Conversion of infrared radiation into visible emission in NaGd(WO4)2:Yb3+, Ho3+ crystals

NaGd(WO₄)₂:Yb³⁺, Ho³⁺ single crystals have been grown by the Czochralski technique along the (0 0 1) orientation. Conversion of the infrared (IR) radiation at 980 nm into the visible emission in NaGd(WO₄)₂ crystals containing several different concentrations of Yb³⁺ and Ho³⁺ has been investigated. The NaGd(WO₄)₂: 8 at. % Yb³⁺, 4 at. % Ho³⁺ system exhibits intense red upconverted emission originating from the ⁵F₅ level. The upconversion mechanism in a Ho³⁺-Yb³⁺ system under near infrared excitation is discussed. It is concluded that the green emission is excited by energy transfers from Yb³⁺ to Ho³⁺, whereas excited state absorption is involved in the excitation of red emission. The emission cross-section of the ⁵F₅→⁵I₈ transition at about 660 nm was estimated by using the Füchtbauer–Ladengurg formula. PACS 78.55.Hx; 78.20.-e     

Photoluminescence of a BaSiO3:Yb3+ crystal

We present the results of a study of the luminescence and luminescence excitation spectra, and also the luminescence kinetics of a BaSiO₃:Yb³⁺ crystal. We have established the mechanism for emission by the matrix and energy transfer from the matrix to the rare earth ion. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 478–482, July–August, 2006.     

Optical spectra of octahedral cubic and trigonal Yb3+ impurity centers in KMgF3 and KZnF3 crystals

Groups of lines corresponding to octahedral cubic and trigonal impurity centers have been isolated in complex many-center luminescence and excitation spectra of Yb³⁺-doped KMgF₃ and KZnF₃ crystals. The crystal-field potentials derived from the spectra are in good agreement with those of similar centers in CsCaF₃:Yb³⁺ crystal studied earlier. Fiz. Tverd. Tela (St. Petersburg) 40, 2029–2034 (November 1998)     

Avidin conjugation to up-conversion phosphor NaYF4:Yb3+, Er3+ by the oxidation of the oligosaccharide chains

NaYF₄:Yb³⁺, Er³⁺ nanoparticles were successfully prepared by a polyol process using diethyleneglycol (DEG) as solvent. After being functionalized with SiO₂–NH₂ layer, these NaYF₄:Yb³⁺, Er³⁺ nanoparticles can conjugate with activated avidin molecules (activated by the oxidation of the oligosaccharide chain). The as-formed NaYF₄:Yb³⁺, Er³⁺ nanoparticles, NaYF₄:Yb³⁺, Er³⁺ nanoparticles functionalized with amino groups, avidin conjugated amino-functionalized NaYF₄:Yb³⁺, Er³⁺ nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic force microscopy (AFM), Fourier transform infrared (FT-IR), UV/Vis absorption spectra, and up-conversion luminescence spectra, respectively. The biofunctionalization of the NaYF₄:Yb³⁺, Er³⁺ nanoparticles has less effect on their luminescence properties, i.e., they still show the up-conversion emission (from Er³⁺, with ⁴S_3/2 → ⁴I_15/2 at ~540 nm and ⁴F_9/2 → ⁴I_15/2 at ~653 nm), indicative of the great potential for these NaYF₄:Yb³⁺, Er³⁺ nanoparticles to be used as fluorescence probes for biological system.     

Variation in luminescence behavior of Yb3+ doped GdAlO3 phosphor with gradual increase in Yb3+ concentration

The present paper reports the combustion synthesis of Yb³⁺ doped GdAlO₃ phosphors. The structural characterization and luminescence spectra of Yb³⁺ doped GdAlO₃ phosphors have been discussed. The effects of variable concentration of Yb³⁺ on Photoluminescence (PL) behavior were studied. The structural characterization was done by X-ray diffraction (XRD) and Transmission electron microscope technique (TEM). The good connectivity with grains and the semi-sphere line structure was found by TEM. The functional group analysis was carried out by Fourier transform infrared (FTIR) spectroscopic techniques. The prepared phosphor gives emission spectra in visible as well as NIR region. Both emissions were studied as a function of Yb³⁺ concentration. The emission intensity variation with Yb³⁺ ion concentration for visible and NIR region were discussed separately. The NIR emission luminescence of GdAlO₃:Yb³⁺ phosphor luminescence continuously increases with increasing Yb³⁺ ion concentration.     

