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Photocatalysts for oxidation reactions are crucial for a wide variety of industrial activities. Here, we describe a framework consisting of silver nanomaterials atop Mg-doped lithium niobate. This substrate under white light irradiation is demonstrated to support the oxidation of compounds, such as p-aminothiophenol, through the activation of charge transfer processes. This study highlights the use of doped lithium niobate materials as semiconductor platforms for plasmonic photocatalysis. [ABSTRACT FROM AUTHOR]

The bactericidal properties of chemically patterned lithium niobate substrates under a super-bandgap UV light source is established. UV irradiation of lithium niobate surfaces inoculated with bacteria leads to antimicrobial activity compared to a glass substrate under similar conditions, as determined by surface enhanced Raman spectroscopy and corroborated with a fluorescence-based live/dead assay. This finding may expand the possible biomedical applications of lithium niobate. [ABSTRACT FROM AUTHOR]

Conductivity in Mg doped lithium niobate (Mg:LN) plays a key role in the reduction of photorefraction and is therefore widely exploited in optical devices. However, charge transport through Mg:LN and across interfaces such as electrodes also yields potential electronic applications in devices with switchable conductivity states. Furthermore, the introduction of proton exchanged (PE) phases in Mg:LN enhances ionic conductivity, thus providing tailorability of conduction mechanisms and functionality dependent on sample composition. To facilitate the construction and design of such multifunctional electronic devices based on periodically PE Mg:LN or similar ferroelectric semiconductors, fundamental understanding of charge transport in these materials, as well as the impact of internal and external interfaces, is essential. In order to gain insight into polarization and interface dependent conductivity due to band bending, UV illumination, and chemical reactivity, wedge shaped samples consisting of polar oriented Mg:LN and PE phases were investigated using conductive atomic force microscopy. In Mg:LN, three conductivity states (on/off/transient) were observed under UV illumination, controllable by the polarity of the sample and the externally applied electric field. Measurements of currents originating from electrochemical reactions at the metal electrode-PE phase interfaces demonstrate a memresistive and rectifying capability of the PE phase. Furthermore, internal interfaces such as domain walls and Mg:LN-PE phase boundaries were found to play a major role in the accumulation of charge carriers due to polarization gradients, which can lead to increased currents. The insight gained from these findings yield the potential for multifunctional applications such as switchable UV sensitive micro- and nanoelectronic devices and bistable memristors. [ABSTRACT FROM AUTHOR]

The preferential deposition of metal nanoparticles onto periodically poled lithium niobate surfaces, whereby photogenerated electrons accumulate in accordance with local electric fields and reduce metal ions from solution, is known to depend on the intensity and wavelength of the illumination and the concentration of the solution used. Here, it is shown that for identical deposition conditions (wavelength, intensity, concentration), post-poling annealing for 10 h at 200 °C modifies the surface reactivity through the reorientation of internal defect fields. Whereas silver nanoparticles deposit preferentially on the +z domains on unannealed crystals, the deposition occurs preferentially along 180° domain walls for annealed crystals. In neither case is the deposition selective; limited deposition occurs also on the unannealed -z domain surface and on both annealed domain surfaces. The observed behavior is attributed to a relaxation of the poling-induced defect frustration mediated by Li+ ion mobility during annealing, which affects the accumulation of electrons, thereby changing the surface reactivity. The evolution of the defect field with temperature is corroborated using Raman spectroscopy. [ABSTRACT FROM AUTHOR]

Controlling ferroelectric switching in Mg doped lithium niobate (Mg:LN) is of fundamental importance for optical device and domain wall electronics applications that require precise domain patterns. Stable ferroelectric switching has been previously observed in undoped LN layers above proton exchanged (PE) phases that exhibit reduced polarization, whereas PE layers have been found to inhibit lateral domain growth. Here, Mg doping, which is known to significantly alter ferroelectric switching properties including coercive field and switching currents, is shown to inhibit domain nucleation and stability in Mg:LN above buried PE phases that allow for precise ferroelectric patterning via domain growth control. Furthermore, piezoresponse force microscopy (PFM) and switching spectroscopy PFM reveal that the voltage at which polarization switches from the "up" to the "down" state increases with increasing thickness in pure Mg:LN, whereas the voltage required for stable back switching to the original "up" state does not exhibit this thickness dependence. This behavior is consistent with the presence of an internal frozen defect field. The inhibition of domain nucleation above PE interfaces, observed in this study, is a phenomenon that occurs in Mg:LN but not in undoped samples and is mainly ascribed to a remaining frozen polarization in the PE phase that opposes polarization reversal. This reduced frozen depolarization field in the PE phase also influences the depolarization field of the Mg:LN layer above due to the presence of uncompensated polarization charge at the PE-Mg:LN boundary. These alterations in internal electric fields within the sample cause long-range lattice distortions in Mg:LN via electromechanical coupling, which were corroborated with complimentary Raman measurements. [ABSTRACT FROM AUTHOR]

