Optical characterization of Cr3+ centers in LiNbO3

Low-temperature luminescence spectra of stoichiometric Cr:LiNbO₃, congruent Cr:LiNbO₃ and congruent Cr,Mg:LiNbO₃ were studied. Dominant low-field and minor high-crystal-field optical centers are the Cr³⁺ impurity ions that preferentially occupy Li⁺ sites (Cr_Li) in the Cr:LiNbO₃ crystals. Low-field centers related to Cr³⁺ substitution of Nb⁵⁺ (Cr_Nb) occur in addition to Cr_Li in co-doped Cr,Mg:LiNbO₃ samples. Application of high hydrostatic pressure leads to the transformation of dominant Cr³⁺ centers from low- to high-field type due to strong pressure-induced blue shift of the ⁴ T ₂ state, resulting in its crossing with the ² E state of Cr³⁺. This level-crossing effect was observed for the dominant Cr³⁺ _Li and Cr³⁺ _Nb centers at pressures that correlate well with estimations based on the ⁴ T ₂-² Eenergy gap (230 cm^-1 and 1160 cm^-1) and on the rate of their pressure-induced change (14.35 and 11.4 cm^-1/kbar, respectively). We also studied inhomogeneous broadeningof the ² E?⁴ A ₂transitions at ambient pressure for the minor high-field “defect” Cr³⁺ _Li centers in congruent LiNbO₃. A fine structure in the spectral response of these centers was observed. The obtained results are discussed on the basis of a microscopic hierarchic model for perturbed Cr³⁺ ions in the LiNbO₃ lattice. Received: 25 June 2001 / Published online: 2 November 2001     

Dominant Cr3+ centers in LiNbO3 under hydrostatic pressure

Low-temperature luminescence spectra of stoichiometric Cr: LiNbO₃ and of congruent Cr, Mg: LiNbO₃ were studied. Cr³⁺ impurity ions preferentially occupy Li⁺ sites (Cr_Li) in the LiNbO₃ crystal lattice, while Cr³⁺ ions substituting for Nb⁵⁺ ions (Cr_Nb) occur in addition to Cr_Li centers in codoped Cr, Mg: LiNbO₃ crystals. Application of a high hydrostatic pressure leads to a transformation of (dominant in concentration) Cr³⁺ centers from low-to high-crystal-field centers. Due to a strong pressure-induced blue shift of the ⁴ T ₂ state resulting in crossing with the ² E state, the replacement of the broad band ⁴ T ₂ → ⁴ A ₂ emission by a narrow R-line emission ² E → ⁴ A ₂ occurs in the luminescence spectra of the samples. This effect of level crossing was observed for the dominant Cr _Li ³⁺ and Cr _Nb ³⁺ centers at pressures which correlated well with estimations based on the ⁴ T ₂-² E energy gap (230 and 1160 cm^?1) and on the rate of their pressure-induced change (14.35 and 11.4 cm^?1/kbar, respectively).     

Effect of external electric field on R line absorption spectra in LiNbO3:Cr3+ crystals

The effect of an external electric field on the R absorption lines of LiNbO₃:Cr³⁺ crystals has been studied by a high-sensitivity differential technique at 77 K. Linear Stark effect has been observed in a field directed along the trigonal crystal axis. No effect of the field was observed when directed perpendicular to this axis. These characteristics of the Stark effect provide a convincing argument for the electric dipole moments of Cr³⁺ centers being oriented along the trigonal C ₃ axis of the crystal and indicate that the chromium centers in LiNbO₃ have C ₃ symmetry. Fiz. Tverd. Tela (St. Petersburg) 39, 2053–2056 (November 1997)     

Infrared energy transfer in Tm3+:LiNbO3

The infrared optical properties of LiNbO₃ crystals doped with variable thulium concentrations have been studied. In particular, the infrared emissions that appear after direct pumping to the ³H₄ multiplet (795 nm) have been analyzed. The emission spectra, as well as the lifetimes, show that an efficient energy transfer between ³F₄ and ³H₄ levels takes place. The concentration dependence of the lifetimes has been studied and the transfer probability has been characterized.     

