A Hemispherical Image Sensor Array Fabricated with Organic Photomemory Transistors.

Hemispherical image sensors simplify lens designs, reduce optical aberrations, and improve image resolution for compact wide-field-of-view cameras. To achieve hemispherical image sensors, organic materials are promising candidates due to the following advantages: tunability of optoelectronic/spectral response and low-temperature low-cost processes. Here, a photolithographic process is developed to prepare a hemispherical image sensor array using organic thin film photomemory transistors with a density of 308 pixels per square centimeter. This design includes only one photomemory transistor as a single active pixel, in contrast to the conventional pixel architecture, consisting of select/readout/reset transistors and a photodiode. The organic photomemory transistor, comprising light-sensitive organic semiconductor and charge-trapping dielectric, is able to achieve a linear photoresponse (light intensity range, from 1 to 50 W m-2 ), along with a responsivity as high as 1.6 A W-1 (wavelength = 465 nm) for a dark current of 0.24 A m-2 (drain voltage = -1.5 V). These observed values represent the best responsivity for similar dark currents among all the reported hemispherical image sensor arrays to date. A transfer method was further developed that does not damage organic materials for hemispherical organic photomemory transistor arrays. These developed techniques are scalable and are amenable for other high-resolution 3D organic semiconductor devices.

Understanding the Mechanism of High Capacitance in Nickel Hexaaminobenzene-Based Conductive Metal-Organic Frameworks in Aqueous Electrolytes.

Recently, intrinsically conductive metal-organic frameworks (MOFs) have demonstrated promising performance in fast-charging energy storage applications and may outperform some current electrode materials (e.g., porous carbons) for supercapacitors in terms of both gravimetric and volumetric capacitance. In this report, we examine the mechanism of high capacitance in a nickel hexaaminobenzene-based MOF (NiHAB). Using a combination of in situ Raman and X-ray absorption spectroscopies, as well as detailed electrochemical studies in a series of aqueous electrolytes, we demonstrate that the charge storage mechanism is, in fact, a pH-dependent surface pseudocapacitance, and unlike typical inorganic systems, where transition metals change oxidation state during charge/discharge cycles, NiHAB redox activity is ligand-centered.

Deformable Organic Nanowire Field-Effect Transistors.

Deformable electronic devices that are impervious to mechanical influence when mounted on surfaces of dynamically changing soft matters have great potential for next-generation implantable bioelectronic devices. Here, deformable field-effect transistors (FETs) composed of single organic nanowires (NWs) as the semiconductor are presented. The NWs are composed of fused thiophene diketopyrrolopyrrole based polymer semiconductor and high-molecular-weight polyethylene oxide as both the molecular binder and deformability enhancer. The obtained transistors show high field-effect mobility >8 cm2 V-1 s-1 with poly(vinylidenefluoride-co-trifluoroethylene) polymer dielectric and can easily be deformed by applied strains (both 100% tensile and compressive strains). The electrical reliability and mechanical durability of the NWs can be significantly enhanced by forming serpentine-like structures of the NWs. Remarkably, the fully deformable NW FETs withstand 3D volume changes (>1700% and reverting back to original state) of a rubber balloon with constant current output, on the surface of which it is attached. The deformable transistors can robustly operate without noticeable degradation on a mechanically dynamic soft matter surface, e.g., a pulsating balloon (pulse rate: 40 min-1 (0.67 Hz) and 40% volume expansion) that mimics a beating heart, which underscores its potential for future biomedical applications.

Investigating Limiting Factors in Stretchable All-Carbon Transistors for Reliable Stretchable Electronics.

Stretchable form factors enable electronic devices to conform to irregular 3D structures, including soft and moving entities. Intrinsically stretchable devices have potential advantages of high surface coverage of active devices, improved durability, and reduced processing costs. This work describes intrinsically stretchable transistors composed of single-walled carbon nanotube (SWNT) electrodes and semiconductors and a dielectric that consists of a nonpolar elastomer. The use of a nonpolar elastomer dielectric enabled hysteresis-free device characteristics. Compared to devices on SiO2 dielectrics, stretchable devices with nonpolar dielectrics showed lower mobility in ambient conditions because of the absence of doping from water. The effect of a SWNT band gap on device characteristics was investigated by using different SWNT sources as the semiconductor. Large-band-gap SWNTs exhibited trap-limited behavior caused by the low capacitance of the dielectric. In contrast, high-current devices based on SWNTs with smaller band gaps were more limited by contact resistance. Of the tested SWNT sources, SWNTs with a maximum diameter of 1.5 nm performed the best, with a mobility of 15.4 cm2/Vs and an on/off ratio >103 for stretchable transistors. Large-band-gap devices showed increased sensitivity to strain because of a pronounced dependence on the dielectric thickness, whereas contact-limited devices showed substantially less strain dependence.

