Search

Ferroelectric domain walls (DWs) are promising structures for assembling future nano-electronic circuit elements on a larger scale since reporting domain wall currents of up to 1 mA per single DW. One key requirement hereto is their reproducible manufacturing by gaining preparative control over domain size and domain wall conductivity (DWC). To date, most works on DWC have focused on exploring the fundamental electrical properties of individual DWs within single-shot experiments, with an emphasis on quantifying the origins of DWC. Very few reports exist when it comes to comparing the DWC properties between two separate DWs, and literally nothing exists where issues of reproducibility in DWC devices have been addressed. To fill this gap while facing the challenge of finding guidelines for achieving predictable DWC performance, we report on a procedure that allows us to reproducibly prepare single hexagonal domains of a predefined diameter into uniaxial ferroelectric lithium niobate single crystals of 200 and 300 μ m thickness, respectively. We show that the domain diameter can be controlled with an uncertainty of a few percent. As-grown DWs are then subjected to a standard procedure of current-limited high-voltage DWC enhancement, and they repetitively reach a DWC increase of six orders of magnitude. While all resulting DWs show significantly enhanced DWC values, their individual current–voltage (I–V) characteristics exhibit different shapes, which can be explained by variations in their 3D real structure reflecting local heterogeneities by defects, DW pinning, and surface-near DW inclination. [ABSTRACT FROM AUTHOR]

Piezoresponse force microscopy (PFM) is one of the most widespread methods for investigating and visualizing ferroelectric domain structures down to the nanometer length scale. PFM makes use of the direct coupling of the piezoelectric response to the crystal lattice, and hence, it is most often applied to spatially map the three-dimensional (3D) near-surface domain distribution of any polar or ferroic sample. Nonetheless, since most samples investigated by PFM are at least semiconducting or fully insulating, the electric ac field emerging from the conductive scanning force microscopy (SFM) tip penetrates the sample and, hence, may also couple to polar features that are deeply buried into the bulk of the sample under investigation. Thus, in the work presented here, we experimentally and theoretically explore the contrast and depth resolution capabilities of PFM, by analyzing the dependence of several key parameters. These key parameters include the depth of the buried feature, i.e., here a domain wall (DW), as well as PFM-relevant technical parameters such as the tip radius, the PFM drive voltage and frequency, and the signal-to-noise ratio. The theoretical predictions are experimentally verified using x-cut periodically poled lithium niobate single crystals that are specially prepared into wedge-shaped samples, in order to allow the buried feature, here the DW, to be "positioned" at any depth into the bulk. This inspection essentially contributes to the fundamental understanding in PFM contrast analysis and to the reconstruction of 3D domain structures down to a 1 μ m-penetration depth into the sample. [ABSTRACT FROM AUTHOR]

Lithium niobate and lithium tantalate are among the most widespread materials for nonlinear, integrated photonics. Mixed crystals with arbitrary Nb–Ta ratios provide an additional degree of freedom to not only tune materials properties, such as the birefringence but also leverage the advantages of the singular compounds, for example, by combining the thermal stability of lithium tantalate with the larger nonlinear or piezoelectric constants of lithium niobate. Periodic poling allows to achieve phase-matching independent of waveguide geometry and is, therefore, one of the commonly used methods in integrated nonlinear optics. For mixed crystals, periodic poling has been challenging so far due to the lack of homogeneous, mono-domain crystals, which severely inhibit domain growth and nucleation. In this work, we investigate surface-near (< 1 μ m depth) domain inversion on x-cut lithium niobate tantalate mixed crystals via electric field poling and lithographically structured electrodes. We find that naturally occurring head-to-head or tail-to-tail domain walls in the as-grown crystal inhibit domain inversion at a larger scale. However, periodic poling is possible if the gap size between the poling electrodes is of the same order of magnitude or smaller than the average size of naturally occurring domains. This work provides the basis for the nonlinear optical application of lithium niobate tantalate mixed crystals. [ABSTRACT FROM AUTHOR]

