Materials and devices for stretchable and self-healing bioelectronics

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Electron beam induced deposition of rhodium nanostructures

Electron Beam Induced Deposition (EBID) allows deposition of three-dimensional micro- and nano-structures of conductive and insulating materials on a wide range of substrates. The process is based on the decomposition of molecules of a pre-selected precursor by a focused electron beam. In recent decades EBID of several metals, namely Au, W, Cu and Pt, from different families of precursors, has been achieved and the technique has found some application for small-scale production of laboratory devices and for repair of masks and micro-optoelectronic devices. The weak point of the technique is at present the low purity of the deposited material, caused by metal-organic precursors and by the lack of selectivity of the electron-induced decomposition process. This work is dedicated to EBID of Rh nanostructures from the precursor [RhCl(PF3)2]2. High metal content deposits are expected because the precursor does not contain C atoms and because Rh is one of the less reactive metals. [RhCl(PF3)2]2 as EBID precursor has been characterized by vapor pressure, mass spectrometry and surface residence time measurements. The vapor pressure of 7.5 Pa at room temperature reveals that the precursor is sufficiently volatile for room temperature EBID. The knowledge of the vapor pressure allows also to estimate the number of precursor molecules delivered to the reaction area per unit time. Mass spectrometry measurements allow to know the decomposition path of the precursor under electron impact in the gas phase. The measured spectrum indicates that the molecule decomposes by successive loss of PF3 groups, as confirmed by density functional theory calculations. This is compatible with a high metal content deposit. Residence time measurements show that [RhCl(PF3)2]2 does not decompose on stainless steel surfaces. The measured residence time of 2 ms allows to estimate that the activation energy for desorption of [RhCl(PF3)2]2 on stainless steel is about 0.6 eV and that precursor molecules can travel distances in the micrometer range before being desorbed. EBID structures obtained from [RhCl(PF3)2]2 have been characterized with a wide range of techniques for a better knowledge of the material properties and the deposition process. The deposit morphology has been studied by Transmisssion Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) to characterize the different steps of the deposition process. Crystallographic analysis is carried out by TEM in diffraction mode. Chemical analysis is carried out by Auger Electron Spectroscopy (AES) and Electron Energy Loss Spectroscopy (EELS). Morphological analysis of deposits carried out at different exposure times reveals that the first phase of the growth process, in close proximity to the substrate, is characterized by an increase of the deposit height and the deposit diameter. On the other hand the second phase of the growth process is characterized by increasing height and constant diameter. TEM contrast profiles of dots and Atomic Force Microscopy (AFM) sections of lines have clearly shown that the EBID rate is highest in the center of the beam and decreases in the peripheral regions. Deposition at variable distances from the precursor source allowed to obtain hollow structures, whose morphology reveals that the precursor reaches the reaction area mainly by direct gas phase transport. Structural analysis and TEM revealed that, independently of the deposition conditions, the deposited material is made up of Rh nanocrystals immersed in a lighter amorphous matrix. Chemical analysis by Auger Electron Spectroscopy revealed that, after removal of the C rich contamination layer by Ar ion sputtering, the average composition of the deposits is about: 60 at.% Rh, 20 at.% P, 5 at.% Cl, 7 at.% N, 8 at.% O. The absence of C and the presence of N and O in the deposit bulk have been confirmed by Electron Energy Loss Spectroscopy. This technique allowed also to prove that Rh is dominant also in deposits of sub-micrometer size (not analyzable with AES) and to determine the elemental distribution in the deposit with nanometer resolution. Comparison of the deposit composition and the positive ions detected by mass spectrometry revealed that EBID, compared to low pressure gas phase ionization, involves a higher number of events, i.e. multi-electron decomposition and rearrangements of partially decomposed species

Stretchable kirigami-inspired conductive polymers for strain sensors applications

RÉSUMÉ: Kirigami metamaterials can be exploited in stretchable electronics owing to their architecture, which can be leveraged to amplify stretchability, bendability and deformability. Herein, we report a stretchable kirigami-structured poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS)/polydimethylsiloxane (PDMS) polymer composite. The electromechanical response and mechanical behavior of kirigami PEDOT:PSS-coated PDMS and polymer composite specimens were investigated and compared with their non-kirigami counterparts. The kirigami structure exhibited improved electromechanical properties owing to its characteristic architecture. This study illustrates the application of a kirigami polymer composite as a strain sensor for human motion detection

Flexible organic ion-gated transistors with low operating voltage and light-sensing application

ABSTRACT: Ion-gated transistors are attracting significant attention due to their low operating voltage (<1 V) and modulation of charge carrier density by ion-gating media. Here we report flexible organic ion-gated transistors based on the high mobility donor–acceptor conjugated copolymer poly[4-(4,4-dihexadecyl 4H-cyclopenta[1,2-b:5,4-b']-dithiophen-2-yl)-alt[1,2,5]thiadiazolo[3,4c]pyridine](PCDTPT) and the ionic liquid [1-ethyl-3 methylimidazolium bis(trifluoromethylsulfonyl)imide] as the ion-gating medium. Electrical characteristics of devices made on both [rigid (SiO2/Si) and flexible (polyimide (PI))] substrates showed very similar values of hole mobility (∼1 cm2 V−1 s−1) and ON–OFF ratio (∼105). Flexible ion-gated transistors showed good mechanical stability at different bending curvature radii and under repetitive bending cycles. The mobility of flexible ion-gated transistors remained almost unchanged upon bending. After 1000 bending cycles the mobility decreased by 20% of its initial value. Flexible photodetectors based on PCDTPT ion-gated transistors showed photosensitivity and photoresponsivity values of 0.4 and 93 AW−1