Universal Selective Dispersion of Semiconducting Carbon Nanotubes from Commercial Sources Using a Supramolecular Polymer.

Selective extraction of semiconducting carbon nanotubes is a key step in the production of high-performance, solution-processed electronics. Here, we describe the ability of a supramolecular sorting polymer to selectively disperse semiconducting carbon nanotubes from five commercial sources with diameters ranging from 0.7 to 2.2 nm. The sorting purity of the largest-diameter nanotubes (1.4 to 2.2 nm; from Tuball) was confirmed by short channel measurements to be 97.5%. Removing the sorting polymer by acid-induced disassembly increased the transistor mobility by 94 and 24% for medium-diameter and large-diameter carbon nanotubes, respectively. Among the tested single-walled nanotube sources, the highest transistor performance of 61 cm2/V·s and on/off ratio >104 were realized with arc discharge carbon nanotubes with a diameter range from 1.2 to 1.7 nm. The length and quality of nanotubes sorted from different sources is compared using measurements from atomic force microscopy and Raman spectroscopy. The transistor mobility is found to correlate with the G/D ratio extracted from the Raman spectra.

Highly stretchable polymer semiconductor films through the nanoconfinement effect.

Soft and conformable wearable electronics require stretchable semiconductors, but existing ones typically sacrifice charge transport mobility to achieve stretchability. We explore a concept based on the nanoconfinement of polymers to substantially improve the stretchability of polymer semiconductors, without affecting charge transport mobility. The increased polymer chain dynamics under nanoconfinement significantly reduces the modulus of the conjugated polymer and largely delays the onset of crack formation under strain. As a result, our fabricated semiconducting film can be stretched up to 100% strain without affecting mobility, retaining values comparable to that of amorphous silicon. The fully stretchable transistors exhibit high biaxial stretchability with minimal change in on current even when poked with a sharp object. We demonstrate a skinlike finger-wearable driver for a light-emitting diode.

Surpassing the Exciton Diffusion Limit in Single-Walled Carbon Nanotube Sensitized Solar Cells.

Semiconducting single-walled carbon nanotube (s-SWNT) light sensitized devices, such as infrared photodetectors and solar cells, have recently been widely reported. Despite their excellent individual electrical properties, efficient carrier transport from one carbon nanotube to another remains a fundamental challenge. Specifically, photovoltaic devices with active layers made from s-SWNTs have suffered from low efficiencies caused by three main challenges: the overwhelming presence of high-bandgap polymers in the films, the weak bandgap offset between the LUMO of the s-SWNTs and the acceptor C60, and the limited exciton diffusion length from one SWNT to another of around 5 nm that limits the carrier extraction efficiency. Herein, we employ a combination of processing and device architecture design strategies to address each of these transport challenges and fabricate photovoltaic devices with s-SWNT films well beyond the exciton diffusion limit of 5 nm. While our solution processing method minimizes the presence of undesired polymers in our active films, our interfacial designs led to a significant increase in current generation with the addition of a highly doped C60 layer (n-doped C60), resulting in increased carrier separation efficiency from the s-SWNTs films. We create a dense interconnected nanoporous mesh of s-SWNTs using solution shearing and infiltrate it with the acceptor C60. Thus, our final engineered bulk heterojunction allows carriers from deep within to be extracted by the C60 registering a 10-fold improvement in performance from our preliminary structures.

Direct Uniaxial Alignment of a Donor-Acceptor Semiconducting Polymer Using Single-Step Solution Shearing.

