Now showing 1 - 10 of 12
  • Publication
    Local piezoresponse and polarization switching in nucleobase thymine microcrystals
    Thymine (2-oxy-4-oxy-5 methyl pyrimidine) is one of the four nucleobases of deoxyribonucleic acid (DNA). In the DNA molecule, thymine binds to adenine via two hydrogen bonds, thus stabilizing the nucleic acid structure and is involved in pairing and replication. Here, we show that synthetic thymine microcrystals grown from the solution exhibit local piezoelectricity and apparent ferroelectricity, as evidenced by nanoscale electromechanical measurements via Piezoresponse Force Microscopy. Our experimental results demonstrate significant electromechanical activity and polarization switchability of thymine, thus opening a pathway for piezoelectric and ferroelectric-based applications of thymine and, perhaps, of other DNA nucleobase materials. The results are supported by molecular modeling of polarization switching under an external electric field.
    Scopus© Citations 12  623
  • 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.
      372Scopus© Citations 2
  • Publication
    Thermal and aqueous stability improvement of graphene oxide enhanced diphenylalanine nanocomposites
    Nanocomposites of diphenylalanine (FF) and carbon based materials provide an opportunity to overcome drawbacks associated with using FF micro- and nanostructures in nanobiotechnology applications, in particular, their poor structural stability in liquid solutions. In this study, FF/graphene oxide (GO) composites were found to self-assemble into layered micro- and nanostructures, which exhibited improved thermal and aqueous stability. Dependent on the FF/GO ratio, the solubility of these structures was reduced to 35.65% after 30 min as compared to 92.4% for pure FF samples. Such functional nanocomposites may extend the use of FF structures to, e.g., biosensing, electrochemical, electromechanical or electronic applications.
      495
  • Publication
    Non-destructive determination of collagen fibril width in extruded collagen fibres by piezoresponse force microscopy
    Extruded collagen fibres are a promising platform for tissue engineering applications. Ensuring that the functional properties of the engineered tissues possess similar structural properties as native tissues is important for biomedical applications. Advanced imaging tools including scanning electron microscopy (SEM) and atomic force microscopy (AFM) have revealed the structural features of collagen fibrils within such fibres; however, these techniques often require modification steps that can alter the sample in the process. Here, lateral piezoresponse force microscopy (LPFM), which is sensitive to the polar orientation of piezoelectric collagen fibrils, is demonstrated as a promising tool to assess the width of individual fibrils and moreover map their organisation and polar orientation without altering the sample. Within the fibres studied, the collagen fibrils showed a highly anisotropic arrangement with preferred alignment along the length of the fibre. Fibril widths of 74 ± 18 nm and 73 ± 19 nm in untreated and bleached fibres, respectively, were measured from LPFM amplitude images. These values agreed with values from SEM (70 ± 10 nm) and AFM (71 ± 19 nm) measurements that could only be obtained from bleached fibres.
    Scopus© Citations 4  352
  • Publication
    Giant negative electrostriction and dielectric tunability in a van der Waals layered ferroelectric
    The interest in ferroelectric van der Waals crystals arises from the potential to realize ultrathin ferroic systems owing to the reduced surface energy of these materials and the layered structure that allows for exfoliation. Here, we quantitatively unravel giant negative electrostriction of van der Waals layered copper indium thiophosphate (CIPS), which exhibits an electrostrictive coefficient Q33 as high as -3.2m4/C2 and a resulting bulk piezoelectric coefficient d33 up to -85 pm/V. As a result, the electromechanical response of CIPS is comparable in magnitude to established perovskite ferroelectrics despite possessing a much smaller spontaneous polarization of only a few μC/cm2. In the paraelectric state, readily accessible owing to low transition temperatures, CIPS exhibits large dielectric tunability, similar to widely used barium strontium titanate, and as a result both giant and continuously tunable electromechanical response. The persistence of electrostrictive and tunable responses in the paraelectric state indicates that even few-layer films or nanoparticles will sustain significant electromechanical functionality, offsetting the inevitable suppression of ferroelectric properties in the nanoscale limit. These findings can likely be extended to other ferroelectric transition metal thiophosphates and (quasi-) two-dimensional materials, and might facilitate the quest toward alternative ultrathin functional devices incorporating electromechanical response.
