Molecular Engineering of a Donor-Acceptor Polymer To Realize Single Band Absorption toward a Red-Selective Thin-Film Organic Photodiode.

Herein, we explore the strategy of realizing a red-selective thin-film organic photodiode (OPD) by synthesizing a new copolymer with a highly selective red-absorption feature. PCZ-Th-DPP, with phenanthrocarbazole (PCZ) and diketopyrrolopyrrole (DPP) as donor and acceptor units, respectively, was strategically designed/synthesized based on a time-dependent density functional theory calculation, which predicted the significant suppression of the band II absorption of PCZ-Th-DPP due to the extremely efficient intramolecular charge transfer. We demonstrate that the synthesized PCZ-Th-DPP exhibits not only a high absorption coefficient within the red-selective band I region, as theoretically predicted, but also a preferential face-on intermolecular structure in the thin-film state, which is beneficial for vertical charge extraction as an outcome of a glancing incidence X-ray diffraction study. By employing PCZ-Th-DPP as a photoactive layer of Schottky OPD, to fully match its absorption characteristic to the spectral response of the red-selective OPD, we demonstrate a genuine red-selective specific detectivity in the order of 1012 Jones while maintaining a thin active layer thickness of ∼300 nm. This work demonstrates the possibility of realizing a full color image sensor with a synthetic approach to the constituting active layers without optical manipulation.

Doping-Dedoping Interplay to Realize Patterned/Stacked All-Polymer Optoelectronic Devices.

One of the remaining keys to the success of polymer electronics is the ability to systematically pattern/stack polymer semiconductors with high precision. This paper reports the precise patterning and stacking of various polymer semiconductors with the assistance of a molecular oxidizing agent and reducing agent for donor and acceptor semiconductors, respectively. Such doping-induced solubility control methods have been previously well developed; however, practical applications to various optoelectronic devices have been limited. To pattern/stack various polymers in various dimensions, it is important to carefully design not only the doping method for desolubilizing polymer semiconductors but also the dedoping method for recovering the genuine characteristics of each polymer semiconductor. Based on a systematic approach for such a doping-dedoping interplay, various high-performance optoelectronic devices are demonstrated: (1) all-polymer complementary inverter pattern with a high gain of 176, (2) all-polymer planar heterojunction photodiode with green-selective nature and high specific detectivity over 1012 Jones, and (3) all-polymer ambipolar transistor pattern with balanced hole and electron mobilities. The results of the study indicate the potential of practical application of the doping-dedoping interplay to lateral/vertical patterning of different polymer semiconductors with high precision.

Reactive Dedoping of Polymer Semiconductors To Boost Self-Powered Schottky Diode Performances.

A facile and strategic junction tuning technology is reported to boost self-powered organic Schottky photodiode (OPD) performances by synergetic contributions of reactive dedoping effects. It is shown that dedoping poly(3-hexylthiophene-2,5-diyl) (P3HT) films with 1-propylamine (PA) solution significantly reduces not only acceptor-defect density but also intrinsic doping level, leading to dramatically enlarged depletion width of metal/polymer Schottky junctions, as confirmed by ultraviolet photoelectron spectroscopy and Mott-Schottky junction analyses. As a result, whole penetration regions of photons corresponding to absorption bands of P3HT can be fully covered by the depletion region of Schottky junctions, even without the assistance of external electric fields. In addition, it is shown that non-solvent exposure effects of PA dedoping further enable lower paracrystalline disorder and, thus, higher charge carrier mobility, by means of grazing incidence X-ray diffraction, field-effect mobility, and space-charge-limited current analyses. As a result of such synergetic advantages of the PA dedoping method, non-power-driven green-selective OPDs were demonstrated with a high specific detectivity exceeding 6 × 1012 Jones and a low noise-equivalent power of 5.05 × 10-14 W Hz-0.5. Together with a fast temporal response of 26.9 µs and a wide linear dynamic range of 201 dB, the possibility of realizing non-power-driven, near-ideal optimization of solution-processed OPDs with a facile dedoping method is demonstrated.

Polyvinyl alcohol covalently grafted CNT for free-standing, flexible, and high-performance thermoelectric generator film.

We introduce a strategic approach to synthesize covalntly cross-linked carbon nanotube (CNT)-polymer nanocomposites, which can be applied as a free-standing and flexible organic thermoelectric generator film. Esterification of polyvinyl alcohol (PVA) to render PVA-COOH followed by an amide reaction with single-walled CNTs (SWCNTs) functionalized with amino groups (SWCNT-NH2) yielded a covalently grafted PVA/SWCNT composite film with an excellent dispersion of SWCNTs within the polymer matrix as confirmed using Fourier-transform infrared spectroscopy and scanning electron microscopy. This amide reaction could be further optimized with the addition of a small amount of Triton™ X-100, which resulted in a better dispersion of SWCNT prior to the amide condensation reaction. Consequently, a covalently cross-linked PVA/SWCNT composite film showed better Seebeck coefficients than those of previously reported non-covalently, physically wrapped polymer/CNT composite films, resulting in a high power factor up to 275 µW m-1 K-2. Furthermore, a covalent amide-linking between PVA and SWCNT yielded a free-standing film (30 × 30 mm) with excellent flexibility and notable shelf stability as confirmed by negligible changes in thermoelectric parameters after bending test for 10 000 times with a bending radius of 2 mm and also shelf stability test in ambient condition without any passivation layer for 30 d.

Facile Tuning the Detection Spectrum of Organic Thin Film Photodiode via Selective Exciton Activation.

