Cooperative energy transfer and frequency upconversion in Yb3+-Tb 3+ and Nd 3+-Yb 3+-Tb 3+ codoped GdAl3(BO3)4 phosphors

Polycrystalline GdAl₃(BO₃)₄ phosphors codoped with Yb³⁺/Tb³⁺ and/or Nd³⁺/Yb³⁺/Tb³⁺ have been synthesized by combustion method. Upon excitation with a 980 nm laser diode, an intense green upconversion luminescence has been observed in GdAl₃(BO₃)₄:Yb,Tb phosphor. The quadratic dependence of the luminescence on the pump-laser power indicating a cooperative energy transfer process. Meanwhile, it is noticed that upon excitation with 808 nm laser diode, intense luminescence has clearly been detected in GdAl₃(BO₃)₄:Nd,Yb,Tb phosphor. The luminescence intensity exhibits also a quadratic dependence on incident pump-laser power. However, no green-emission has been observed in GdAl₃(BO₃)₄ phosphors codoped with Yb³⁺/Tb³⁺ or Nd³⁺/Tb³⁺ respectively upon excited at 808 nm laser diode. A proposed upconversion mechanism involving energy transfer from Nd³⁺ to Yb³⁺, and then a cooperative energy transfer process from two excited Yb³⁺ to Tb³⁺ has been presented.     

Electron paramagnetic resonance of Mn<Superscript>2+</Superscript> ions in single crystals of yttrium aluminum borate YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Single crystals of yttrium aluminum borate YAl₃(BO₃)₄ doped with manganese ions are studied using electron paramagnetic resonance spectroscopy. It is shown that manganese ions introduced at low concentrations into the sample predominantly occupy yttrium ion sites in the crystal structure. The shape of the electron paramagnetic resonance spectrum unambiguously indicates that the valence of manganese ions in this case is equal to 2+. The parameters of the spin Hamiltonian of Mn²⁺ ions in the YAl₃(BO₃)₄ matrix are determined at room temperature. The magnitude and sign of the fine structure parameter D allow the conclusion that the YAl₃(BO₃)₄ single crystals doped with manganese ions have a strong crystal field at the yttrium ion sites and easy-axis anisotropy.     

Luminescence of yttrium aluminum borate single crystals doped with manganese

The optical absorption and luminescence spectra of single crystals of yttrium aluminum borate YAl₃(BO₃)₄ doped with manganese ions are measured. It is established that the optical absorption spectra of yttrium aluminum borate single crystals doped with manganese ions are determined primarily by the contribution from the Mn⁴⁺ ions. The luminescence spectra of the YAl₃(BO₃)₄ single crystals doped with manganese exhibit narrow lines attributed to the Mn⁴⁺ ions and an extended multiband structure which is associated primarily with the contribution from the Mn²⁺ ions.     

Thermo-optic characterization of Yb:YAl3(BO3)4 laser crystal

Principal thermo-optic coefficients, dn _o/dT and dn _e/dT, are determined for 7at.%Yb: YAl₃(BO₃)₄ crystal by the use of a minimum deviation method, modified for anisotropic, optically uniaxial crystals. Direct measurements are accompanied by modeling of the dn/dT versus light wavelength dependence, yielding analytic thermo-optic dispersion formulae for the spectral range of 0.4–1.6 μm. At the wavelength of 1030 nm, dn _o/dT = 3.5 and dn _e/dT = 6.0 [10^?6 K^?1]. Sellmeier formulas are evaluated for the principal refractive indices n _o and n _e. The thermal coefficients of the optical path are determined for the principal crystal cuts of Yb:YAl₃(BO₃)₄, a-cut and c-cut, and light polarizations, π or σ. Finally, thermal lens parameters are evaluated for Yb:YAl₃(BO₃)₄ crystals on the basis of measured material parameters.     

Group delay dispersion measurement of Yb:YAl3(BO3)4 crystal with white-light interferometry

We report the group delay dispersion of Yb³⁺:YAl₃(BO₃)₄ (Yb:YAB) crystal measured by a white-light interferometer, and compare with that calculated from the Sellmeier formulae provided by the crystal supplier, over the wavelength range from 1000 nm to 1080 nm. The data should be useful for the dispersion compensation for femtosecond pulse generation in Yb:YAB lasers.     