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     

ESR of Ti3+ in LiNbO3

In reduced LiNbO₃ and ESR signal was identified which is attributed to Ti³⁺ (3d)¹ by comparison with known (4d)¹ and (5d)¹ centers. The signal can be increased many times by Ti in-diffusion. It is photosensitive, being quenched by near UV-illumination.     

Optical properties of LiNbO3:Cr crystals co-doped with germanium oxide

Lithium niobate (LiNbO₃) crystals doped with chromium ions show a clear green colouring reflecting the absorption profile of the dominating [Cr]_Li defect centres. A significant change in its colouration takes place when it is co-doped with other valency impurities such as Mg²⁺, Sc³⁺ and W⁶⁺, above a certain threshold concentration. This concentration singularity has been attributed to the formation of [Cr]_Nb centres coexisting with the [Cr]_Li centres.In this work, we extended the investigation on the effect of co-dopant ions in Cr:LiNbO₃ to tetravalent cation such as GeO₂. A singularity in the relative intensity of the ⁴A₂→⁴T₁ and ⁴A₂→⁴T₂ absorption band was observed for a concentration of ～1.5 mol%, compared with 4.5 mol% for Mg²⁺. The photoluminescence emission spectra also reveal a new emission band, at a lower energy than the [Cr]_Li centre, corresponding to this threshold concentration. A charge compensation model is proposed to explain the role of cation impurities and results are compared with those of other valence impurities.     

LiNbO3∶Cr∶Cu晶体吸收特性及非挥发全息存储研究

研究了LiNbO3∶Cr∶Cu晶体的吸收特性,发现LiNbO3∶Cr∶Cu（含0.14 wt.% Cr2O3 和 0.011 wt.% CuO）晶体存在两个明显的吸收峰,中心波长分别位于480 nm和660 nm; 随着Cr的含量逐渐减小,Cu的含量逐渐增大,短波段不存在明显吸收峰,掺Cr的含量越大,中心波长在660 nm处的吸收越大；633 nm红光虽然位于中心波长为660 nm的吸收峰内,但它无助于光折变过程.分别采用390 nm紫外光和488 nm蓝光作为敏化光,514 nm绿光作为记录光的记录方案,实现了非挥发全息记录,掺入适量的Cr( 比如NCr=2.795×1025 m－3,NCr/ NCu=1)有助于全息记录性能的提高.     

Optical spectroscopy of Cr3+ and Cr3+-Tm3+ in alkaline silicate glasses

Conclusions Alkaline silicate glasses seem to be good candidates as host materials for codoping with Cr³⁺ and Tm³⁺. Cr³⁺ ions occupy mainly low-field sites in them, and their broadband emission overlaps Tm³⁺ excitation. As a consequence very high efficiency for the energy transfer Cr³⁺→Tm³⁺ is achieved with moderate concentrations of these ions. Moreover, the average lifetime of the Cr³⁺ ions in codoped glasses is long enough to allow significant energy storage by flashlamp pumping. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 5, pp. 115–120, September–October, 1995.     

