Now showing 1 - 10 of 10
  • Publication
    Photoreduction of SERS-active metallic nanostructures on chemically-patterned ferroelectric crystals
    Photodeposition of metallic nanostructures onto ferroelectric surfaces is typically based on patterning local surface reactivity via electric field poling. Here, we demonstrate metal deposition onto substrates which have been chemically patterned via proton exchange (i.e., without polarization reversal). The chemical patterning provides the ability to tailor the electrostatic fields near the surface of lithium niobate crystals and these engineered fields are used to fabricate metallic nanostructures. The effect of the proton exchange process on the piezoelectric and electrostatic properties of the surface is characterized using voltage modulated atomic force microscopy techniques, which combined with modeling of the electric fields at the surface of the crystal, reveal that the deposition occurs preferentially along the boundary between ferroelectric and proton exchanged regions. The metallic nanostructures have been further functionalized with a target probe molecule, 4-aminothiophenol, from which surface enhanced Raman scattering (SERS) signal is detected, demonstrating the suitability of chemically patterned ferroelectrics as SERS-active templates.
      504Scopus© Citations 56
  • Publication
    Biocompatible Gold Nanoparticle Arrays Photodeposited on Periodically Proton Exchanged Lithium Niobate
    Photodeposition of silver nanoparticles onto chemically patterned lithium niobate having alternating lithium niobate and proton exchanged regions has been previously investigated. Here, the spatially defined photodeposition of gold nanoparticles onto periodically proton exchanged lithium niobate is demonstrated. It is shown that the location where the gold nanoparticles form can be tailored by altering the concentration of HAuCl4. This enables the possibility to sequentially deposit gold and silver in different locations to create bimetallic arrays. The cytocompatibility of photodeposited gold, silver, and bimetallic ferroelectric templates to osteoblast-like cells is also investigated. Gold samples provide significantly greater cell biocompatibility than silver samples. These results highlight a potential route for using photodeposited gold on lithium niobate as a template for applications in cellular biosensing.
      382Scopus© Citations 15
  • Publication
    Photoreduction of metal nanostructures on periodically proton exchanged MgO-doped lithium niobate crystals
    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.
      385Scopus© Citations 12
  • Publication
    Single-Molecule Nonresonant Wide-Field Surface-Enhanced Raman Scattering from Ferroelectrically Defined Au Nanoparticle Microarrays
    Single-molecule detection by surface-enhanced Raman scattering (SERS) is a powerful spectroscopic technique that is of interest for the sensor development field. An important aspect of optimizing the materials used in SERS-based sensors is the ability to have a high density of "hot spots" that enhance the SERS sensitivity to the single-molecule level. Photodeposition of gold (Au) nanoparticles through electric-field-directed self-assembly on a periodically proton-exchanged lithium niobate (PPELN) substrate provides conditions to form well-ordered microscale features consisting of closely packed Au nanoparticles. The resulting Au nanoparticle microstructure arrays (microarrays) are plasmon-active and support nonresonant single-molecule SERS at ultralow concentrations (<10-9-10-13 M) with excitation power densities <1 × 10-3 W cm-2 using wide-field imaging. The microarrays offer excellent SERS reproducibility, with an intensity variation of <7.5% across the substrate. As most biomarkers and molecules do not support resonance enhancement, this work demonstrates that PPELN is a suitable template for high-sensitivity, nonresonant sensing applications.
      150Scopus© Citations 12
  • Publication
    Growth mechanism of photoreduced silver nanostructures on periodically proton exchanged lithium niobate: Time and concentration dependence
    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±0.02µm and a height of 1.61±0.98nm, 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±0.06µm, 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±0.58nm) compared to that at low (10¯4M) concentrations (0.78±0.35nm), 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±1.52nm, compared to 4.50±0.76nm at 10 ¯² M. For longer exposure times (30min) at 10 ¯² M the nanostructure height is 4.72±0.59nm, 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. 30.40nm, which suggests the Debye length plays a role in the availability of Ag+ ions at the surface.
      381Scopus© Citations 12
  • Publication
    Photoinduced Enhanced Raman from Lithium Niobate on Insulator Template
    © 2018 American Chemical Society. Photoinduced enhanced Raman spectroscopy from a lithium niobate on insulator (LNOI)-silver nanoparticle template is demonstrated both by irradiating the template with 254 nm ultraviolet (UV) light before adding an analyte and before placing the substrate in the Raman system (substrate irradiation) and by irradiating the sample in the Raman system after adding the molecule (sample irradiation). The photoinduced enhancement enables up to an ∼sevenfold increase of the surface-enhanced Raman scattering signal strength of an analyte following substrate irradiation, whereas an ∼threefold enhancement above the surface-enhanced signal is obtained for sample irradiation. The photoinduced enhancement relaxes over the course of ∼10 h for a substrate irradiation duration of 150 min before returning to initial signal levels. The increase in Raman scattering intensity following UV irradiation is attributed to photoinduced charge transfer from the LNOI template to the analyte. New Raman bands are observed following UV irradiation, the appearance of which is suggestive of a photocatalytic reaction and highlight the potential of LNOI as a photoactive surface-enhanced Raman spectroscopy substrate.
      351Scopus© Citations 13
  • Publication
    Interface modulated currents in periodically proton exchanged Mg doped lithium niobate
    Conductivity in Mg doped lithium niobate (Mg:LN) plays a key role in the reduction of photorefraction and therefore doping is 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, multi composite wedge shaped samples consisting of polar orientated 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 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 the 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.
      294Scopus© Citations 2
  • Publication
    Direct shape control of photoreduced nanostructures on proton exchanged ferroelectric templates
    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.
      333Scopus© Citations 9
  • Publication
    Plasmon Enhanced Raman From Ag Nanopatterns Made Using Periodically Poled Lithium Niobate and Periodically Proton Exchanged Template Methods
    We study Ag nanopattern arrays formed using ferroelectric lithography based on two separate approaches, i.e., periodically poled lithium niobate (PPLN) and periodically proton exchanged (PPE) template methods. We demonstrate that such nanoarrays are plasmon active. Raman spectroscopy was applied to study molecular probe 4-aminothiophenol (4-ABT) absorbed onto a silver nanostructured array. The observed Raman spectra show peaks arising from b2 modes, which occur for plasmon enhanced Raman from 4-ABT in place of a1 modes, which occur in normal Raman scattering. We demonstrate that the PPLN and PPE substrates possess different plasmonic properties with PPE creating a stronger SERS signal relative to PPLN substrates.
      548Scopus© Citations 47
  • Publication
    Nanoscale characterization of β-phase HxLi1−xNbO3 layers by piezoresponse force microscopy
    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 d 33 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 5 mol. % MgO-doped substrates, respectively.
      309Scopus© Citations 7