Measuring the Glass Transition Temperature of Conjugated Polymer Films with Ultraviolet–Visible Spectroscopy

The glass transition temperature (<i>T</i>_g) of a conjugated polymer can be used to predict its morphological stability and mechanical properties. Despite the importance of this parameter in applications from organic solar cells to wearable electronics, it is not easy to measure. The <i>T</i>_g is often too weak to detect using conventional differential scanning calorimetry (DSC). Alternative methodse.g., variable temperature ellipsometryrequire specialized equipment. This paper describes a technique for measuring the <i>T</i>_g of thin films of semicrystalline conjugated polymers using only a hot plate and an ultraviolet–visible (UV–vis) spectrometer. UV–vis spectroscopy is used to measure changes in the absorption spectrum due to molecular-scale rearrangement of polymers when heated past <i>T</i>_g, corresponding to the onset of the formation of photophysical aggregates. A deviation metric, defined as the sum of the squared deviation in absorbance between as-cast and annealed films, is used to quantify shifts in the absorption spectra. The glass transition is observed as a change in slope in a plot of the deviation metric versus temperature. To demonstrate the usefulness of this technique, a variety of semiconducting polymers are tested: P3BT, PBTTT-C14, F8BT, PDTSTPD, PTB7, PCDTBT, TQ1, and MEH-PPV. These polymers represent a range of solid-state morphologies, from highly ordered to predominantly amorphous. A successful measurement of <i>T</i>_g depends on the ability of the polymer to form photophysical aggregates. The results obtained using this method for P3BT, PBTTT-C14, F8BT, and PDTSTPD are in agreement with values of <i>T</i>_g that have been reported in the literature. Molecular dynamics simulations are used to show how the morphology evolves upon annealing: above the <i>T</i>_g, an initially kinetically trapped morphology undergoes structural rearrangement to assume a more thermodynamically preferred structure. The temperature at which onset of this rearrangement occurs in the simulation is concomitant with the spectroscopically determined value of <i>T</i>_g

Overview of the gesture-decoding glove.

<p>(a) Photograph of the glove. (b) Photograph detailing the breakout boards for the MCU, accelerometer, and Bluetooth on the PCB. (c) A circuit diagram of a voltage divider. (d) Schematic drawing of wireless gesture recognition system and the flow of information. Step 1: a gesture was made and the strain sensors transduced the positions of the knuckles into variable resistance values. Step 2: the variable values of resistance were converted into voltages by the voltage dividers. Step 3: the MCU measured the nine voltages and, through a binary comparison process, used them to generate a nine-bit key. Step 4: the binary key was used to determine which letter was to be transmitted wirelessly.</p

The Language of Glove: Wireless gesture decoder with low-power and stretchable hybrid electronics

<div><p>This communication describes a glove capable of wirelessly translating the American Sign Language (ASL) alphabet into text displayable on a computer or smartphone. The key components of the device are strain sensors comprising a piezoresistive composite of carbon particles embedded in a fluoroelastomer. These sensors are integrated with a wearable electronic module consisting of digitizers, a microcontroller, and a Bluetooth radio. Finite-element analysis predicts a peak strain on the sensors of 5% when the knuckles are fully bent. Fatigue studies suggest that the sensors successfully detect the articulation of the knuckles even when bent to their maximal degree 1,000 times. In concert with an accelerometer and pressure sensors, the glove is able to translate all 26 letters of the ASL alphabet. Lastly, data taken from the glove are used to control a virtual hand; this application suggests new ways in which stretchable and wearable electronics can enable humans to interface with virtual environments. Critically, this system was constructed of components costing less than $100 and did not require chemical synthesis or access to a cleanroom. It can thus be used as a test bed for materials scientists to evaluate the performance of new materials and flexible and stretchable hybrid electronics.</p></div

Overview of the wearable piezoresistive sensors.

<p>(a) Photograph of the sensor. (b) Schematic diagram of the sensor. (c) Cross-sectional optical micrograph of the sensor. (d) SEM image of the surface of the conductive fluoroelastomer. (e) SEM image of the nanoscopic carbon particles.</p

Graphene–Metal Composite Sensors with Near-Zero Temperature Coefficient of Resistance

This article describes the design of piezoresistive thin-film sensors based on single-layer graphene decorated with metallic nanoislands. The defining characteristic of these composite thin films is that they can be engineered to exhibit a temperature coefficient of resistance (TCR) that is close to zero. A mechanical sensor with this property is stable against temperature fluctuations of the type encountered during operations in the real world, for example, in a wearable sensor. The metallic nanoislands are grown on graphene through thermal deposition of metals (gold or palladium) at a low nominal thickness. Metallic films exhibit an increase in resistance with temperature (positive TCR), whereas graphene exhibits a decrease in resistance with temperature (negative TCR). By varying the amount of deposition, the morphology of the nanoislands can be tuned such that the TCRs of a metal and graphene cancel out. The quantitative analysis of scanning electron microscope images reveals the importance of the surface coverage of the metal (as opposed to the total mass of the metal deposited). The stability of the sensor to temperature fluctuations that might be encountered in the outdoors is demonstrated by subjecting a wearable pulse sensor to simulated solar irradiation