Structural and optical characterization of Er3+/Yb3+-doped LiNbO3

We report the dependence of the unit-cell parameters and the extraordinary and ordinary refractive indices of Er³⁺/Yb³⁺-codoped LiNbO₃ crystals. Both properties depend in a non-monotonic manner on the Er³⁺/Yb³⁺ content. A singularity was observed at concentrations of 1.1-1.2 mol. % in the crystal (0.6-0.7 mol. % in the melt). In the same way the Er and Yb concentration influences the periodically poled lithium niobate formation. The observed behavior of refractive indices and unit-cell parameters of Er³⁺/Yb³⁺-codoped LiNbO₃ crystals could be explained in terms of the RE³⁺-ion concentration affecting the Li-vacancy concentration and the RE³⁺-ion positions in the crystal. Received: 21 May 2001 / Revised version: 22 August 2001 / Published online: 23 October 2001     

Nonlinear refractive properties of Yb3+-doped KY(WO4)2 and YVO4 laser crystals

The nonlinear refractive indices of Yb³⁺: KY(WO₄)₂ and Yb³⁺:YVO₄ laser crystals are characterized using a Z-scan technique at a wavelength of 1.08 μm for different polarizations. The results reveal that the nonlinear refractive index of Yb³⁺:YVO₄ is superior to that of Yb³⁺:KY(WO₄)₂ and is found to be 1.9×10^-15 cm²/W and 1.5×10^-15 cm²/W for E⊥c and E∥c polarizations, respectively. PACS 42.65.Hw; 42.55.Rz; 42.65.Re; 42.70.Hj     

Spectral properties and energy transfer of Yb,Er:GdVO4 crystal

GdVO₄ single crystal co-doped with Yb³⁺ and Er³⁺ was grown by the Czochralski method. The X-ray powder diffraction pattern of Yb,Er:GdVO₄ crystal confirms that the as-grown crystal is isostructural with pure GdVO₄ crystal. Its polarized absorption spectra and non-polarized fluorescence spectra were measured at room temperature. The absorption band at 984 nm for π-polarization has an FWHM of about 36 nm, which is favorable for InGaAs LD laser pumping. The spectrum properties of Er³⁺ in Yb,Er:GdVO₄ crystal were investigated based on Judd–Ofelt theory. There is strong energy transfer from Yb³⁺ to Er³⁺ in this crystal. When excited with 980 nm radiation, this crystal emitted strong fluorescence at about 1529 nm and 552.5 nm. The total energy transfer rate and efficiency from Yb³⁺ to Er³⁺ is 3.33 ms^-1 and 67%, respectively. The energy transfer between Er³⁺ and Yb³⁺ ions is a multistep transfer process, and was investigated based on a random-walk model. The investigation result shows that there is strong cooperative-sensitization effect from Yb³⁺ to Er³⁺, which is the main upconversion energy-transfer process in this crystal. PACS 42.70.Hj; 81.10.Fq; 42.55.Rz     

The optical properties of Yb3+ ions in LiTaO3:Nd,Yb crystals

3+ ions excited by energy transfer from Nd³⁺ ions in LiTaO₃:Nd, Yb crystals are presented. The emission band of Yb³⁺ ions is broad, due to the strong phonon-coupling and to the relative large Stark-splitting of the ground ²F_7/2 multiplet. The emission cross-section was evaluated by the reciprocity method, and a value of 0.53×10^-20 cm² was obtained. The gain coefficients derived for the inversion parameters in the range 0.05 to 0.5 indicate positive gain in the 985–1070 nm range. Received: 17 March 1997/Revised version: 10 June 1997     

Ultraviolet and visible upconversion emission in Tb3+/Yb3+ co-doped fluorophosphate glasses

Ultraviolet and visible upconversion emissions in Tb³⁺/Yb³⁺ co-doped YF₃–BaF₂–Ba(PO₃)₂ glasses were observed under 980-nm laser diode excitation. The dependence of the emission intensities of Tb³⁺ on the pump power reveals that two-photon processes account for blue cooperative emission of Yb³⁺ at 476 nm and green upconversion emission of Tb³⁺ at 543 nm, and three-photon processes for ultraviolet emission of Tb³⁺ in the wavelength range of 379–435 nm. The effects of Tb³⁺ concentration on the emission intensity and the lifetime of Tb³⁺ and Yb³⁺ are investigated in detail. It is found that the cooperative energy transfer from a pair of excited Yb³⁺ ions to a ground Tb³⁺ ion is responsible for the appearance of blue and green upconversion emissions due to the ⁵D₄→⁷F _J (J=6,5,4,3) transitions of Tb³⁺, and the resonance energy transfer from Yb³⁺ to Tb³⁺ accounts for the population on the ⁵D₃,⁵G₆ level and ultraviolet upconversion emission.     

