Wireless Coupling of Conducting Polymer Actuators with Light Emission.

Combining the actuation of conducting polymers with additional functionalities is an interesting fundamental scientific challenge and increases their application potential. Herein we demonstrate the possibility of direct integration of a miniaturized light emitting diode (LED) in a polypyrrole (PPy) matrix in order to achieve simultaneous wireless actuation and light emission. A light emitting diode is used as a part of an electroactive surface on which electrochemical polymerization allows direct incorporation of the electronic device into the polymer. The resulting free-standing polymer/LED hybrid can be addressed by bipolar electrochemistry to trigger simultaneously oxidation and reduction reactions at its opposite extremities, leading to a controlled deformation and an electron flow through the integrated LED. Such a dual response in the form of actuation and light emission opens up interesting perspectives in the field of microrobotics.

Polymer Microtip-Based Fabry-Perot Interferometer for Water Content Determination in the Gas and Liquid Phase.

In this work, we present a Fabry-Perot interferometer (FPI) based on a polymer microtip for water content determination in both the gas and liquid phase. The polymer tip of pentaerythritol triacrylate (PETA) is fabricated at the end of an optical fiber by self-guiding photopolymerization, forming at the same time a low-fineness Fabry-Perot interferometer and a sensing layer for water thanks to hydroxyl groups present in PETA. The PETA tip shows a clear interferometric signal, which is highly sensitive to the change of the water content in the environment. The FPI signal shifts with a constant sensitivity of 90 pm/%RH, which corresponds to a relative sensitivity of 104 ppm/% RH, in the range of relative humidity from 30 to 80%. In liquid, the FPI sensor shows a nonlinear sensitivity, up to 158 pm/wt % as the water content is below 40 wt % in water/glycerol mixtures. The cross effect of the temperature on the PETA tip is demonstrated to be negligible as the FPI signal is insensitive to temperature changes from 23 to 70 °C. More importantly, the interaction between the tip and the environment affecting the FPI signal is demonstrated experimentally. The proposed FPI sensor is therefore promising for the direct, sensitive, and reliable determination of the water content of products.

Optical Fiber-Based Polymer Microcantilever for Chemical Sensing: A Through-Fiber Fabrication Scheme.

Fiber optics offer an emerging platform for chemical and biological sensors when engineered with appropriate materials. However, the large aspect ratio makes the optical fiber a rather challenging substrate for standard microfabrication techniques. In this work, the cleaved end of an optical fiber is used as a fabrication platform for cantilever sensors based on functional polymers. The through-fiber fabrication process is triggered by photo-initiated free-radical polymerization and results in a high-aspect-ratio polymer beam in a single step. The dynamic mode application of these cantilevers is first demonstrated in air. These cantilevers are then tuned for sensing applications, including humidity and chemical sensing based on molecularly imprinted polymers.

Micro and nanofabrication of molecularly imprinted polymers.

Molecularly imprinted polymers (MIPs) are tailor-made receptors that possess the most important feature of biological antibodies and receptors - specific molecular recognition. They can thus be used in applications where selective binding events are of importance, such as chemical sensors, biosensors and biochips. For the development of microsensors, sensor arrays and microchips based on molecularly imprinted polymers, micro and nanofabrication methods are of great importance since they allow the patterning and structuring of MIPs on transducer surfaces. It has been shown that because of their stability, MIPs can be easily integrated in a number of standard microfabrication processes. Thereby, the possibility of photopolymerizing MIPs is a particular advantage. In addition to specific molecular recognition properties, nanostructured MIPs and MIP nanocomposites allow for additional interesting properties in such sensing materials, for example, amplification of electromagnetic waves by metal nanoparticles, magnetic susceptibility, structural colors in photonic crystals, or others. These materials will therefore find applications in particular for chemical and biochemical detection, monitoring and screening.

Nanopatterning molecularly imprinted polymers by soft lithography: a hierarchical approach.

