Re-absorption process in the upconversion green emission of the erbium ion-doped fluorozirconate glass system

In this paper we report the upconversion emission for the ⁴S_3/2→⁴I_15/2 Stark components of Er³⁺ ion-doped fluorozirconate glass at T=2 K. The spectrum shows only seven peaks, one less than expected theoretically, being missing the peak at the wave number 17,996 cm⁻¹ (λ=555 nm). This result is compared with the luminescence for the same transition at the same conditions which exhibits the eight expected lines. Such a discrepancy is attributed to a re-absorption process (ESRA) between the energy levels ⁴I_13/2 and ²H_9/2.     

Luminescence of Er-doped silicon oxide-zirconia thin films

Er-doped silicon oxide-zirconia thin film samples were prepared by rf co-sputtering. Chemical composition was determined by energy-dispersive spectroscopy (EDS) and X-ray diffraction (XRD) showed that the films were amorphous. X-ray photoelectron spectroscopy (XPS) measurements showed that the matrix of the films consists of a ZrO₂ main body with pockets of silicon oxide, containing no Si nanoparticles (np) distributed within it. The samples were annealed to 700 °C. Er³⁺: ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2, ⁴F_9/2→⁴I_15/2, ⁴I_11/2→⁴I_15/2, and ⁴I_13/2→⁴I_15/2 emissions were observed. Excitation wavelength dependence and excitation photon flux dependence results for the ⁴I_13/2→⁴I_15/2 emission were explained as due to resonant energy transfer from defects in the matrix. ⁴I_11/2→⁴I_15/2 emission dependence on ⁴I_13/2→⁴I_15/2 emission showed that no energy transfer upconversion (ETU) processes were involved and that it was due only to branching from higher levels. ⁴I_13/2→⁴I_15/2 peak intensity decay was interpreted as corresponding to two different populations of Er³⁺ ions. Energy transfer from the defects to the Er ions is very efficient. We concluded that Er-doped silicon oxide-zirconia is a promising material for photonic applications, being excitable at low pumping powers and producing broad-band ⁴I_13/2→⁴I_15/2 emission.     

Tunable upconversion in Er-doped orthorhombic lead fluoride compound

Near infrared-visible upconversion in Er³⁺ doped orthorhombic PbF₂ compound is investigated. It is experimentally observed that the red emission intensity increases monotonously with Er³⁺ concentration increase, while the green emission intensity first increases and then decreases. Based on the rate-equation, the energy transfers involved in the upconversion processes have been explored. It is shown that due to the different multipolar nature for the energy transfer processes of ²H_11/2 (⁴S_3/2)+⁴I_15/2→⁴I_9/2+⁴I_13/2 and ⁴I_11/2+⁴I_11/2→⁴F_7/2+⁴I_15/2, the green and red upconversion emissions depend on Er³⁺ concentration in different ways. The theoretical results are in good agreement with the experimental observation. It is shown that the upconverted emission bands can be tuned by controlling Er³⁺ concentration in orthorhombic PbF₂ compound, which has many photonic applications under NIR excitation.     

Competition between green and infrared emission in Er:YLiF4 upconversion lasers

The competition between two laser transitions in Er:YLiF₄ (⁴S_3/2 → ⁴I_15/2 at 551 nm and ⁴S_3/2 → ⁴I_13/2 at 850 nm) is studied using a model based on rate equations. The laser emission is pumped by upconversion at 795 nm; for comparison, we also discuss upconversion pumping by another mechanism, at 970 nm. The conditions that favor laser emission in various regimes on these two transitions are found.     

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.     

Structural and upconversion fluorescence properties of Er/Yb-codoped oxychloride lead-germanium-bismuth glass

Structural and infrared-to-visible upconversion fluorescence properties of Er³⁺/Yb³⁺-codoped oxychloride lead-germanium-bismuth glass have been studied. The Raman spectrum investigation indicates that PbCl₂ plays an important role in the formation of glass network, and has an important influence on the upconversion luminescence owing to lower phonon energy. 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 under 975 nm excitation.     

Conversion of infrared radiation into visible emission in NaY(WO4)2:Yb, Ho crystal

The spectroscopic characteristics and fluorescence dynamics for Yb³⁺/Ho³⁺:NaY(WO₄)₂ crystal were investigated. The parameters of oscillator strengths, the spontaneous transition probabilities, the fluorescence branching ratios, the radiative lifetimes and the stimulated emission cross sections have been calculated based on Judd-Ofelt theory and Füchtbauer-Ladenburg method. The energy transfer efficiency from Yb³⁺ to Ho³⁺ was 65.85%. The green emission (530-570 nm) corresponding to (⁵F₄, ⁵S₂)→⁵I₈ transition, red emission (640-670 nm) due to ⁵F₅→⁵I₈ transition and NIR emission (740-770 nm) attributed to (⁵F₄, ⁵S₂)→⁵I₇ transition were observed on 974 nm excitation at room temperature. Under low pump power, the intensity of green light emission is weaker than that of the red light, while under high pump power, the case is on the contrary. The upconversion is based on the two-photon process either the energy transfer from Yb³⁺ ions or by the excited state absorption. The proposed mechanisms of upconversion emissions were provided.     

