Denise Denning

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.

Applications of piezoresponse force microscopy in materials research: from inorganic ferroelectrics to biopiezoelectrics and beyond

Piezoresponse force microscopy (PFM) probes the mechanical deformation of a sample in response to an electric field applied with the tip of an atomic force microscope. Originally developed more than two decades ago to study ferroelectric materials, this technique has since been used to probe electromechanical functionality in a wide range of piezoelectric materials including organic and biological systems. Piezoresponse force microscopy has also been demonstrated as a useful tool to detect mechanical strain originating from electrical phenomena in non-piezoelectric materials. Parallelling advances in analytical and numerical modelling, many technical improvements have been made in the last decade: switching spectroscopy PFM allows the polarisation switching properties of ferroelectrics to be resolved in real space with nanometric resolution, while dual ac resonance tracking and band excitation PFM have been used to improve the signal-to-noise ratio. In turn, these advances have led to increasingly large multidimensional data sets containing more complete information on the properties of the sample studied. In this review, PFM operation and calibration are described, and recent advances in the characterisation of electromechanical coupling using PFM are presented. The breadth of the systems covered highlights the versatility and wide applicability of PFM in fields as diverse as materials engineering and nanomedicine. In each of these fields, combining PFM with complementary techniques is key to develop future insight into the intrinsic properties of the materials as well as for device applications.

Electromechanical properties of dried tendon and isoelectrically focused collagen hydrogels

Assembling artificial collagenous tissues with structural, functional, and mechanical properties which mimic natural tissues is of vital importance for many tissue engineering applications. While the electro-mechanical properties of collagen are thought to play a role in, for example, bone formation and remodeling, this functional property has not been adequately addressed in engineered tissues. Here the electro-mechanical properties of rat tail tendon are compared with those of dried isoelectrically focused collagen hydrogels using piezoresponse force microscopy under ambient conditions. In both the natural tissue and the engineered hydrogel D-periodic type I collagen fibrils are observed, which exhibit shear piezoelectricity. While both tissues also exhibit fibrils with parallel orientations, Fourier transform analysis has revealed that the degree of parallel alignment of the fibrils in the tendon is three times that of the dried hydrogel. The results obtained demonstrate that isoelectrically focused collagen has similar structural and electro-mechanical properties to that of tendon, which is relevant for tissue engineering applications.

Visualizing molecular polar order in tissues via electromechanical coupling

Electron microscopy (EM) and atomic force microscopy (AFM) techniques have long been used to characterize collagen fibril ordering and alignment in connective tissues. These techniques, however, are unable to map collagen fibril polarity, i.e., the polar orientation that is directed from the amine to the carboxyl termini. Using a voltage modulated AFM-based technique called piezoresponse force microscopy (PFM), we show it is possible to visualize both the alignment of collagen fibrils within a tissue and the polar orientation of the fibrils with minimal sample preparation. We demonstrate the technique on rat tail tendon and porcine eye tissues in ambient conditions. In each sample, fibrils are arranged into domains whereby neighboring domains exhibit opposite polarizations, which in some cases extend to the individual fibrillar level. Uniform polarity has not been observed in any of the tissues studied. Evidence of anti-parallel ordering of the amine to carboxyl polarity in bundles of fibrils or in individual fibrils is found in all tissues, which has relevance for understanding mechanical and biofunctional properties and the formation of connective tissues. The technique can be applied to any biological material containing piezoelectric biopolymers or polysaccharides.

Piezoelectric properties of aligned collagen membranes

Electromechanical coupling, a phenomenon present in collagenous materials, may influence cell-extracellular matrix interactions. Here, electromechanical coupling has been investigated via piezoresponse force microscopy in transparent and opaque membranes consisting of helical-like arrays of aligned type I collagen fibrils self-assembled from acidic solution. Using atomic force microscopy, the transparent membrane was determined to contain fibrils having an average diameter of 76 ± 14 nm, whereas the opaque membrane comprised fibrils with an average diameter of 391 ± 99 nm. As the acidity of the membranes must be neutralized before they can serve as cell culture substrates, the structure and piezoelectric properties of the membranes were measured under ambient conditions before and after the neutralization process. A crimp structure (1.59 ± 0.37 µm in width) perpendicular to the fibril alignment became apparent in the transparent membrane when the pH was adjusted from acidic (pH = 2.5) to neutral (pH = 7) conditions. In addition, a 1.35-fold increase was observed in the amplitude of the shear piezoelectricity of the transparent membrane. The structure and piezoelectric properties of the opaque membrane were not significantly affected by the neutralization process. The results highlight the presence of an additional translational order in the transparent membrane in the direction perpendicular to the fibril alignment. The piezoelectric response of both membrane types was found to be an order of magnitude lower than that of collagen fibrils in rat tail tendon. This reduced response is attributed to less-ordered molecular assembly than is present in D-periodic collagen fibrils, as evidenced by the absence of D-periodicity in the membranes.

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 60.02lm and a height of 1.61 60.98nm, 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 60.06lm, 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 60.58nm) compared to that at low (10 � 4 M) concentrations (0.78 60.35nm), 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 61.52nm, compared to 4.50 60.76nm at 10 � 2 M. For longer exposure times (30min) at 10 � 2 M, the nanostructure height is 4.72 60.59nm, 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 þ ions at

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 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 5 mol. % MgO-doped substrates, respectively.

Piezoelectricity in collagen type II fibrils measured by scanning probe microscopy

The converse piezoelectric effect in collagen type II fibrils, the main collagen constituent in cartilage, was investigated using piezoresponse force microscopy. The fibrils exhibited shear piezoelectric behavior similar to that previously reported in collagen type I fibrils and followed the same cantilever-fibril angle dependence present for type I. A uniform polarization directed from the amine to carboxyl termini, as seen for collagen type I, was observed in all type II fibrils studied. The shear piezoelectric coefficient, d15, however, for type II was roughly 28–32% of the value measured for type I fibrils. Possible explanations for the reduced piezoelectric coefficient of type II collagen are provided.

Piezoresponse Force Microscopy on Proton Exchanged LiNbO 3 Layers

We use piezoresponse force microscopy for high resolution investigations on proton exchanged LiNbO3. We also quantify the reduction of the d33 nonlinear coefficient induced by proton exchange in congruent LiNbO3 substrates with and without Mg-doping