Infrared-to-green up-conversion in Er3+, Yb3+-doped monoclinic KGd(WO4)2 single crystals

Optical spectroscopy of the green emission of erbium in KGd(WO₄)₂ (KGW) single crystals codoped with ytterbium ions is investigated. To do this, we firstly grew good-optical-quality KGW single crystals doped with Er³⁺ and Yb³⁺ at several dopant concentrations by the Top-seeded-solution-growth slow-cooling method (TSSG). Green photoluminescence of Er³⁺ in KGW host was studied at room temperature (RT) and low temperature (10 K) by means of Yb³⁺ sensitization after infrared excitation at 981 nm (10194 cm⁻¹). We calculated the emission and gain cross-sections and compared these with those of other known Er³⁺-doped laser materials like LiYF₄ :Er (YLF:Er) and Y₃Al₅O₁₂:Er (YAG:Er) at RT. Our study also focused on determining the optimal concentration of ions for generating the most intense green emission. We measured the lifetime of the green emission after infrared pump at several Yb³⁺ concentrations. From the low-temperature emission experiments, we determined the energy position of the sublevels of the ground state of erbium.     

Frequency upconversion fluorescence studies of Er/Yb-codoped KNbO3 phosphors

Different concentrations of Er³⁺ and Yb³⁺ ions-doped potassium niobate (K_0.9NbO₃:Yb_(x)Er_{(0.1 − x)} for x = 0, 0.01, 0.05, 0.09 and 0.1) polycrystalline powder phosphors were prepared by the conventional solid state reaction method and were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. Energy transfer and upconversion fluorescence properties of the Yb³⁺ and Er³⁺-codoped phosphors have been discussed. The XRD data has shown mono-phase for pure KNbO₃ while the doped samples represented additional phase formation. The SEM micrographs represented the rectangular crystal growth habit for the KNbO₃ phosphors when doped with 0.1 mol of Er³⁺ ions. An intense green emission at 557 nm along with a red emission at 674 nm was observed when the doped samples were excited with 975 nm IR radiation. The upconversion mechanism has been discussed based on the excited state absorption and energy transfer mechanisms.     

Up-conversion luminescence of trivalent-rare-earth ion-doped LnTaO4 (Ln = Y, Gd, La)

The up-conversion luminescence properties of trivalent-rare-earth ion-doped orthotantalates are studied under 980 nm laser diode excitation. The results indicate that YTaO₄:Tm³⁺/Yb³⁺ emits blue and strong infrared emissions respectively corresponding to ¹G₄→³H₆ and ³H₄→³H₆ transitions of Tm³⁺ ions, while YTaO₄:Er³⁺/Yb³⁺ produces strong green and weak red emissions, resulting from ²H_11/2/⁴S_3/2→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 transitions of Er³⁺ ions, respectively. In contrast to three excellent up-conversion phosphors, viz. NaYF₄:Er³⁺/Yb³⁺, Y₂O₂S:Er³⁺/Yb³⁺ and Y₂O₃:Er³⁺, YTaO₄:Er³⁺/Yb³⁺ shows not only strong green emission, but also larger intensity ratio of green to red emission. In addition, it is found that LaTaO₄: Er³⁺/Yb³⁺ shows the minimum quenching concentration of Yb³⁺ and weakest up-conversion emission intensity, and the main peak presents blue shift (8 nm/556 nm) as compared with YTaO₄:Er³⁺/Yb³⁺ and GdTaO₄:Er³⁺/Yb³⁺. The distinct luminescent characteristics of LaTaO₄: Er³⁺/Yb³⁺ can be attributed to the larger difference of radius between doped ion and La³⁺ ion.     

Effect of Yb concentration on the upconversion of Er ion doped La2O3 nanocrystals under 980 nm excitation

The effect of Yb³⁺ concentration on the upconversion of La₂O₃:Yb³⁺, Er³⁺ nanocrystals was reported. Green (about at 530 and 549 nm) and red (around at 672 nm) upconversion emissions under 980 nm excitation were observed at room temperature. It was found that the ratio of green to red upconversion emission intensity is considered as a function of Yb³⁺ ion concentration. Of the samples doped with varying Er³⁺ or constant Er³⁺ ion concentration, it can be observed that the intensity ratio drastically decreases with an Yb³⁺ ion concentration increase and the Yb³⁺ ions concentration is around 3 mol% as the emission intensity ratio of green to red upconversion is close to 1.     