We use soft lithography to pattern molecularly imprinted polymers (MIPs) at the nanoscale. Patterning occurs via a micro transfer molding process associated with an edge effect. We show using fluorescence microscopy that the nanopatterned synthetic receptors specifically recognize and bind a model target, dansyl-l-phenylalanine. We also demonstrate using AFM a specific swelling of the MIP pattern in the presence of the analyte. We believe that this opens new opportunities for the application of MIPs in microsensors and microbiochips, for example in environmental analysis and biomedical diagnostics.

Exploring the Critical Thickness of Organic Semiconductor Layer for Enhanced Piezoresistive Sensitivity in Field-Effect Transistor Sensors.

Organic semiconductors (OSCs) are promising transducer materials when applied in organic field-effect transistors (OFETs) taking advantage of their electrical properties which highly depend on the morphology of the semiconducting film. In this work, the effects of OSC thickness (ranging from 5 to 15 nm) on the piezoresistive sensitivity of a high-performance p-type organic semiconductor, namely dinaphtho [2,3-b:2,3-f] thieno [3,2-b] thiophene (DNTT), were investigated. Critical thickness of 6 nm thin film DNTT, thickness corresponding to the appearance of charge carrier percolation paths in the material, was demonstrated to be highly sensitive to mechanical strain. Gauge factors (GFs) of 42 ± 5 and -31 ± 6 were measured from the variation of output currents of 6 nm thick DNTT-based OFETs engineered on top of polymer cantilevers in response to compressive and tensile strain, respectively. The relationship between the morphologies of the different thin films and their corresponding piezoresistive sensitivities was discussed.

Directing hMSCs fate through geometrical cues and mimetics peptides.

The native microenvironment of mesenchymal stem cells (hMSCs)-the extracellular matrix (ECM), is a complex and heterogenous environment structured at different scales. The present study aims at mimicking the hierarchical microorganization of proteins or growth factors within the ECM using the photolithography technique. Polyethylene terephthalate substrates were used as a model material to geometrically defined regions of RGD + BMP-2 or RDG + OGP mimetic peptides. These ECM-derived ligands are under research for regulation of mesenchymal stem cells osteogenic differentiation in a synergic manner. The hMSCs osteogenic differentiation was significantly affected by the spatial distribution of dually grafted peptides on surfaces, and hMSCs cells reacted differently according to the shape and size of peptide micropatterns. Our study demonstrates the presence of a strong interplay between peptide geometric cues and stem cell differentiation toward the osteoblastic lineage. These tethered surfaces provide valuable tools to investigate stem cell fate mechanisms regulated by multiple ECM cues, thereby contributing to the design of new biomaterials and improving hMSCs differentiation cues.

Integration of a soft dielectric composite into a cantilever beam for mechanical energy harvesting, comparison between capacitive and triboelectric transducers.

Flexible dielectrics that harvest mechanical energy via electrostatic effects are excellent candidates as power sources for wearable electronics or autonomous sensors. The integration of a soft dielectric composite (polydimethylsiloxane PDMS-carbon black CB) into two mechanical energy harvesters is here presented. Both are based on a similar cantilever beam but work on different harvesting principles: variable capacitor and triboelectricity. We show that without an external bias the triboelectric beam harvests a net density power of 0.3 [Formula: see text] under a sinusoidal acceleration of 3.9g at 40 Hz. In a variable capacitor configuration, a bias of 0.15 [Formula: see text] is required to get the same energy harvesting performance under the same working conditions. As variable capacitors' harvesting performance are quadratically dependent on the applied bias, increasing the bias allows the system to harvest energy much more efficiently than the triboelectric one. The present results make CB/PDMS composites promising for autonomous portable multifunctional systems and intelligent sensors.

Single step patterning of molecularly imprinted polymers for large scale fabrication of microbiochips.

