Moscow, RussiaAbstract
Inter-configurational 4f105d ↔ 4f11 transitions of the Er3+ ion in the YAG host were studied under both VUV photon (using synchrotron radiation) and electron beam excitation. It was found that the lowest low-spin 5d level of the Er3+ ion has a rather large energy gap to the next lower 4f 2D(2)5/2 crystal-field level, which results in a relatively low rate of non-radiative transitions from this 5d level leading to the appearance of weak spin-allowed 5d – 4f luminescence at low temperature. The lowest high-spin 5d level, from which spin-forbidden 5d – 4f radiative transitions could occur potentially, is situated only at ~500 cm-1 above the 4D1/2 level. Such close location allows fast depopulation of the 5d level resulting in the absence of spin-forbidden 5d – 4f luminescence and appearance of 4D1/2 4f – 4f luminescence.
Experiment and samples Photoluminescence experiments were carried out at the SUPERLUMI station of HASYLAB at DESY using for excitation 3.75 – 20 eV synchrotron radiation from the DORIS storage ring [3,4]. The excitation spectra were recorded with an instrumental resolution of ~0.3 nm. Emission in UV/visible spectral range was analysed by using a 0.3 m Czerny-Turner monochromator-spectrograph equipped with a photomultiplier tube. VUV luminescence was recorded through a 0.5 m Pouey-type VUV monochromator equipped with a solar-blind photomultiplier tube. The spectral resolution of both monochromators was ~2 nm. Measured emission spectra were not corrected for the spectral response of the detection system. YAG:Er3+ single crystal was grown by the Czochralski technique. The RE3+ ions occupy in YAG the Y3+ sites with D2 point symmetry, and each site is coordinated to eight oxygens. The crystals were cleaved prior to the mounting onto a copper sample holder attached to a cold finger of a flow-type liquid helium cryostat. The orientation of crystallographic axes of the crystal was arbitrary with respect to polarization vector of exciting synchrotron radiation. All measurements were performed under ultrahigh vacuum conditions. Cathodoluminescence (CL) experiments were carried out with a special setup at the Institute of Physics, University of Tartu [5]. CL was detected in the region of 4 – 12 eV through a double vacuum-grating monochromator equipped with a photomultiplier tube. The CL spectra were measured in the temperature range of 5 – 420 K. The characteristics of the electron gun are: tuneable electron energy 1 – 30 keV and electron current 10 – 100 nA, a typical spot size ~0.5 mm2.
Results and discussion Figures 1 and 2 show emission and excitation spectra of YAG:Er3+ measured at 9 and 292 K, respectively. The excitation spectrum of 4D1/2 4f – 4f luminescence at 9 K shows an intense broad band with the onset at ~6.3 eV, which is assigned to the edge of interconfigurational spin-allowed 4f – 5d transitions in Er3+. The intensity of 4D1/2 luminescence is strongly reduced at excitation photon energies above the edge of YAG host absorption at h 6.7 eV, where mainly 2P3/2 4f – 4f luminescence is observed (Fig. 2). In the case of the host absorption an effective host - Er3+ (2P3/2) energy transfer takes place. The excitation spectrum of 2P3/2 4f – 4f luminescence also shows the band with the onset at ~6.3 eV, but in this case there are no drastic changes in the spectrum above the edge of the host absorption energy at h 6.7 eV, only small increase of intensity confirms the efficient energy transfer process from the host to 2P3/2 multiplet of Er3+. For comparison, the excitation spectrum of excitonic emission from “pure” YAG is also shown. However, in the CL spectrum of YAG:Er at 6 K both 2P3/2 and 4D1/2 4f – 4f luminescence is observed. In addition to narrow-line Er3+ 4f – 4f luminescence the fast broadband emission at 6.2 eV has been detected under both VUV photon and electron beam excitation (Fig. 2). This emission was assigned to 4f105d – 4f11 interconfigurational spin-allowed transitions in the Er3+ ion. The necessary condition for the observation of 5d – 4f radiative transitions in RE3+ is the existence of large enough energy gap between the lowest 5d level and the closest lower-lying excited levels of 4fn configuration. Otherwise 5d – 4f luminescence will be completely quenched due to nonradiative transitions from the lowest RE3+ 5d level to 4f levels. The position of the lowest low-spin 5d level of Er3+ can be located in the middle between 6.2 eV emission band and first excitation band of 4f – 4f emission, i.e. at ~6.3 eV (50800 cm-1). From Er3+ ion’s 4f energy level diagram [1] it is visible (see Fig. 3), that the lowest low-spin 5d level has a considerable energy gap (~1600 cm-1) to the next lower 4f 2D(2)5/2 crystal-field level (situated at ~49200 cm-1), which leads to the appearance of weak 5d – 4f luminescence. At higher temperatures nonradiative processes depopulate 5d level and no 5d – 4f luminescence can be detected. Estimations based on data from [2] show that the lowest high-spin 5d level of Er3+ in YAG should be situated in the same energy range as crystal-field levels of the 2L15/2 multiplet term and only at ~500 cm-1 above the 4D1/2 level. Such an energetic location allows fast nonradiative depopulation channel of the 5d level, which results in complete absence of spin-forbidden 5d – 4f luminescence.In Fig. 4 the temperature dependence of Er3+ 5d – 4f luminescence intensity is shown. At temperatures higher than 40 K the emission intensity is significantly reduced. This thermal quenching is due to circumstance that at higher temperatures mainly non-radiative depopulation of 5d level takes place, whereas at low temperatures radiative transitions clearly compete with non-radiative decay. However, after the strong decrease of intensity at T > 40 K the emission intensity does not reach zero value, and there is a plateau of intensity up to ~200 K after which the emission at 6.2 eV becomes completely quenched. As can be seen from Fig. 4, there is an anti-correlation between the temperature dependencies of 6.2 eV and 4.9 eV (STE) emissions. This effect is from a competition of two channels of energy branching between two processes: energy transfer to Er3+ (with its excitation to 5d level) and thermally activated formation of STEs. Such anti-correlated behavior confirms also that excitonic mechanism of the energy transfer from the host to Er3+ does not lead to the excitation of Er3+ ions to 5d level.
