Temperature-dependent photoluminescence spectra of Er-Tm-codoped Al2O3 thin film

Er-Tm-codoped Al₂O₃ thin films with different Tm to Er concentration ratios were synthesized by cosputtering from separated Er, Tm, Si, and Al₂O₃ targets. The temperature dependence of photoluminescence (PL) spectra was studied. A flat and broad emission band was achieved in the 1.4-1.7 μm and the observed 1470, 1533 and 1800 nm emission bands were attributed to the transitions of Tm³⁺: ³H₄ → ³F₄, Er³⁺: ⁴I_13/2 → ⁴I_15/2 and Tm³⁺: ³F₄ → ³H₆, respectively. The temperature dependence is rather complicated. With increasing measuring temperature, the peak intensity related to Er³⁺ ions increases by a factor of five, while the Tm³⁺ PL intensity at 1800 nm decreases by one order of magnitude. This phenomenon is attributed to a complicated energy transfer (ET) processes involving both Er³⁺ and Tm³⁺ and increase of phonon-assisted ET rate with temperature as well. It should be helpful to fully understand ET processes between Er and Tm and achieve flat and broad emission band at different operating temperatures.     

Multiphoton ultraviolet and visible upconversion luminescence of TmYb co-doped oxyfluoride glass

The ultraviolet upconversion luminescence of Tm³⁺ ions sensitized by Yb³⁺ ions in oxyfluoride glass when excited by a 975 nm diode laser was studied in this paper. One typical ultraviolet upconversion luminescence lines positioned at 362.3 nm was found. It can be attributed to the five-photon upconversion luminescence transition of ¹D₂ → ³H₆. Several visible upconversion luminescence lines at 451.1 nm, (477.9 nm, 462.5 nm), 648.7 nm, (680.5 nm, 699.5 nm) and (777.5 nm, 800.7 nm) were found also, which results from the fluorescence transitions of five-photon ¹D₂ → ³F₄, three-photon ¹G₄ → ³H₆, three-photon ¹G₄ → ³F₄, two-photon ³F₃ → ³H₆ and two-photon ³H₄ → ³H₆ of Tm³⁺ ion, respectively. The theoretical analysis suggests that the upconversion mechanism of the 362.3 nm ¹D₂ → ³H₆ upconversion luminescence is the cross energy transfer of {³H₄(Tm³⁺) → ³F₄(Tm³⁺), ¹G₄(Tm³⁺) → ¹D₂(Tm³⁺)} and {¹G₄(Tm³⁺) → ³F₄(Tm³⁺), ³H₄(Tm³⁺) → ¹D₂(Tm³⁺)} between Tm³⁺ ions. In addition, the upconversion luminescence of ¹G₄ and ³H₄ state results from the sequential energy transfer {²F_5/2(Yb³⁺) → ²F_7/2(Yb³⁺), ³H₄(Tm³⁺) → ¹G₄(Tm³⁺)} and {²F_5/2(Yb³⁺) → ²F_7/2(Yb³⁺), ³F₄(Tm³⁺) → ³F₂(Tm³⁺)} from Yb³⁺ ions to Tm³⁺ions, respectively.     

Spectral performance and intensive green upconversion luminescence in Er/Yb-codoped NaY(WO4)2 crystal

Using Czochralski (CZ) pulling method, an Er³⁺/Yb³⁺-codoped NaY(WO₄)₂ crystal was prepared. Absorption spectra, emission spectra and excitation spectra of this crystal were measured at room temperature. Some optical parameters, such as intensity parameters, spontaneous emission probabilities and lifetimes, were calculated from absorption spectra with Judd-Ofelt (J-O) theory. Upconversion luminescence excited by a 970 nm diode laser was studied. In this crystal, green upconversion luminescence is particularly intensive. Energy transfer mechanisms that play an important role in upconversion processes were analyzed. Two cross-relaxation processes: ⁴G_11/2 + ⁴I_9/2 → ²H_11/2 (or ⁴S_3/2) + ²H_11/2 (or ⁴S_3/2), and ⁴G_11/2 + ⁴I_15/2 → ²H_11/2 (or ⁴S_3/2) + ²I_13/2, which contribute to the intensive green luminescence under 378 nm excitation, were put forward. Background energy transfer ⁴G_11/2(Er³⁺) + ²F_7/2(Yb³⁺) → ⁴F_9/2(Er³⁺) + ²F_5/2(Yb³⁺) was also demonstrated.     