Upconversion emission from Tm:Yb and Tm:Er:Yb doped Y2SiO5 powders prepared by combustion synthesis

Tm³⁺:Er³⁺:Yb³⁺ doped Y₂SiO₅ powders were prepared by combustion synthesis with estimated as-prepared weight (wt.) % concentrations of 0.25:0.0:2.0, 0.25:0.5:2.0 and 0.25:1.0:2.0, respectively. Blue (Tm³⁺: ¹G₄ → ³H₆), green (Er³⁺: ⁴S_3/2, ²H_11/2 → ⁴I_15/2) and red (Er³⁺: ⁴F_9/2 → ⁴I_15/2) upconversion (UC) emissions were observed under 975 nm infrared diode laser excitation. The UC process took place via energy transfer from Yb³⁺ to Er³⁺ and Tm³⁺ ions. The CIE chromaticity coordinates of Tm³⁺:Er³⁺:Yb³⁺ doped Y₂SiO₅ powders were investigated as a function of the diode laser power and Er³⁺ concentration.     

Concentration effect of Nd ion on the spectroscopic properties of Er/Nd co-doped LiYF4 single crystal

High quality Er³⁺/Nd³⁺:LiYF₄ single crystals were grown by a Bridgman method. Their spectroscopic properties were studied to understand the Nd³⁺ concentration effect upon excitation of an 800 nm laser diode. The intensest 2.7 μm emission was observed in the LiYF₄ crystal codoped with 0.99 mol% Er³⁺ and 0.62 mol% Nd³⁺. Meanwhile, the emission intensity for the green up-conversion and 1.5 μm downconversion of Er³⁺ decreased with increasing of the Nd³⁺ concentration. The modified Inokuti–Hirayama model was used to analyze the decay curves of the 1.06 (Nd³⁺) and 1.5 (Er³⁺) μm emissions. The results indicated that the energy transfer process (Er³⁺:⁴I_13/2 + Nd³⁺:⁴I_9/2 → Er³⁺:⁴I_15/2 + Nd³⁺:⁴I_15/2) is mainly due to the electric dipole–dipole interaction. The energy transfer efficiencies between Nd³⁺ and Er³⁺ ions were calculated. All results suggested that the Er³⁺/Nd³⁺:LiYF₄ single crystals may have potential applications in mid-infrared lasers.     

Preparation and upconversion property of TeO2:Er/Yb nanoparticles

Different crystal structure of TeO₂ nanoparticles were used as the host materials to prepare the Er³⁺/Yb³⁺ ions co-doped upconversion luminescent materials. The TeO₂ nanoparticles mainly kept the original morphology and phase after having been co-doped the Er³⁺/Yb³⁺ ions. All the as-prepared TeO₂:Er³⁺/Yb³⁺ nanoparticles showed the green emissions (525 nm, 545 nm) and red emission (667 nm) under 980 nm excitation. The green emissions at 525 nm, 545 nm and red emission at 667 nm were attributed to the ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of the Er³⁺ ions, respectively. For the α-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles, three-photon process involved in the green (²H_11/2 → ⁴I_15/2) emission, while two-photon process involved in the green (⁴S_3/2→⁴I_15/2) and red (⁴F_9/2 → ⁴I_15/2) emissions. For the β-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles, two-photon process involved in the green (²H_11/2 → ⁴I_15/2), green (⁴S_3/2 → ⁴I_15/2) and red (⁴F_9/2 → ⁴I_15/2) emissions. It suggested that the crystal structure of TeO₂ nanoparticles had an effect on transition processes of the Er³⁺/Yb³⁺ ions. The emission intensities of the α-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles and β-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles were much stronger than those of the (α + β)-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles.     