Yb3+掺杂浓度对Er3+/Yb3+共掺SiO2-Al2O3-La2O3玻璃光谱性质的影响

测量了不同Yb3+ 离子掺杂浓度下 ,Er3+ /Yb3+ 共掺SiO2 Al2 O3 La2O3玻璃的吸收光谱、荧光光谱和Yb3+离子2 F5/ 2 的能级寿命 ,应用迈克康伯 (McCumber)理论计算了Er3+ 的受激发射截面σemi,讨论了Yb3+ 离子浓度对其自身吸收性质、Er3+ 离子发光性质 ,以及Yb3+ →Er3+ 能量传递效率 (η)的影响 ,初步探明该基质玻璃中Yb3+ 离子掺杂数浓度的最佳范围为 3 .94× 1 0 2 0 cm- 3至 5 .92× 1 0 2 0 cm- 3,在此掺杂范围内 ,Yb3+ 离子的最大吸收系数为9.8cm- 1 ,Er3+ 的峰值发射截面和Yb3+ →Er3+ 能量传递效率 (η)分别为 0 64× 1 0 - 2 4 m2 和 92 %。     

Growth and Spectroscopic Properties of Er:Yab Single Crystals

The Er-doped YAB (YAl₃(BO₃)₄) is a potential self-frequency-doubling laser material. Single crystals were grown by the top-seeded flux method. The absorption spectra of the infrared Er^3? transitions were monitored in YAB crystals in the 9–300 K temperature range by high-resolution Fourier transform spectroscopy. In the whole spectral range the energy levels and Stark components of 12 transitions were detectable. In this paper the two infrared transitions (from the ⁴I_15/2 ground state to the ⁴I_13/2 and ⁴I_11/2 levels) were analyzed in detail. The low temperature absorption spectra of Er:YAB consist of sharp lines, the number of which corresponds to the theoretical predictions. This suggests that Er^3? ions occupy one specific lattice site (yttrium positions) with negligible aggregation at the higher dopant concentrations investigated (i.e. 0.12 Fr atom/YAB mole).     

Optical spectroscopy and laser parameters of Zn2+/Er3+/Yb3+-tridoped LiNbO3 crystal

The Zn/Er/Yb:LiNbO₃ and Er/Yb:LiNbO₃ crystals were grown by the Czochralski technique. The laser characteristics of 1.54 μm emission were predicted based on the Judd–Ofelt theory, and the intensity parameters Ω_t (Ω₂=7.23×10^?20 cm², Ω₄=3.15×10^?20 cm² and Ω₆=1.43×10^?20 cm²) were obtained. The stimulated emission cross sections (σ_em) at 1.54 μm emission in Zn/Er/Yb:LiNbO₃ were calculated based on the McCumber theory and the Füchtbauer–Ladenburg theory. The gain cross section spectrum of Zn/Er/Yb:LiNbO₃ crystal was also investigated. Under 980 nm excitation, a lenghthening lifetime of 1.54 μm emission and an enhancement of green upconversion emission were observed for Zn/Er/Yb:LiNbO₃ crystal. The studies on the power pump dependence and the upconversion mechanism suggested that both green and red upconversion emissions were populated via the three-photon process, and Zn²⁺ ion tridoping increases the probability of cross relaxation process between the two neighboring Er³⁺ ions.     

A study of the quantum efficiency of multichannel relaxation in LiNbO<Subscript>3</Subscript>:Yb,Er crystals

Luminescence spectra of gradient-activated LiNbO₃:Yb, Er crystals with predefined concentration profiles of the optical centers are studied in different spectral regions. The process of electronic excitation energy transfer in the Yb³⁺–Er³⁺ system inside the LiNbO₃ matrix is calculated and dependences of the quantum efficiency of the up-conversion processes for the green and red luminescences of erbium ions on the time of excitation energy deactivation are obtained.     