Spectral analysis of Pr-, Sm- and Dy-doped transparent GeO2-BaO-TiO2 glass ceramics

In this paper, we present the photoluminescence properties of Pr³⁺-, Sm³⁺- and Dy³⁺-doped germanate glasses and glass ceramics. From the X-ray diffraction measurement, the host glass structure was determined. These glasses have shown strong absorption bands in the near-infrared (NIR) region. Compared to Pr³⁺-, Sm³⁺- and Dy³⁺-doped glasses, their respective glass ceramics have shown stronger emissions due to the Ba₂TiGe₂O₈ crystalline phase. For Pr³⁺-doped glass and glass ceramic, emission bands centered at 530 nm (³P₀→³H₅), 614 nm (³P₀→³H₆), 647 nm (³P₀→³F₂) and 686 nm (³P₀→³F₃) have been observed with 485 nm (³H₄→³P₀) excitation wavelength. Of them, 647 nm (³P₀→³F₂) has shown bright red emission. Emission bands of ⁴G_5/2→⁶H_5/2 (565 nm), ⁴G_5/2→⁶H_7/2 (602 nm) and ⁴G_5/2→⁶H_9/2 (648 nm) for the Sm³⁺:glass and glass ceramic, with excitation at ⁶H_5/2→⁴F_7/2 (405 nm) have been recorded. Of them, ⁴G_5/2→⁶H_7/2 (602 nm) has shown a bright orange emission. With regard to the Dy³⁺:glass and glass ceramic, a bright fluorescent yellow emission at 577 nm (⁴F_9/2→⁶H_13/2) has been observed, apart from ⁴F_9/2→⁶H_11/2 (667 nm) emission transition with an excitation at 454 nm (⁶H_15/2→⁴I_15/2) wavelength. The stimulated emission cross-sections of all the emission bands of Pr³⁺, Sm³⁺ and Dy³⁺:glasses and glass ceramics have been computed based on their measured full-width at half-maxima (FWHM, Δλ) and lifetimes (τ_m).     

Upconversion luminescence and mechanisms in Yb-sensitized Tm-doped oxyhalide tellurite glasses

Effect of Yb₂O₃ content on upconversion luminescence and mechanisms in Yb³⁺-sensitized Tm³⁺-doped oxyhalide tellurite glasses were investigated under 980 nm excitation. Intense blue and relatively weak red upconversion emission centered at 476 and 649 nm corresponding to the transitions ¹G₄→³H₆ and ¹G₄→³H₄ of Tm³⁺, respectively, are simultaneously observed at room temperature. The results show that upconversion blue and red emission intensities of Tm³⁺ first increase, reach its maximum at Yb₂O₃%=3 mol%, and then decrease with increasing Yb₂O₃ content. The effect of Yb₂O₃ content on upconversion intensity is discussed, and possible effect mechanisms are evaluated. The investigated results were conducing to increase upconversion luminescence efficiency of Tm³⁺.     

Spectroscopic investigations of Nd-, Er-, Er/Yb-, and Tm-ions doped SiO2-Al2O3-CaF2-GdF3 glasses

This paper reports on the absorption, visible and near-infrared luminescence properties of Nd³⁺, Er³⁺, Er³⁺/2Yb³⁺, and Tm³⁺ doped oxyfluoride aluminosilicate glasses. From the measured absorption spectra, Judd-Ofelt (J-O) intensity parameters (Ω₂, Ω₄ and Ω₆) have been calculated for all the studied ions. Decay lifetime curves were measured for the visible emissions of Er³⁺ (558 nm, green), and Tm³⁺ (650 and 795 nm), respectively. The near infrared emission spectrum of Nd³⁺ doped glass has shown full width at half maximum (FWHM) around 45 nm (for the ⁴F_3/2→⁴I_9/2 transition), 45 nm (for the ⁴F_3/2→⁴I_11/2 transition), and 60 nm (for the ⁴F_3/2→⁴I_13/2 transition), respectively, with 800 nm laser diode (LD) excitation. For Er³⁺, and Er³⁺/2Yb³⁺ co-doped glasses, the characteristic near infrared emission bands were spectrally centered at 1532 and 1544 nm, respectively, with 980 nm laser diode excitation, exhibiting full width at half maximum around 50 and 90 nm for the erbium ⁴I_13/2→⁴I_15/2 transition. The measured maximum decay times of ⁴I_13/2→⁴I_15/2 transition (at wavelength 1532 and 1544 nm) are about 5.280 and 5.719 ms for 1Er³⁺ and 1Er³⁺/2Yb³⁺ (mol%) co-doped glasses, respectively. The maximum stimulated emission cross sections for ⁴I_13/2→⁴I_15/2 transition of Er³⁺ and Er³⁺/Yb³⁺ are 10.81×10⁻²¹ and 5.723×10^-21 cm². These glasses with better thermal stability, bright visible emissions and broad near-infrared emissions should have potential applications in broadly tunable laser sources, interesting optical luminescent materials and broadband optical amplification at low-loss telecommunication windows.     

