Soft Polymer Substrate Research Articles

Structural and optical properties of Cu:CdS thin films on soft polymer substrate

Structural and optical properties of Cu:CdS thin films on soft polymer substrate

Flexible multifunctional titania nanotube array platform for biological interfacing

The current work presents a novel flexible multifunctional platform for biological interface applications. The use of titania nanotube arrays (TNAs) as a multifunctional material is explored for soft-tissue interface applications. In vitro biocompatibility of TNAs to brain-derived cells was first examined by culturing microglia cells—the resident immune cells of the central nervous system on the surface of TNAs. The release profile of an anti-inflammatory drug, dexamethasone from TNAs-on-polyimide substrates, was then evaluated under different bending modes. Flexible TNAs-on-polyimide sustained a linear release of anti-inflammatory dexamethasone up to ~11 days under different bending conditions. Finally, microfabrication processes for patterning and transferring TNA microsegments were developed to facilitate structural stability during device flexing and to expand the set of compatible polymer substrates. The techniques developed in this study can be applied to integrate TNAs or other similar nanoporous inorganic films onto various polymer substrates.Impact statementTitania nanotube arrays (TNAs) are highly tunable and biocompatible structures that lend themselves to multifunctional implementation in implanted devices. A particularly important aspect of titania nanotubes is their ability to serve as nano-reservoirs for drugs or other therapeutic agents that slowly release after implantation. To date, TNAs have been used to promote integration with rigid, dense tissues for dental and orthopedic applications. This work aims to expand the implant applications that can benefit from TNAs by integrating them onto soft polymer substrates, thereby promoting compatibility with soft tissues. The successful direct growth and integration of TNAs on polymer substrates mark a critical step toward developing mechanically compliant implantable systems with drug delivery from nanostructured inorganic functional materials. Diffusion-driven release kinetics and the high drug-loading efficiency of TNAs offer tremendous potential for sustained drug delivery for scientific investigations, to treat injury and disease, and to promote device integration with biological tissues. This work opens new opportunities for developing novel and more effective implanted devices that can significantly improve patient outcomes and quality of life.Graphical abstract

Large-area deposition of protective (Ti,Al)N coatings onto polycarbonate

Polycarbonate (PC) and protective (Ti,Al)N coatings exhibit extremely different material properties, specifically crystal structure, thermal stability, and elastic and plastic behavior, as well as thermal expansion coefficients. These differences present formidable challenges for the deposition process development as low-temperature synthesis routes have to be explored to avoid a thermal overload of the polymer substrate. Here, a large-area sputtering process is developed to address the challenges by systematically adjusting target peak power density and duty cycle. Adhering (Ti,Al)N coatings with a critical residual tensile stress of 2.2 ± 0.2 GPa are obtained in the pulsed direct current magnetron sputtering range, whereas depositions at higher target peak power densities, realized by high power pulsed magnetron sputtering, lead to stress-induced adhesive and/or cohesive failure. The stress-optimized (Ti,Al)N coatings deposited onto PC with a target peak power density of 0.036 kW cm−2 and a duty cycle of 5.3% were investigated by the cross-cut test, confirming adhesion. By investigating the bond formation at the PC|(Ti,Al)N interface, mostly interfacial CNx bonds and a small fraction of (C−O)−(Ti,Al) bonds are identified by x-ray photoelectron spectroscopy, indicating reactions at the hydrocarbon and the carbonate groups during deposition. Nanoindentation reveals an elastic modulus of 296 ± 18 GPa for the (Ti,Al)N coating, while a Ti–Al–O layer is formed during electrochemical impedance spectroscopy in a borate buffer solution, indicating protective passivation. This work demonstrates that the challenge posed by the extremely different material properties at the interface of soft polymer substrates and hard coatings can be addressed by the systematical variation in the pulsing parameters to reduce the residual film stress.

Soft wetting with (a)symmetric Shuttleworth effect.

The wetting of soft polymer substrates brings in multiple complexities when compared with the wetting on rigid substrates. The contact angle of the liquid is no longer governed by Young’s Law, but is affected by the substrate’s bulk and surface deformations. On top of that, elastic interfaces exhibit a surface energy that depends on how much they are stretched—a feature known as the Shuttleworth effect (or as surface-elasticity). Here, we present two models through which we explore the wetting of drops in the presence of a strong Shuttleworth effect. The first model is macroscopic in character and consistently accounts for large deformations via a neo-Hookean elasticity. The second model is based on a mesoscopic description of wetting, using a reduced description of the substrate’s elasticity. While the second model is more empirical in terms of the elasticity, it enables a gradient dynamics formulation for soft wetting dynamics. We provide a detailed comparison between the equilibrium states predicted by the two models, from which we deduce robust features of soft wetting in the presence of a strong Shuttleworth effect. Specifically, we show that the (a)symmetry of the Shuttleworth effect between the ‘dry’ and ‘wet’ states governs horizontal deformations in the substrate. Our results are discussed in the light of recent experiments on the wettability of stretched substrates.