Conclusion Fast UV luminescence at 6.2 eV has been detected at low temperature from Er3+ doped YAG under both photon and electron beam excitation. This luminescence was assigned to 5d – 4f spin-allowed radiative transitions in Er3+. Under the YAG host absorption the 2P3/2 4f – 4f luminescence of Er3+ is efficiently excited whereas under the Er3+ 4f – 5d excitation the radiative transitions from the 4f 4D1/2 level dominate in the emission spectrum.
Figure 2. Excitation spectra of the 4D1/2 and 2P3/2 4f – 4f luminescence from YAG:Er3+ and of intrinsic emission from “pure” YAG. Temperature is 9 K. For comparison d – f emission spectra (VUV range) under both photon and electron (CL at 5.6 K) excitation is also shown.
Figure 1. Emission spectrum of YAG:Er3+ crystal in UV/visible spectral range upon Er3+ 4f – 5d (6.67 eV, black line) at 9 K and host absorption (7.5 eV, red line) at 292 K excitation.
References [1] R. Wegh, Ph.D. Thesis, Utrecht University, Netherlands, 1999.[2] P. Dorenbos, J. Lumin. 91 (2000) 91, 155.[3] G. Zimmerer, Nucl. Instr. Meth. A 308 (1991) 178.[4] G. Zimmerer, Radiation Measurements 42 (2007) 859.[5] E. Feldbach, A. Kotlov, I. Kudryavtseva, P. Liblik, A. Lushchik, A. Maaroos, I. Martinson, V.Nagirnyi, E. Vasil’chenko, Nucl. Instr. Meth. B 250 (2006) 156.
200 300 400 500 600 700
4I15/2
4I15/2
4I11/2
4I13/2
2P3/2
2H11/2 4F
3/2
4F5/2
4F7/2
4F9/2
4I13/2
4I11/2
4I9/2 T=292 K
hex
=7.5 eV
hex
=6.7 eV
T=9 K
YAG:Er3+
Inte
nsi
ty
Wavelength (nm)
4D1/2
4S3/2
6 7 8
hex
=6.7 eV
em
=404 nm (Er3+: 2P3/2
4I13/2
)
Inte
nsi
ty
Photon energy (eV)
YAG:Er3+T=9 K
em
=317.4 nm (Er3+: 4D1/2
4F9/2
)
T=5.6 K
CL
x50
YAG "pure"
hem
=4.7 eV (STE)
Figure 3. Energy level diagram illustrating the relative positions of 4f and 5d levels of Er3+ in YAG. Solid arrows mark radiative decay and dashed arrows non-radiative transitions.
44
48
52
56
2L15/2
4f11
2I13/2
4D1/2
2D(2)5/2
2H(1)11/2
2F(2)7/2
2D(2)3/2
4f105d
En
erg
y (1
03 cm
-1)
LS
HS
0 50 100 150 200 250 300
hem
=6.2 eV
hem
=4.9 eV
Lu
min
esc
en
ce in
ten
sity
Temperature (K)
Figure 4. Temperature dependencies of Er3+ 5d – 4f luminescence (6.2 eV) and STE emission (4.9 eV) from YAG:Er3+ crystal under excitation with 5 keV electron beam.
Acknowledgements
This work has been supported by by the European Community under Contract RII3-CT-2004-506008 (IA-SFS) (VUV studies), and by the Estonian Science Foundation (grant 6538). E. Aleksanyan gratefully acknowledges a PhD fellowship by SA Archimedes.