We use photolithography to pattern molecularly imprinted polymers for the wafer-scale production of biochips. We are able to produce multiplexed, spatially resolved micrometer-sized features of functional materials capable of molecular recognition. Using a fluorescent probe, dansyl-L-Phe, we show specific analyte binding to MIP patterns imprinted with boc-L-Phe, by fluorescence microscopy. Advantages of this technique are the control of shape and size of the patterns with a resolution of 1.5 microm, and the possibility of depositing a number of different MIPs on the same chip (parallelization). Multiplexing chips on the same substrate paves the road to their mass-production. Because of the simplicity of the method and the low cost of chip fabrication, we believe that mass production of portable microbiochips based on stable MIPs is now in close reach. Their combination with integrated transducers fabricated by micromachining techniques appears also possible.

A simple protocol to stabilize gold nanoparticles using amphiphilic block copolymers: stability studies and viable cellular uptake.

Di- and triblock non-ionic copolymers based on poly(ethylene oxide) and poly(propylene oxide) were studied for the stabilization of nanoparticles in water at high ionic strength. The effect of the molecular architecture (di- vs. triblock) of these amphiphilic copolymers was investigated by using gold nanoparticles (AuNPs) as probes for colloidal stability. The results demonstrate that both di- and triblock copolymers can provide long term stability, and that in both cases AuNPs are individually embedded within globules of polymers. However, in the case of diblock copolymers, the colloidal stability was related to the formation of micelles, in contrast with the case of triblock copolymers, which were previously shown to provide good stability even at concentrations at which micelles do not form. Quartz crystal microbalance (QCM) experiments showed that the presence of the hydrophobic block in the structure of the polymer is important to ensure quantitative adsorption upon a gold surface and to limit desorption. We demonstrate that with an appropriate choice of polymer, the polymer/AuNP hybrids can also undergo filtration and freeze-drying without noticeable aggregation, which can be very convenient for further applications. Finally, preliminary studies of the cytotoxicity effect on fibroblast cells show that the polymer/AuNP hybrids were not cytotoxic. TEM micrographs on ultrathin sections of cells after incubation with the colloidal solutions show that the nanoparticles were internalized into the cells, conserving their initial size and shape.

Remote imaging of single cell 3D morphology with ultrafast coherent phonons and their resonance harmonics.

Cell morphological analysis has long been used in cell biology and physiology for abnormality identification, early cancer detection, and dynamic change analysis under specific environmental stresses. This work reports on the remote mapping of cell 3D morphology with an in-plane resolution limited by optics and an out-of-plane accuracy down to a tenth of the optical wavelength. For this, GHz coherent acoustic phonons and their resonance harmonics were tracked by means of an ultrafast opto-acoustic technique. After illustrating the measurement accuracy with cell-mimetic polymer films we map the 3D morphology of an entire osteosarcoma cell. The resulting image complies with the image obtained by standard atomic force microscopy, and both reveal very close roughness mean values. In addition, while scanning macrophages and monocytes, we demonstrate an enhanced contrast of thickness mapping by taking advantage of the detection of high-frequency resonance harmonics. Illustrations are given with the remote quantitative imaging of the nucleus thickness gradient of migrating monocyte cells.

Engineering polymer MEMS using combined microfluidic pervaporation and micro-molding.

In view of the extensive increase of flexible devices and wearable electronics, the development of polymer micro-electro-mechanical systems (MEMS) is becoming more and more important since their potential to meet the multiple needs for sensing applications in flexible electronics is now clearly established. Nevertheless, polymer micromachining for MEMS applications is not yet as mature as its silicon counterpart, and innovative microfabrication techniques are still expected. We show in the present work an emerging and versatile microfabrication method to produce arbitrary organic, spatially resolved multilayer micro-structures, starting from dilute inks, and with possibly a large choice of materials. This approach consists in extending classical microfluidic pervaporation combined with MIcro-Molding In Capillaries. To illustrate the potential of this technique, bilayer polymer double-clamped resonators with integrated piezoresistive readout have been fabricated, characterized, and applied to humidity sensing. The present work opens new opportunities for the conception and integration of polymers in MEMS.