Synthesis and luminescence properties of Yb3+–Er3+ co-doped LaOCl nanostructures

LaOCl:Yb³⁺, Er³⁺ nanofibers and hollow nanofibers were prepared by electrospinning combined with a double-crucible chlorination technique using NH₄Cl as chlorinating agent. X-ray powder diffraction analysis indicated that LaOCl:Yb³⁺, Er³⁺ nanostructures were tetragonal with space group P4/nmm. Scanning electron microscope analysis and histograms revealed that diameters of LaOCl:Yb³⁺, Er³⁺ nanofibers and hollow nanofibers, respectively, were 117.87 ± 15.48 and 141.09 ± 17.10 nm under the 95 % confidence level. Up-conversion (UC) emission spectra analysis manifested that LaOCl:Yb³⁺, Er³⁺ nanostructures exhibited strong green and red UC emission centering at 526, 548, and 671 nm, respectively, attributed to ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2, and ⁴F_9/2 → ⁴I_l5/2 transitions of Er³⁺ ions under the excitation of a 980-nm diode laser. It was found that the relative intensities of green and red emissions vary obviously with the addition of Yb³⁺ ions, and the optimized molar ratio of Yb³⁺ to Er³⁺ was 10:1 in the as-prepared nanofibers. Moreover, the near-infrared characteristic emissions of LaOCl:Yb³⁺, Er³⁺ nanostructures were achieved under the excitation of a 532-nm laser. CIE analysis demonstrated that color-tuned luminescence can be obtained by changing doping concentration of Yb³⁺ (and/or Er³⁺) ions and morphologies of nanomaterials, which could be applied in the fields of optical telecommunication and optoelectronic devices. The UC luminescent mechanism and the formation mechanisms of LaOCl:Yb³⁺, Er³⁺ nanofibers and hollow nanofibers were also proposed.     

Sol-gel synthesis and green upconversion luminescence in BaGd2(MoO4)4:Yb,Er phosphors

Yb³⁺/Er³⁺ codoped BaGd₂(MoO₄)₄ phosphor powders were prepared by the Sol-gel method and the upconversion luminescence properties were investigated in detail. Under 980 nm semiconductor laser excitation, BaGd₂(MoO₄)₄:Yb³⁺,Er³⁺ phosphor exhibits green upconversion luminescence with peaks at 530 and 550 nm, which are due to the transitions of Er³⁺ (²H_11/2) → Er³⁺ (⁴I_15/2) and Er³⁺ (⁴S_3/2) → Er³⁺ (⁴I_15/2), respectively. Both of the two green emission lines are produced by populating Er³⁺ ions to the excited state through a two-photon process. By monitoring the intensities of the green upconversion luminescence, the optimum conditions for the Sol-gel synthesis were determined when the molar ratio of citric acid to total chelate metal cations was 2:1 and the sintering temperature was at 1073 K. The concentration quenching effect for Er³⁺ was found at the optimum doping concentration of 6 mol%, and the critical distance for the neighboring Er³⁺ was determined to be about 21.5 Å.     

Up-conversion emission in KGd(WO4)2 single crystals triply-doped with Er/Yb/Tm, Tb/Yb/Tm and Pr/Yb/Tm ions

Triply-doped single crystals KGd(WO₄)₂:Er³⁺/Yb³⁺/Tm³⁺, KGd(WO₄)₂:Tb³⁺/Yb³⁺/Tm³⁺ and KGd(WO₄)₂:Pr³⁺/Yb³⁺/Tm³⁺ were grown by the Top Seeded Solution Growth (TSSG) method, with an aim of getting efficient up-converted multicolored luminescence, which subsequently can be used for generation of white light. Such an aim determined the choice of the triply doped compounds: excitation of the Yb³⁺ ions in the infrared spectral region is followed by red, green and blue emission from other dopants. It was shown that all these systems exhibit multicolor up-conversion fluorescence under 980 nm laser irradiation. Detailed spectroscopic studies of their absorption and luminescence spectra were performed. From the analysis of the dependence of the intensity of fluorescence on the excitation power the conclusion was made about significant role played by the host’s conduction band and other possible defects of the KGd(WO₄)₂ crystal lattice in the up-conversion processes.     