Synthesis and luminescence investigation of RE (Eu, Tb and Ce)-doped lithium silicate (Li2SiO3)

Synthesis and photoluminescence (PL) investigations of lithium metasilicate doped with Eu³⁺, Tb³⁺ and Ce³⁺ were carried out. PL spectra of Eu-doped sample showed peaks corresponding to the ⁵D₀→⁷F_j (j=1, 2, 3 and 4) transitions under ultraviolet excitation. Strong red emission coming from the hypersensitive ⁵D₀→⁷F₂ transition of Eu³⁺ ion suggested the presence of the dopant ion in structurally disordered environment. Tb³⁺-doped silicate sample showed blue-green emission corresponding to the ⁵D₄→⁷F_j (j=6, 5 and 4) transitions. Ce-doped sample under excitation from UV, showed a broad emission band in the region 350-370 nm with shoulders around 410 nm. The fluorescence lifetimes of Eu³⁺ and Tb³⁺ ions were found out to be 790 and 600 μs, respectively. For Ce³⁺, the lifetime was of the order of 45 ns. PL spectra of the europium- and terbium-doped samples were compared with commercial red (Y₂O₃:Eu³⁺) and green (LaPO₄:Tb³⁺) phosphors, respectively. It was found that the emission from the doped silicate sample was 37% of the commercial phosphor in case of the Tb-doped sample and 8% of the commercial phosphor in case of the Eu-doped sample.     

Effect of composition on the spontaneous emission probabilities, stimulated emission cross-sections and local environment of Tm in TeO2-WO3 glass

Effect of composition on the structure, spontaneous and stimulated emission probabilities of various 1.0 mol% Tm₂O₃ doped (1−x)TeO₂+(x)WO₃ glasses were investigated using Raman spectroscopy, ultraviolet-visible-near-infrared (UV/VIS/NIR) absorption and luminescence measurements.Absorption measurements in the UV/VIS/NIR region were used to determine spontaneous emission probabilities for the 4f-4f transitions of Tm³⁺ ions. Six absorption bands corresponding to the absorption of the ¹G₄, ³F₂, ³F₃ and ³F₄, ³H₅ and ³H₄ levels from the ³H₆ ground level were observed. Integrated absorption cross-section of each band except that of ³H₅ level was found to vary with the glass composition. Luminescence spectra of the samples were measured upon 457.9 nm excitation. Three emission bands centered at 476 nm (¹G₄→³H₆ transition), 651 nm (¹G₄→³H₄ transition) and 800 nm (¹G₄→³H₅ transition) were observed. Spontaneous emission cross-sections together with the luminescence spectra measured upon 457.9 nm excitation were used to determine the stimulated emission cross-sections of these emissions.The effect of glass composition on the Judd-Ofelt parameters and therefore on the spontaneous and the stimulated emission cross-sections for the metastable levels of Tm³⁺ ions were discussed in detail. The effect of temperature on the stimulated emission cross-sections for the emissions observed upon 457.9 nm excitation was also discussed.     