Comparison of Methods for Determining the Mechanical Properties of Semiconducting Polymer Films for Stretchable Electronics

This paper describes a comparison of two characterization techniques for determining the mechanical properties of thin-film organic semiconductors for applications in soft electronics. In the first method, the film is supported by water (film-on-water, FOW), and a stress–strain curve is obtained using a direct tensile test. In the second method, the film is supported by an elastomer (film-on-elastomer, FOE), and is subjected to three tests to reconstruct the key features of the stress–strain curve: the buckling test (tensile modulus), the onset of buckling (yield point), and the crack-onset strain (strain at fracture). The specimens used for the comparison are four poly­(3-hexylthiophene) (P3HT) samples of increasing molecular weight (<i>M</i>_n = 15, 40, 63, and 80 kDa). The methods produced qualitatively similar results for mechanical properties including the tensile modulus, the yield point, and the strain at fracture. The agreement was not quantitative because of differences in mode of loading (tension vs compression), strain rate, and processing between the two methods. Experimental results are corroborated by coarse-grained molecular dynamics simulations, which lead to the conclusion that in low molecular weight samples (<i>M</i>_n = 15 kDa), fracture occurs by chain pullout. Conversely, in high molecular weight samples (<i>M</i>_n > 25 kDa), entanglements concentrate the stress to few chains; this concentration is consistent with chain scission as the dominant mode of fracture. Our results provide a basis for comparing mechanical properties that have been measured by these two techniques, and provide mechanistic insight into fracture modes in this class of materials

Metallic Nanoislands on Graphene as Highly Sensitive Transducers of Mechanical, Biological, and Optical Signals

This article describes an effect based on the wetting transparency of graphene; the morphology of a metallic film (≤20 nm) when deposited on graphene by evaporation depends strongly on the identity of the substrate supporting the graphene. This control permits the formation of a range of geometries, such as tightly packed nanospheres, nanocrystals, and island-like formations with controllable gaps down to 3 nm. These graphene-supported structures can be transferred to any surface and function as ultrasensitive mechanical signal transducers with high sensitivity and range (at least 4 orders of magnitude of strain) for applications in structural health monitoring, electronic skin, measurement of the contractions of cardiomyocytes, and substrates for surface-enhanced Raman scattering (SERS, including on the tips of optical fibers). These composite films can thus be treated as a platform technology for multimodal sensing. Moreover, they are low profile, mechanically robust, semitransparent and have the potential for reproducible manufacturing over large areas

Stretchable and Degradable Semiconducting Block Copolymers

This paper describes the synthesis and characterization of a class of highly stretchable and degradable semiconducting polymers. These materials are block copolymers (BCPs) in which the semiconducting blocks are based on the diketo­pyrrolopyrrole (DPP) unit flanked by furan rings and the insulating blocks are poly­(ε-caprolactone) (PCL). The combination of stiff conjugated segments with flexible aliphatic polyesters produces materials that can be stretched >100%. Remarkably, BCPs containing up to 90 wt % of insulating PCL have the same field-effect mobility as the pure semiconductor. Spectroscopic (ultraviolet–visible absorption) and morphological (atomic force microscopic) evidence suggests that the semiconducting blocks form aggregated and percolated structures with increasing content of the insulating PCL. Both PDPP and PCL segments in the BCPs degrade under simulated physiological conditions. Such materials could find use in wearable, implantable, and disposable electronic devices

Measurement of Cohesion and Adhesion of Semiconducting Polymers by Scratch Testing: Effect of Side-Chain Length and Degree of Polymerization

Most advantages of organic electronic materials are enabled by mechanical deformability, as flexible (and stretchable) devices made from these materials must be able to withstand roll-to-roll printing and survive mechanical insults from the external environment. Cohesion and adhesion are two properties that dictate the mechanical reliability of a flexible organic electronic device. In this paper, progressive-load scratch tests are used for the first time to correlate the cohesive and adhesive behavior of poly­(3-alkylthiophenes) (P3ATs) with respect to two molecular parameters: length of the alkyl side chain and molecular weight. In contrast to metrological techniques based on buckling or pull testing of pseudofreestanding films, scratch tests reveal information about both the cohesive and adhesive properties of thin polymeric films from a single procedure. Our data show a decrease in cohesion and adhesion, that is, a decrease in overall mechanical robustness, with increasing length of the side chain. This behavior is likely due to increases in free volume and concomitant decreases in the glass transition temperature. In contrast, we observe increases in both the cohesion and adhesion with increasing molecular weight. This behavior is attributed to an increased density of entanglements with high molecular weight, which manifests as increased extensibility. These observations are consistent with the results of molecular dynamics simulations. Interestingly, the normal (applied) forces associated with cohesive and adhesive failure are directly proportional to the average degree of polymerization, as opposed to simply the molecular weight, as the length of the alkyl side chain increases the molecular weight without increasing the degree of polymerization