Enhanced electrical surface conductivity of LiNbO3 induced by argon-ion bombardment

The surface conductivity of pure and proton exchanged LiNbO₃ was studied. After bombarding the surface with Ar⁺ ions having an energy of about 2000 eV the samples showed an enhanced specific conductivity near the surface (5 nm) of 6 orders of magnitude. This corresponds to a specific conductivity of 10^–5 S/cm at room temperature. The enhanced conductivity is thermally activated with an energy of 0.41±0.04 eV, and it seems to be a non-ionic conductivity, because no polarization behaviour was observed. This enhanced conductivity was observed at the surface of both pure and proton exchanged LiNbO₃.     

Acoustic properties of proton exchanged LiNbO3 investigated by Brillouin scattering

The propagation of surface acoustic waves at microwave frequencies (10¹⁰ Hz) was studied on proton exchanged LiNbO₃ crystals by means of Brillouin scattering. The proton exchange causes a large velocity reduction for surface acoustic waves propagating in the x–y plane of ay-cut crystal as well as for longitudinal bulk acoustic waves travelling in the proton exchanged sub-surface region. The velocity reduction amounts to about 20% for both types of waves. The corresponding elastic constants are reduced even by about 40% since the density remains almost constant. This softening seems to involve both the shear and compressional elastic constants, but in an anisotropic way.Thus by proton exchange it is possible to build acoustic waveguides adjacent to the surface, similar to the construction of optical waveguides. By a lateral control of the proton exchange rate optical elements for ultrasonic waves, for example, acoustic lenses can be produced without deformation of the flat surface.The absorption of surface acoustic waves on proton exchanged surfaces is stronger than on pure LiNbO₃ indicating a novel absorption mechanism becoming active in the proton exchanged material.     

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     

Surface acoustic wave distribution and acousto-optic interaction in proton exchanged LiNbO3 waveguides

The efficiency of acoustooptic (AO) interaction in YZ-cut proton exchanged (PE) LiNbO₃ waveguides is theoretically analysed by determining the overlap between the optical and acoustic field distributions. The present analysis takes into account the perturbed SAW field distribution due to the presence of the PE layer on the LiNbO₃ substrate determined by the rigorous layered medium approach. The overlap is found to be significant upto very high acoustic frequencies of the order of 5 GHz, whereas in the earlier analysis by vonHelmolt and Schaffer [6] for diffused waveguides, it was shown that the overlap integral rolls down to nearly zero at this high frequency range.     

Comparison of the electro-optic coefficient r33 in well-defined phases of proton exchanged LiNbO3 waveguides

The electro-optic coefficient, r₃₃, of proton exchanged LiNbO₃ waveguides has been measured in well-defined phases of the exchanged layer. Namely, in two low index-jump α-phases, i.e. unannealed soft-exchanged (SPE) and annealed (APE) guides, and in two high index-jump phases, i.e. β₁ guides and, for comparison, ordinary proton exchanged (PE) guides (having a mixture of phases). The following values have been obtained (in pm/V): 22.1±0.6 for SPE; 20.9±0.7 for APE; 0.33±0.01 for β₁; and 0.76±0.04 for PE. Differences between these values are discussed in terms of the structure of the phase involved. Received: 18 May 2001 / Revised version: 22 August 2001 / Published online: 30 October 2001     

Phase transition study of H:LiNbO3 waveguides by Raman spectroscopy

New results on Raman spectra of protonated LiNbO₃ are reported in order to clarify the structural and compositional changes in waveguide layers during proton exchange and post-exchange annealing processes. Samples with different degree of Li-H substitution exchanged in either neat or buffered benzoic and pyrophosphoric acid melts are investigated providing Raman and optical measurements simultaneously. The question of phase state of protonated layers at slow and rapid cooling after the annealing procedure is discussed. Qualitative and quantitative agreement between the structural data reported earlier for proton-exchanged powders and the Raman data obtained for protonated single crystals is established. A new band at 69 cm^–1 is observed which is strongly intensity dependent upon the hydrogen presence in waveguide layers. By using this band the degree of proton exchange is determined for different treatment conditions of the samples.     

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     

Praseodymium-doped Ti:LiNbO3 waveguides

3 by diffusion doping is investigated by means of secondary neutral mass spectrometry and secondary ion mass spectrometry. The diffusion of praseodymium in LiNbO₃ can be described by Fick’s laws of diffusion with a concentration-independent diffusion coefficient and a limited solubility of praseodymium in LiNbO₃ increasing exponentially with rising temperature. The diffusion depends on the Li₂O content of the LiNbO₃ crystal. For LiNbO₃ crystals with a nominal slight difference in the congruent composition, the diffusion constants and activation energies for Z-cut LiNbO₃ are 3.28×10^-5 cm²/s and 2.27 eV, and 1.39×10^-5 cm²/s and 2.24 eV, respectively. Titanium-doped waveguides are formed in Pr:LiNbO₃ and characterised in relation to waveguide loss and absorption in the visible and near infrared. Received: 17 September 1998 / Accepted: 11 November 1998     