Thin-film lithium niobate (TFLN) in the form of x- or z-cut lithium-niobate-on-insulator has attracted considerable interest as a very promising and novel platform for developing integrated optoelectronic (nano)devices and exploring fundamental research. Here, we investigate the coherent interaction length l c of optical second-harmonic generation (SHG) microscopy in such samples, that are purposely prepared into a wedge shape, in order to elegantly tune the geometrical confinement from bulk thicknesses down to approximately 50 nm. SHG microscopy is a very powerful and non-invasive tool for the investigation of structural properties in the biological and solid-state sciences, especially for visualizing and analyzing ferroelectric domains and domain walls. However, unlike in bulk lithium niobate (LN), SHG microscopy in TFLN is impacted by interfacial reflections and resonant enhancement, both of which rely on film thickness and substrate material. In this paper, we show that the dominant SHG contribution measured on TFLN in backreflection is the co-propagating phase-matched SHG signal and not the counter-propagating SHG portion as is the case for bulk LN samples. Moreover, l c depends on the incident pump laser wavelength (sample dispersion) but also on the numerical aperture of the focussing objective in use. These experimental findings on x- and z-cut TFLN are excellently backed up by our advanced numerical simulations. [ABSTRACT FROM AUTHOR]

Quasi-phase-matched grating structures in lithium niobate waveguides with sub-micrometer periodicities will benefit the development of short-wavelength nonlinear optical devices. Here, we report on the reproducible formation of periodically poled domains in x-cut single-crystalline thin-film lithium niobate with periodicities as short as 600 nm. Shaped single-voltage poling pulses were applied to electrode structures that were fabricated by a combination of electron-beam and direct-writing laser lithography. Evidence of successful poling with good quality was obtained through second-harmonic microscopy and piezoresponse force microscopy imaging. For the sub-micrometer period structures, we observed patterns with a double periodicity formed by domain interactions and features with sizes < 200 nm. [ABSTRACT FROM AUTHOR]

Specific heat capacity measurements by differential scanning calorimetry (DSC) of single crystals of solid solutions of LiNbO3 and LiTaO3 are reported and compared with corresponding ab initio calculations, with the aim to investigate the variation of the ferroelectric Curie temperature as a function of composition. For this purpose, single crystals of these solid solutions were grown with Czochralski pulling along the c-axis. Elemental composition of Nb and Ta was investigated using XRF analysis, and small samples with homogeneous and well known composition were used for the DSC measurements. We observed that the ferroelectric Curie temperature decreases linearly with increasing Ta concentration in the LiNb 1 − x Ta x O3 solid solution crystals. Furthermore, the ferroelectric transition width of a mixed crystal appears to be smaller, as compared to pure LiTaO3. [ABSTRACT FROM AUTHOR]

Spontaneous Raman spectroscopy (SR) is a versatile method for analysis and visualization of ferroelectric crystal structures, including domain walls. Nevertheless, the necessary acquisition time makes SR impractical for in situ analysis and large scale imaging. In this work, we introduce broadband coherent anti-Stokes Raman spectroscopy (B-CARS) as a high-speed alternative to conventional Raman techniques and demonstrate its benefits for ferroelectric domain wall analysis. Using the example of poled lithium niobate, we compare the spectral output of both techniques in terms of domain wall signatures and imaging capabilities. We extract the Raman-like resonant part of the coherent anti-Stokes signal via a Kramers–Kronig-based phase retrieval algorithm and compare the raw and phase-retrieved signals to SR characteristics. Finally, we propose a mechanism for the observed domain wall signal strength that resembles a Čerenkov-like behavior, in close analogy to domain wall signatures obtained by second-harmonic generation imaging. We, thus, lay here the foundations for future investigations on other poled ferroelectric crystals using B-CARS. [ABSTRACT FROM AUTHOR]

Infrared nano-spectroscopy based on scattering-type scanning near-field optical microscopy (s-SNOM) is commonly employed to probe the vibrational fingerprints of materials at the nanometer length scale. However, due to the elongated and axisymmetric tip shank, s-SNOM is less sensitive to the in-plane sample anisotropy in general. In this article, we report an easy-to-implement method to probe the in-plane dielectric responses of materials with the assistance of a metallic disk micro-antenna. As a proof-of-concept demonstration, we investigate here the in-plane phonon responses of two prototypical samples, i.e. in (100) sapphire and x-cut lithium niobate (LiNbO3). In particular, the sapphire in-plane vibrations between 350 cm−1 to 800 cm−1 that correspond to LO phonon modes along the crystal b- and c-axis are determined with a spatial resolution of < λ/10, without needing any fitting parameters. In LiNbO3, we identify the in-plane orientation of its optical axis via the phonon modes, demonstrating that our method can be applied without prior knowledge of the crystal orientation. Our method can be elegantly adapted to retrieve the in-plane anisotropic response of a broad range of materials, i.e. subwavelength microcrystals, van-der-Waals materials, or topological insulators. s-SNOM is a powerful tool, but it is less sensitive to in-plane variations. Here the authors present a method to improve this with a metallic microdisk antenna, which they demonstrate by probing in-plane phonon responses. [ABSTRACT FROM AUTHOR]

