High-aspect-ratio (HAR) pillar arrays offer large surface area, well-defined surface topography, and large mechanical compliance. In this Prospective, we showcase micro- and nanopillar array systems that exploit the responsiveness and/or harness the mechanical instabilities for myriad surface-mediated applications, including tunable wetting, adhesion, optical properties, and actuation. In each application, we start with biological examples with HAR pillar structures, and discuss strategies to fabricate responsive HAR polymer pillar structures. We then discuss approaches to tune the surface topography, such as via bending, tilting, expansion or contraction, and collapsing of the pillars, and the resulting change of surface and optical properties, and their dynamic actuation. In each system, we discuss the controllability and recoverability of pillar deformation.

As multifunctional electroactive materials, ferroelectric polymers are unique owing to their exceptionally high dielectric strength (>600 MV/m), high flexibility, and easy and low-temperature fabrication into required shapes. Although polyvinylidene difluoride (PVDF)-based ferroelectric polymers have been known for several decades, recent findings reveal the potential of this class of electroactive polymers (EAPs) to achieve giant electroactive responses by tuning the molecular, nano, and meso-structures. This paper presents these advances, including giant electrocaloric effect, giant electroactuation, and large, hysteresis-free polarization response. New developments in materials benefit applications, such as environmentally benign and potentially highly energy-efficient electrical field controlled solid-state refrigeration, artificial muscles, and high-energy and power density electric energy storage devices. The challenges in developing these materials to realize these applications, and strategies to further improve the responses of EAPs will be also discussed.

Conjugated polymers are being considered for use at the interface between hard inorganic metallic and semiconducting electrodes and soft biological tissues. These organic materials have properties that are intermediate to these two extremes, and their chemistry, structure, and performance can be precisely manipulated over a large range. Examples of current interest included copolymers of poly(3,4-ethylene dioxythiophene) and poly(3,4-propylene dioxythiophene). This paper will review past efforts, recent activities, and future possibilities in this rapidly expanding area of materials research and technology.

The design of π-conjugated molecules and polymers has driven the increase in efficiency of bulk heterojunction organic photovoltaic devices from <1% to over 12%. The pathways to generation of free charge carriers are still being uncovered. By focusing on blends of conjugated polymers with fullerenes, recent work has highlighted the impact of the design of donor–acceptor polymers on optoelectronic properties and phase-separated morphologies. This morphology of the active layer is largely controlled by processing conditions, such as use of processing additives. Developing a deep understanding of the impact of polymer chemistry and processing at the laboratory scale is key to translating the technology of organic photovoltaics from the research scale to large-area modules.

Conjugated polymers (CPs) are widely investigated because of their intriguing optical and semiconducting properties in various optoelectronic device applications. Because of the one-dimensional p-orbital overlap along the main chain, CPs exhibit strong anisotropy in optoelectronic characteristics. Therefore, macroscopic assembly and alignment of CPs are essential to fully utilize their potential properties in real device applications. Here we review various processing strategies and material design principles for efficient CP alignment that result in highly anisotropic optical and electronic characteristics. Furthermore, we thoroughly review the incorporation of aligned CPs layers in organic light-emitting diodes, organic thin film transistors, and organic photovoltaic devices. The achieved macroscopic CP alignment has increased the optoelectronic properties and greatly improved device performance.

Depolymerizable polymers are stimuli-responsive materials triggered to depolymerize rapidly and completely into their constituent monomers on command. Applications include triggerable vehicles for controlled release, restructurable materials, disappearing or sacrificial composites, and lithographic resists. Owing to their widespread utility, significant efforts have aimed to prepare and explore depolymerizable polymers and their corresponding triggers. This “Prospective” highlights advances since their discovery over a half-century ago, discusses methods in their preparation, and presents recent developments in triggered depolymerization. It also surveys applications that harness these polymers’ unique properties, while offering insights into research directions that may contribute to progress in this dynamic field.

The thermal history of amorphous polymers near the glass-transition temperature determines the extent to which macromolecules structurally relax, and ultimately their properties. Here, we report the correlation between physical aging, dielectric breakdown, and capacitive energy storage of polystyrene, poly(methyl-methacrylate), and associated silica nanocomposites. Guided by enthalphic recovery rates, dielectric breakdown strength increased from 20% to 40% when aged at Tg−10 °C before use. The generality of improvement and connection to enthalpic recovery afford a means to design pre-service processing of new polymers and additive manufacturing techniques to reduce excess volume within the glass; and thereby reduce initiation and inhibit propagation of electronic failure.