YAB晶体中Yb3+到Er3+的能量传递

1.55 μm波段是光通讯的一个重要波段,而且对人眼安全,有高的大气透过率,因此可以广泛应用于通讯和遥感测距等领域。由于Er³⁺离子对商品化的InGaAs激光二极管的抽运波长不能有效吸收,因此一般通过在基质中共掺杂Yb³⁺和Er³⁺离子来获得1.55 μm波段激光输出。采用助熔剂法生长了不同Yb³⁺和Er³⁺掺杂浓度的YAl₃(BO₃)₄(YAB)晶体。运用速率方程模型研究了晶体中Yb³⁺到Er³⁺能量传递过程,得到了根据Yb³⁺离子的荧光寿命计算能量传递系数的简单计算公式。计算了不同掺杂离子浓度的YAB晶体中的能量传递系数等相关参数。结果表明,在YAB晶体中,Yb³⁺到Er³⁺能量传递非常有效,YAB晶体可以作为一种能获得1.55 μm激光输出的良好介质材料。     

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.     

Er,Yb:YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>—efficient 1.5 μm laser crystal

This article summarizes the latest achievements in the growth and characterization of Er,Yb:YAl₃(BO₃)₄ laser crystal emitting in the 1.5–1.6 μm spectral range. Fundamental spectroscopic parameters relevant to laser performance of Er,Yb:YAB derived from absorption and emission spectra and from excited state dynamics are presented. The laser performance of Er,Yb:YAB in the cw and mode-locked regimes is reported.     

Growth, polarized spectral properties, and 1.5–1.6 μm laser operation of Er:Yb:Sr3Gd2(BO3)4 crystal

An Er:Yb:Sr₃Gd₂(BO₃)₄ crystal was grown by the Czochralski method. The polarized spectral properties of the crystal were investigated, including the polarized absorption and fluorescence spectra and fluorescence decay. The fluorescence quantum efficiency of the upper laser level ⁴I_13/2 of Er³⁺ ions and the efficiency of the energy transfer from Yb³⁺ to Er³⁺ ions were calculated. End-pumped by a diode laser at 970 nm in a hemispherical cavity, a 1.6 W quasi-cw laser at 1.5–1.6 μm with a slope efficiency of 18% and an absorbed pump threshold of 5.9 W was achieved in a 1.8-mm-thick Z-cut Er:Yb:Sr₃Gd₂(BO₃)₄ crystal. This crystal has a flat and broad gain curve at 1.5–1.6 μm and so is also a potential gain medium for tunable and short pulse lasers.     

Visible upconversion emission and non-radiative direct Yb to Er energy transfer processes in nanocrystalline ZrO2:Yb,Er

Wide band gap Yb³⁺ and Er³⁺ codoped ZrO₂ nanocrystals have been synthesized by a modified sol-gel method. Under 967 nm excitation strong green and red upconversion emission is observed for several Er³⁺ to Yb³⁺ ions concentration ratios. A simple microscopic rate equation model is used to study the effects of non-radiative direct Yb³⁺ to Er³⁺ energy transfer processes on the visible and near infrared fluorescence decay trends of both Er³⁺ and Yb³⁺ ions. The microscopic rate equation model takes into account the crystalline phase as well as the size of nanocrystals. Nanocrystals phase and size were estimated from XRD patterns. The rate equation model succeeds to fit simultaneously all visible and near infrared fluorescence decay profiles. The dipole-dipole interaction parameters that drive the non-radiative energy transfer processes depend on doping concentration due to crystallite phase changes. In addition the non-radiative relaxation rate (⁴I_11/2→⁴I_13/2) is found to be greater than that estimated by the Judd-Ofelt parameters due to the action of surface impurities. Results suggest that non-radiative direct Yb³⁺ to Er³⁺ energy transfer processes in ZrO₂:Yb,Er are extremely efficient.     

