Shape Memory Polymer Substrate Research Articles

Organic light-emitting diodes on shape memory polymer substrates for wearable electronics

Green electrophosphorescent organic light-emitting diodes (OLEDs) with inverted top-emitting structures are demonstrated on bio-compatible shape memory polymer (SMP) substrates for wearable electronic applications. The combination of the unique properties of SMP substrates with the light-emitting properties of OLEDs pave to the way for new applications, including conformable smart skin devices, minimally invasive biomedical devices, and flexible lighting/display technologies. In this work, SMPs were designed to exhibit a considerable drop in modulus when a thermal stimulus is applied, allowing the devices to bend and conform to new shapes when its glass transition temperature is reached. These SMP substrates were synthesized using 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TATATO), trimethylolpropane tris(3-mercaptopropionate) (TMTMP), and tricyclo[5.2.1.02,6]decanedimethanol diacrylate (TCMDA), and show a low glass transition temperature of 43°C, as measured using dynamic mechanical analysis (DMA). The OLEDs fabricated on these substrates exhibit high performance with a maximum efficacy of 33cd/A measured at a luminance of 1000cd/m2, and a peak luminance of over 30,000cd/m2.

Implementation of poly(ε-caprolactone) sheet-based shape-memory polymer microvalves into plastic-based microfluidic devices

Implementation of shape-memory polymer (SMP) sheet-based microvalves into plastic-based microfluidic devices has been studied toward the use in disposable and mass producible micro total analysis devices. Poly(ε-caprolactone) (PCL) and poly(methyl methacrylate-co-styrene) (MS) were used as SMP and main substrate materials, respectively. Bonding between PCL sheets and MS plates was the critical issue in the practical implementation. We found the pristine PCL sheet has relatively rough surface with Ra of 85.14 nm, which is the cause of poor bonding. Hence, by introducing the post-anneal treatment with sandwiched between two flat glass plates, the PCL surface could be smoothed to Ra of 12.50 nm, and tight bonding could be obtained. Consequently, microfluidic devices consisting of plastic/PCL/plastic layers were successfully fabricated and therein the actuation of SMP valves without any leakage was demonstrated. The present technology is expected to be applicable to disposable microfluidic devices as required for point-of-care testing.

Heterogeneous, three-dimensional texturing of graphene.

We report a single-step strategy to achieve heterogeneous, three-dimensional (3D) texturing of graphene and graphite by using a thermally activated shape-memory polymer substrate. Uniform arrays of graphene crumples can be created on the centimeter scale by controlling simple thermal processing parameters without compromising the electrical properties of graphene. In addition, we show the capability to selectively pattern crumples from otherwise flat graphene and graphene/graphite in a localized manner, which has not been previously achievable using other methods. Finally, we demonstrate 3D crumpled graphene field-effect transistor arrays in a solution-gated configuration. The presented approach has the capability to conform onto arbitrary 3D surfaces, a necessary prerequisite for adaptive electronics, and will enable facile large-scale topography engineering of not only graphene but also other thin-film and 2D materials in the future.

Shape-memory polymers as flexible resonator substrates for continuously tunable organic DFB lasers

We introduce shape-memory polymers (SMP) as substrate material for active optical devices. As an exemplary application we build a tunable organic semiconductor distributed feedback (DFB) laser. Hence, we transfer a second order Bragg grating with a period of 400 nm into SMP foils by hot embossing. The composite organic gain medium Alq3:DCM evaporated on the SMP substrate serves as laser active material. Mechanical stretching of the substrate increases the grating period temporarily and triggering the shape-memory effect afterwards reduces the period on demand. In this way, we can adjust the grating period to achieve a broad continuously tuning of the laser emission wavelength by 30 nm.