Synthesis of Er<Superscript>3+</Superscript> and Er<Superscript>3+</Superscript> : Yb<Subscript>3+</Subscript> doped sol-gel derived silica glass and studies on their optical properties

Er₃₊ and Er₃₊ : Yb₃₊ doped optical quality, crack and bubble free glasses for possible use in making laser material have been prepared successfully through sol-gel route. The thermal and optical, including UV-visible absorption, FTIR etc characterizations were undertaken on the samples. The absorption characteristics of Er₃₊ doped samples clearly revealed the absorption due to Er₃₊ ions. On the other hand Yb₃₊ : Er₃₊ doped samples showed enhanced absorption due to² F _7/2 →² F _5/2 transition. The absorption and emission cross-section for² F _7/2 ↔² F _5/2 of Yb³⁺ were estimated. FTIR absorption spectra have clearly shown the reduction of the absorption peak intensity with heat treatment in the range 3700–2900 cm⁻¹. The 960 cm^-1 band also showed progressive decrease in the absorption band peak intensity with heat treatment. The result of the investigations with essential discussions and conclusions have been reported in this paper.     

Synthesis and luminescence properties of Yb3+–Er3+ co-doped LaOCl nanobelts via electrospinning combined with chlorination technique

LaOCl:Yb³⁺, Er³⁺ nanobelts were prepared by electrospinning combined with a double-crucible chlorination technique using NH₄Cl as chlorinating agent. X-ray powder diffraction analysis indicated that LaOCl:Yb³⁺, Er³⁺ nanobelts were tetragonal with space group P4/nmm. Scanning electron microscope analysis and histograms revealed that width of LaOCl:Yb³⁺, Er³⁺ nanobelts was 6.12 ± 0.18 μm under the 95% confidence level, and the thickness was 113 nm. Transmission electron microscope observation showed that as-obtained LaOCl:Yb³⁺, Er³⁺ nanobelts were composed of nanoparticles. LaOCl:Yb³⁺, Er³⁺ nanobelts emitted strong green and red up-conversion emission centring at 523, 551 and 667 nm, respectively, attributed to ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_l5/2 transitions of Er³⁺ under the excitation of a 980-nm diode laser (DL) excitation. Moreover, the near-infrared characteristic emission of LaOCl:Yb³⁺, Er³⁺ nanobelts was achieved under the excitation of a 532-nm laser. Commission Internationale de L'Eclairage analysis demonstrated that colour-tuned luminescence can be obtained by changing doping concentration of Yb³⁺ and Er³⁺, which could be applied in the fields of optical telecommunication and optoelectronic devices. The up-conversion luminescent mechanism and the formation mechanism of LaOCl:Yb³⁺, Er³⁺ nanobelts were also proposed.     

Upconversion luminescence of Ba(MoO4)h(WO4)1−h:Yb3+/Er3+ nanocrystals synthesized through hydrothermal method

A series of Yb³⁺/Er³⁺ co-doped Ba(MoO₄)_h(WO₄)_1−h upconversion nanocrystals (UCNCs) were prepared via hydrothermal method. The effects of different concentration ratios of Yb³⁺/Er³⁺ and Mo₄O²⁻/WO₄²⁻ on the upconversion luminescence were investigated, and the optimum doping concentrations of Yb³⁺ and Er³⁺ in the Ba(MoO₄)_0.5(WO₄)_0.5 host were found to be 3 mol% and 1 mol%, respectively. Structure of Ba(MoO₄)_0.5(WO₄)_0.5:0.03Yb³⁺/0.01Er³⁺ was identified as the tetragonal in the X-ray diffraction (XRD) results and the particle size observed in the scanning electron microscope (SEM) was about 40 nm. Under excitation of 980 nm semiconductor laser, three emission bands centered at 528, 550 and 660 nm, originating from ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺ ion, respectively, were observed for Ba(MoO₄)_0.5(WO₄)_0.5:0.03Yb³⁺/0.01Er³⁺. The pump power dependence research suggested that these bands arise due to two-photon absorption. The variation of CIE coordinate at different excitation powers was observed.     

