Electrical properties of strained off-stoichiometric Cu-Cr-O delafossite thin films.

Off-stoichiometric Cu-Cr-O delafossite thin films with different thicknesses were grown by metal organic chemical vapor deposition on substrates with different coefficients of thermal expansion. Seebeck thermoelectric coefficient and resistivity measurements were performed on the range of 300-850 K. A qualitative change in the temperature-dependence of the resistivity is observed at the temperature corresponding to the deposition process, where the transition from tensile to compressive strain takes place. Arrhenius plots reveal different slopes in these two thermal ranges. The fact that the shift is more pronounced for the thinner films might indicate the induced strain plays a role in changing electrical behaviour. Furthermore, changes below 0.1% in electrical mobility were measured when the strain is induced by mechanical bending.

Low-Temperature Growth of AlN Films on Magnetostrictive Foils for High-Magnetoelectric-Response Thin-Film Composites.

This study reports a strong ME effect in thin-film composites consisting of nickel, iron, or cobalt foils and 550 nm thick AlN films grown by PE-ALD at a (low) temperature of 250 °C and ensuring isotropic and highly conformal coating profiles. The AlN film quality and the interface between the film and the foils are meticulously investigated by means of high-resolution transmission electron microscopy and the adhesion test. An interface (transition) layer of partially amorphous AlxOy/AlOxNy with thicknesses of 10 and 20 nm, corresponding to the films grown on Ni, Fe, and Co foils, is revealed. The AlN film is found to be composed of a mixture of amorphous and nanocrystalline grains at the interface. However, its crystallinity is improved as the film grew and shows a highly preferred (002) orientation. High self-biased ME coefficients (αME at a zero-bias magnetic field) of 3.3, 2.7, and 3.1 V·cm-1·Oe-1 are achieved at an off-resonance frequency of 46 Hz in AlN/Ni thin-film composites with different Ni foil thicknesses of 7.5, 15, and 30 µm, respectively. In addition, magnetoelectric measurements have also been carried out in composites made of 550 nm thick films grown on 12.5 µm thick Fe and 15 µm thick Co foils. The maximum magnetoelectric coefficients of AlN/Fe and AlN/Co composites are 0.32 and 0.12 V·cm-1·Oe-1, measured at 46 Hz at a bias magnetic field (Hdc) of 6 and 200 Oe, respectively. The difference of magnetoelectric transducing responses of each composite is discussed according to interface analysis. We report a maximum delivered power density of 75 nW/cm3 for the AlN/Ni composite with a load resistance of 200 kΩ to address potential energy harvesting and electromagnetic sensor applications.

Evidence of Negative Capacitance and Capacitance Modulation by Light and Mechanical Stimuli in Pt/ZnO/Pt Schottky Junctions.

We report on the evidence of negative capacitance values in a system consisting of metal-semiconductor-metal (MSM) structures, with Schottky junctions made of zinc oxide thin films deposited by Atomic Layer Deposition (ALD) on top of platinum interdigitated electrodes (IDE). The MSM structures were studied over a wide frequency range, between 20 Hz and 1 MHz. Light and mechanical strain applied to the device modulate positive or negative capacitance and conductance characteristics by tuning the flow of electrons involved in the conduction mechanisms. A complete study was carried out by measuring the capacitance and conductance characteristics under the influence of both dark and light conditions, over an extended range of applied bias voltage and frequency. An impact-loss process linked to the injection of hot electrons at the interface trap states of the metal-semiconductor junction is proposed to be at the origin of the apparition of the negative capacitance values. These negative values are preceded by a local increase of the capacitance associated with the accumulation of trapped electrons at the interface trap states. Thus, we propose a simple device where the capacitance values can be modulated over a wide frequency range via the action of light and strain, while using cleanroom-compatible materials for fabrication. These results open up new perspectives and applications for the miniaturization of highly sensitive and low power consumption environmental sensors, as well as for broadband impedance matching in radio frequency applications.

Nanomechanical properties of distinct fibrillar polymorphs of the protein α-synuclein.