The alignment of organic semiconductors (OSCs) in the active layers of electronic devices can confer desirable properties, such as enhanced charge transport properties due to better ordering, charge transport anisotropy for reduced device cross-talk, and polarized light emission or absorption. The solution-based deposition of highly aligned small molecule OSCs has been widely demonstrated, but the alignment of polymeric OSCs in thin films deposited directly from solution has typically required surface templating or complex pre- or postdeposition processing. Therefore, single-step solution processing and the charge transport enhancement afforded by alignment continue to be attractive. We report here the use of solution shearing to tune the degree of alignment in poly(diketopyrrolopyrrole-terthiophene) thin films by controlling the coating speed. A maximum dichroic ratio of ∼7 was achieved on unpatterned substrates without any additional pre- or postdeposition processing. The degree of polymer alignment was found to be a competition between the shear alignment of polymer chains in solution and the complex thin film drying process. Contrary to previous reports, no charge transport anisotropy was observed because of the small crystallite size relative to the channel length, a meshlike morphology, and the likelihood of increased grain boundaries in the direction transverse to coating. In fact, the lack of aligned morphological structures, coupled with observed anisotropy in X-ray diffraction data, suggests the alignment of polymer molecules in both the crystalline and the amorphous regions of the films. The shear speed at which maximum dichroism is achieved can be controlled by altering deposition parameters such as temperature and substrate treatment. Modest changes in molecular weight showed negligible effects on alignment, while longer polymer alkyl side chains were found to reduce the degree of alignment. This work demonstrates that solution shearing can be used to tune polymer alignment in a one-step deposition process not requiring substrate patterning or any postdeposition treatment.

Hierarchical N-Doped Carbon as CO2 Adsorbent with High CO2 Selectivity from Rationally Designed Polypyrrole Precursor.

Carbon capture and sequestration from point sources is an important component in the CO2 emission mitigation portfolio. In particular, sorbents with both high capacity and selectivity are required for reducing the cost of carbon capture. Although physisorbents have the advantage of low energy consumption for regeneration, it remains a challenge to obtain both high capacity and sufficient CO2/N2 selectivity at the same time. Here, we report the controlled synthesis of a novel N-doped hierarchical carbon that exhibits record-high Henry's law CO2/N2 selectivity among physisorptive carbons while having a high CO2 adsorption capacity. Specifically, our synthesis involves the rational design of a modified pyrrole molecule that can co-assemble with the soft Pluronic template via hydrogen bonding and electrostatic interactions to give rise to mesopores followed by carbonization. The low-temperature carbonization and activation processes allow for the development of ultrasmall pores (d < 0.5 nm) and preservation of nitrogen moieties, essential for enhanced CO2 affinity. Furthermore, our described work provides a strategy to initiate developments of rationally designed porous conjugated polymer structures and carbon-based materials for various potential applications.

A chameleon-inspired stretchable electronic skin with interactive colour changing controlled by tactile sensing.

Some animals, such as the chameleon and cephalopod, have the remarkable capability to change their skin colour. This unique characteristic has long inspired scientists to develop materials and devices to mimic such a function. However, it requires the complex integration of stretchability, colour-changing and tactile sensing. Here we show an all-solution processed chameleon-inspired stretchable electronic skin (e-skin), in which the e-skin colour can easily be controlled through varying the applied pressure along with the applied pressure duration. As such, the e-skin's colour change can also be in turn utilized to distinguish the pressure applied. The integration of the stretchable, highly tunable resistive pressure sensor and the fully stretchable organic electrochromic device enables the demonstration of a stretchable electrochromically active e-skin with tactile-sensing control. This system will have wide range applications such as interactive wearable devices, artificial prosthetics and smart robots.

Ultrahigh Surface Area Three-Dimensional Porous Graphitic Carbon from Conjugated Polymeric Molecular Framework.

Porous graphitic carbon is essential for many applications such as energy storage devices, catalysts, and sorbents. However, current graphitic carbons are limited by low conductivity, low surface area, and ineffective pore structure. Here we report a scalable synthesis of porous graphitic carbons using a conjugated polymeric molecular framework as precursor. The multivalent cross-linker and rigid conjugated framework help to maintain micro- and mesoporous structures, while promoting graphitization during carbonization and chemical activation. The above unique design results in a class of highly graphitic carbons at temperature as low as 800 °C with record-high surface area (4073 m(2) g(-1)), large pore volume (2.26 cm(-3)), and hierarchical pore architecture. Such carbons simultaneously exhibit electrical conductivity >3 times more than activated carbons, very high electrochemical activity at high mass loading, and high stability, as demonstrated by supercapacitors and lithium-sulfur batteries with excellent performance. Moreover, the synthesis can be readily tuned to make a broad range of graphitic carbons with desired structures and compositions for many applications.