Radiation Resistance of Yb:LaSc<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> and Yb:LuYSiO<Subscript>5</Subscript> Laser Crystals

The optical transmission (OT) spectra of Yb:LaSc₃(BO₃)₄ and Yb:LuYSiO₅ laser crystals have been analyzed before and after irradiation from a ⁶⁰Co source with doses up to 45 Mrad. The OT spectra of the Yb:LuYSiO₅ crystal are found to be the same (within the measurement error) before and after irradiation. The irradiation of the 10 at.%Yb:LaSc₃(BO₃)₄ crystal significantly changes its OT spectra in a wide spectral range (330 to 700 nm). A 975-nm laser based on a previously irradiated 4 at.%Yb:LuYSiO₅ crystal has exhibited a differential efficiency of 23% under diode pumping. The up-conversion luminescence spectra in the visible range of the crystals under study have been explained.     

Er~(3+)/Eu~(3+)及Yb~(3+)/Er~(3+)/Eu~(3+)共掺杂硼硅酸盐玻璃的上转换发光分析

采用高温固相烧结法制备了Er3+/Eu3+共掺杂和Yb3+/Er3+/Eu3+共掺杂系列硼硅酸盐玻璃样品。在978 nm半导体激光器抽运下,测量了样品的光致发光谱,分析了上转换机制。结果表明:随着Er3+浓度的增加,Eu3+的595 nm光谱强度增强;Eu3+的692 nm光谱强度随Yb3+浓度增加而增强,并明显强于595 nm光谱。Er3+/Eu3+、Yb3+/Eu3+之间的能量传递和合作上转换等机制导致Eu3+离子上转换发射。     

Dynamics of the Yb3+ to Er3+ energy transfer in LiNbO3

The energy transfer dynamics between Yb³⁺ and Er³⁺ ions in lithium niobate is investigated after ytterbium-pulsed excitation at 920 nm. The sensitisation of the LiNbO₃:Er³⁺ system with Yb³⁺ ions does not modify the lifetime of the ⁴I_13/2 erbium level (1.5-μm emission), whereas it induces a marked, concentration-dependent change in the lifetime of the ²F_5/2 (Yb³⁺) and ⁴S_3/2 (Er³⁺) multiplets (1060-nm and 550-nm emissions, respectively). The results are analysed by using the rate-equation formalism and cross-relaxation model for the energy transfer. Received: 15 October 1998 / Revised version: 24 November 1998 / Published online: 24 February 1999     

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     

Er,Yb:YAG微晶玻璃发光特性的研究

高温熔制Er³⁺，Yb³⁺离子掺杂CaO-Y₂O₃-Al₂O₃-SiO₂系统玻璃，并进行微晶化处理，研究了微晶玻璃中Er³⁺离子的发光及上转换发光特性，分析了微晶玻璃上转换发光机理.结果表明：原始玻璃经热处理得到了Er,Yb:YAG微晶玻璃，微晶玻璃中Er³⁺离子在室温下⁴I_13/2→⁴I_15/2跃迁产生横盖1450—1650nm区间的超宽带荧光，荧光半高宽达180nm，这可能由于YAG微晶相中Er³⁺离子与玻璃相中残留Er³⁺离子的共同发光；Er³⁺与Yb³⁺离子局域基质声子能量的降低使微晶玻璃Er³⁺离子上转换发光强度与原始玻璃相比显著提高，绿光、红光上转换荧光强度比玻璃样品分别增强约7和3倍；微晶化后Er³⁺，Yb³⁺离子局域环境发生变化也导致微晶玻璃中Er³⁺离子绿光、红光上转换发光相对强度发生变化. 关键词： 铒 镱:钇铝石榴石 微晶玻璃 荧光光谱     

Preparation and upconversion emission properties of TiO2 :Yb, Er inverse opals

Inverse opal photonic crystals of Y b³⁺, Er³⁺ co-doped TiO₂ (TiO₂:Yb, Er) were prepared by a self-assembly technique in combination with a sol-gel method. Upconversion (UC) luminescence properties of the inverse opals were investigated. The results show that photonic bandgap has significant influence on the upconversion emission of the TiO₂:Yb, Er inverse opal photonic crystals. Significant suppression of the upconversion emission was detected if the photonic bandgap overlapped with the Er³⁺ ions emission band.