Emission analysis of Dy and Pr:Bi2O3-ZnF2-B2O3-Li2O-Na2O glasses

In this paper, we present the spectral results of Dy³⁺ and Pr³⁺ (1.0 mol%) ions doped Bi₂O₃-ZnF₂-B₂O₃-Li₂O-Na₂O glasses. Measurements of X-ray diffraction (XRD), differential scanning calorimetry (DSC) profiles of these rare-earth ions doped glasses have been carried out. From the DSC thermograms, glass transition (T_g), crystallization (T_c) and melting (T_m) temperatures have been evaluated. The direct and indirect optical band gaps have been calculated based on the glasses UV absorption spectra. The emission spectrum of Dy³⁺:glass has shown two emission transitions ⁴F_7/2→⁶H_15/2 (482 nm) and ⁴F_7/2→⁶H_13/2 (576 nm) with an excitation at 390 nm wavelength and Pr³⁺:glass has shown a strong emission transition ¹D₂→³H₄ (610 nm) with an excitation at 445 nm. Upon exposure to UV radiation, Dy³⁺ and Pr³⁺ glasses have shown bright yellow and reddish colors, respectively, from their surfaces.     

Growth and spectral properties of Tm/Er:NaGd(MoO4)2 single crystal

The Tm³⁺/Er³⁺:NaGd(MoO₄)₂ crystal with dimensions of Φ22×30 mm³ was grown by Czochralski method. Polarized spectra and fluorescence lifetime for the ⁴I_13/2(Er³⁺)→⁴I_15/2(Er³⁺) transition at room temperature were investigated. Based on the Judd-Ofelt theory, the spontaneous transition probabilities, the fluorescent branching ratios and the radiative lifetimes were calculated. The fluorescence lifetime was measured to be 1.81 ms. The detailed excited-transition mechanism with 800 nm radiation is also discussed.     

Role of Yb and Tm ions in upconversion emission of Tb under 798 and 980 nm laser excitations in Tb-Tm-Yb doped tellurite glass

Upconversion emission and energy transfer processes in singly, doubly and triply doped tellurite glasses have been studied under 798 and 980 nm laser excitations. Emissions have been observed at 482, 544, 584, 655 nm and at 477, 655, 698, 800 nm corresponding to Tb³⁺: ⁵D₄ → ⁷F₆, ⁷F₅, ⁷F₄, ⁷F_J (J = 0, 1, 2, 3) and Tm³⁺: ¹G₄ → ³H₆, ¹G₄ → ³F₄, ³F₃ → ³H₆, ³H₄ → ³H₆ transitions, respectively. Among Tm³⁺, Yb³⁺and Tb³⁺ ions only Tm³⁺ has a ground state absorption at 798 nm excitation due to ³H₄ ← ³H₆ transition. For 980 nm excitation only Yb³⁺ can absorb the incident radiation. However, for both types of excitations, emission from all the three ions Tb, Yb and Tm has been observed. Possible mechanisms are proposed as follows: under 798 nm excitation Tm³⁺ ions are excited which excite Yb³⁺ ions through energy transfer. Finally “cooperative energy transfer” from a pair of Yb³⁺ ions to Tm³⁺ and Tb³⁺ ions takes place. Under 980 nm excitation Yb³⁺ ions absorb the incident energy and excite Tm³⁺ and Tb³⁺ ions via cooperative energy transfer. Variation of emission intensity with the ion concentrations of Yb³⁺, Tm³⁺ and Tb³⁺ has been studied. The lifetime of the ¹G₄ level has also been measured.     

Energy transfer and upconversion luminescence in Tm/Yb co-doped lanthanum-zinc-lead-tellurite glasses

A series of Tm³⁺/Yb³⁺ co-doped lanthanum-zinc-lead-tellurite (TPZL) glasses pumped by a 980 nm laser diode (LD) were demonstrated to obtain a high efficiency of infrared-to-visible upconversion. Effects of PbO content on the thermal stability, structure and upconversion properties of Tm³⁺/Yb³⁺ co-doped TPZL glasses had been investigated. The efficient visible upconversion fluorescences corresponding to the ¹G₄→³H₆, ¹G₄→³F₄ and ³H₄→³H₆ transitions of Tm³⁺ were observed under 980 nm excitation. The upconversion intensities of blue, red and near infrared emissions in Tm³⁺/Yb³⁺ co-doped TPZL glasses were obviously enhanced with increasing PbO content. The dependence of upconversion intensities on excitation power and the possible upconversion mechanisms had been evaluated by a proper rate equation model. Population density in different levels and coefficients of the energy transfer rate C_Di (i=2, 4, 6) between Tm³⁺ and Yb³⁺ were estimated by fitting the simulated curves to the measured ones. The obtained three energy transfer coefficients C_D2, C_D4, and C_D6 were determined to be 5.7×10⁻¹⁷, 1.3×10⁻¹⁶ and 8.6×10⁻¹⁷ cm³/s, respectively.     