    Scopus© Citations 51  232
  • Publication
    Decoupling Mesoscale Functional Response in PLZT across the Ferroelectric-Relaxor Phase Transition with Contact Kelvin Probe Force Microscopy and Machine Learning
    Relaxor ferroelectrics exhibit a range of interesting material behavior, including high electromechanical response, polarization rotations, as well as temperature and electric field-driven phase transitions. The origin of this unusual functional behavior remains elusive due to limited knowledge on polarization dynamics at the nanoscale. Piezoresponse force microscopy and associated switching spectroscopy provide access to local electromechanical properties on the micro- and nanoscale, which can help to address some of these gaps in our knowledge. However, these techniques are inherently prone to artefacts caused by signal contributions emanating from electrostatic interactions between tip and sample. Understanding functional behavior of complex, disordered systems like relaxor materials with unknown electromechanical properties therefore requires a technique that allows distinguishing between electromechanical and electrostatic response. Here, contact Kelvin probe force microscopy (cKPFM) is used to gain insight into the evolution of local electromechanical and capacitive properties of a representative relaxor material lead lanthanum zirconate across the phase transition from a ferroelectric to relaxor state. The obtained multidimensional data set was processed using an unsupervised machine learning algorithm to detect variations in functional response across the probed area and temperature range. Further analysis showed the formation of two separate cKPFM response bands below 50 °C, providing evidence for polarization switching. At higher temperatures only one band is observed, indicating an electrostatic origin of the measured response. In addition, the junction potential difference, which was extracted from the cKPFM data, becomes independent of the temperature in the relaxor state. The combination of this multidimensional voltage spectroscopy technique and machine learning allows to identify the origin of the measured functional response and to decouple ferroelectric from electrostatic phenomena necessary to understand the functional behavior of complex, disordered systems like relaxor materials.
    Scopus© Citations 8  212
  • 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.
    Scopus© Citations 17  495
  • Publication
    Thickness, humidity, and polarization dependent ferroelectric switching and conductivity in Mg doped lithium niobate
    Mg doped lithium niobate (Mg:LN) exhibits several advantages over undoped LN such as resistance to photorefraction, lower coercive fields, and p-type conductivity that is particularly pronounced at domain walls and opens up a range of applications, e.g., in domain wall electronics. Engineering of precise domain patterns necessitates well founded knowledge of switching kinetics, which can differ significantly from that of undoped LN. In this work, the role of humidity and sample composition in polarization reversal has been investigated under application of the same voltage waveform. Control over domain sizes has been achieved by varying the sample thickness and initial polarization as well as atmospheric conditions. In addition, local introduction of proton exchanged phases allows for inhibition of domain nucleation or destabilization, which can be utilized to modify domain patterns. Polarization dependent current flow, attributed to charged domain walls and band bending, demonstrates the rectifying ability of Mg:LN in combination with suitable metal electrodes that allow for further tailoring of conductivity.
    Scopus© Citations 17  426
  • Publication
    Influence of annealing on the photodeposition of silver on periodically poled lithium niobate
    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.
    Scopus© Citations 10  616
  • Publication
    Locally controlled Cu-ion transport in layered ferroelectric CuInP2S6
    Metal thiophosphates are attracting growing attention in the context of quasi-two-dimensional van der Waals functional materials. Alkali thiophosphates are investigated as ion conductors for solid electrolytes, and transition-metal thiophosphates are explored as a new class of ferroelectric materials. For the latter, a representative copper indium thiophosphate is ferrielectric at room temperature and, despite low polarization, exhibits giant negative electrostrictive coefficients. Here, we reveal that ionic conductivity in this material enables localized extraction of Cu ions from the lattice with a biased scanning probe microscopy tip, which is surprisingly reversible. The ionic conduction is tracked through local volume changes with a scanning probe microscopy tip providing a current-free probing technique, which can be explored for other thiophosphates of interest. Nearly 90 nm-tall crystallites can be formed and erased reversibly on the surface of this material as a result of ionic motion, the size of which can be sensitively controlled by both magnitude and frequency of the electric field, as well as the ambient temperature. These experimental results and density functional theory calculations point to a remarkable resilience of CuInP2S6 to large-scale ionic displacement and Cu vacancies, in part enabled by the metastability of Cu-deficient phases. Furthermore, we have found that the piezoelectric response of CuInP2S6 is enhanced by about 45% when a slight ionic modification is carried out with applied field. This new mode of modifying the lattice of CuInP2S6, and more generally ionically conducting thiophosphates, posits new prospects for their applications in van der Waals heterostructures, possibly in the context of catalytic or electronic functionalities.
    Scopus© Citations 67  782