Emission characteristics, crystalline phase and composition of vapor-transport-equilibrated Er:LiNbO3 crystal codoped with 6 mol% MgO

Polarized downconversion, 980-nm-upconversion and near-infrared emission characteristics of vapor-transport-equilibrated (VTEed) bulk Er (0.4 mol%)/MgO (6 mol%)-codoped LiNbO₃ crystals were investigated. The downconversion and upconversion visible emissions display similar VTE effects including the drop of emission intensity and the weakening of polarization dependence. At 0.98 and 1.5 μm regions, the VTE has a weak effect on the emission intensity, but a strong effect on the spectral shape. The crystalline phases in these bulk Er/Mg-codoped VTE crystals are determined by comparing their infrared emission characteristics with those of pure ErNbO₄ powder and locally Er-doped MgO (4.5 mol%):LiNbO₃ crystal. The results show that the Er³⁺ ions present in these bulk Er/Mg-codoped VTE crystals as a mixture of Er:LiNbO₃ and ErNbO₄ phases. The percentages of the ErNbO₄ phase contained in these VTE crystals were evaluated from the 1531 and 1536 nm characteristic absorption areas. The contents of constituent elements were determined by chemical analysis.     

Absorption and emission characteristics of Er3NbO7 phosphor: A comparison with ErNbO4 phosphor and Er:LiNbO3 single crystal

Er₃NbO₇ phosphor was synthesized by sintering a mixture of Er₂O₃ and Nb₂O₅ powder in a molar ratio of 3:1 at 1600 °C over 55 h. Optical absorption and emission characteristics of Er³⁺ ions in the calcined Er₃NbO₇ powder were investigated and discussed compared with ErNbO₄ phosphor and a Z-cut congruent Er (2 mol%):LiNbO₃ single crystal. The absorption and emission studies show that, due to different crystal structures, the spectroscopic properties of these niobates have some differences in spectral shape, peak position, and relative intensity, especially at 1.5 μm. The most obvious spectral feature of the Er₃NbO₇ is that the spectral structure of band instead of peak is observed in its absorption or emission spectrum due to the existence of local structural disorder and multiple Er³⁺ sites. The Er₃NbO₄ shows stronger upconversion emission than the single crystal but weaker than the ErNbO₄. Experimental results show that energy transfer upconversion and/or excited state absorption play a dominant role in the upconversion emissions, and, at higher pump level (>200 mW), the thermal effect becomes significant and results in drop of the upconversion intensity. The 1.5 μm lifetimes of Er³⁺ ion in the Er₃NbO₇, ErNbO₄ phosphor, and in the Er:LiNbO₃ crystal are measured to be ∼5.3, 2.0, and 2.4 ms, respectively. In combination with the measured Raman spectra, the quantum efficiency, multiphonon nonradiative decay rate, and theoretical radiative lifetime of the 1.5 μm emission of the two powder materials are expected. The differences in upconversion intensity and measured 1.5 μm lifetime between the three materials are explained qualitatively.     

X-ray diffraction study on precipitate of Er:LiNbO3 induced by vapor transport equilibration

An X-ray powder diffraction study was performed on vapor transport equilibration (VTE) treated Er:LiNbO₃ crystals with different doping levels (0.2, 0.4 and 2.0% Er per cation site), different cut orientations (X- and Z-cuts) and different VTE durations (120, 150 and 180 h). Their diffraction characteristics were compared with those of pure congruent LiNbO₃ and as-grown Er:LiNbO₃. The most significant characteristic is the appearance of additional weak and broad peaks around the 2θ angles 30° and 59° in the diffraction patterns of both X- and Z-cut 2.0 mol% doped VTE crystals, confirming that they precipitated. A further comparison of their diffraction data with the powder diffraction files indicated that the new phase in these precipitated crystals is ErNbO₄, which has an approximate concentration of 1.0%, 1.065%, 1.485% for 120, 150 and 180 h crystals, respectively. The crystalline grain sizes of the new phase are 132.2∼184.1?. The unit cell parameters of the as-grown and VTE crystals were also determined from diffraction data; the variation from pure LiNbO₃ to as-grown Er:LiNbO₃ was qualitatively explained according to the crystal structure of LiNbO₃ and using the concept of ionic radius. VTE brings the crystal closer to a stoichiometric composition, thus causing the contraction of the lattice constants. Finally, a tentatively qualitative explanation for precipitate formation is given on the basis of crystal structure. Received: 2 August 2000 / Accepted: 29 March 2001 / Published online: 20 June 2001     

Influence of vapor transport equilibration on Raman spectra of Er:LiNbO3 crystals