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.     

Crystalline-structure-dependent green and red upconversion emissions of Er-Yb-Li codoped TiO2

Crystalline structures and infrared-to-visible upconversion luminescence spectra have been investigated in 1 mol% Er³⁺, 10 mol% Yb³⁺ and 0-20 mol% Li⁺ codoped TiO₂ [1Er10Yb(0-20)Li:TiO₂] nanocrystals. The crystalline structures of 1Er10Yb(0-20)Li:TiO₂ were divided into three parts by the addition of Yb³⁺ and Li⁺. Both green and red upconversion emissions were observed from the ²H_11/2/⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺ in Er³⁺-Yb³⁺-Li⁺ codoped TiO₂, respectively. The green and red upconversion emissions of 1Er:TiO₂ were enhanced significantly by Yb³⁺ and Li⁺ codoping, in which the intensities of green and red emissions and the intensity ratio of green to red emissions (I_green/I_red) were highly dependent on the crystalline structures. The significant enhanced upconversion emissions resulted from the energy migration between Er³⁺ and Yb³⁺ as well as the distortion of crystal field symmetry of Er³⁺ caused by the dissolving of Li⁺ at lower Li⁺ codoping concentration and the phase transformation at higher Li⁺ concentration. It is concluded that codoping with ions of smaller ionic radius like Li⁺ can efficiently improve the upconversion emissions of Er³⁺ or other rare-earth ions doped luminsecence materials.     

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.     

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.     

Afterglow phenomenon in Erbium and Titanium codoped GD2O2S phosphors

A series of new long-lasting phosphor Gd₂O₂S:xEr,Ti are prepared by the conventional high-temperature solid-state method and their luminescent properties are systematically investigated in this paper. The characteristic afterglow emission of Er, which is due to the transition of ⁴F_9/2→⁴I_15/2 and ⁴S_3/2→⁴I_15/2, is reported for the first time. XRD, photoluminescence, long-lasting phosphorescence and decay curves are used to characterize the synthesized phosphors. The possible energy transfer mechanism of Gd₂O₂S:xEr,Ti is also investigated.     

Strong infrared-to-visible frequency upconversion in Er-doped Sr2CeO4 powders

Efficient upconversion (UC) luminescence is demonstrated in Er³⁺:Sr₂CeO₄ powders prepared by combustion synthesis and exposed to near-infrared (∼975 nm) radiation. The UC emission lines observed at ∼530, ∼550 and ∼665 nm correspond, respectively, to ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 4f-4f transitions of Er³⁺. X-ray powder diffraction data showed that the SrCO₃ phase (impurity) is dramatically reduced when Sr²⁺ is partially substituted by Mg²⁺ ions. The UC phenomenon was investigated by use of continuous wave and pulsed laser excitation and the UC mechanism was attributed to energy transfer between excited Er³⁺ ions.     

Ultraviolet upconversion luminescence enhancement in Yb/Er-codoped Y2O3 nanocrystals induced by tridoping with Li ions

Ultraviolet (UV) upconversion (UC) luminescence in Yb³⁺/Er³⁺-codoped yttrium oxide (Y₂O₃) nanocrystals can be enhanced by orders of magnitude via tridoping further with Li⁺ ions under diode laser excitation of 970 nm. Sensitized three-photon UC radiations at 390 and 409 nm, corresponding to the ⁴G_11/2→⁴I_15/2 and ⁴H_9/2→⁴I_15/2 of Er³⁺ ions, respectively, present an enhancement time of about 33 times, which is larger than the 24 times enhancement for the UC green radiation. The UV UC radiation at 320 nm that corresponds to the ²P_3/2→⁴I_15/2 of Er³⁺ ions has also been greatly enhanced. Theoretical calculations interpret that all the observed enhancement times of UV UC radiations arise from the prolonged lifetimes of their intermediate states.     

Spectral broadening and luminescence quenching of 1.53 μm emission in Er-doped zinc tellurite glass

The emission spectra and the lifetime of the lasing transition ⁴I_13/2→⁴I_15/2 in Er³⁺-doped TeO₂-ZnO binary glass have been studied. The investigation includes Raman scattering spectroscopy as well as optical absorption, luminescence, and lifetime measurements techniques. The influence of erbium concentration on the line-shape of this electron transition has been analyzed. It was observed that the increasing of Er³⁺ ion concentration, in the 0.2-4 mol% range, results in a structural changes and a significant spectral broadening of the 1.53 μm emission band. Reabsorption has been evoked to explain the broadening of the ⁴I_13/2→⁴I_15/2 emission line. In the paper, is also reported the effect of the erbium content on the emission intensity of the ⁴I_13/2→⁴I_15/2 transition as well as on the lifetime of the ⁴I_13/2 level. Based on the electrical-dipole interaction theory, the luminescence concentration quenching mechanism by hydroxyl groups is analyzed. The data suggest that <10% of hydroxyl groups are coupled to erbium ions in the zinc tellurite glass network.     