Efficient blue upconversion emission due to confined radiative energy transfer in Tm-Nd co-doped Ta2O5 waveguides under infrared-laser excitation

Intense blue upconversion emission at 480 nm has been obtained at room temperature in Tm³⁺-Nd³⁺ co-doped Ta₂O₅ channel waveguides fabricated on a Si substrate, when the sample is excited with an infrared laser at 793 nm. The upconversion mechanism is based on the radiative relaxation of the Nd³⁺ ions (⁴F_3/2 → ⁴I_11/2) at about 1064 nm followed by the absorption of the emitted photons by Tm³⁺ ions in the ³H₄ excited state. A coefficient of energy transfer rate as high as 3 × 10⁻¹⁶ cm³/s has been deduced using a rate equation analysis, which is the highest reported for Tm-Nd co-doped systems. The confinement of the 1064 nm emitted radiation in the waveguide structure is the main reason of the high energy transfer probability between Nd³⁺ and Tm³⁺ ions.     

Upconversion fluorescence property of Er/Yb-codoped novel bismuth-germanium glass

Infrared-to-visible upconversion fluorescence property of Er³⁺/Yb³⁺-codoped novel bismuth-germanium glass under 975 nm LD excitation has been studied. Intense green and red emissions centered at 525, 546 and 657 nm, corresponding to the transitions ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2, respectively, were observed at room temperature. The quadratic dependence of the 525, 546 and 657 nm emissions on excitation power indicates that a two-photon absorption process occurs. The structure of the bismuth-germanium glass has been investigated by peak-deconvolution of FT-Raman spectrum, and the structural information was obtained from the peak wavenumbers. This novel bismuth-germanium glass with low maximum phonon energy (∼750 cm⁻¹) can be used as potential host material for upconversion lasers.     

Upconversion studies in Er doped TeO2-M2O (M=Li, Na and K) binary glasses

The luminescence properties of Er³⁺ doped alkali tellurite [ TeO₂-M₂O (M=Li, Na and K)] glasses are investigated. Infrared to visible upconversion emissions are observed at 410, 525, 550 and 658 nm using 797 nm excitation. These bands are assigned to the ²H_9/2  →⁴I_15/2, ²H_11/2  →⁴I_15/2, ⁴S_3/2  →⁴I_15/2, ⁴F_9/2  →⁴I_15/2 transitions of Er³⁺ respectively. Detailed study reveals that the ²H_9/2  →⁴I_15/2 transition at 410 nm involves a three-step process while the other transitions involve two-steps. Excitation with 532 nm radiation gives additional bands at 380, 404, 475 and 843 nm wavelengths due to the ⁴G_11/2  →⁴I_15/2, ²P_3/2  →⁴I_13/2, ²P_3/2  →⁴I_11/2, and ⁴S_3/2  →⁴I_13/2 transitions, respectively, along with the bands observed on NIR excitation. The fluorescence yield is found to be largest for the TeO₂-Na₂O glass. The lifetime of the ⁴S_3/2 level has been measured for all the three cases and used to explain the upconversion mechanisms. The fluorescence intensity ratio corresponding to the two thermally coupled levels (²H_11/2, ⁴S_3/2) has been used to estimate the temperature of the glass. It is observed that the temperature sensing capacity of TeO₂-Li₂O glass is better than the other two glasses.     

Luminescence properties of red-emitting praseodymium-activated BaTi4O9 phosphor

The photoluminescence and low-voltage cathodoluminescence characteristics of BaTi₄O₉:Pr³⁺ were investigated. The excitation band of intervalence charge transfer (IVCT) of BaTi₄O₉:Pr³⁺ emerged distinctly at 330 nm. The resultant emissions appeared at 606-643 nm corresponding to the ¹D₂→³H₄ transition. In BaTi₄O₉:Pr³⁺, the emission of ³P₀→³H₄ transition at 490 nm was not observed. The results were in a pure red color emission.     