Printable, adhesive, and self-healing dry epidermal electrodes based on PEDOT:PSS and polyurethane diol

ABSTRACT: Printable, self-healing, stretchable, and conductive materials have tremendous potential for the fabrication of advanced electronic devices. Poly(3,4-ethylenedioxithiopene) doped with polystyrene sulfonate (PEDOT:PSS) has been the focus of extensive research due to its tunable electrical and mechanical properties. Owing to its solution-processability and self-healing ability, PEDOT:PSS is an excellent candidate for developing printable inks. In this study, we developed printable, stretchable, dry, lightly adhesive, and self-healing materials for biomedical applications. Polyurethane diol (PUD), polyethylene glycol, and sorbitol were investigated as additives for PEDOT:PSS. In this study, we identified an optimal printable mixture obtained by adding PUD to PEDOT:PSS, which improved both the mechanical and electrical properties. PUD/PEDOT:PSS free-standing films with optimized composition showed a conductivity of approximately 30 S cm−1, stretchability of 30%, and Young's modulus of 15 MPa. A low resistance change (<20%) was achieved when the strain was increased to 30%. Excellent electrical stability under cyclic mechanical strain, biocompatibility, and 100% electrical self-healing were also observed. The potential biomedical applications of this mixture were demonstrated by fabricating a printed epidermal electrode on a stretchable silicone substrate. The PUD/PEDOT:PSS electrodes displayed a skin-electrode impedance similar to commercially available ones, and successfully captured physiological signals. This study contributes to the development of improved customization and enhanced mechanical durability of soft electronic materials

Solvent-induced changes in PEDOT:PSS films for organic electrochemical transistors

ABSTRACT: Organic electrochemical transistors based on the conducting polymer poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate) (PEDOT: PSS) are of interest for several bioelectronic applications. In this letter, we investigate the changes induced by immersion of PEDOT: PSS films, processed by spin coating from different mixtures, in water and other solvents of different polarities. We found that the film thickness decreases upon immersion in polar solvents, while the electrical conductivity remains unchanged. The decrease in film thickness is minimized via the addition of a cross-linking agent to the mixture used for the spin coating of the films

Ion-gated transistors based on porous and compact TiO2 films: Effect of Li ions in the gating medium

Ion-gated transistors (IGTs) are attractive for chemo- and bio-sensing, wearable electronics, and bioelectronics, because of their ability to act as ion/electron converters and their low operating voltages (e.g., below 1 V). Metal oxides are of special interest as transistor channel materials in IGTs due to their high mobility, chemical stability, and the ease of processing in air at relatively low temperatures (<350 °C). Titanium dioxide is an abundant material that can be used as a channel material in n-type IGTs. In this work, we investigate the role of the morphology of the TiO2 channel (porous vs compact films) and the size of the cations in the gating media ([EMIM][TFSI] and [Li][TFSI] dissolved in [EMIM][TFSI]) to study their role on the electrical characteristics of IGTs. We found that both the film morphology and the type of gating medium highly affect the electrical response of the devices

Solution-Processed Titanium Dioxide Ion-Gated Transistors and Their Application for pH Sensing

ABSTRACT: Titanium dioxide (TiO₂) is an abundant metal oxide, widely used in food industry, cosmetics, medicine, water treatment and electronic devices. TiO₂ is of interest for next-generation indium-free thin-film transistors and ion-gated transistors due to its tunable optoelectronic properties, ambient stability, and solution processability. In this work, we fabricated TiO₂ films using a wet chemical approach and demonstrated their transistor behavior with room temperature ionic liquids and aqueous electrolytes. In addition, we demonstrated the pH sensing behavior of the TiO2 IGTs with a sensitivity of ~48 mV/pH. Furthermore, we demonstrated a low temperature (120°C), solution processed TiO2-based IGTs on flexible polyethylene terephthalate (PET) substrates, which were stable under moderate tensile bending

Diazonium-based anchoring of PEDOT on Pt/Ir electrodes via diazonium chemistry

Conducting polymers, specifically poly (3,4-ethylenedioxythiophene) (PEDOT), have recently been coated onto Pt/Ir electrodes intended for neural applications, such as deep brain stimulation (DBS). This modification reduces impedance, increases biocompatibility, and increases electrochemically active surface area. However, direct electropolymerization of PEDOT onto a metallic surface results in physically adsorbed films that suffer from poor adhesion, precluding their use in applications requiring in vivo functionality (i.e. DBS treatment). In this work, we propose a new attachment strategy, whereby PEDOT is covalently attached to an electrode surface through an intermediate phenylthiophene layer, deposited by electrochemical reduction of a diazonium salt. Our electrodes retain their electrochemical performance after more than 1000 redox cycles, whereas physically adsorbed films begin to delaminate after only 40 cycles. Additionally, covalently attached PEDOT maintained strong adhesion even after 10 minutes of ultrasonication (vs. 10 s for physically adsorbed films), confirming its suitability for long-term implantation in the brain. The simple two-step covalent attachment strategy proposed here is particularly useful for neural applications and could also be adapted to introduce other functionalities on the conducting surface