Formation of a stable bivalent state of Yb ions in Na4Y6F22:Ce3+, Yb3+ crystal under intense UV irradiation

The evolution dynamics of absorption spectra induced in samples of Na₄Y₆F₂₂:Ce³⁺, Yb³⁺ crystal by radiation resonant with 4f-5d transitions of Ce³⁺ ions was studied and analyzed. It was found that at least two types of color centers with different life times are induced in the studied crystal. It is established that the group of absorption bands in the UV spectral range that demonstrate long-term stability after excitation is caused by the 4f ¹³–4f ¹²5d transitions of bivalent ytterbium ions. The sequence of processes that lead to the reduction of ytterbium ions from the trivalent to the bivalent state is proposed.     

Yb3+ site occupation and host sensitization luminescence of a novel near‐infrared emitting Sr2CaMoO6:Yb3+ phosphor

The host sensitized near‐infrared (NIR) emitting phosphor Sr₂CaMoO₆:Yb³⁺ was fabricated by the solid state reaction method. The structural refinement and Raman spectra elucidate that Yb³⁺ ions preferentially occupy Ca²⁺ sites. The phosphor can harvest ultraviolet (UV)–blue photons and exhibits intense NIR emission at around 1012 nm with full‐width‐at‐half‐maximum of 1635 cm^–1. Moreover, the absolute NIR photoluminesence quantum yield (PLQY) is estimated to be about 9%. The Sr₂CaMoO₆:Yb³⁺ phosphor may be a promising luminescence downshifting material for improving the spectral response of solar cells in the UV region. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Energy transfer between Yb3+ and Er3+ ions in an Er,Yb:YAl3(BO3)4 crystal

The electron-excitation energy transfer between Er³⁺ and Yb³⁺ ions in Er,Yb:YAl₃(BO₃)₄ crystals has been investigated. Crystals with different concentrations of active ions have been grown, and their luminescence decay kinetics in the spectral range near 1 μm have been experimentally measured. The energy-transfer microparameters have been calculated. It is shown that, to correctly describe the energy transfer in Er,Yb:YAl₃(BO₃)₄ crystals, one must take into account the interactions of higher orders than dipole-dipole interactions.     

Nd3+ → Yb3+ energy transfer in a codoped metaphosphate glass as a model for Yb3+ laser operation around 980 nm

A complete spectroscopic investigation of a metaphosphate glass with composition Pb(PO₃)₂ doped with various amounts of Nd³⁺ and Yb³⁺ (1 up to 10 at.%) is reported. Efficient Nd³⁺ → Yb³⁺ energy transfers occur both radiatively and non-radiatively, the latter being dominant and partly resonant and partly phonon-assisted by phonons of the order of 950 cm⁻¹, which fits well with the reported Raman spectrum of the material. These transfers mainly concern the ⁴F_3/2 → ⁴I_9/2 emission and the ²F_7/2 → ²F_5/2 absorption transitions of the Nd³⁺ and Yb³⁺ ions around 900 nm, respectively. They are analysed both via spectral and temporal data. The results show that about 5% Nd³⁺ and 5% Yb³⁺ ions have to be incorporated to reach energy transfers exceeding about 65%, which is in agreement with data recently reported in the case of a YAl₃(BO₃)₄ crystal. Simulations based on the obtained data show that laser thresholds of a few tens of mW should be easily attainable by operating the materials in a channel waveguide configuration.     

Infrared-to-visible frequency upconversion in SrAl2O4 powders containing Er3+ and Yb3+

The phenomenon of frequency upconversion (UC) is observed in Er³⁺:Yb³⁺:SrAl₂O₄ powders prepared by combustion synthesis. Strong UC emission at the green (bands peaked at 521, 538, 547, and 562 nm) and weak UC emission at the red (bands peaked at 659 and 682 nm) corresponding to 4f–4f transitions of Er³⁺ were observed when the samples were irradiated with near-infrared laser excitation at ～980 nm. Saturation of UC emission is observed for concentrations of 1.5 wt.% of Er³⁺ and 1.5 wt.% of Yb³⁺. The green-to-red intensity ratio, on the other hand, increases linearly with Er³⁺ concentration (Er³⁺ concentration varying from 0.5 to 1.5 wt.%) while keeping Yb³⁺ concentration fixed (at 1.5 wt.%). The green UC decay time was measured and Er³⁺–Er³⁺ interaction was suggested as a possible mechanism to explain the luminescence quenching effect observed.     