Integrated Electromechanical Transduction Schemes for Polymer MEMS Sensors.

Polymer Micro ElectroMechanical Systems (MEMS) have the potential to constitute a powerful alternative to silicon-based MEMS devices for sensing applications. Although the use of commercial photoresists as structural material in polymer MEMS has been widely reported, the integration of functional polymer materials as electromechanical transducers has not yet received the same amount of interest. In this context, we report on the design and fabrication of different electromechanical schemes based on polymeric materials ensuring different transduction functions. Piezoresistive transduction made of carbon nanotube-based nanocomposites with a gauge factor of 200 was embedded within U-shaped polymeric cantilevers operating either in static or dynamic modes. Flexible resonators with integrated piezoelectric transduction were also realized and used as efficient viscosity sensors. Finally, piezoelectric-based organic field effect transistor (OFET) electromechanical transduction exhibiting a record sensitivity of over 600 was integrated into polymer cantilevers and used as highly sensitive strain and humidity sensors. Such advances in integrated electromechanical transduction schemes should favor the development of novel all-polymer MEMS devices for flexible and wearable applications in the future.

Application of Rubrene Air-Gap Transistors as Sensitive MEMS Physical Sensors.

Micro-electromechanical systems (MEMS) made of organic materials have attracted efforts for the development a new generation of physical, chemical, and biological sensors, for which the electromechanical sensitivity is the current major concern. Here, we present an organic MEMS made of a rubrene single-crystal air-gap transistor. Applying mechanical pressure on the semiconductor results in high variations in drain current: an unparalleled gauge factor above 4000 has been measured experimentally. Such a high sensitivity is induced by the modulation of charge injection at the interface between the gold electrode and the rubrene semiconductor as an unusual transducing effect. Applying these devices to the detection of acoustic pressure shows that force down to 230 nN can be measured with a resolution of 40 nN. This study demonstrates that MEMS based on rubrene air-gap transistors constitute a step forward in the development of high-performance flexible sensors.

Correlating Crystal Thickness, Surface Morphology, and Charge Transport in Pristine and Doped Rubrene Single Crystals.

The relationship between charge transport and surface morphology is investigated by utilizing rubrene single crystals of varying thicknesses. In the case of pristine crystals, the surface conductivities decrease exponentially as the crystal thickness increases until ∼4 µm, beyond which the surface conductivity saturates. Investigation of the surface morphology using optical and atomic force microscopy reveals that thicker crystals have a higher number of molecular steps, increasing the overall surface roughness compared with thin crystals. The density of molecular steps as a surface trap is further quantified with the subthreshold slope of rubrene air-gap transistors. This thickness-dependent surface conductivity is rationalized by a shift from in-plane to out-of-plane transport governed by surface roughness. The surface transport is disrupted by roughening of the crystal surface and becomes limited by the slower vertical crystallographic axis on molecular step edges. Separately, we investigate surface-doping of rubrene crystals by using fluoroalkyltrichrolosilane and observe a different mechanism for charge transport which is independent of surface roughness. This work demonstrates that the correlation between crystal thickness, surface morphology, and charge transport must be taken into account when measuring organic single crystals. Considering the fact that these molecular steps are universally observed on organic/inorganic and single/polycrystals, we believe that our findings can be widely applied to improve charge transport understanding.

Molecule-based microelectromechanical sensors.

Incorporating functional molecules into sensor devices is an emerging area in molecular electronics that aims at exploiting the sensitivity of different molecules to their environment and turning it into an electrical signal. Among the emergent and integrated sensors, microelectromechanical systems (MEMS) are promising for their extreme sensitivity to mechanical events. However, to bring new functions to these devices, the functionalization of their surface with molecules is required. Herein, we present original electronic devices made of an organic microelectromechanical resonator functionalized with switchable magnetic molecules. The change of their mechanical properties and geometry induced by the switching of their magnetic state at a molecular level alters the device's dynamical behavior, resulting in a change of the resonance frequency. We demonstrate that these devices can be operated to sense light or thermal excitation. Moreover, thanks to the collective interaction of the switchable molecules, the device behaves as a non-volatile memory. Our results open up broad prospects of new flexible photo- and thermo-active hybrid devices for molecule-based data storage and sensors.