Alpha-synuclein (α-Syn) is a small presynaptic protein of 140 amino acids. Its pathologic intracellular aggregation within the central nervous system yields protein fibrillar inclusions named Lewy bodies that are the hallmarks of Parkinson's disease (PD). In solution, pure α-Syn adopts an intrinsically disordered structure and assembles into fibrils that exhibit considerable morphological heterogeneity depending on their assembly conditions. We recently established tightly controlled experimental conditions allowing the assembly of α-Syn into highly homogeneous and pure polymorphs. The latter exhibited differences in their shape, their structure but also in their functional properties. We have conducted an AFM study at high resolution and performed a statistical analysis of fibrillar α-Syn shape and thermal fluctuations to calculate the persistence length to further assess the nanomechanical properties of α-Syn polymorphs. Herein, we demonstrated quantitatively that distinct polymorphs made of the same protein (wild-type α-Syn) show significant differences in their morphology (height, width and periodicity) and physical properties (persistence length, bending rigidity and axial Young's modulus).

Piezoelectric tuning fork probe for atomic force microscopy imaging and specific recognition force spectroscopy of an enzyme and its ligand.

Piezoelectric quartz tuning fork has drawn the attention of many researchers for the development of new atomic force microscopy (AFM) self-sensing probes. However, only few works have been done for soft biological materials imaging in air or aqueous conditions. The aim of this work was to demonstrate the efficiency of the AFM tuning fork probe to perform high-resolution imaging of proteins and to study the specific interaction between a ligand and its receptor in aqueous media. Thus, a new kind of self-sensing AFM sensor was introduced to realize imaging and biochemical specific recognition spectroscopy of glucose oxidase enzyme using a new chemical functionalization procedure of the metallic tips based on the electrochemical reduction of diazonium salt. This scanning probe as well as the functionalization strategy proved to be efficient respectively for the topography and force spectroscopy of soft biological materials in buffer conditions.

Gentle and fast atomic force microscopy with a piezoelectric scanning probe for nanorobotics applications.

A novel dual tip nanomanipulation atomic force microscope (AFM) platform operating in ambient conditions is presented. The system is equipped with a high frequency quartz piezoelectric self-sensing scanning probe for fast imaging and a passive cantilever for manipulation. The system is validated by imaging and selective pushing/pulling of gold colloid beads (diameters from 80 to 180 nm). This provides a more compact integration compared to an external optical lever and avoids several of its drawbacks such as optical interference and noise, and recalibration in the case of a moving cantilever and a fixed laser source and photodiode sensor. Moreover, as the quartz oscillator exhibits oscillation amplitudes in the sub-picometer range with a resonant frequency in the megahertz range, this dynamic force sensor is ideal for fast AFM imaging. Experiments show an increase by five times in imaging speed compared to a classical AFM system.

Rapid and serial quantification of adhesion forces of yeast and Mammalian cells.

Cell adhesion to surfaces represents the basis for niche colonization and survival. Here we establish serial quantification of adhesion forces of different cell types using a single probe. The pace of single-cell force-spectroscopy was accelerated to up to 200 yeast and 20 mammalian cells per probe when replacing the conventional cell trapping cantilever chemistry of atomic force microscopy by underpressure immobilization with fluidic force microscopy (FluidFM). In consequence, statistically relevant data could be recorded in a rapid manner, the spectrum of examinable cells was enlarged, and the cell physiology preserved until approached for force spectroscopy. Adhesion forces of Candida albicans increased from below 4 up to 16 nN at 37°C on hydrophobic surfaces, whereas a Δhgc1-mutant showed forces consistently below 4 nN. Monitoring adhesion of mammalian cells revealed mean adhesion forces of 600 nN of HeLa cells on fibronectin and were one order of magnitude higher than those observed for HEK cells.

A tuning fork based wide range mechanical characterization tool with nanorobotic manipulators inside a scanning electron microscope.

This study proposes a tuning fork probe based nanomanipulation robotic system for mechanical characterization of ultraflexible nanostructures under scanning electron microscope. The force gradient is measured via the frequency modulation of a quartz tuning fork and two nanomanipulators are used for manipulation of the nanostructures. Two techniques are proposed for attaching the nanostructure to the tip of the tuning fork probe. The first technique involves gluing the nanostructure for full range characterization whereas the second technique uses van der Waals and electrostatic forces in order to avoid destroying the nanostructure. Helical nanobelts (HNB) are proposed for the demonstration of the setup. The nonlinear stiffness behavior of HNBs during their full range tensile studies is clearly revealed for the first time. Using the first technique, this was between 0.009 N/m for rest position and 0.297 N/m before breaking of the HNB with a resolution of 0.0031 N/m. For the second experiment, this was between 0.014 N/m for rest position and 0.378 N/m before detaching of the HNB with a resolution of 0.0006 N/m. This shows the wide range sensing of the system for potential applications in mechanical property characterization of ultraflexible nanostructures.

Parallel AFM imaging and force spectroscopy using two-dimensional probe arrays for applications in cell biology.