We investigate a non-destructive approach for the characterization of proton exchanged layers in LiNbO3 with sub-micrometric resolution by means of piezoresponse force microscopy (PFM). Through systematic analyses, we identify a clear correlation between optical measurements on the extraordinary refractive index and PFM measurements on the piezoelectric d33 coefficient. Furthermore, we quantify the reduction of the latter induced by proton exchange as 83±2% and 68±3% of the LiNbO3 value, for undoped and 5mol. % MgO-doped substrates, respectively. [ABSTRACT FROM AUTHOR]

In this work, the influence of substrate surface charge on in vitro osteoblast cell proliferation on ferroelectric lithium niobate (LN) crystal surfaces is investigated. LN has a spontaneous polarization along the z-axis and is thus characterized by positive and negative bound polarization charge at the + z and - z surfaces. Biocompatibility of LN was demonstrated via culturing and fluorescence imaging of MC3T3 osteoblast cells for up to 11 days. The cells showed enhanced proliferation rates and improved osteoblast function through mineral formation on the positively and negatively charged LN surfaces compared to electrostatically neutral x-cut LN and a glass cover slip control. These results highlight the potential of LN as a template for investigating the role of charge on cellular processes. © 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 103A: 2540-2548, 2015. [ABSTRACT FROM AUTHOR]

Local reactivity on periodically proton exchanged lithium niobate (PPE:LN) surfaces is a promising route for the fabrication of regularly spaced nanostructures. Here, using MgO-doped PPE:LN templates, we investigate the influence of the doping on the nanostructure formation as a function of the proton exchange (PE) depth. The deposition is found to occur preferentially along the boundary between MgO-doped LN and the PE region when the PE depth is at least 1.73 μm, however, for shallower depths, deposition occurs across the entire PE region. The results are found to be consistent with an increased photoconductivity of the MgO-doped LN. [ABSTRACT FROM AUTHOR]

Photodeposition of metallic nanostructures onto ferroelectric surfaces, which have been chemically patterned using a proton exchange process, has recently been demonstrated. By varying the molar concentration of the AgNO3 solution and the illumination time, one can determine the initial nucleation sites, control the rate of nucleation and the height of silver nanostructures formed, and study the mechanisms by which these processes occurs. The nanoparticles are found to deposit preferentially in the boundary between ferroelectric and proton exchanged regions, in an area proton exchanged via lateral diffusion under the masking layer used for chemical patterning, consistent with our previous results. Using a short illumination time (3 min), we are able to determine that the initial nucleation of the silver nanostructure, having a width of 0.17 ± 0.02 μm and a height of 1.61 ± 0.98 nm, occurs near the edge of the reactive ion etched area within this lateral diffusion region. Over longer illumination times (15 min), we find that the silver deposition has spread to a width of 1.29 ± 0.06 μm, extending across the entire lateral diffusion region. We report that at a high molar concentration of AgNO3 (10-2 M), the amount of silver deposition for 5 min UV illumination is greater (2.88 ± 0.58 nm) compared to that at low (10-4 M) concentrations (0.78 ± 0.35 nm), however, this is not the case for longer time periods. With increasing illumination time (15 min), experiments at 10-4 M had greater overall deposition, 6.90 ± 1.52 nm, compared to 4.50 ± 0.76 nm at 10-2 M. For longer exposure times (30 min) at 10-2 M, the nanostructure height is 4.72 ± 0.59 nm, suggesting a saturation in the nanostructure height. The results are discussed in terms of the electric double layer that forms at the crystal surface. There is an order of magnitude difference between the Debye lengths for 10-2 and 10-4 M solutions, i.e., 3.04 vs. 30.40 nm, which suggests the Debye length plays a role in the availability of Ag+ ions at the surface. [ABSTRACT FROM AUTHOR]

Photoreduction on a periodically proton exchanged ferroelectric crystal leads to the formation of periodic metallic nanostructures on the surface. By varying the depth of the proton exchange (PE) from 0.59 to 3.10 μm in congruent lithium niobate crystals, the width of the lateral diffusion region formed by protons diffusing under the mask layer can be controlled. The resulting deposition occurs in the PE region with the shallowest PE depth and preferentially in the lateral diffusion region for greater PE depths. PE depth-control provides a route for the fabrication of complex metallic nanostructures with controlled dimensions on chemically patterned ferroelectric templates. [ABSTRACT FROM AUTHOR]