Host dependent frequency upconversion of Er-doped oxyfluoride germanate glasses

Er³⁺-doped oxyfluoride germanate glasses have been synthesized by the conventional melting and quenching method. The Judd-Ofelt intensity parameters were calculated based on the Judd-Ofelt theory and absorption spectra measurements. With the substitution of PbF₂ for PbO, the Ω₂ parameter decreases, while the Ω₆ parameter increases. These change trends indicate that fluoride anions come to coordinate erbium cations and the covalency of the Er-O bond decreases. Structural and thermal stability properties were obtained by Raman spectra and differential thermal analysis, indicating that PbF₂ 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 simultaneously observed at room temperature. With increasing PbF₂ content, the intensity of red (657 nm) emissions increases significantly, while that of the green (525 and 546 nm) emission increases slightly. The results indicate that PbF₂ has more influence on the red (657 nm) emission than the green (525 and 546 nm) emissions in oxyfluoride germanate glasses. The possible upconversion luminescence mechanisms have also been estimated and discussed.     

Upconversion emission in CaTiO3:Er3+ nanocrystals

CaTiO₃:Er³⁺ (5%) nanocrystals were obtained by sol–gel method under acidic conditions. The sizes of nanocrystals were 40 nm. Strong green anti-Stokes emission was observed after excitation of the ⁴I_9/2 and ⁴I_11/2 level. The emission is due to excited state absorption (ESA) and energy transfer upconversion (ETU).     

NIR to visible upconversion emission from Dy: ZBLYAN glasses

This paper reports on the near infrared (730-783 nm) to the visible upconversion emissions at 482 nm (⁴F_9/2→⁶H_15/2), 576 nm (⁴F_9/2→⁶H_13/2) and 662 nm (⁴F_9/2→⁶H_11/2) from the Dy³⁺doped 53ZrF₄-20BaF₂-2LaF₃-2YF₃-3AlF₃-19NaF-1DyF₃ glasses. We have also carried out a systematic study on the normal emission properties of these glasses in order to understand their performance both as a NIR upconverted visible luminescent and as normal visible fluorescent optical systems of technical importance. With an increase in Dy³⁺ concentration beyond a particular value (1 mol%), activator-activator interaction becomes a significant cause of concentration quenching in the luminescence properties. The dependence of the emission spectra on the excitation wavelengths has also been examined and 451 nm was found to be the ideal excitation wavelength in the measurement of normal fluorescence spectra. In the case of NIR upconverted visible emission, we have observed that the NIR excitation at 783 nm as the suitable pump wavelength in demonstrating prominent visible emission colours from these glasses. The relevance in undertaking these optical materials lies in their potential for upconversion laser application in the visible wavelength region. The NIR upconversion phenomenon has been explained in terms of energy level schemes due to excited state absorption (ESA) and energy transfer upconversion (ETU) processes.     

Ultraviolet upconversion luminescence in Er-doped Y2O3 excited by 532 nm CW compact solid-state laser

Ultraviolet upconversion emissions at 262, 276, 308 and 320 nm were observed from Er³⁺-doped Y₂O₃ with a 532 nm continuous wave compact solid-state laser excitation. Power-dependence analysis demonstrates that two-photon upconversion process populates the ⁴D_5/2, ²H_9/2 and ²P_3/2 states. The energy transfer upconversion (ETU) plays an important role in populating ⁴D_5/2 and ²P_3/2 states. It appears that ²P_3/2 state population originates from ETU ²H_11/2+²H_11/2→⁴I_13/2+²P_3/2, moreover, a subsequent excited state absorption (ESA) from the ⁴I_9/2 level.     

Improvement of Er:I11/2→Ce:F5/2 energy transfer rate in Er/Ce co-doped TeO2-ZnO-Na2O-Nb2O5 glasses

The B₂O₃ component was introduced into Er³⁺/Ce³⁺ co-doped TeO₂-ZnO-Na₂O-Nb₂O₅ glass to improve energy transfer rate of Er³⁺:⁴I_11/2→Ce³⁺:²F_5/2 phonon-assisted cross-relaxation process. With the 6 mol% substitution of B₂O₃ for TeO₂, the energy transfer rate increased from 1300 to 1831 s⁻¹ and the fluorescence intensity increased by about 13.4%. However, the more B₂O₃ substitution in the same glass system reduced the quantum efficiency of Er³⁺:⁴I_13/2→⁴I_15/2 transition due to the higher OH⁻ group concentration. The results show that an appropriate amount of B₂O₃ component can be used to improve the phonon-assisted energy transfer rate and enhance 1.53 μm fluorescence emission by increasing the phonon energy of host glass. The effect of B₂O₃ on the energy transfer process, the lifetimes of the ⁴I_11/2 and ⁴I_13/2 levels, and the upconversion emission have also been investigated.