Energy transfer in crystalline Er,Yb:Sc2O3

The use of Yb³⁺ as a sensitizer for Er³⁺ doped laser materials is a common technique because of the high Yb³⁺ absorption cross sections. Energy transfer processes from Yb³⁺ to Er³⁺ in Sc₂O₃ are studied by two different methods. Transfer parameters describing the interactions between Er³⁺ and Yb³⁺ ions are obtained on the one hand from the ratio of emitted photons around 1.55 μm by Er³⁺ ions and around 1 μm by Yb³⁺ ions at cw excitation of Yb³⁺, on the other hand by lifetime measurements of Yb³⁺ ions in the codoped samples. Laser experiments are performed to study the suitability of Er³⁺,Yb³⁺:Sc₂O₃ as a laser material. Comparisons with energy transfer in Er³⁺,Yb³⁺:glass are made.     

Design and achieving mechanism of upconversion white emission based on Yb/Tm/Er tri-doped KY3F10 nanocrystals

KY₃F₁₀:Yb³⁺/Tm³⁺/Er³⁺ upconversion nanocrystals are synthesized via a simple hydrothermal procedure. The nanocrystals emit the near equal energy white light with high brightness and favorable color balance when excited using a 980 nm continuous wave diode laser. The research of upconversion mechanism indicates that in addition to the energy transfer processes from Yb³⁺ to Tm³⁺ and Er³⁺, respectively, there exists a new process ¹G₄ (Tm³⁺) + ⁴I_11/2 (Er³⁺) → ³H₄ (Tm³⁺) + ⁴S_3/2 (Er³⁺).     

Significant reduction of upconversion emission in CaTiO3: Yb, Er inverse opals

Inverse opal photonic crystals of Yb³⁺, Er³⁺ co-doped CaTiO₃ (CaTiO₃: Yb, Er) were prepared using self-assembled polystyrene templates combined with the infiltration of sol-gel precursor. The influence of the photonic band gap on upconversion emission of Er³⁺ has been investigated in the CaTiO₃: Yb, Er inverse opals. Significant reduction of the upconversion emission was detected if the photonic band-gap overlaps with the Er³⁺ ions emission band.     

Effects of GeO2 on the thermal stability and optical properties of Er/Yb-codoped oxyfluoride tellurite glasses

The aim of this article was to study the influence of GeO₂ on the thermal stability and optical properties of Er³⁺/Yb³⁺ codoped (70 − x)TeO₂–xGeO₂–PbF₂–BaF₂ (TGEYx) glasses prepared by using a melting method. The properties of Er³⁺/Yb³⁺ codoped glasses were investigated by using differential scanning calorimetry, upconversion luminescence, Raman and optical absorption spectra. The results indicated that TGEY35 glass with the germanate–tellurite mixed network showed the best thermal stability and poor crystallization tendency. With increasing the GeO₂ content, the maximum phonon energy of oxyfluoride tellurite glass network increased, while the phonon density decreased. The upconversion emission intensities enhanced obviously based on the decreasing phonon density of glass hosts, while the increasing red emission (657 nm) with the increase of GeO₂ concentration was attributed to the relative larger maximum phonon energy which matching the energy gap between the pertinent ⁴S_3/2 and ⁴F_9/2 levels.     

Synthesis and upconversion luminescence properties of Yb/Er codoped BaGd2(MoO4)4 powder

Synthesis and upconversion luminescence properties of the new BaGd₂(MoO₄)₄:Yb³⁺,Er³⁺ phosphor were reported in this paper. The phosphor powder was obtained by the traditional high temperature solid-state method, and its phase structure was characterized by the XRD pattern. Based on the upconversion luminescence properties studies, it is found that, under 980 nm semiconductor laser excitation, BaGd₂(MoO₄)₄:Yb³⁺,Er³⁺ phosphor exhibits intense green upconversion luminescence, which is ascribed to ²H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transition of Er³⁺. While the observed much weaker red emission is due to the non-radiative relaxation process of ⁴S_3/2 → ⁴F_9/2 and ⁴F_9/2 → ⁴I_15/2 transition originating from the same Er³⁺. The concentration quenching effects for both Yb³⁺ and Er³⁺ were found, and the optimum doping concentrations of 0.5 mol% Yb³⁺ and 0.08 mol% Er³⁺ in the new BaGd₂(MoO₄)₄ Gd³⁺ host were established.     