Raman spectra of as-grown and vapor transport equilibration (VTE) treated Er:LiNbO₃ crystals, which have different cut orientations (X-cut and Z-cut), different Er-doping levels (Er:(0.2, 0.4 and 2.0 mol%)LiNbO₃) and different VTE durations (80, 120, 150 and 180 h), were recorded at room temperature in the wavenumber range 50-1000 cm⁻¹ by using backward scattering geometry. The spectra were attributed on the basis of their spectral features and the previous experimental work and the most recent theoretical progress in lattice dynamics on pure LiNbO₃. In comparison with the pure crystal the most remarkable effect of Er-doping on the Raman spectrum is observed for the E(TO₉) mode. It does not appear at 610 cm⁻¹ as the pure crystal, but locates at 633 cm⁻¹. In addition, the doping also results in the lowering of the Raman phonon frequency, the broadening of the Raman linewidth and the changes of the relative Raman intensity of some peaks. The VTE treatment results in the narrowing of the linewidth, the recovery of the lowered phonon frequency and the further changes of relative Raman intensity. The narrowing of Raman linewidth indicates that the VTE processing has brought these crystals closer to stoichiometric composition. The VTE treatment has induced the formation of a precipitate ErNbO₄ in the high-doped Er(2.0%):LiNbO₃ crystals whether X- or Z-cut. For these precipitated crystals, besides above linewidth and phonon frequency features, they also display more significant Raman intensity changes compared with those not precipitated crystals. In addition, a slight mixing between A₁(TO) and E(TO) spectra is also observed for these precipitated crystals. Above doping and VTE effects on Raman spectra were quantitatively or qualitatively correlated with the characteristics of the crystal structure and phonon vibrational system.     

Dopant occupancy and optical properties of Er3+ in Er/Zn-codoped lithium niobate crystal

The effect of Zn²⁺ ion on the dopant occupancy and optical characteristic of Er³⁺ ion in Er/Zn-codoped LiNbO₃ crystal is reported. The intense 1.54 μm and relatively weak green upconversion emissions are observed for Er (1 mol%)/Zn (6 mol%):LiNbO₃ crystal. The OH^? absorption and the time-resolved spectra show that the Zn²⁺ codoping decreases the threshold concentration of Er³⁺ ion in Er/Zn-codoped LiNbO₃ crystal. The experimental results here imply that the potential application of Er³⁺-doped LiNbO₃ crystal can be designed and optimized on the basis of the theoretical investigations.     

The influence of Zn2+ ion on the 1.5 μm laser properties of LiNbO3 crystal heavily doped with Er3+ ion

The spectral characteristics of 1.54 μm emission in a series of Zn/Er:LiNbO₃ crystals with heavy Er content and variable Zn content were reported. The inductively coupled plasma mass spectrometry (ICP-MS) was used to determine the concentration of Er³⁺ ion in the crystal. The absorption and emission spectra of Zn/Er:LiNbO₃ crystals were measured. Based on Judd–Ofelt theory, the spectral parameters such as intensity parameters Ω_t (t=2, 4 and 6), transition strengths, radiative transition probabilities, radiative lifetime and fluorescence branching ratio have been obtained in Zn/Er:LiNbO₃ system. The emission cross section corresponding to ⁴I_13/2→⁴I_15/2 transition of Er³⁺ ion was obtained according to Füchtbauer–Ladenburg theory. The gain cross section of Er:LiNbO₃ crystal codoped with 6 mol% Zn²⁺ ions were also discussed in this work.     

Site-selective spectroscopy of Er3+:Ti:LiNbO3 waveguides

Starting from previous investigations in LiNbO₃ bulk crystals, we studied the optical properties of Er³⁺ ions in Ti:LiNbO₃ channel waveguides and investigated the waveguide-specific lattice environment of the Er³⁺ ions (“sites”) caused by the doping method used and the presence of a large number of Ti⁴⁺ ions. For that purpose the method of combined excitation–emission spectroscopy was applied for the first time to waveguides at low temperatures. Comparing the spectroscopic results obtained for the green, red, and near-IR luminescence (λ≈550, ≈650 and ≈980 nm) under direct (450 nm), 2-step (980 nm), and 3-step (1.5 μm) laser excitation, we found several distinguishable Er³⁺ sites which in terms of energy levels and relative numbers are similar to those in bulk material, but exhibit significantly different up-conversion efficiencies and strongly inhomogeneously broadened transitions. Moreover, we were able to distinguish isolated and cluster Er³⁺ sites by their characteristic excitation and emission transition energies and studied the respective excitation/relaxation channels. The cluster sites are most efficient in the up-conversion process, especially under 3-step excitation. Using accepted microscopic models for Er³⁺ and Ti⁴⁺ incorporation into the LiNbO₃ crystal lattice, the site distribution and up-conversion mechanisms are elucidated and their consequences for laser applications in different spectral regions are discussed. Received: 16 November 2000 / Published online: 21 March 2001     