High‐Conductivity Crack‐Free 3D Electrical Interconnects Directly Printed on Soft PDMS Substrates

AbstractNanoparticle 3D printing and sintering is a promising method to achieve freeform interconnects on compliant substrates for applications such as soft robotics and wearable healthcare devices. However, previous strategies to sinter metallic nanoparticles while preserving the soft polymer substrate are rife with problems such as cracking and low conductivity of the metallic features. In this paper, the mechanisms of cracking in nanoparticle‐based 3D printed and sintered stretchable interconnects are identified and architecture and processing strategies are demonstrated to achieve crack‐free interconnects fully embedded in thin (<100 μm in thickness) stretchable polydimethylsiloxane (PDMS) with external connectivity. Capillary forces between nanoparticles developed through rapid solvent evaporation in the colloidal ink is hypothesized to initiate cracking during drying. Additionally, the presence of oxygen promotes the removal of organic surfactants and binders in the nanoparticle ink which increases nanoparticle agglomeration, grain growth, and subsequently conductivity. An experimental step‐wise variation of the thermal/atmospheric process conditions supports this hypothesis and shows that the presence of air during a low temperature drying step reduces the capillary stress to produce crack‐free interconnects with high conductivities (up to 56% of bulk metal) while having an excellent compatibility with the underlying polymer materials. Finally, stretchable interconnects fully‐encapsulated in PDMS polymer, with 3D pillar architectures for external connectivity are demonstrated, thus also solving an important “last‐mile” problem in the packaging of stretchable electronics.

Определение модуля упругости нанопокрытия с помощью испытания на трехточечный изгиб

Technologies for creating nanocoatings with unique properties on polymeric materials are being actively developed and used in human activities. The possibilities of using such composite materials will depend on the physical and mechanical properties of the coatings. To determine the mechanical characteristics of nanocoatings on polymeric materials, there are used nanoindentation methods. The results of nanoindentation of a hard coating are significantly affected by a soft polymer substrate. On the other hand, there are various experimental methods and analytical models for determining the mechanical properties of materials at the macroscopic level. The use of these approaches would make it possible to obtain the values of the mechanical properties of nanocoatings, which could be used to calculate and analyze the stress-strain state of products with nanocoatings. In this study, we demonstrate the application of a three-point bending test to determine the elastic modulus of a carbonized nanolayer formed by high-energy nitrogen ion treatment of a polyurethane surface. By selecting the optimal thickness of the test samples, it is possible to create conditions for determining the modulus of elasticity of a nanolayer on a polymer substrate using a three-point bending test. We have obtained statistically significant differences between the values of the elastic modulus of untreated and plasma-treated samples. Using a composite beam model, the modulus of elasticity of the carbonized nanolayer was determined.

A novel thermal-mechanical model and the characteristics of interfacial stress in the laminated structure for flexible electronics

Flexible electronics have attracted rapidly growing interest owing to their great potential utility in numerous fundamental and emerging fields. However, there are urgent issues that remain as pending challenges in the interfacial stress and resulting failures of flexible electronics, especially for heterogeneous laminates of hard films adhered to soft polymer substrates under thermal and mechanical loads. This study focuses on the interfacial stress of a representative laminated structure, that is, the Si film is adhesively bonded to soft polydimethylsiloxane with a plastic polyethylene terephthalate substrate. An novel thermal-mechanical coupling model for this flexible structure is established in this paper, which presents the essential characteristics of interfacial shear stress. In addition, under thermal and mechanical loads, a typical case is investigated by combining an analytical solution with numerical results using the differential quadrature method. Furthermore, thermal and mechanical loads, material and geometry parameters are quantitatively explored for their influences on the interfacial shear stress. Targeted strategies for decreasing stress are also suggested. In conclusion, the thermal-mechanical model and application case analyses contribute to enhancing the design of interfacial reliability for flexible laminated structures.