The 1.53 μm spectroscopic properties of Er3+/Ce3+/Yb3+ tri-doped tellurite glasses containing silver nanoparticles

The metallic silver nanoparticles (NPs) was introduced into the Er³⁺/Ce³⁺/Yb³⁺ tri-doped tellurite glasses with composition TeO₂–ZnO–La₂O₃ to improve the 1.53 μm band fluorescence. The UV/Vis/NIR absorption spectra, 1.53 μm band fluorescence spectra, fluorescence lifetimes, X-ray diffraction (XRD) curves, differential scanning calorimeter (DSC) curves and transmission electron microscopy (TEM) image of tri-doped tellurite glasses were measured, together with the Judd–Ofelt intensity parameters, emission cross-sections, absorption cross-sections and radiative quantum efficiencies were calculated to investigate the effects of silver NPs on the 1.53 μm band spectroscopic properties of Er³⁺ ions, structural nature and thermal stability of glass hosts. It is shown that Er³⁺/Ce³⁺/Yb³⁺ tri-doped tellurite glasses can emit intense 1.53 μm band fluorescence through the combined energy transfer (ET) processes from Yb³⁺ to Er³⁺ ions and Er³⁺ to Ce³⁺ ions under the 980 nm excitation. At the same time, the introduction of an appropriate amount of silver NPs can further improve the 1.53 μm band fluorescence owing to the enhanced local electric field effect induced by localized surface Plasmon resonance (LSPR) of silver NPs and the possible energy transfer from silver NPs to Er³⁺ ions, and an improvement by about 120% of fluorescence intensity is found in the studied Er³⁺/Ce³⁺/Yb³⁺ tri-doped tellurite glass containing 0.5 mol% amount of silver NPs with average diameter of ∼15 nm. The energy transfer mechanisms from Yb³⁺ to Er³⁺ ions and Er³⁺ to Ce³⁺ ions were also quantitatively investigated by calculating energy transfer microparameters and phonon contribution ratios. Furthermore, the thermal stability of glass host increases slightly with the introduction of silver NPs while the glass structure maintains the amorphous nature. The results indicate that the prepared Er³⁺/Ce³⁺/Yb³⁺ tri-doped tellurite glass with an appropriate amount of silver NPs is an excellent gain medium applied for 1.53 μm band EDFA pumped with a 980 nm laser diode (LD).     

Synthesis and two-color emission properties of BaGd2(MoO4)4:Eu3+,Er3+,Yb3+ phosphors

Eu³⁺, Er³⁺ and Yb³⁺ co-doped BaGd₂(MoO₄)₄ two-color emission phosphor was synthesized by the high temperature solid-state method. The structure of the sample was characterized by XRD, and its luminescence properties were investigated in detail. Under the excitation of 395 nm ultraviolet light, the BaGd₂(MoO₄)₄:Eu³⁺,Er³⁺,Yb³⁺ phosphor emitted an intense red light at 595 and 614 nm, which can be attributed to ⁵D₀ → ⁷F₁ and ⁵D₀ → ⁷F₂ transitions of Eu³⁺, respectively. The phosphor will also show bright green light under 980 nm infrared light excitation. The green emission peaks centred at 529 and 552 nm, were attributed to ⁴H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transitions of Er³⁺, respectively. It indicated that the two-color emission can be achieved from the same BaGd₂(MoO₄)₄:Eu³⁺,Er³⁺,Yb³⁺ host system based on the different pumping source, 395 nm UV light and 980 nm infrared light, respectively. The obtained results showed that this kind of phosphor may be potential in the field of multi-color fluorescence imaging and anti-counterfeiting.