Material research and development is increasingly focusing on achieving specialized functionality in materials. For example, the ability to “self-heal (SH)”, or naturally repair accrued damage, is attractive because it extends the lifetime of the material by increasing resistance to damaging conditions and prolonging preservation of material properties. Additionally, shape memory (SM) materials, including SM polymers, are actively considered for their ability to change shape one or more times upon application of an external stimulus. Here, we present a polymer composite, composed of poly(vinyl acetate) (PVAc) and poly(ε-caprolactone) (PCL), exhibiting both SH and SM functionalities. In fact, the SM assists in the SH ability in a process developed by our group termed, shape memory-assisted self-healing (SMASH). The advantage of the SH composite presented here is its simple fabrication. Dual-electrospinning is used to simultaneously electrospin PVAc and PCL, achieving an interwoven polymeric composite of otherwise immiscible polymers. The dual-electrospinning method facilitates precise control of the relative weight fractions of the components, and thus allows for tuning of the material properties. Upon thermal activation, damaged PVAc–PCL composites exhibited SH under a variety of testing conditions. Furthermore, the composites exhibited impressive dual and triple SM capabilities in the dry and hydrated states, respectively. Together, the commercial availability of the components and the simplicity of preparation translate to a SMASH system that could be mass produced and used as a SH coating or alone, as a packaging material.

We report on the ability to switch an optical material composed of a polymer stabilized cholesteric liquid crystal (polymer stabilized cholesteric texture, PSCT) between stable transparent (reflective) and scattering modes. The degree of scattering is controllable with the strength of the applied electric field. The mechanism for bistable switching of the PSCT is distinguished from prior examinations by employing electromechanical displacement of a stabilizing polymer network. The stable transparent (reflective) or scattering modes are induced with a variety of driving schemes employing both alternating and direct current fields. The relative degree of scattering can be varied to allow for grayscale control potentially useful in smart window and display applications.

All-polymer solar cells composed of binary blends of donor poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b′]dithiophene-2,6-diyl-alt-(4-(2-ethylhexanoyl)-thieno[3,4-b]thiophene-)-2–6-diyl)] (PBDTTT-CT ), and acceptor polymers naphthalene diimide-selenophene copolymer (PNDIS-HD) and perylene diimide-selenophene copolymer (PPDIS) had power conversion efficiencies (PCEs) of 1.3 and 2.1%, respectively. Ternary blend solar cells composed of [PBDTTT-CT][PNDIS-HD]1−x[PPDIS]x at 75 wt% PPDIS had a PCE of 3.2%, which is about a 50%–140% enhancement compared with the binary blend devices. Equality of the ternary blend short-circuit current to the sum of those of the binary blend devices, among other results, provided evidence of a parallel-like bulk heterojunction mechanism in the ternary blend solar cells. These results provide the first example of enhanced performance in ternary blend all-polymer solar cells.

We report the use of electrospray to continuously deposit thin films, including patterned films, of a block copolymer (BCP). High substrate temperatures led to vertically oriented cylindrical microdomains at the film surface independent of the solvent composition and deposition rates utilized. Conversely, low substrate temperatures resulted in morphologies that were more sensitive to these parameters, with poorly ordered films of globular structures observed at the lowest temperatures considered. The deposition pattern is defined by spatially varying the electric field at the substrate using an underlying charged grid. These results open up new possibilities for patterned deposition of BCP films with morphological control.

A model with which to predict the effect of coplanar electrode geometry on diffraction uniformity in photorefractive polymer display devices was developed. Assumptions made in the standard use cases are no longer valid in the regions of extreme electric fields present in this type of device. Using electric-field induced second-harmonic generation through multiphoton microscopy, the physical response in regions of internal electric fields which fall outside the standard regimes of validity were probed. Adjustments to the standard model were made and the results of the new model corroborated through holographic four-wave mixing measurements.

We detail the influence of tapered interfaces on the nanoscale morphologies of ion-doped poly(styrene-b-oligo-oxyethylene methacrylate) block polymers (BPs). Most significantly, the location of double-gyroid network phase window was found in ion-doped normal-tapered materials, and a similar window was not detectable in the corresponding non-tapered and inverse-tapered BPs. Additionally, the effective interaction parameters, χeff, were reduced substantially in the tapered materials in comparison with their non-tapered counterparts. Overall, this work demonstrates that tapering between polymer blocks provides unique control over BP morphologies and improves the material processability (due to lower χeff), potentially facilitating the development of future ion-conducting devices.