Development of miniaturized peel experiments to quantify interfacial adhesion between 2D monolayers and viscoelastic polymers

ABSTRACT In this work, a miniaturized peel-testing setup capable of performing peel tests for viscoelastic polymer strips attached to rigid substrate at different peel rates (20 nm/s–20 µm/s) and at constant peel angles (45°–135°) was developed. A mathematical framework accounting for competition between the delamination from rigid substrate as well as bending and extension of the peel arm during the peel test was employed for modeling the viscoelastic response of the soft polymeric strips attached to a rigid substrate. The efficacy of the novel miniaturized peel-testing setup was evaluated for linear elastic and viscoelastic peel arms attached to rigid substrates. The adhesion measurements for the linear elastic peel arms were found to be insensitive to peel angles and the values were in great agreement with standardized macroscale adhesion measurements for the same interface. The peel tests revealed that the interfacial adhesion measurements for the viscoelastic PDMS peel arms were highly sensitive to the nominal peel rates. An elaborate specimen fabrication process was developed to evaluate the interfacial adhesion between large area 2D materials and soft polymer substrates. A series of peel-testing experiments were performed to ensure that the developed fabrication process does not adverse effects on the interfacial adhesion measurements. The peel-testing methodology was then employed to quantify the interfacial adhesion between graphene monolayers and PDMS substrates. Due to the weak van der Waals interactions associated with the graphene/PDMS interface, the interfacial adhesion measurements for this interface was significantly lower than the adhesion values for a PDMS/PDMS interface.

Droplets on Soft Surfaces Exhibit a Reluctance to Coalesce due to an Intervening Wetting Ridge

AbstractMicroscale interactions with deformable substrates are of fundamental interest for studying self‐assembly processes and the mobility of cells on soft surfaces, with applications in traction force microscopy. The behavior of microscale water droplets on a soft polymer substrate is investigated. Droplets formed by condensation on the soft substrate are reluctant to coalesce, which leads to coverage of the surface with clusters of droplets assembled in a honeycomb‐like pattern. Cryogenically fixed in this state, scanning electron microscopy of these droplets reveals the presence of an intervening wetting ridge of the polymer that acts as a barrier between neighboring droplets and prevents coalescence. A linear elastic deformation model is developed to predict this surface profile and corroborate the observed behavior.

Soft, Wirelessly Powered Humidity Sensor Based on SnO2 Nanowires for Wireless/Wearable Sensor Application.

Humidity, along with temperature, is one of the most important environmental variables in people’s lives. The control of humidity is an important matter that is related to material properties and stability in various industries, as well as basic living. In order to detect humidity, changes in the physical, chemical, and electrical properties of materials related to humidity are used, and studies using various methods are conducted. In this study, a field-effect transistor (FET) device was fabricated on a soft polymer substrate with SnO2 nanowires (NWs), whose electrical properties change in response to water molecules. The SnO2 NWs, synthesized by chemical vapor deposition (CVD), were transferred onto a polymer substrate, using a sliding transfer method. The NW FET device, which was connected to an aluminum (Al)-based radio frequency (RF) receiving antenna, was wirelessly operated as a humidity sensor, based on the change in electrical properties of SnO2 NWs according to the relative humidity (RH). It was configured with a wireless antenna and light emitting diode (LED) indicator to implement a soft wirelessly powered humidity sensor that senses high RH and is expected to be used as a wearable electronic/sensor in the future.

An Instrumented Urethral Catheter with a Distributed Array of Iontronic Force Sensors.

This paper develops a novel instrumented urethral catheter with an array of force sensors for measuring the distributed pressure in a human urethra. The catheter and integrated portions of the force sensors are fabricated by the use of 3D printing using a combination of both soft and hard polymer substrates. Other portions of the force sensors consisting of electrodes and electrolytes are fabricated separately and assembled on top of the 3D-printed catheter to create a soft flexible device. The force sensors use a novel supercapacitive (iontronic) sensing mechanism in which the contact area between a pair of electrodes and a paper-based electrolyte changes in response to force. This provides a highly sensitive measure of force that is immune to parasitic noise from liquids. The developed catheter is tested using a force calibration test rig, a cuff-based pressure application device, an extracted bladder and urethra from a sheep and by dipping inside a beaker of water. The force sensors are found to have a sensitivity of 30-50 nF/N, which is 1000 times larger than that of traditional capacitive force sensors. They exhibit negligible capacitance change when dipped completely in water. The pressure cuff tests and the extracted sheep tissue tests also verify the ability of the sensor array to work reliably in providing distributed force measurements. The developed catheter could help diagnose ailments related to urinary incontinence and inadequate urethral closure pressure.