Facile 3D Metal Electrode Fabrication for Energy Applications via Inkjet Printing and Shape Memory Polymer

This paper reports on a simple 3D metal electrode fabrication technique via inkjet printing onto a thermally contracting shape memory polymer (SMP) substrate. Inkjet printing allows for the direct patterning of structures from metal nanoparticle bearing liquid inks. After deposition, these inks require thermal curing steps to render a stable conductive film. By printing onto a SMP substrate, the metal nanoparticle ink can be cured and substrate shrunk simultaneously to create 3D metal microstructures, forming a large surface area topology well suited for energy applications. Polystyrene SMP shrinkage was characterized in a laboratory oven from 150-240°C, resulting in a size reduction of 1.97-2.58. Silver nanoparticle ink was patterned into electrodes, shrunk, and the topology characterized using scanning electron microscopy. Zinc-Silver Oxide microbatteries were fabricated to demonstrate the 3D electrodes compared to planar references. Characterization was performed using 10M potassium hydroxide electrolyte solution doped with zinc oxide (57g/L). After a 300s oxidation at 3Vdc, the 3D electrode battery demonstrated a 125% increased capacity over the reference cell. Reference cells degraded with longer oxidations, but the 3D electrodes were fully oxidized for 4 hours, and exhibited a capacity of 5.5mA-hr/cm2 with stable metal performance.

A comparison of polymer substrates for photolithographic processing of flexible bioelectronics

Flexible bioelectronics encompass a new generation of sensing devices, in which controlled interactions with tissue enhance understanding of biological processes in vivo. However, the fabrication of such thin film electronics with photolithographic processes remains a challenge for many biocompatible polymers. Recently, two shape memory polymer (SMP) systems, based on acrylate and thiol-ene/acrylate networks, were designed as substrates for softening neural interfaces with glass transitions above body temperature (37°C) such that the materials are stiff for insertion into soft tissue and soften through low moisture absorption in physiological conditions. These two substrates, acrylate and thiol-ene/acrylate SMPs, are compared to polyethylene naphthalate, polycarbonate, polyimide, and polydimethylsiloxane, which have been widely used in flexible electronics research and industry. These six substrates are compared via dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), and swelling studies. The integrity of gold and chromium/gold thin films on SMP substrates are evaluated with optical profilometry and electrical measurements as a function of processing temperature above, below and through the glass transition temperature. The effects of crosslink density, adhesion and cure stress are shown to play a critical role in the stability of these thin film materials, and a guide for the future design of responsive polymeric materials suitable for neural interfaces is proposed. Finally, neural interfaces fabricated on thiol-ene/acrylate substrates demonstrate long-term fidelity through both in vitro impedance spectroscopy and the recording of driven local field potentials for 8weeks in the auditory cortex of laboratory rats.

In vitro wrinkle formation via shape memory dynamically aligns adherent cells

Surface wrinkling of materials offers a simple yet elegant approach to fabricating cell culture substrates with highly ordered topographies for investigating cell mechanobiology. In this study we present a tunable shape memory polymer (SMP) bilayer system that is programmed to form, under cell compatible conditions, wrinkles with feature sizes on the micron and sub-micron length scale. We found that with increasing deformation fixed into the SMP substrate, wrinkled topographies with increasing amplitudes, decreasing wavelengths, and increasing degree of wrinkle orientation were achieved. Analysis of the cellular response to previously wrinkled (static) substrates revealed that cell nuclear alignment increased as SMP deformation increased. Analysis of the cellular response to an actively wrinkling substrate demonstrated that cell alignment can be controlled by triggering wrinkle formation. These findings demonstrate that the amount of deformation fixed (and later recovered) in an SMP bilayer system can be used to control the resulting wrinkle characteristics and cell mechanobiological response. The tailored and dynamic substrate functionality provided by this approach is expected to enable new investigation and understanding of cell mechanobiology.

Three-Dimensional Flexible Electronics Enabled by Shape Memory Polymer Substrates for Responsive Neural Interfaces.

Planar electronics processing methods have enabled neural interfaces to become more precise and deliver more information. However, this processing paradigm is inherently 2D and rigid. The resulting mechanical and geometrical mismatch at the biotic-abiotic interface can elicit an immune response that prevents effective stimulation. In this work, a thiol-ene/acrylate shape memory polymer is utilized to create 3D softening substrates for stimulation electrodes. This substrate system is shown to soften in vivo from more than 600 to 6 MPa. A nerve cuff electrode that coils around the vagus nerve in a rat and that drives neural activity is demonstrated.

Fabrication of Responsive, Softening Neural Interfaces

AbstractA novel processing method is described using photolithography to pattern thin‐film flexible electronics on shape memory polymer substrates with mechanical properties tailored to improve biocompatability and enhance adhesion between the polymer substrate and metal layers. Standard semiconductor wafer processing techniques are adapted to enable robust device design onto a variety of softening substrates with tunable moduli. The resulting devices are stiff enough (shear modulus of ≈700 MPa) to assist with device implantation and then soften in vivo (≈300 kPa) approaching the modulus of brain tissue (≈10 kPa) within 24 h. Acute in vivo studies demonstrate that these materials are capable of recording neural activity. Softening multi‐electrode arrays offer a highly customizable interface, which can be optimized to improve biocompatibility, enabling the development of robust, reliable neural electrodes for neural engineering and neuroscience.

