Lattice Site of Rare-Earth Ions in Stoichiometric Lithium Niobate Probed by OH− Vibrational Spectroscopy

Rare-earth (RE = Er3+, Nd3+, or Yb3+) ion-doped stoichiometric LiNbO3 crystals were grown by the Czochralski and the high-temperature top-seeded solution growth methods. For the 0.22–0.87 mol% concentration range of the RE oxides in the melt/solution, in addition to the well-known hydroxyl (OH−) vibrational band in undoped stoichiometric LiNbO3, a new infrared absorption band was observed at about 3500 cm−1, similar to the case of the trivalent optical damage resistant (ODR) dopants In3+ and Sc3+. By comparing the frequencies and polarization dependences of the bands to those detected for ODR ion containing crystals, they are attributed to the stretching vibration of OH− ions in RE3+Nb-OH− complexes. Consequently, above a given concentration threshold, some of the rare-earth ions are assumed to occupy niobium sites in the LiNbO3 lattice. The same model is also suggested for RE-doped congruent LiNbO3 crystals containing over-threshold (>5 mol %) amounts of the Mg-co-dopant

Photorefractive damage resistance threshold in stoichiometric LiNbO_3:Zr crystals

Several optical methods including ultraviolet absorption, infrared absorption of the hydroxyl ions, Raman spectroscopy, and the Z-scan method have been used to determine the damage resistance threshold in 0–0.72 mol. % Zr-containing, flux-grown, nearly stoichiometric LiNbO3 single crystals. All spectroscopical methods used indicate that samples containing at least ≈0.085 mol: % Zr in the crystal are above the threshold while Z-scan data locate the photorefractive damage threshold between 0.085 and 0.314 mol. % Zr

Growth and study of nonlinear optical crystals at the Hungarian Academy of Sciences, Journal of Telecommunications and Information Technology, 2000, nr 1,2

The former Research Laboratory for Crystal Physics continues the growth and defect structure investigation of nonlinear optical single crystals in a new organization, as a part of the Research Institute for Solid State Physics and Optics, Hungarian Academy of Sciences. The aim of the activity is to prepare specific crystals for basic and applied research as well as for applications. We improve the quality or modify the properties of well known nonlinear oxide and borate crystals and develop new materials. The principle nonlinear optical crystals in our profile are the followings: Paratellurite (TeO2), congruent, Mg-doped and stoichiometric lithium niobate (LiNbO3), a variety of sillenite structured crystals (Bi12MeO20, Me=Si, Ge, Ti, etc.), bismuth tellurite (Bi2TeO5) and nonlinear borates (BBO–b-BaB2O4, LBO–LiB3O5, LTB–Li2B4O7, CLBO–CsLiB6O10 and YAB–YAl3(BO3)4). Details of the crystal preparation and the major achievements are discussed in the paper

Polaron-Mediated Luminescence in Lithium Niobate and Lithium Tantalate and Its Domain Contrast

In this review article, we discuss photoluminescence phenomena mediated by polarons in lithium niobate (LNO). At first we present the fundamentals on polaron states in LNO and their energy levels, i.e., on free and bound electron polarons, on hole polarons as well as on bipolarons. We discuss the absorption measurements on reduced as well as on doped LNO that made the characterization of the formed polaron states possible by their absorption bands. Next, we proceed by reporting on the two polaron-mediated photoluminescence bands that have been observed in LNO: (1) A near-infrared luminescence band in the range of 1.5 eV shows a mono-exponential decay and a strong dependence on iron doping. This luminescence is emitted by bound polarons returning from an excited state to the ground state. (2) A luminescence band at visible wavelengths with a maximum at 2.6 eV shows a stretched-exponential decay and is strongly enhanced by optical damage resistant doping around the doping threshold. This luminescence stems from the recombination of free electron and hole polarons. The next major topic of this review are domain contrasts of the visible photoluminescence that have been observed after electrical poling of the substrate, as singly inverted domains show a slightly reduced and faster decaying luminescence. Subsequent annealing results in an exponential decrease of that domain contrast. We show that this contrast decay is strongly related to the mobility of lithium ions, thus confirming the role of polar defect complexes, including lithium vacancies, for these domain contrasts. Finally we discuss the extension of our investigations to lithium tantalate (LTO) samples. While the results on the domain contrast and its decay are similar to LNO, there are remarkable differences in their luminescence spectra

Measurement of Refractive Index and Absorption Coefficient of Congruent and Stoichiometric Lithium Niobate in the Terahertz Range

Time domain THz spectroscopy measurements were performed on a series of undoped and Mg-doped congruent lithium niobate crystals with 1.2, 6.1, and 8.4 mol% Mg concentrations and on undoped and Mg-doped stoichiometric lithium niobate crystals with 0.7, 1.5, and 4.2 mol% Mg concentrations with polarization parallel (extraordinary) and perpendicular (ordinary) to the z axis of the crystal at 300 K. The absorption coefficient and refractive index spectra were determined in the THz frequency range from 0.25 to ~2.5 THz. In the case of congruent samples for both polarizations, both the refractive index and the absorption coefficient have minimal values for compositions close to the photorefractive threshold. In the case of stoichiometric samples, similar tendencies close to the photorefractive threshold at lower Mg concentration were observed but only for extraordinary polarization, while for ordinary polarization the measured values, especially for the absorption coefficient, were only weakly dependent on the Mg content