Finite Element Analysis of the Nanomechanics of Hard Coatings on a Soft Polymer Substrate by a Spherical Indenter

Composite has been widely used in various fields due to its advanced performance. To reveal the relation between the mechanical properties of the composite and that of each individual component, finite element analysis (FEA) has usually been adopted. In this study, in order to predict the mechanical properties of hard coating on a soft polymer, the response of this coating system during nanoindentation was modelled. Various models, such as a viscoelastic model and fitting model, were adopted to analyse the indentation response of this coating system. By varying the substrate properties (i.e., Young’s modulus, viscoelasticity, and Poisson’s ratio), Young’s modulus, energy loss, and the viscoelastic model of the coating system were analysed, and how the mechanical properties of the substrate will affect the indentation response of the coating system was discussed.

Recent Advances on Thermal Management of Flexible Inorganic Electronics.

Flexible inorganic electronic devices (FIEDs) consisting of functional inorganic components on a soft polymer substrate have enabled many novel applications such as epidermal electronics and wearable electronics, which cannot be realized through conventional rigid electronics. The low thermal dissipation capacity of the soft polymer substrate of FIEDs demands proper thermal management to reduce the undesired thermal influences. The biointegrated applications of FIEDs pose even more stringent requirements on thermal management due to the sensitive nature of biological tissues to temperature. In this review, we take microscale inorganic light-emitting diodes (μ-ILEDs) as an example of functional components to summarize the recent advances on thermal management of FIEDs including thermal analysis, thermo-mechanical analysis and thermal designs of FIEDs with and without biological tissues. These results are very helpful to understand the underlying heat transfer mechanism and provide design guidelines to optimize FIEDs in practical applications.

Simplified All‐Solid‐State WO3 Based Electrochromic Devices on Single Substrate: Toward Large Area, Low Voltage, High Contrast, and Fast Switching Dynamics

AbstractElectrochromic devices (ECDs) represent one of the most promising energy saving and solar control technology for the market of energy‐efficient building and optoelectronic devices. A continuous and intense effort is currently devoted to the development of effective solid‐state ECDs and their integration in multifunctional systems, such as photoelectrochromics. Here, the fabrication of simplified all‐solid‐state WO3 based ECDs on single‐substrate is reported, demonstrating how the rational design of highly interconnected WO3 columnar nanostructures with Nafion polymer matrix remarkably decreases the charge transport barrier at the hybrid electrolyte/electrochromic interface (EEI), thus determining an impressive improvement of overall device performances. The soft polymer substrate of the electrolyte plays a key role on the formation of WO3 pillar‐like structures and on the increase of interfacial contact area by affecting the vacuum‐deposition WO3 growth. Apart from providing higher transmittance in bleached state, the resulting device, entirely manufactured at room temperature by bottom‐up process, exhibits lower activation voltages (0.5–3 V) and faster switching kinetics (5–10 s) compared with monolithic ECDs based on both bulk and mesoporous WO3 films. Furthermore, the enhanced EEI enables the scale‐up on large area and flexible substrate ensuring simultaneously a wide optical contrast (ΔT = 70%), and high coloration efficiency.

Structural-mechanical AFM study of inhomogeneous stiff nanocoating of soft polymer substrate

Modification of polymer with low-energy gas plasma is used to change the wettability of the surface and, as a consequence, to improve the interactions with biological objects. As a result of such treatment, a nanolayer, which is stiffer than the initial surface, is formed on a broad class of polymers. Elastic polyurethane is one of the widely used polymers. This is two-phase material consisting of soft and hard blocks. Its surface was treated by low-energy argon plasma and studied by an atomic force microscopy (AFM): the structure becomes rough and mechanically inhomogeneous depending on the part of the surface treated (hard or soft blocks of the material). The average value of elastic modulus increases with the treatment time, but the average thickness of the coating does not change, having a wide dispersion. All these features are related with the heterogeneous surface peculiarities of the initial polymer.

Localization of wrinkle patterns by crack-tip induced plasticity: Experiments and simulations

Regulating surface wrinkles have received considerable attention because of their potential applications in stretchable electronics, microfluidics, bionics, sensors, stamps, optical devices and smart materials. In this work, optical microscopy and atomic force microscopy revealed that tunable film thickness and substrate stiffness effectively regulate localized wrinkle patterns in metal films deposited on soft polymer substrates. Theoretical analysis and numerical simulation found that the high tensile stress developed during the film deposition leads to channel cracks in the film and creates a stripe-like plastic zone around each crack. The subsequently developed compressive stress in the plastic zone is anisotropic, resulting in the formation of localized straight wrinkles perpendicular to the crack. The width of the wrinkle is consistent with the size of the plastic zone, which decreases with increasing the film thickness or substrate stiffness, in good agreement with the experimental observations. The report in this work not only elucidates how the subtle correlation among crack, plasticity and buckle leads to such localized wrinkling pattern but also demonstrates an efficient way to produce crack-network-guided localized wrinkle patterns.