Spectral line broadening mechanism of Er3+ transitions in Er:Ti:LiNbO3 channel waveguides

In order to elucidate the interaction effects among the various defects present in a LiNbO₃-based integrated optical device, we investigated the change of the optical properties of Er³⁺ ions under the application of an external electric field and hydrostatic pressure. We obtained for stoichiometric bulk material a complete picture of the field-induced spectral shifts as a function of transition and site. As a first important application of these results we were able to clarify the mechanism of spectral broadening of the Er³⁺ transitions in Ti:Er:LiNbO₃ channel waveguides. By selecting different waveguide modes for excitation and using highly selective double-resonance excitation with two lasers, we found that the [Ti⁴⁺] concentration gradient caused by the indiffusion results in an internal E-field gradient. This translates, due to the averaging within the guided mode, into mode-dependent spectral line broadening. Received: 24 May 2001 / Published online: 23 October 2001     

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     

Nonvolatile hologram storage properties of tri-doped Zn:Ce:Cu:LiNbO3 crystals

Congruent Zn(7 mol%):Ce:Cu:LiNbO₃ single crystal was grown by the Czochralski method in air. The occupation mechanism of the Zn²⁺ was discussed by an infrared transmittance spectrum. The nonvolatile holographic recording in Zn(7 mol%):Ce:Cu:LiNbO₃ single crystal was measured by two-photon fixed method. Zn(7 mol%):Ce:Cu:LiNbO₃ single crystals present the faster recording time and higher light-induced scattering resistance ability comparing with Ce:Cu:LiNbO₃ single crystals.     

Light-induced absorption instability in weakly reduced congruent Er:LiNbO3 crystal

Light-induced absorption (LIA) characteristics in weakly reduced (or strongly annealed) congruent and/or vapor transport equilibration (VTE)-treated Er-doped LiNbO₃ crystals have been investigated in comparison with their corresponding as-grown ones and undoped crystals by using a polarized 632.8-nm beam as probe light and another polarized 632.8- or 488-nm beam as pump light. Under He-Ne pump, the LIA was observed only in strongly reduced pure VTE LiNbO₃ crystal. Under 488-nm pump, LIA is still not observed in the doped or undoped as-grown crystals. The weakly reduced VTE-treated Er(0.2 mol %):LiNbO₃ crystal displays weak and stable LIA. On the other hand, the corresponding weakly reduced congruent crystal displays a rather unpredictable light-induced absorption instability phenomenon. The instability was shown by the random competition of the LIA and light-induced transparency (LIT). When both crystals were further reduced, the VTE sample still shows stable LIA but with increased LIA, while the LIA in the congruent sample also becomes stable enough. The instability was experimentally proved to be associated with the presence of the Er³⁺ ion that performs the role of an extrinsic defect instead of photoluminescence. A three-level model is suggested that consists of a deep level (the bipolaron) and two shallow levels: the small polaron level and the level with respect to the Er³⁺ ion. The model has been employed to qualitatively explain the LIA characteristics of the weakly reduced congruent Er:LiNbO₃ crystal, including the the instability, the effect of the state of reduction, the pump intensity and the pump–probe polarization dependences. The inhomogeneity of the defects caused by the weak reduction and the simultaneous participation of the two shallow levels in the light-induced electron-transport process result in the random competition between LIA and LIT, and consequently result in the LIA instability. PACS 42.70.Hj; 42.70.Ln; 42.70.Mp; 42.65.Hw; 81.05.-t     

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.     

Photoelectric fields in lithium niobate crystals

Photovoltaic and diffusion fields in nominally pure single crystals of stoichiometric composition (R = Li/Nb = 1) grown in the presence of 6 wt% K₂O flux (LiNbO₃ stoich. K₂O) in nominally pure single crystals of complementary composition (LiNbO₃), complementary single crystals doped with Zn²⁺, Er³⁺ at wavelength of 476, 514.5, 530 nm are defined according to parameters of photo induced light scattering indicatrix. Photo induced changes of crystals’ refractive index are defined.     

Modelling of optical amplification in Er/Yb co-doped LiNbO3 waveguides

The optical amplification of LiNbO₃:Er³⁺/Yb³⁺ channel waveguides has been modelled in the small signal regime using the overlapping integrals method and the rate-equation formalism. It has been found that Yb³⁺ -sensitisation improves the pump efficiency at 980 nm and a higher gain is achievable in the high power-limit compared to singly-doped LiNbO₃:Er³⁺ amplifiers.     