Hydrothermal synthesis and the enhanced blue upconversion luminescence of NaYF4:Nd3+,Tm3+,Yb3+

Nd³⁺, Tm³⁺ and Yb³⁺ co-doped NaYF₄ upconversion (UC) material was synthesized by the hydrothermal method. The structure of the sample was characterized by the X-ray diffraction, and its UC luminescence properties were investigated in detail. Under the 980 nm semiconductor laser excitation, its UC spectra exhibited distinct emission peaks at 451 nm, 475 nm and 646 nm respectively. On the basis of the comparison of UC spectra between NaYF₄:Nd³⁺,Tm³⁺,Yb³⁺ and NaYF₄:Tm³⁺,Yb³⁺, it was indicated that the existence of Nd³⁺ ion enhanced the blue emission intensity. The law of luminescence intensity versus pump power proved that the blue emission at 475 nm, and the red emission at 646 nm were the two-photon processes, while the blue emission at 451 nm was a three-photon process.     

Spectroscopic properties of Yb ions in La2(WO4)3 crystal

Yb³⁺-doped La₂(WO₄)₃ single crystals were grown by the Czochralski technique. Absorption and fluorescence spectra of the crystal were recorded at the room temperature. The stimulated emission cross-sections of Yb³⁺ ions were calculated using the reciprocity method and Fuchtbauer-Ladenburg formula, respectively. The fluorescence decay curves of ²F_5/2 manifold of Yb³⁺ ions were recorded at room temperature for both crystal and powder samples. The effect of radiation trapping on the spectroscopic properties is discussed. Comparison with other Yb³⁺-doped laser crystals is made. The results show that Yb³⁺:La₂(WO₄)₃ crystal is a promising laser material.     

Photoluminescence of LiNbO3 crystals doped with Er3+ and Yb3+ ions

Results of cooperative phenomena investigations in the impurity subsystem of lithium niobate crystals doped with Er³⁺ and co-doped with Yb³⁺ impurity ions under continuous wave and pulsed excitation at 975 nm and 1064 nm wavelengths are presented. Dependences of some spectroscopic characteristics on the intensity of laser pumping are studied. Based on the pair centers model the analysis of the cooperative luminescence behavior in LiNbO₃:Yb³⁺+Er³⁺ crystals is performed.     

Downconversion for Solar Cells in YF3:Pr3+, Yb3+

ABSTRACT

Energy losses in solar cells caused by the spectral mismatch can be reduced by adapting the solar spectrum using a downconversion material where one higher energy visible photon is ‘cut' into two lower energy near-infrared photons that both can be absorbed by the solar cell. Downconversion with the (Pr³⁺, Yb³⁺) couple in YF₃ is investigated. Based on analysis of luminescence and diffuse reflectance spectra it is evident that two-step energy transfer takes place from the ³P₀ level of Pr³⁺ (around 490 nm) exciting two Yb³⁺ to the ²F_5/2 level giving emission around 980 nm. The transfer efficiency increases with Yb³⁺ concentration and is 86% for YF₃ doped with 0.5% Pr³⁺ and 30% Yb³⁺. Due to concentration quenching the intensity of emission from Yb³⁺ is strongly reduced and the ²F_5/2 emission intensity reaches a maximum for the sample with 0.5% Pr³⁺ and 2–5% Yb³⁺ at 300 K. Temperature dependent measurements reveal the role of the Pr^{3+ 1}G₄ level in the energy transfer between Pr³⁺ and Yb³⁺. Back-transfer of excitation energy from the Yb^{3+ 2}F_5/2 level to the ¹G₄ level of Pr³⁺ occurs and quenches the Yb³⁺ emission. The quenching is shown to become more efficient between 4 and 50 K due to faster phonon-assisted energy transfer between the Yb³⁺ donors. Upon raising the temperature from 50 to 300 K, the luminescence life time of the Yb³⁺ emission increases again because the small energy difference between the Pr³⁺ (¹G₄) level and the Yb³⁺ (²F_5/2) level (～300 cm^?1) which makes the ¹G₄ less efficient as a trap for the excitation energy. The present results give insight into factors involved in the concentration quenching in downconversion materials based on the (Pr³⁺, Yb³⁺) couple.     

Broadband downconversion based near-infrared quantum cutting via cooperative energy transfer in YNbO4:Bi3+, Yb3+ phosphor

YNbO₄:Bi³⁺, Yb³⁺ phosphor was prepared to study the quantum cutting process of converting one ultraviolet photon into two near-infrared photons. An intense near-infrared emission of Yb³⁺:²F_5/2 → ²F_7/2 around 1 μm was observed under the ultraviolet excitation belonging to the broadband absorption of the [NbO₄]^3- group and the Bi³⁺ ion. The photoluminescence spectra and decay lifetime measurements indicate efficient energy transfer from Bi³⁺ to Yb³⁺ ions, which is attributed to be of a cooperative energy transfer mechanism. The YNbO₄:Bi³⁺, Yb³⁺ phosphor with optimized doping concentration may be applicable in improving the efficiency of silicon-based solar cells.