Soft Elastomers with Programmable Stiffness as Strain-Isolating Substrates for Stretchable Electronics.

Stretchable electronics are of rapidly increasing interest due to their unique ability to function under complex deformations. Strain isolation of stiff functional components from the substrate represents a key challenge in the development of stretchable electronics since their mechanical mismatch may yield undesirable strains to degrade the device performance. The results presented here report an approach to develop a soft strain-isolating polymer substrate with programmable stiffness by spatioselective ultraviolet exposure for stretchable electronics. The approach being compatible with the well-established lithographic process reduces the fabrication complexity significantly and offers a simple yet robust strain-isolation mechanism to ensure the system stretchability of more than 100%. Combined experimental and numerical studies reveal the fundamental aspects of the design, fabrication, and operation of the strain-isolating substrate. Demonstration of this concept in a stretchable inorganic metal-based resistive temperature sensor and a stretchable organic photodiode array with unusually high performance shows the simplicity of the approach and the robustness in strain isolation in both component and device levels. This type of strain-isolation design not only creates promising routes for potential scalable manufacturing of stretchable electronics but also engineering opportunities for stretchable electronics involving the integration of various functional components, which require the quantitative control of the strain levels to achieve optimal performance.

Silver nano platelet films on soft micro grating surface

PurposePolymer substrates with micron size roughness features have been found to play an important role in the mechanical performance of thin functional films which are used extensively in stretchable and flexible micro electromechanical systems. The purpose of this study is to report the stretchability and flexibility limits of micro size silver nano platelet films on a soft polymer substrate having two different orientations of micro grating with respect to the applied load.Design/methodology/approachParallel and perpendicular micro gratings on the surface of a soft polymer substrate polydimethylsiloxane were patterned using a carefully machined master aluminum block and thin aluminum foils. Silver nano platelet-based films were rod coated on the substrate surface containing the micro gratings. These films were dried in ambient air and were tested for their stretchability and flexibility limits using homemade tools. Finite element modeling has also been performed and was found to support the experimental observations.FindingsExperiments indicate that stretchability of silver nano platelet-based thin films tends to increase when the grating orientation remains parallel to the axis of the applied load, while its flexibility improves when the orientation becomes perpendicular to the loading axis.Originality/valueThe effect of grating orientation with respect to the applied load was investigated. The experiments show that micro grating roughness features are capable of enhancing the mechanical performance of nano platelet-based silver films on a soft polymer substrate and can be used in various stretchable and flexible micro electro mechanical device applications.

Waveguide Plasmon Resonance of Arrayed Metallic Nanostructures Patterned on a Soft Substrate by Direct Contact Printing Lithography.

This paper presents a direct contact printing method to obtain arrayed metallic nanostructures on a soft polymer substrate. It utilizes a polydimethylsiloxane (PDMS) mold replicated from silicon molds to transfer metallic nanopatterns onto a polymer substrate based on differences in interfacial bonding energy. Arrayed metallic nanodisks with a disk diameter down to 180 nm and a center-to-center pitch around 400 nm are experimentally patterned on a PET substrate. The patterned metallic nanostructures are then spin-coated with a polymer layer; which mechanically secures the patterned nanostructures and optically allows waveguide plasmon resonance being excited by incident EM waves. Both experimental works and theoretical modeling are given to illustrate the behaviors of different types of plasmon resonance. These arrayed metallic nanostructures patterned on a soft polymer substrate and their tunable optical characteristics open up many possibilities in future engineering applications.

Enhancing the Elasticity of Ultrathin Single-Wall Carbon Nanotube Films with Colloidal Nanocrystals.

Thin bilayers of contrasting nanomaterials are ubiquitous in solution-processed electronic devices and have potential relevance to a number of applications in flexible electronics. Motivated by recent mesoscopic simulations demonstrating synergistic mechanical interactions between thin films of single-wall carbon nanotubes (SWCNTs) and spherical nanocrystal (NC) inclusions, we use a thin-film wrinkling approach to query the compressive mechanics of hybrid nanotube/nanocrystal coatings adhered to soft polymer substrates. Our results show an almost 2-fold enhancement in the Young modulus of a sufficiently thin SWCNT film associated with the presence of a thin interpenetrating overlayer of semiconductor NCs. Mesoscopic distinct-element method simulations further support the experimental findings by showing that the additional noncovalent interfaces introduced by nanocrystals enhance the modulus of the SWCNT network and hinder network wrinkling.