We apply here spectral-domain optical coherence tomography (SD-OCT) for the precise detection and temporal tracking of ferroelectric domain walls (DWs) in magnesium-doped periodically poled lithium niobate (Mg:PPLN). We reproducibly map static DWs at an axial (depth) resolution down to ∼ 0.6 μm, being located up to 0.5 mm well inside the single crystalline Mg:PPLN sample. We show that a full 3-dimensional (3D) reconstruction of the DW geometry is possible from the collected data, when applying a special algorithm that accounts for the nonlinear optical dispersion of the material. Our OCT investigation provides valuable reference information on the DWs' polarization charge distribution, which is known to be the key to the electrical conductivity of ferroelectric DWs in such systems. Hence, we carefully analyze the SD-OCT signal dependence both when varying the direction of incident polarization, and when applying electrical fields along the polar axis. Surprisingly, the large backreflection intensities recorded under extraordinary polarization are not affected by any electrical field, at least for field strengths below the switching threshold, while no significant signals above noise floor are detected under ordinary polarization. Finally, we employed the high-speed SD-OCT setup for the real-time DW tracking upon ferroelectric domain switching under high external fields. [ABSTRACT FROM AUTHOR]

Lithium niobate (LNO) and lithium tantalate (LTO) see widespread use in fundamental research and commercial technologies reaching from electronics over classical optics to integrated quantum communication. The mixed crystal system lithium niobate tantalate (LNT) allows for the dedicate engineering of material properties by combining the advantages of the two parental materials LNO and LTO. Vibrational spectroscopies such as Raman spectroscopy or (Fourier transform) infrared (IR) spectroscopy are vital techniques to provide detailed insight into the material properties, which is central to the analysis and optimization of devices. This work presents a joint experimental–theoretical approach allowing to unambiguously assign the spectral features in the LNT material family through both Raman and IR spectroscopy, as well as providing an in‐depth explanation for the observed scattering efficiencies based on first‐principles calculations. The phononic contribution to the static dielectric tensor is calculated from the experimental and theoretical data using the generalized Lyddane–Sachs–Teller relation and compared with the results of the first‐principles calculations. [ABSTRACT FROM AUTHOR]

Nonlinear and quantum optical devices based on periodically-poled thin film lithium niobate (PP-TFLN) have gained considerable interest lately, due to their significantly improved performance as compared to their bulk counterparts. Nevertheless, performance parameters such as conversion efficiency, minimum pump power, and spectral bandwidth strongly depend on the quality of the domain structure in these PP-TFLN samples, e.g., their homogeneity and duty cycle, as well as on the overlap and penetration depth of domains with the waveguide mode. Hence, in order to propose improved fabrication protocols, a profound quality control of domain structures is needed that allows quantifying and thoroughly analyzing these parameters. In this paper, we propose to combine a set of nanometer-to-micrometer-scale imaging techniques, i.e., piezoresponse force microscopy (PFM), second-harmonic generation (SHG), and Raman spectroscopy (RS), to access the relevant and crucial sample properties through cross-correlating these methods. Based on our findings, we designate SHG to be the best-suited standard imaging technique for this purpose, in particular when investigating the domain poling process in x-cut TFLNs. While PFM is excellently recommended for near-surface high-resolution imaging, RS provides thorough insights into stress and/or defect distributions, as associated with these domain structures. In this context, our work here indicates unexpectedly large signs for internal fields occurring in x-cut PP-TFLNs that are substantially larger as compared to previous observations in bulk LN. [ABSTRACT FROM AUTHOR]

