Lanthanide level location in transition metal complex compounds

Dorenbos, P.; Krumpel, A.H.; Kolk, Erik van der; Boutinaud, Philippe; Bettinelli, Marco; Cavalli, Enrico

doi:10.1016/j.optmat.2010.02.021

Cited by 144 publications

(117 citation statements)

References 20 publications

Supporting

Mentioning

111

Contrasting

Order By: Relevance

“…Since we now know the energy of the first 4f n 5d state for Sm 2+ , the energy of the first 4f n 5d states for all other divalent lanthanides in YPO 4 can be predicted. 14,24 The curve labeled 5d͑2+͒ in Fig. 7 connects those predicted level energies.…”

Section: Discussionmentioning

confidence: 82%

Carrier recombination processes and divalent lanthanide spectroscopy inYPO4:Ce3+;L3+
Dorenbos
¹
,
Bos
²
,
Poolton
³

2010
Phys. Rev. B
Self Cite
20
2
15
0
View full text Add to dashboard Cite

We studied charge carrier trapping, detrapping, and recombination phenomena in Ce 3+ doped YPO 4 , codoped with Sm 3+ , Dy 3+ , or Tm 3+ . Ce ions trap the holes and Sm, Dy, and Tm trap electrons created during x-ray irradiation. By means of red to infrared stimulation, the trapped electrons can be back transferred to Ce leading to shorter wavelength Ce 3+ 5d-4f luminescence. Excitation spectra for this recombination luminescence were recorded from 10 K to room temperature. It provides information on the excited state energies of divalent Sm, Dy, and Tm with respect to the lanthanide ground state energy and with respect to the mobility edge energy of YPO 4 . From the temperature dependence, insight is obtained on the carrier recombination pathways. We will identify temperature independent tunneling recombination, recombination by thermal excitation to the conduction band, and phonon-assisted delocalization of electrons from impurity states within the conduction band.

show abstract

Section: Discussionmentioning

confidence: 82%

Carrier recombination processes and divalent lanthanide spectroscopy inYPO4:Ce3+;L3+
Dorenbos
¹
,
Bos
²
,
Poolton
³

2010
Phys. Rev. B
Self Cite
20
2
15
0
View full text Add to dashboard Cite

show abstract

“…The binding energies with respect to the conduction band are almost the same as in TiO 2 , and like in TiO 2 emission from the 3 For SrTiO 3 , and BaTiO 3 again U (6, A) = 6.7 eV is chosen. The absorption onset in SrTiO 3 is at 3.27 eV [36][37][38] 29 and a renewed evaluation will be made here. The VRBE scheme made with the data collected in Table I is shown in Fig.…”

Section: Methodsmentioning

confidence: 99%

The Electronic Structure of Lanthanide Impurities in TiO₂, ZnO, SnO₂, and Related Compounds

Dorenbos

2013

ECS J. Solid State Sci. Technol.

View full text Add to dashboard Cite

The vacuum referred binding energy of electrons in the 4f n levels for all divalent and trivalent lanthanide impurity states in TiO 2 , ZnO, SnO 2 , and related compounds MTiO 3 and MSnO 3 (M = Ca 2+ , Sr 2+ , Ba 2+ ) and Ca 2 SnO 4 are presented. They are obtained by collecting data from the literature on the spectroscopy of lanthanide ions, and by combining that data with the chemical shift model. The model provides the energy at the top of the valence band and at the bottom of the conduction band, and it will be shown that those energies are in excellent agreement with what is known from techniques like photo-electron spectroscopy and electrochemical studies. Electronic level diagrams are presented that explain and predict aspects like absence or presence of lanthanide 4f-4f or 5d-4f emissions and the preferred lanthanide valence. © 2013 The Electrochemical Society. [DOI: 10.1149/2.005403jss] All rights reserved.Manuscript received October 17, 2013. Published December 20, 2013 Recently the chemical shift model was introduced 1 for the lanthanide impurities in compounds. By using spectroscopic data for different lanthanides like Ce 3+ , Pr 3+ , Tb 3+ , Eu 3+ , Yb 3+ in the same compound, the model enables to derive the electronic structure with the absolute electron binding energies, i.e., relative to the energy of the electron at rest in vacuum, in all divalent and all trivalent lanthanides.2 It has been applied to about 50 different compounds (fluorides, chlorides, aluminates, phosphates, borates etc.) and full consistency with available experimental data from different fields of science was demonstrated.2-4 It was found that in inorganic compounds based on rare earth cations, like YPO 4 and LaBO 3 , and/or alkaline and/or alkaline earth cations like CaF 2 and CaGa 2 S 4 , the binding energy at the bottom of the conduction band E C is typically near −2 eV. Sc-based compounds like ScBO 3 and ScPO 4 tend to show lower values for E C which was attributed to a large binding energy of electrons in the 3d-shell of Sc 3+ /Sc 2+ that forms the bottom of the conduction band. 4 In this work the model will be applied to TiO 2 , ZnO, SnO 2 , and related ternary compounds. The compounds were selected because of their high importance for many applications.TiO 2 has been and still is thoroughly investigated for its photocatalytic activity and ability for photoelectrochemical water splitting. 5The activity can be enhanced or modified by doping with transition metal or rare earth ions. 6,7 Much is already known on the electronic structure and properties of this compound in its various crystallographic appearances, i.e., rutile-TiO 2 , anatase-TiO 2 , and brookiteTiO 2 . Here we will focus on the anatase-phase. ZnO is an important member of the II-VI semiconductor family. An extensive review on the physical and optical properties of ZnO can be found in Ref. 8. At ambient conditions only the wurtzite phase is thermodynamic stable and all data and schemes in this work will pertain to that phase. SnO 2 has much in common with Zn...