Antibody-antigenic peptide interactions monitored by SPR and QCM-D. A model for SPR detection of IA-2 autoantibodies in human serum.

This work reports on a complementary use of surface plasmon resonance (SPR) and quartz crystal microbalance with dissipation monitoring (QCM-D) technologies to study interactions between a peptide antigen and polyclonal antibodies, in an experimental format suitable for diagnostic assays of autoimmune diseases. In the chosen model, a synthetic peptide from the juxtamembrane region of IA-2 (a type 1 diabetes associated antigen) was immobilized by an optimized chemical protocol applicable to both BIACORE and QCM-D sensors. A thorough study of the peptide immobilization was performed to optimize the signal-to-noise ratio using mixed self-assembled monolayers (SAM) on a gold surface. Introduction of polyethylene glycol (EG(6)) chains into mixed SAM layers and addition of an anionic surfactant to the human serum reduced non-specific binding without modifying the viscoelasticity properties of the layer. Under our conditions, the antibody SPR detection limit was determined to be 0.2 nM in diluted human serum. This value is in agreement with the reported rank distribution of IA-2 antibodies in diabetic patient sera. Label-free and real-time technologies such as SPR and/or QCM-D could be precious tools in future diagnostic assays.

Optimization Of PVDF-TrFE Processing Conditions For The Fabrication Of Organic MEMS Resonators.

This paper reports a systematic optimization of processing conditions of PVDF-TrFE piezoelectric thin films, used as integrated transducers in organic MEMS resonators. Indeed, despite data on electromechanical properties of PVDF found in the literature, optimized processing conditions that lead to these properties remain only partially described. In this work, a rigorous optimization of parameters enabling state-of-the-art piezoelectric properties of PVDF-TrFE thin films has been performed via the evaluation of the actuation performance of MEMS resonators. Conditions such as annealing duration, poling field and poling duration have been optimized and repeatability of the process has been demonstrated.

Piezoelectric polymer gated OFET: Cutting-edge electro-mechanical transducer for organic MEMS-based sensors.

The growth of micro electro-mechanical system (MEMS) based sensors on the electronic market is forecast to be invigorated soon by the development of a new branch of MEMS-based sensors made of organic materials. Organic MEMS have the potential to revolutionize sensor products due to their light weight, low-cost and mechanical flexibility. However, their sensitivity and stability in comparison to inorganic MEMS-based sensors have been the major concerns. In the present work, an organic MEMS sensor with a cutting-edge electro-mechanical transducer based on an active organic field effect transistor (OFET) has been demonstrated. Using poly(vinylidenefluoride/trifluoroethylene) (P(VDF-TrFE)) piezoelectric polymer as active gate dielectric in the transistor mounted on a polymeric micro-cantilever, unique electro-mechanical properties were observed. Such an advanced scheme enables highly efficient integrated electro-mechanical transduction for physical and chemical sensing applications. Record relative sensitivity over 600 in the low strain regime (<0.3%) was demonstrated, which represents a key-step for the development of highly sensitive all organic MEMS-based sensors.

Rapid Prototyping of Chemical Microsensors Based on Molecularly Imprinted Polymers Synthesized by Two-Photon Stereolithography.

Two-photon stereolithography is used for rapid prototyping of submicrometre molecularly imprinted polymer-based 3D structures. The structures are evaluated as chemical sensing elements and their specific recognition properties for target molecules are confirmed. The 3D design capability is exploited and highlighted through the fabrication of an all-organic molecularly imprinted polymeric microelectromechanical sensor.