Excitation energy transfer between Er3+ and Tm3+ in LiNbO3

Conclusions Nonradiative energy transfer between similar and different rare-earth ions in LiNbO₃ has been evidenced for the first time. The contribution of nonradiative energy transfer to the decay of the¹G₄ and³H₄ levels of thulium and the⁴S_3/2 and⁴I_13/2 levels of erbium is significant for activator concentrations of the order of several thousand ppm in LiNbO₃. The excitation of higher-lying levels of both activators is transferred faster in codoped crystal to the lowest luminescent levels, from which the luminescence in the 1–2-μm spectral region occurs. This accelerated relaxation is advantageous for broadband optical pumping since the contribution of radiative transitions competing with the³F₄−³H₆ laser transition of thulium is reduced. On the other hand, it appears that erbium ions will influence adversely the efficiency of a laser-diode-pumped LiNbO₃∶Er, Tm laser operating near 1.8 μm since the part of the³H₄ excitation transferred to erbium ions is emitted from the long-lived⁴I_11/2 level of Er³⁺. Furthermore, the⁴I_13/2 excitation is not transferred fully to thulium ions and is lost in⁴I_13/2−⁴I_15/2 emission. Lithium niobate singly doped with thulium is more promising since the cross-relaxation process that transfers the excitation from the³H₄ level to the³F₄ level appears to be efficient in this host. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 5, pp. 125–133, September–October, 1995.     

LiNbO3:Cr:ZnO晶体生长和光谱特性的研究

采用提拉法从近化学计量比的熔体中生长出尺寸为φ20 mm×50 mm的优质LiNbO3:Cr:ZnO(CZLN)晶体,其光学均匀度为7.59(10-5).进行了吸收和荧光光谱的测定研究.吸收谱测试表明:Cr3 离子在晶体中有2个宽且强的吸收带及1个微弱的吸收线,两宽带中心波长分别为480和660 nm,对应于4A2→4T1和4A2→4T2两个具有相同的总自旋能级之间的跃迁,在4A2→4T2吸收宽带的长波边缘处有个很小的吸收峰,其波长为727nm,对应于4A2→2E(R线)的跃迁.荧光测试表明:当激发波长为660 nm时,CZLN晶体荧光宽带和1个较弱的荧光线峰并存,宽带范围为802～988 nm,峰值波长为871 nm,对应于4T2→2E,4A2的联合能级跃迁,荧光线峰波长约为754 nm,其强度较弱,相应于2E→4A2(零声子线)能级跃迁.计算了晶场强度和Racah参数,其Dq/B=2.72,晶体属于强场介质.研究表明,CZLN晶体具备可调谐激光晶体的基本光谱要求,且有良好的物化性能,可以实现宽频带可调谐激光输出.它又具有较大的倍频系数,有望实现420 nm附近紫外的自倍频激光输出.     

Ti扩散Er3+:LiNbO3沟道波导的模式分析

本文采用有效折射率方法对Ti扩散Er³⁺:LiNbO₃沟道波导的模式特性进行了分析,分析中考虑了Er³⁺:LiNbO₃晶体的各向异性,并与变分法分析进行了比较,二者结果相一致。     

Polarized emission and absorption cross-section calculation in LiNbO3:Tm3+

Absorption and emission cross-sections are essential spectroscopic parameters that determine the performance of rare-earth solid state lasers and amplifiers. A precise characterization of such parameters is of great interest in order to proceed with the necessary optimization stage which will assure the development of photonic devices with high efficiency. In particular, in order to model Tm³⁺ infrared lasers under 800 nm pumping, the absorption and emission cross-sections associated with optical transitions involving the ³H₄ and ³F₄ manifolds are needed. In this work, the classical McCumber theory is applied to evaluate the polarized absorption and emission cross-sections of Tm³⁺ ions in LiNbO₃.     

Modelling of Tm3+-doped LiNbO3 Waveguide Lasers

In this work, CW laser operation of Tm³⁺-doped LiNbO₃ channel waveguides has been modelled. The model is based on time dependent laser rate equations coupled with the laser signal and pump photon flux equations. Steady state solutions for the population densities, pump and signal powers are obtained by using finite difference discretization of the active volume. The effects of spectroscopic parameters such as concentration dependent cross-relaxation and excess waveguide loss have been analyzed. We demonstrate good agreement with experimental data previously reported in Zn-diffused LiNbO₃:Tm³⁺ channel waveguide lasers. It is shown also that laser performance can be substantially improved by optimizing the cavity length.     

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.