Here, we introduce a method of tuning the high-detectivity spectra of the organic photodiode (OPD) to fabricate a thin-film filter-less full-color image sensor. The strategically introduced PIN junction enables a selective activation of excitons generated from the photons with low extinction coefficient in the active layer such that the separated holes/electrons can contribute to the external current. In addition, we show that a well-defined PIN junction blocks the injection of nonallowed charge carriers, leading to very low dark current and near-ideal diode characteristics. Consequently, the high specific detectivity over 1.0 × 1012 Jones are observed from R/G/B-selective thin-film OPDs.

Spatial Confinement of the Optical Sensitizer to Realize a Thin Film Organic Photodetector with High Detectivity and Thermal Stability.

A thin film planar heterojunction organic photodetector (PHJ-OPD) is demonstrated. Different from a conventional sensitizer-doped photodetector, the limited spatial distribution of sensitizer in a PHJ-OPD enables significantly reduced thickness of the active layer without allowing the formation of unnecessary trap sites and electron percolation pathways. As a result, peak external quantum efficiency (EQE) of 120 700% and detectivity over 1013 Jones are demonstrated with thin active layer thickness of 150 nm, which can be a significant benefit for high-resolution image sensor application. Furthermore, the operating voltage can be decreased to -5 V while maintaining high detectivity over 1012 Jones. Remarkable thermal stability is also observed with minor change in detectivity for 2 h of continuous operation at 60 °C due to morphological robustness of PHJ. This work opens up a possibility of using a thin film PHJ-OPD as a key unit of high-resolution image sensor.

Synergetic Evolution of Diketopyrrolopyrrole-Based Polymeric Semiconductor for High Reproducibility and Performance: Random Copolymerization of Similarly Shaped Building Blocks.

A new random copolymer consisting of similarly shaped donor-acceptor building blocks of diketopyrrolopyrrole-selenophene-vinylene-selenophene (DPP-SVS) and DPP-thiophene-vinylene-thiophene (DPP-TVT) is designed and synthesized. The resulting P-DPP-SVS(5)-TVT(5) with an equal molecular ratio of the two building blocks produced significantly enhanced solubility when compared to that of the two homopolymers, PDPP-SVS and PDPP-TVT. More importantly, despite the maximum segmental randomness of the PDPP-SVS(5)-TVT(5) copolymer, its crystalline perfectness and preferential orientation are outstanding, even similar to those of the homopolymers thanks to the similarity of the two building blocks. This unique property produces a high charge carrier mobility of 1.23 cm2 V-1 s-1 of PDPP-SVS(5)-TVT(5), as determined from polymer field-effect transistor (PFET) measurements. The high solubility of PDPP-SVS(5)-TVT(5) promotes formulation of high-viscosity solutions which could be successfully processed to fabricate large-areal PFETs onto hydrophobically treated 4 in. wafers. A total of 269 individual PFETs are fabricated. These devices exhibit extremely narrow device-to-device deviations without a single failure and demonstrate an average charge carrier mobility of 0.66 cm2 V-1 s-1 with a standard deviation of 0.064. This is the first study to report on successfully realizing large-areal reproducibility of high-mobility polymeric semiconductors.

Morphology-Driven High-Performance Polymer Transistor-based Ammonia Gas Sensor.

Developing high-performance gas sensors based on polymer field-effect transistors (PFETs) requires enhancing gas-capture abilities of polymer semiconductors without compromising their high charge carrier mobility. In this work, cohesive energies of polymer semiconductors were tuned by strategically inserting buffer layers, which resulted in dramatically different semiconductor surface morphologies. Elucidating morphological and structural properties of polymer semiconductor films in conjunction with FET studies revealed that surface morphologies containing large two-dimensional crystalline domains were optimal for achieving high surface areas and creating percolation pathways for charge carriers. Ammonia molecules with electron lone pairs adsorbed on the surface of conjugated semiconductors can serve as efficient trapping centers, which negatively shift transfer curves for p-type PFETs. Therefore, morphology optimization of polymer semiconductors enhances their gas sensing abilities toward ammonia, leading to a facile method of manufacturing high-performance gas sensors.

High Charge-Carrier Mobility of 2.5 cm(2) V(-1) s(-1) from a Water-Borne Colloid of a Polymeric Semiconductor via Smart Surfactant Engineering.

Semiconducting polymer nanoparticles dispersed in water are synthesized by a novel method utilizing non-ionic surfactants. By developing a smart surfactant engineering technique involving a selective post-removal process of surfactants, an unprecedentedly high mobility of 2.51 cm(2) V(-1) s(-1) from a water-borne colloid is demonstrated for the first time.

Thin Film Transistor Gas Sensors Incorporating High-Mobility Diketopyrrolopyrole-Based Polymeric Semiconductor Doped with Graphene Oxide.

In this work, we fabricated a diketopyrrolopyrole-based donor-acceptor copolymer composite film. This is a high-mobility semiconductor component with a functionalized-graphene-oxide (GO) gas-adsorbing dopant, used as an active layer in gas-sensing organic-field-effect transistor (OFET) devices. The GO content of the composite film was carefully controlled so that the crystalline orientation of the semiconducting polymer could be conserved, without compromising its gas-adsorbing ability. The resulting optimized device exhibited high mobility (>1 cm(2) V(-1) s(-1)) and revealed sensitive response during programmed exposure to various polar organic molecules (i.e., ethanol, acetone, and acetonitrile). This can be attributed to the high mobility of polymeric semiconductors, and also to their high surface-to-volume ratio of GO. The operating mechanism of the gas sensing GO-OFET is fully discussed in conjunction with charge-carrier trap theory. It was found that each transistor parameter (e.g., mobility, threshold voltage), responds independently to each gas molecule, which enables high selectivity of GO-OFETs for various gases. Furthermore, we also demonstrated practical GO-OFET devices that operated at low voltage (<1.5 V), and which successfully responded to gas exposure.