Raman characterization of H:LiNbO3 waveguides

In this work we present polarized Raman measurements of z-cut multimode H:LiNbO₃ waveguides in the κ_i- and β_i-phase states. A spectrum with unexpected form and behaviour, originating from the layer at the very surface, was observed in samples with various degrees of Li–H substitution. Possible reasons for the presence of this strange spectrum are considered. Received: 16 May 2001 / Revised version: 7 August 2001 / Published online: 23 October 2001     

Mössbauer study of proton-exchanged LiNbO3:Fe

Topotactic proton exchange (Li against H) can be achieved by treating LiBnO₃ with appropriate acids. In order to investigate the effect of proton exchange on Fe-impurities we studied LiNbO₃:Fe powder material treated in sulphuric acid and LiNbO₃:Fe single crystals treated in benzoic acid by Mössbauer spectroscopy. During the topotactic ion exchange only the Li-ions are exchanged for protons, whereas the Fe-impurities are retained in the material.     

Damage profiles in LiNbO3 by low-energy H+ implantation

Low-energy 120 and 150 keV H⁺ was implanted in z-cut LiNbO₃ at room temperature. The fluence of H⁺ is 5?×?10¹⁶ ions/cm². The damage profiles in LiNbO₃ induced by implantation were investigated using Rutherford backscattering/channelling. The damage profiles were extracted using the channelling results. The experimental damage profiles in LiNbO₃ were analyzed and compared to the simulated results from TRIM. The results show a good consistency between experimental and simulated results. The present results are useful for the fabrication of H-implanted waveguides of oxide crystals, especially LiNbO₃.     

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     

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.     

Stabilization of Fe2+ centers in LiNbO3: Ti waveguides

Holographic measurements in LiNbO₃: Ti waveguides are reported indicating a mode dependent enhancement of photoconductivity. This enhancement can be explained by a stabilization of Fe²⁺ centers in the waveguide which are responsible for optical damage effects.     

Laser induced memory bits in photorefractive LiNbO3 and LiTaO3

We study experimentally the formation of refractive index voxels (volume elements) in photorefractive LiNbO₃ and LiTaO₃ crystals illuminated with high irradiance femtosecond laser pulses. We used 150 fs pulses at 800 nm wavelength (energy 6–50 nJ) tightly focused inside the crystals in a single shot regime. This resulted in a formation of a micrometer size region of elevated refractive index, which may be used as memory bits in information storage/retrieval application. The maximum refractive index change of 5×10⁻⁴ was recorded in undoped LiNbO₃ at an average light intensity of ∼TW/cm² that is close to the breakdown threshold. A simple setup for photorefractive recording and in situ monitoring of the refractive index changes has been proposed. M. Sūdžius leaves from: the Institute of Materials Science and Applied Research of Vilnius University, Lithuania.     

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.     

Light-induced refractive index changes in LiNbO3:Ti waveguides

Holographic measurements of light-induced refractive index changes in LiNbO₃Ti waveguides are reported. The results demonstrate that Fe²⁺ centers are stabilized against oxidation in the region of large Ti concentration near the surface thus increasing the sensitivity to optical damage considerably. This undesired effect may be largely abolished by additional in-diffusion of protons.     

Studies of absorption spectra and the photovoltaic effect in LiNbO3:Mg:Fe crystals

The absorption spectra, photoconductivities and photovoltaic currents of LiNbO₃:Fe crystals with different Mg doping levels and Li/Nb ratios in the oxidized state have been investigated at room temperature. The Fe²⁺ ions in LiNbO₃:Mg:Fe with Mg content above a critical value are more easily oxidized than in crystals with Mg content below a critical value. The photoconductivity of LiNbO₃:Mg:Fe crystals with Mg content above a critical value is one order of magnitude higher than those with Mg content below a critical value, however, the photovoltaic current of the former is one order of magnitude lower than the latter. The differences are postulated to be due to different sites of Fe in these two classes of crystals.     

Photorefractive properties of LiNbO3:Zn crystals related to the defect structure

LiNbO₃:Zn single crystals and powders were studied by precise X-ray diffraction methods. Structural refinement yielded new models of the intrinsic defect structure valid for different Zn concentration ranges. For concentrations up to 7 at. % in the crystal, Zn ions incorporate onto Li sites; at higher concentrations Zn ions are found on both Li and Nb sites. Photorefractive properties of LiNbO₃:Zn are discussed in the context of the deduced defect models. A smooth increase in the photoconductivity up to 7 at. % Zn is accounted for by a decrease of Nb antisites. Steeper growth of the photoconductivity at higher Zn concentrations is related to vanishing Li vacancies. Received: 17 November 2000 / Revised version: 23 January 2001 / Published online: 20 April 2001     

Charge transport processes in LiNbO3:Fe at high intensity laser pulses

Light-induced refractive index changes in LiNbO₃:Fe crystals are investigated at high light intensities (>10⁹ Wm^–2). Holographic gratings are recorded and erased with frequency-doubled pulses of a Q-switched Nd:YAG laser. We find new intensity dependent contributions to the holographic sensitivity, to the photoconductivity, and to the saturation value of refractive index change. Light-induced absorption changes are also detected. These results indicate that the Fe²⁺/Fe³⁺ charge transport model, well established for low intensities, has to be modified for high intensities by assuming additional centers which trap and supply electrons.