Electronically active block polymers based on π-conjugated macromolecules have been investigated for applications where nanostructured electrodes are of prime import; however, controlling the nanoscale order of these materials has proven challenging. Here, we demonstrate that diblock copolymers that utilize a non-conjugated radical polymer moiety as the electronically active block assemble into ordered thin-film nanostructures. Specifically, the diblock copolymer polydimethylsiloxane-b-poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate) (PDMS–PTMA) was synthesized via atom transfer radical polymerization to generate polymers with readily controlled molecular properties. Importantly, solvent annealing of the PDMS–PTMA thin films led to well-defined nanostructures with domain spacings of the order of ~30–40 nm.

The emergence of methyl-ammonium lead halide (MAPbX3) perovskites motivates the identification of unique properties giving rise to exceptional bulk transport properties, and identifying future materials with similar properties. Here, we propose that this “defect tolerance” emerges from fundamental electronic-structure properties, including the orbital character of the conduction and valence band extrema, the charge-carrier effective masses, and the static dielectric constant. We use MaterialsProject.org searches and detailed electronic-structure calculations to demonstrate these properties in other materials than MAPbX3. This framework of materials discovery may be applied more broadly, to accelerate discovery of new semiconductors based on emerging understanding of recent successes.

The role of substrate orientation on interface registry and nanocrystal shape has been investigated for epitaxial manganese oxide (Mn3O4) nanocrystals. Mn3O4 (101) nanoplatelets and (112)-orientated nanowires have been successfully deposited on (111) and (110) SrTiO3 (STO) substrates, respectively. Under higher magnifications, the (101) platelets were found to exhibit step-like growth, spiraling outward from a local dislocation site at the Mn3O4–STO interface. Selected area electron diffraction analysis from transmission electron microscope (TEM) was carried out to determine the in-plane edge directionalities of (101) and (112) Mn3O4. We found the (101) Mn3O4 orientation to exhibit a complex in-plane epitaxial relation of $[2\overline {31} ]$Mn3O4//[100]STO and an out-of-plane relation of $[\overline 1 01]$Mn3O4//$[\overline 1 11]$STO. Furthermore, lattice misorientations of 58° in-plane and 35° out-of-plane have been calculated, attributed to the shear caused by the spiral growth. For the (112) Mn3O4 nanowires, the TEM diffraction pattern indicates pyramidal cross-sections based along $[0\overline {11} ]$ STO. Subsequent calculations reveal that the (112) nanowires have their long axis (c-axis) such that [001]Mn3O4//[110]STO. Thus the nanowires grow preferentially along its longest axis giving rise to the observed shape and anisotropic nature.

Nanostructured carbon materials, especially activated carbon, carbon nanotubes, and graphene, have been widely studied for supercapacitor applications. To maximize the efficacy of these materials for electrochemical energy storage, a detailed understanding of the relationship between the nanostructure of these materials and their performance as supercapacitors is required. A fundamental structural parameter obtained from the Raman spectra of these materials, the in-plane correlation length or nanocrystalline domain size, is found to correlate with the electrochemical capacitance, regardless of other morphological features. This correlation for a common nanostructural characteristic is believed to be the first result of its kind to span several distinct nanostructured carbon morphologies, including graphene–carbon nanotubes hybrid materials, and may allow more effective nanoscale engineering of supercapacitor electrode materials.

Poly(acrylic acid) (PAA) and poly(vinylpyrrolidone) (PVP) are both highly safe synthetic polymers approved as pharmaceutical excipients. When their aqueous solutions are mixed, insoluble rigid complex is precipitated. On the other hand, if the dried PAA film was immersed in aqueous PVP solution, swollen PAA/PVP soft hydrogel was obtained. Heated drying of the gel afforded a transparent water-swellable film. The swellable PAA/PVP complex film exhibited favorable properties in medical use. If the film was put on a bleeding site, it swelled, and stuck to a hemorrhaging spot, and efficiently arrested bleeding. It could also prevent the adhesion formation by injured intestines.

The hybrid halide perovskites combine the low-cost processing characteristics of organic materials with the performance factors of inorganic compounds. Recently the power conversion efficiencies of perovskite photovoltaic solar cells have reached a respective value of ~20%. The charge transport properties were indirectly approximated in these compounds because of lack of available field-effect transistors (FETs). Here we report the fabrication and room-temperature operation of FETs based on the hybrid perovskites. We obtained balanced electron and hole transport with mobilities of ~1 cm2/Vs. We also found that the yield, as well as the operational and environmental stability of the fabricated transistors is limited.