Micro and Nanowrinkled Conductive Polymer Surfaces on Shape-memory Polymer Substrates: Tuning of Surface Microfeatures Towards Smart Biointerfaces.

ABSTRACTWith the aim of providing an easy and versatile method for realizing conductive polymer surfaces with controlled micro and nano-scale topographical cues patterning, we deposited a ultra-thin film of the conductive polymer poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) on a thermo-retractable polystyrene sheet. Biaxial and uniaxial micro and nano-wrinkles were formed with different features depending on clamping geometry during shrinking of the substrate upon heating. Homogeneous nano and micro-patterning of surface topography over large areas (several cm2) was obtained. The formed wrinkles were very robust and adhered strongly to the substrate because of their penetration into the soft substrate during the heat-shrink process. In the case of uniaxial wrinkles a very well aligned quasi-periodic structure is formed with different populations of wavelengths ranging from submicrometric to 10-20 μm, depending on PEDOT:PSS thickness. Surface topography, wrinkles amplitude and wavelength have been evaluated by means of SEM and AFM and the results have been related to sheet resistance as measured with a four point probe technique. The realized conductive surfaces can offer new opportunities in the field of cell stimulation and growth.

Dynamic cell behavior on shape memory polymer substrates

Cell culture substrates of defined topography have emerged as powerful tools with which to investigate cell mechanobiology, but current technologies only allow passive control of substrate properties. Here we present a thermo-responsive cell culture system that uses shape memory polymer (SMP) substrates that are programmed to change surface topography during cell culture. Our hypothesis was that a shape-memory-activated change in substrate topography could be used to control cell behavior. To test this hypothesis, we embossed an initially flat SMP substrate to produce a temporary topography of parallel micron-scale grooves. After plating cells on the substrate, we triggered shape memory activation using a change in temperature tailored to be compatible with mammalian cell culture, thereby causing topographic transformation back to the original flat surface. We found that the programmed erasure of substrate topography caused a decrease in cell alignment as evidenced by an increase in angular dispersion with corresponding remodeling of the actin cytoskeleton. Cell viability remained greater than 95% before and after topography change and temperature increase. These results demonstrate control of cell behavior through shape-memory-activated topographic changes and introduce the use of active cell culture SMP substrates for investigation of mechanotransduction, cell biomechanical function, and cell soft-matter physics.

Bimetallic nanopetals for thousand-fold fluorescence enhancements

We present a simple, ultra-rapid and robust method to create sharp nanostructures—nanopetals—in a shape memory polymer substrate demonstrating unprecedented enhancements for surface enhanced sensing over large surface areas. These bimetallic nanostructures demonstrate extremely strong surface plasmon resonance effects due to the high density multifaceted petal structures that increase the probability of forming nanogaps. We demonstrate that our nanopetals exhibit extremely strong surface plasmons, confining the emission and enhancing the fluorescence intensity of the nearby high-quantum yield fluorescein by >4000×. The enhancements are confined to the extremely small volumes at the nanopetal borders. This enables us to achieve single molecule detection at relatively high and physiological concentrations.

Structural Color: Encoding Localized Strain History Through Wrinkle Based Structural Colors (Adv. Mater. 39/2010)

Spatially localized surface wrinkles are created on a metallic film supported on a shape-memory polymer substrate. The wrinkle wavelength approaches that of visible light, resulting in diffraction colors. The spatial and geometric distribution of the wrinkles can be controlled in an arbitrary fashion, allowing the capture of a three dimensional image on a macroscopically flat surface, as reported on p. 4390 by Tao Xie and co-workers.

Encoding Localized Strain History Through Wrinkle Based Structural Colors

Surface wrinkles are created on a metallic film supported on a shape memory polymer substrate. The wrinkle wavelength approaches that of visible lights, resulting in diffraction colors. The spatial and geometric distribution of the surface wrinkles can be controlled in an arbitrary fashion, allowing the capture of a three dimensional arbitrary image on a macroscopically flat surface.