Raman study on vapor-phase equilibrated Er:LiNbO3 and Er:Ti:LiNbO3 crystals

Raman spectra of Er:LiNbO₃ crystal and Ti-diffusedEr:LiNbO₃ strip waveguide, in which the Li/Nb ratio was altered using a vapor-phase equilibration (VPE) technique, were measured at room temperature in the wave-number range 50–3500 cm^-1. Both 488 and 514.5 nm radiations were used to excite Raman scattering, A₁(TO) and E(TO) modes were recorded at backward scattering geometry. The results indicated that the lattice vibrational spectra of the as-grown Er:LiNbO₃ are almost the same as those of pure LiNbO₃ except for the little shift of the peak position and the change of relative intensity of some peaks. In comparison with the spectra of as-grown Er:LiNbO₃ crystal the vapor-phase equilibrated Er:LiNbO₃ and Er:Ti:LiNbO₃ crystals in the lattice vibrational region exhibit the following features: firstly, Raman peaks become narrow, indicating that the VPE process has brought Er:LiNbO₃ and Er:Ti:LiNbO₃ crystals closer to a stoichiometric composition; secondly, relative intensity of some peaks varies with the VPE time; and finally, slight blue shifting in peak position was observed. Some of these features were correlated with the NbO₆ octahedra and with the site distribution of the doped Er ions. In addition, green fluorescence peaks and/or bands associated with the electron transitions ² H _11/2?⁴ I _15/2 and ⁴ S _3/2?⁴ I _15/2 of the doped Er³⁺ were also observed. For 488 nm excitation they appear in the wavenumber range of 1200–3000 cm^-1 and are well separated from lattice vibrational region; for 514.5 nm excitation, however, these fluorescence peaks shift towards the low wavenumber region and overlap partially with the lattice vibrational spectra. Received: 24 May 2000 / Accepted: 29 May 2000 / Published online: 13 September 2000     

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.     

Luminescence spectroscopy of Er-doped and Er, Yb-codoped LaPO4 single crystals

LaPO₄ single crystals lightly doped with Er³⁺, and codoped with Er³⁺ and Yb³⁺ have been grown by spontaneous nucleation in a lead phosphate flux. Absorption and luminescence spectra have been measured in the visible and near-IR regions and the excited state dynamics has been studied upon pulsed laser excitation. The obtained results have allowed the evaluation of the effective emission cross-sections around 1.5 μm, that have been found to be similar to important oxide laser crystals doped with Er³⁺. Efficient visible upconversion has been observed upon excitation at 980 nm in the codoped crystals. This behaviour is attributed to Yb³⁺-Er³⁺ energy transfer processes.     

Luminescence kinetics of LiNbO3:Yb3+-Er3+, LiNbO3:Er3+, and LiNbO3:Yb3+ crystals under selective excitations in the impurity subsystem

The results of investigations of luminescent radiations’ kinetic characteristics for LiNbO₃:Yb³⁺-Er³⁺, LiNbO₃:Er³⁺, and LiNbO₃:Yb³⁺ crystals under optical excitations at 532 nm and 1064 nm wavelengths are presented. The shapes and times of rise and damping of luminescent signals at 550 nm, 980 nm and 1555 nm wavelengths under selective excitations in the impurity subsystem of the investigated materials are determined. Comparison of the temporal characteristics of luminescent responses of LiNbO₃ crystals doped separately with Yb³⁺ and Er³⁺ ions with those of the LiNbO₃:Yb³⁺-Er³⁺ crystal allows identifying the contributions from different energy transfer processes of optical excitation taking place in the impurity subsystem of the material.     

ESR study of rare-earth ions with the effective spin of 1/2 in LiNbO3 crystals

Rare-earth ions of Nd³⁺ and Er³⁺ in nearly stoichiometric and MgO-doped LiNbO₃ crystals, respectively, have been investigated by employing an X-band electron spin resonance (ESR) spectrometer. The grown crystal was heated in Li-rich powder at 1100°C in order to make it nearly stoichiometric by the vapor transport equilibrium technique. Due to the fact that the ESR linewidth is much narrower in the stoichiometric crystal than in the congruent LiNbO₃, we were able to determine the hyperfine constants of¹⁴³Nd and¹⁴⁵Nd at 4 K. By codoping MgO into LiNbO₃, a new Er³⁺ center has been observed with a differentg-tensor. We propose that the new Er³⁺ center in Mg-doped LiNbO₃ occupies the niobium site due to the local excessive Mg²⁺ ion at the lithium site, whereas Nd³⁺ and Er³⁺ in congruent crystals reside at the lithium site. The proposal is consistent with theg-value anisotropy.     

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.