Atomic force microscopy (AFM) investigations of living cells provide new information in both biology and medicine. However, slow cell dynamics and the need for statistically significant sample sizes mean that data collection can be an extremely lengthy process. We address this problem by parallelizing AFM experiments using a two-dimensional cantilever array, instead of a single cantilever. We have developed an instrument able to operate a two-dimensional cantilever array, to perform topographical and mechanical investigations in both air and liquid. Deflection readout for all cantilevers of the probe array is performed in parallel and online by interferometry. Probe arrays were microfabricated in silicon nitride. Proof-of-concept has been demonstrated by analyzing the topography of hard surfaces and fixed cells in parallel, and by performing parallel force spectroscopy on living cells. These results open new research opportunities in cell biology by measuring the adhesion and elastic properties of a large number of cells. Both properties are essential parameters for research in metastatic cancer development.

Microscopic study of a ligand induced electroless plating process onto polymers.

The ligand induced electroless plating (LIEP) process was recently developed and thoroughly demonstrated with one of the most used polymers for plating processes: acrylonitrile-butadiene-styrene (ABS). This generic process is based, thanks to the use of diazonium salts as precursors, on the covalent grafting of a thin layer of poly(acrylic acid) (PAA) acting as ligand for metallic salts onto pristine polymer surfaces. This strategy takes advantage of the PAA ion exchange properties. Indeed, carboxylate groups contained in PAA allow one to complex copper ions which are eventually reduced and used as catalysts of the metallic deposition. Essentially based on ABS, ABS-PC (ABS-polycarbonate) and PA (polyamide) substrates, the present paper focuses on the role of the polymer substrate and the relationships between the macroscopic properties and microscopic characterizations such as infrared (IR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The adhesion strength of the metallic layer deposited via that LIEP process with the bulk polymer substrates was successfully compared with the adhesion of similar copper films deposited by the usual process based on chromic acid etching and palladium-based seed layer, by measuring the T-peel adhesion strength, and by carrying out the common industrial scotch tape test. Lastly, the electrical properties of the deposited layer were studied thanks to a four-point probe and scanning tunneling microscopy (STM) measurements.

FluidFM: combining atomic force microscopy and nanofluidics in a universal liquid delivery system for single cell applications and beyond.

We describe the fluidFM, an atomic force microscope (AFM) based on hollow cantilevers for local liquid dispensing and stimulation of single living cells under physiological conditions. A nanofluidic channel in the cantilever allows soluble molecules to be dispensed through a submicrometer aperture in the AFM tip. The sensitive AFM force feedback allows controlled approach of the tip to a sample for extremely local modification of surfaces in liquid environments. It also allows reliable discrimination between gentle contact with a cell membrane or its perforation. Using these two procedures, dyes have been introduced into individual living cells and even selected subcellular structures of these cells. The universality and versatility of the fluidFM will stimulate original experiments at the submicrometer scale not only in biology but also in physics, chemistry, and material science.

Poly(N-isopropylacrylamide) thin films densely grafted onto gold surface: preparation, characterization, and dynamic AFM study of temperature-induced chain conformational changes.

Thermally responsive poly(N-isopropylacrylamide) (PNIPAM) films are attracting considerable attention since they offer the possibility to achieve reversible control over surface wettability and biocompatibility. In this paper, we first report a new and simple method for the grafting under melt of amine-terminated PNIPAM chains onto gold surfaces modified with a self-assembled monolayer (SAM) of reactive thiols. The formation of homogeneous tethered PNIPAM films, whose thickness can be tuned by adjusting polymer molecular weight or SAM reactivity, is evidenced by using the combination of ellipsometry, X-ray photon spectroscopy, infrared spectroscopy (PM-IRRAS), and atomic force microscopy. The calculation of grafting parameters from experimental measurements indicated the synthesis of densely grafted PNIPAM films and allowed us to predict a "brushlike" regime for the chains in good solvent. In a second part, the temperature-induced responsive properties are studied in situ by conducting dynamic AFM measurements using the amplitude modulation technique. Imaging in water environment first revealed the reversible modification of surface morphology below and above the theoretical lower critical solution temperature (LCST) of PNIPAM. Then, the determination of amplitude and phase approach curves at various temperatures provided direct measurement of the evolution of the damping factor, or similarly the dissipated energy, as a function of the probe indentation into the PNIPAM film. Most interestingly, we clearly showed the subtle and progressive thermally induced chain conformational change occurring at the scale of several nanometers around the expected LCST.