A strongly temperature-dependent photo-induced transient absorption is measured in 6.5 mol% magnesium-doped lithium niobate at temperatures ranging from 45 K to 225 K. This phenomenon is interpreted as resulting from the generation and subsequent recombination of oppositely charged small polarons. Initial two-photon absorptions generate separated oppositely charged small polarons. The existence of these small polarons is monitored by the presence of their characteristic absorption. The strongly temperature-dependent decay of this absorption occurs as series of thermally assisted hops of small polarons that facilitate their merger and ultimate recombination. Our measurements span the high-temperature regime, where small-polaron jump rates are Arrhenius and strongly dependent on temperature, and the intermediate-temperature regime, where small-polaron jump rates are non-Arrhenius and weakly dependent on temperature. Distinctively, this model provides a good representation of our data with reasonable values of its two parameters: Arrhenius small-polaron hopping's activation energy and the material's characteristic phonon frequency. [ABSTRACT FROM AUTHOR]

Ferroelectric domain wall conductance is a rapidly growing field. Thin-film lithium niobate, as in lithium niobate on insulators (LNOI), appears to be an ideal template, which is tuned by the inclination of the domain wall. Thus, the precise tuning of domain wall inclination with the applied voltage can be used in non-volatile memories, which store more than binary information. In this study, we present the realization of this concept for non-volatile memories. We obtain remarkably stable set voltages by the ferroelectric nature of the device as well as a very large increase in the conduction, by at least five orders of magnitude at room temperature. Furthermore, the device conductance can be reproducibly tuned over at least two orders of magnitude. The observed domain wall (DW) conductance tunability by the applied voltage can be correlated with phase-field simulated DW inclination evolution upon poling. Furthermore, evidence for polaron-based conduction is given. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Poling and structuring of ferroelectric domains form the basis for developing prospective applications using materials from the lithium‐niobate (LN) family. Applications range from second harmonic generation to electro‐optic modulators or surface acoustic wave devices. In the work presented here, hysteresis measurements are used as a standard method to quantitatively determine the poling properties of these ferroelectrics, including their spontaneous polarization Ps as well as their forward and reverse coercive fields Ec,+ and Ec,−. Systematic measurements that depend on parameters such as the ramp rate R of the applied poling voltage and the waiting time twait between domain inversions are investigated and compared between the congruent variants of LN, lithium tantalate (LT), their magnesium‐doped analogues, and stoichiometric LN. For bulk magnesium‐doped LN, for example, it is found that the resulting coercive field strongly depends on the speed of the voltage ramp, with Ec$E_{\text{c}}$ values ranging from 11 to 21 kV mm−1. These investigations are used as fundamental input for poling ferroelectric lithium niobate‐tantalate solids (LNT), a system that offers a high potential for tuning the material parameters beyond what is possible for LN or LT. [ABSTRACT FROM AUTHOR]

Lithium niobate tantalate (LiNb 1− x Ta x O 3 , LNT) solid solutions offer exciting new possibilities for applications ranging from optics, piezotronics, and electronics beyond the capabilities of the widely used singular compounds of lithium niobate (LiNbO 3 , LN) or lithium tantalate (LiTaO 3 , LT). Crystal growth of homogeneous LNT single crystals by the Czochralski method is still challenging. One key aspect of homogeneous growth is the accurate knowledge of thermal conductivity through the crystal boule during the growth, which is central to control the crystal growth. Therefore, the temperature dependent thermal conductivity of pure LN, LT, and LNT solid solutions, as well as of selected doped LN and LT crystals (Mg, Zn) was investigated across the temperature range from 300 to 1300 K. The results that span across the whole composition range can directly be applied for optimizing growth conditions of both LNT solid solutions as well as doped and undoped LN and LT crystals. [ABSTRACT FROM AUTHOR]

Here, we report on the photochemical deposition of Rhodamine 6G (Rh6G) and Alexa647 molecules from aqueous and methanolic solution along 180° ferroelectric (FE) domain walls (DWs) of z-cut lithium niobate (LNO) single crystals. Molecules and FE domains were investigated by means of dynamic-mode AFM, piezoresponse force microscopy (PFM), and confocal scanning fluorescence microscopy. A high deposition affinity for 180° DWs on the LNO surface is observed, leading to the formation of molecular nanowires. Additionally, a more complex deposition pattern for Rh6G adsorbed to the domain areas of freshly poled samples was equally observed, being associated with the DW dynamics. These results are explained by considering contributions from screening-charge-dependent photochemistry as confined to the DWs, UV-induced DW motion, and transient electrostatic fields arising from the metastable defect distribution shortly after poling. Hence, tuning these effects offers the possibility for accurately controlling the complex bottom-up assembly of functional molecular nanostructures through domain-structured ferroelectric templates. [ABSTRACT FROM AUTHOR]