show abstract

“…Lines 1 and 2 in Fig. 8 7 Eu ion plus two electrons in its own 6s shell. The experimental 4f -VRBE is −9.99 eV (Ref.…”

Section: Consider the Eumentioning

confidence: 99%

“…Such a so-called host referred 4f -electron binding energy (4f -HRBE) scheme can be constructed routinely for many different compounds using relatively few experimental data as input. [7][8][9] The double zigzag curves connect the lanthanide 4f -HRBE as a function of the number of electrons in the 4f shell. The lower curve (in blue) pertains to the trivalent lanthanide ion and the upper curve (in red) to the divalent lanthanide ion.…”

Section: Introductionmentioning

confidence: 99%

Modeling the chemical shift of lanthanide4felectron binding energies

2012

View full text Add to dashboard Cite

). The 4f -electron binding energy depends on the charge Q of the lanthanide ion and its chemical environment A. Experimental data on three environments (i.e., the bare lanthanide ions where A = vacuum, the pure lanthanide metals, and the lanthanides in aqueous solutions) are employed to determine the 4f -electron binding energies in all divalent and trivalent lanthanides. The action of the chemical environment on the 4f -electron binding energy will be represented by an effective ambient charge Q A = −Q at an effective distance from the lanthanide. This forms the basis of a model that relates the chemical shift of the 4f -electron binding energy in the divalent lanthanide with that in the trivalent one. Eu will be used as the lanthanide of reference, and special attention is devoted to the 4f -electron binding energy difference between Eu 2+ and Eu 3+ . When that difference is known, the model provides the 4f -electron binding energies of all divalent and all trivalent lanthanide ions relative to the vacuum energy.

show abstract

Lanthanide level location in transition metal complex compounds

Cited by 144 publications

References 20 publications

Carrier recombination processes and divalent lanthanide spectroscopy inYPO4:Ce3+;L3+
Dorenbos
¹
,
Bos
²
,
Poolton
³

2010
Phys. Rev. B
Self Cite
20
2
15
0
View full text Add to dashboard Cite

Carrier recombination processes and divalent lanthanide spectroscopy inYPO4:Ce3+;L3+
Dorenbos
¹
,
Bos
²
,
Poolton
³

2010
Phys. Rev. B
Self Cite
20
2
15
0
View full text Add to dashboard Cite

The Electronic Structure of Lanthanide Impurities in TiO₂, ZnO, SnO₂, and Related Compounds

Modeling the chemical shift of lanthanide4felectron binding energies

Contact Info

Product

Resources

About

Lanthanide level location in transition metal complex compounds

Cited by 144 publications

References 20 publications

Carrier recombination processes and divalent lanthanide spectroscopy inYPO4:Ce3+;L3+Dorenbos1, Bos2, Poolton3 2010Phys. Rev. BSelf Cite202150View full textAdd to dashboardCite

Carrier recombination processes and divalent lanthanide spectroscopy inYPO4:Ce3+;L3+Dorenbos1, Bos2, Poolton3 2010Phys. Rev. BSelf Cite202150View full textAdd to dashboardCite

The Electronic Structure of Lanthanide Impurities in TiO2, ZnO, SnO2, and Related Compounds

Modeling the chemical shift of lanthanide4felectron binding energies

Contact Info

Product

Resources

About

Carrier recombination processes and divalent lanthanide spectroscopy inYPO4:Ce3+;L3+
Dorenbos
¹
,
Bos
²
,
Poolton
³

2010
Phys. Rev. B
Self Cite
20
2
15
0
View full text Add to dashboard Cite

Carrier recombination processes and divalent lanthanide spectroscopy inYPO4:Ce3+;L3+
Dorenbos
¹
,
Bos
²
,
Poolton
³

2010
Phys. Rev. B
Self Cite
20
2
15
0
View full text Add to dashboard Cite

The Electronic Structure of Lanthanide Impurities in TiO₂, ZnO, SnO₂, and Related Compounds