Sensitized red luminescence from Bi co-doped Eu: ZnO-B2O3 glasses

Photoluminescence properties of Bi³⁺ co-doped Eu³⁺ containing zinc borate glasses have been investigated and the results are reported here. Bright red emission due to a dominant electric dipole transition ⁵D₀→⁷F₂ of the Eu³⁺ ions has been observed from these glasses. The nature of Stark components from the measured fluorescence transitions of Eu³⁺ ions reveal that the rare earth ions could take the lattice sites of C_s or lower point symmetry in the zinc borate glass hosts. The significant enhancement of Eu³⁺ emission intensity by 346 nm excitation (¹S₀→³P₁ of Bi³⁺ ions) elucidates the sensitization effect of co-dopant. The energy transfer mechanism between sensitizer (Bi³⁺) and activator (Eu³⁺) ions has been explained.     

Optical absorption and emission properties of Nd in TeO2-WO3 and TeO2-WO3-CdO glasses

Effects of WO₃ and CdO on the spectroscopic properties of Nd³⁺ doped tellurite glasses were investigated. The optical band gaps and Urbach energies of the samples were determined using the dependence of the absorption coefficient on the photon energy. The Urbach energies were found to vary from 0.18 to 0.25 eV as the WO₃ content in the binary glasses decreased from 20.0 to 10.0 mol% while the optical band gap of the same glasses did not show an appreciable dependence on the glass composition. Judd-Ofelt (Ω_t) parameters were calculated from the optical absorption spectra measured at room temperature. In all the glasses the J-O parameters follow the same trend as Ω₂>Ω₆>Ω₄. The J-O intensity parameters were used to compute the radiative properties such as the radiative transition probabilities (A_ed), branching ratios (β) and radiative lifetimes (τ_r) for all the possible fluorescence bands. The fluorescence spectra obtained upon 805.2 nm excitation exhibited an intense emission band centered at 1064 nm (⁴F_3/2→⁴I_11/2) and two weak bands at 910 nm (⁴F_3/2→⁴I_9/2), and 1340 nm (⁴F_3/2→⁴I_13/2). The stimulated emission cross-section for the 1064 nm emission was determined using the emission spectra. The highest gain bandwidth (σ_e×Δλ_P) was determined to be 155.4 for the 0.79TeO₂-0.15WO₃-0.05CdO ternary glass composition, which could be more useful as promising material for the design and development of fiber amplifiers and lasers.     

Composition dependent frequency upconversion luminescence in Er-doped oxychloride germanate glasses

Er³⁺-doped oxychloride germanate glasses have been synthesized by conventional melting and quenching method. Structural and thermal stability properties were obtained based on the Raman spectra and differential thermal analysis, indicating that PbCl₂ plays an important role in the formation of glass network and has an important influence on the maximum phonon energy and thermal stability of host glasses. Intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2, respectively, were observed at room temperature. With increasing PbCl₂ content, the intensity of green (525 and 546 nm) emissions increases significantly, while the red (657 nm) emission increases slowly. The results indicate that PbCl₂ has more influence on the green emissions than the red emission in oxychloride germanate glasses. The possible upconversion luminescence mechanisms has also been estimated and discussed.     

VUV spectroscopic properties of Ce and Pr-doped AREP2O7-type alkali rare earth diphosphates (A=Na, K, Rb, Cs; RE=Y, Lu)

Spectroscopic properties of Ce³⁺ and Pr³⁺-doped AREP₂O₇-type alkali rare earth diphosphates (A=Na, K, Rb, Cs; RE=Y, Lu) have been investigated using VUV spectroscopy technique. Ce³⁺-doped samples show typical Ce³⁺ emission in the range of 325-450 nm. The strong host absorption band starting at around 160 nm indicates that the optical band gap of AREP₂O₇ hosts is at least 7.7 eV, and the host→Ce³⁺ energy transfer process is rather efficient. However, AREP₂O₇:Pr³⁺ samples show less efficient host→Pr³⁺ energy transfer. The direct Pr³⁺ 4f²→4f¹5d¹ excitation, which are 12160±640 cm⁻¹ higher respect to that of Ce³⁺, leads to strong 4f¹5d¹→4f² emission bands in the range of 230-325 nm but no obvious 4f²→4f² emission lines.