NIR-to-NIR Imaging: Extended Excitation Up to 2.2 μm Using Harmonic Nanoparticles with a Tunable hIGh EneRgy (TIGER) Widefield Microscope

Near-infrared (NIR) marker-based imaging is of growing importance for deep tissue imaging and is based on a considerable reduction of optical losses at large wavelengths. We aim to extend the range of NIR excitation wavelengths particularly to values beyond 1.6 μm in order to profit from the low loss biological windows NIR-III and NIR-IV. We address this task by studying NIR-excitation to NIR-emission conversion and imaging in the range of 1200 up to 2400 nm at the example of harmonic Mg-doped lithium niobate nanoparticles (i) using a nonlinear diffuse femtosecond-pulse reflectometer and (ii) a Tunable hIGh EneRgy (TIGER) widefield microscope. We successfully demonstrate the existence of appropriate excitation/emission configurations in this spectral region taking harmonic generation into account. Moreover, NIR-imaging using the most striking configurations NIR-III to NIR-I, based on second harmonic generation (SHG), and NIR-IV to NIR-I, based on third harmonic generation (THG), is demonstrated with excitation wavelengths from 1.6–1.8 μm and from 2.1–2.2 μm, respectively. The advantages of the approach and the potential to additionally extend the emission range up to 2400 nm, making use of sum frequency generation (SFG) and difference frequency generation (DFG), are discussed

NIR-to-NIR Imaging: Extended Excitation Up to 2.2 μm Using Harmonic Nanoparticles with a Tunable hIGh EneRgy (TIGER) Widefield Microscope

Near-infrared (NIR) marker-based imaging is of growing importance for deep tissue imaging and is based on a considerable reduction of optical losses at large wavelengths. We aim to extend the range of NIR excitation wavelengths particularly to values beyond 1.6 μm in order to profit from the low loss biological windows NIR-III and NIR-IV. We address this task by studying NIR-excitation to NIR-emission conversion and imaging in the range of 1200 up to 2400 nm at the example of harmonic Mg-doped lithium niobate nanoparticles (i) using a nonlinear diffuse femtosecond-pulse reflectometer and (ii) a Tunable hIGh EneRgy (TIGER) widefield microscope. We successfully demonstrate the existence of appropriate excitation/emission configurations in this spectral region taking harmonic generation into account. Moreover, NIR-imaging using the most striking configurations NIR-III to NIR-I, based on second harmonic generation (SHG), and NIR-IV to NIR-I, based on third harmonic generation (THG), is demonstrated with excitation wavelengths from 1.6–1.8 μm and from 2.1–2.2 μm, respectively. The advantages of the approach and the potential to additionally extend the emission range up to 2400 nm, making use of sum frequency generation (SFG) and difference frequency generation (DFG), are discussed

Three-photon and four-photon absorption in lithium niobate measured by the Z-scan technique

In conclusion, our study employed open-aperture Z-scan measurements to explore the determination of three-photon (3 PA) and four-photon absorption (4 PA) coefficients in congruent and stoichiometric lithium niobate (cLN, sLN) with varying concentrations of Mg doping, utilizing laser pulses at 800 nm and 1030 nm wavelengths. Remarkably, we observed that the 3 PA and 4 PA coefficients exhibited distinctive variations at different Mg doping concentration with different intensities. Both cLN and sLN displayed minima in their absorption coefficients at a specific Mg doping concentration, corresponding to the point at which photo-refraction was effectively suppressed. This finding indicating the role of the interplay of second harmonic and the defect center related polarons, shedding light on the underlying mechanisms governing these nonlinear optical phenomena. Furthermore, our investigation revealed a difference in the nonlinear absorption behavior between 3 PA at 800 nm and 4 PA at 1030 nm, with the latter exhibiting greater absorption under similar intensity levels, the analysis of 3 PA and 4 PA coefficients in these lithium niobate crystals holds significant promise for selecting the most suitable crystal type for efficient terahertz (THz) generation and other nonlinear optical processes that demand high pump intensities

Polaron-Mediated Luminescence in Lithium Niobate and Lithium Tantalate and Its Domain Contrast

In this review article, we discuss photoluminescence phenomena mediated by polarons in lithium niobate (LNO). At first we present the fundamentals on polaron states in LNO and their energy levels, i.e., on free and bound electron polarons, on hole polarons as well as on bipolarons. We discuss the absorption measurements on reduced as well as on doped LNO that made the characterization of the formed polaron states possible by their absorption bands. Next, we proceed by reporting on the two polaron-mediated photoluminescence bands that have been observed in LNO: (1) A near-infrared luminescence band in the range of 1.5 eV shows a mono-exponential decay and a strong dependence on iron doping. This luminescence is emitted by bound polarons returning from an excited state to the ground state. (2) A luminescence band at visible wavelengths with a maximum at 2.6 eV shows a stretched-exponential decay and is strongly enhanced by optical damage resistant doping around the doping threshold. This luminescence stems from the recombination of free electron and hole polarons. The next major topic of this review are domain contrasts of the visible photoluminescence that have been observed after electrical poling of the substrate, as singly inverted domains show a slightly reduced and faster decaying luminescence. Subsequent annealing results in an exponential decrease of that domain contrast. We show that this contrast decay is strongly related to the mobility of lithium ions, thus confirming the role of polar defect complexes, including lithium vacancies, for these domain contrasts. Finally we discuss the extension of our investigations to lithium tantalate (LTO) samples. While the results on the domain contrast and its decay are similar to LNO, there are remarkable differences in their luminescence spectra