Optical nonlinearities of small polarons in lithium niobate

An overview of optical nonlinearities of small bound polarons is given, which can occur in the congruently melting composition of LiNbO3. Such polarons decisively influence the linear and nonlinear optical performance of this material that is important for the field of optics and photonics. On the basis of an elementary phenomenological approach, the localization of carriers in a periodic lattice with intrinsic defects is introduced. It is applied to describe the binding energies of four electron and hole small polarons in LiNbO3: small free Nb4+Nb polarons, small bound Nb4+Li polarons, small bound Nb4+Li:Nb4+Nb bipolarons, and small bound O− hole polarons. For the understanding of their linear interaction with light, an optically induced transfer between nearest-neighboring polaronic sites is assumed. It reveals spectrally well separated optical absorption features in the visible and near- infrared spectral range, their small polaron peak energies and lineshapes. Nonlinear interaction of light is assigned to the optical formation of short- lived small polarons as a result of carrier excitation by means of band-to- band transitions. It is accompanied by the appearance of a transient absorption being spectrally constituted by the individual fingerprints of the small polarons involved. The relaxation dynamics of the transients is thermally activated and characterized phenomenologically by a stretched exponential behavior, according to incoherent 3D small polaron hopping between regular and defect sites of the crystal lattice. It is shown that the analysis of the dynamics is a useful tool for revealing the recombination processes between small polarons of different charge. Nonlinear interaction of small polarons with light furthermore results in changes of the index of refraction. Besides its causal relation to the transients via Kramers-Kronig relation, pronounced index changes may occur due to optically generated electric fields modulating the index of refraction via the linear electro-optic effect, also. Based on a microscopic picture and by considering the local structural environment of bound polarons, the appearance of photovoltaic currents is explained straightforwardly as a result of the optically induced carrier transfer. Both transient absorption and index changes are spatially confined to the intensity profile of the interacting light allowing for the recording of efficient mixed absorption and phase volume holograms. By means of holographic spectroscopy, these small-polaron based optical nonlinearities are verified either without or with the action of the linear electro-optic effect; their prominent features are highlighted by appropriate experimental studies wherin the ultrafast response on the picosecond time scale is the most recognized one. Based on these findings, the consequences for applications of LiNbO3 in the field of nonlinear optics and photonics are presented. Besides visionary examples like real-time, 3D holographic displays, the impact of optical nonlinearities of small polarons for present applications are discussed with frequency conversion and respective limiting effects, such as green-induced infrared absorption and optical damage, as important example

Holographic Spectroscopy: Wavelength-Dependent Analysis of Photosensitive Materials by Means of Holographic Techniques

material

Atomic insight to lattice distortions caused by carrier self-trapping in oxide materials

We gain hitherto missing access to the spatio-temporal evolution of lattice distortions caused by carrier self-trapping in the class of oxide materials - and beyond. The joint experimental/theoretical tool introduced combines femtosecond mid-infrared probe spectroscopy with potential landscape modeling and is based on the original approach that the vibration mode of a biatomic molecule is capable to probe strongly localized, short-lived lattice distortions in its neighborhood. Optically generated, small, strong-coupling polarons in lithium niobate, mediated by OH− ions present as ubiquitous impurities, serve as a prominent example. Polaron trapping is found to result in an experimentally determined redshift of the OH− stretching mode amounting to Δνvib = −3 cm−1, that is successfully modeled by a static Morse potential modified by Coulomb potential changes due to the displacements of the surrounding ions and the trapped charge carrier. The evolution of the trapping process can also be highlighted by monitoring the dynamics of the vibrational shift making the method an important tool for studying various systems and applications

Superposed picosecond luminescence kinetics in lithium niobate revealed by means of broadband fs-fluorescence upconversion spectroscopy

Various manifestations of small polarons strongly affect the linear and nonlinear optical properties of the oxide crystal lithium niobate (LiNbO3, LN). While related transient absorption phenomena in LN have been extensively studied in recent decades, a sound microscopic picture describing the blue-green (photo)luminescence of lithium niobate single crystals is still missing. In particular, almost nothing is known about: (i) the luminescence build-up and (ii) its room temperature decay. We present here the results of our systematic experimental study using nominally undoped and Mg-doped LN crystals with different Mg concentration. Picosecond luminescence was detected by means of femtosecond fluorescence upconversion spectroscopy (FLUPS) extended to the inspection of oxide crystals in reflection geometry. Two distinct luminescence decay components on the picosecond time scale are revealed. While a short exponential decay is present in each sample, a longer non-exponential decay clearly depends on the crystal composition. Since transient absorption spectroscopy excludes geminate small polaron annihilation as microscopic cause of the luminescence, both decay components are discussed in the context of self-trapped exciton (STE) transport and decay

A modular optical breadboard realized with 3D-printable building bricks and industrial aluminum extrusions

We here present the supplemental video to the open access article "A modular optical breadboard realized with 3D-printable building bricks and industrial aluminum extrusions" (under review)

Small Polaron Hopping in Fe:LiNbO3 as a Function of Temperature and Composition

Small-polaron hopping involved in charge transport in Fe-doped congruent lithium niobate is investigated as a function of temperature and composition by means of light-induced transient absorption spectroscopy. The relaxation dynamics of the light-induced polaron population is characterized by individual activation energies within different temperature ranges. A numerical investigation carried out by Monte Carlo simulations reveals that these findings may be understood in terms of the varying abundance of the different types of hops that the polarons may perform among regular or defective lattice sites. The role of the temperature and of the sample composition on the distribution of the different hop types is thus explored for a wide range of parameters, allowing one to preview the charge transport properties for a given set of experimental conditions

Transition Metal Compounds Towards Holography

We have successfully proposed the application of transition metal compounds in holographic recording media. Such compounds feature an ultra-fast light-induced linkage isomerization of the transition-metal–ligand bond with switching times in the sub-picosecond regime and lifetimes from microseconds up to hours at room temperature. This article highlights the photofunctionality of two of the most promising transition metal compounds and the photophysical mechanisms that are underlying the hologram recording. We present the latest progress with respect to the key measures of holographic media assembled from transition metal compounds, the molecular embedding in a dielectric matrix and their impressive potential for modern holographic applications