Triggering ZT to 0.40 by Engineering Orientation in One Polymeric Semiconductor.

Breaking the thermoelectric (TE) trade-off relationship is an important task for maximizing the TE performance of polymeric semiconductors. Existing efforts have focused on designing high-mobility semiconductors and achieving ordered molecular doping, ignoring the critical role of the molecular orientation during TE conversion. Herein, the achievement of ZT to 0.40 is reported by fine-tuning the molecular orientation of one diketopyrrolopyrrole (DPP)-based polymer (DPP-BTz). Films with bimodal molecular orientation yield superior doping efficiency by increasing the lamellar spacing and achieve increased splitting between the Fermi energy and the transport energy to enhance the thermopower. These factors contribute to the simultaneous improvement in the Seebeck coefficient and electrical conductivity in an unexpected manner. Importantly, the bimodal film exhibits a maximum power factor of up to 346 µW m-1 K-2 , >400% higher than that of unimodal films. These results demonstrate the great potential of molecular orientation engineering in polymeric semiconductors for developing state-of-the-art organic TE (OTE) materials.

Perfluoroalkylated alternating copolymer possessing solubility in fluorous liquids and imaging capabilities under high energy radiation.

A highly fluorinated alternating polymer, P(RFMi-St), possessing improved thermal properties and patterning capabilities over perfluoroalkyl polymethacrylates under high energy radiation was achieved with semi-perfluorododecyl maleimide (RFMi) and styrene (St). RFMi could be synthesised efficiently via a Mitsunobu reaction condition and copolymerised with St by free radical and reversible-deactivation radical polymerisation protocols. P(RFMi-St) showed a satisfactory glass-transition temperature (108 °C) and intermolecular cross-linking behaviour under electron-beam and commercially more important extreme UV (λ = 13.5 nm) irradiation. The exposed regions lost their solubility, resulting in the successful formation of mechanically non-deteriorated negative-tone images down to 50 nm. In addition, P(RFMi-St) could be solution-processed with chemically non-damaging fluorous liquids, which enabled the polymer to be applied effectively on top of an organic semiconductor layer as a dielectric material (dielectric constant 2.7) for the organic field-effect transistor fabrication.

Role of Multivalent Interactions in Dynamic-Template-Directed Assembly of Conjugated Polymers.

Dynamic-template-directed assembly is a promising method to enhance molecular ordering and electronic properties of solution-coated polymer semiconductor thin films over a large area. In this work, we establish that multicomponent dynamic templates of complementary chemistries can promote polymer crystallization through cooperative multivalent interactions. We investigate this phenomenon using a combination of templating substrates including a fluoropolymer, a hydrogen-bonded liquid, and an ionic liquid (IL). Template-dependent multiscale morphology is studied by a comprehensive set of characterization techniques to understand how introducing diverse chemical moieties modulates polymer assembly. Our results clearly confirm synergistic effects between components of complementary chemistries constituting the dynamic template. The relative degree of crystallinity is improved by 50-150% for films deposited on multicomponent dynamic templates compared to their neat constituents. In addition, macroscopic alignment is increased significantly (2-5 times) compared to single-component templates. As a result, highly anisotropic charge transport is observed with apparent hole mobilities up to 3.6 cm2 V-1 s-1. In contrast, such a synergistic effect is not observed when using a multicomponent dynamic template of comparable chemistries (i.e., IL and polymerized IL). We elucidate the origin of this synergistic effect by using attenuated total reflectance Fourier transform infrared spectroscopy and isothermal titration calorimetry. When the dynamic template comprises two or more components interacting with complementary binding sites on the conjugated polymer (CP) (esp. backbone vs side chain), the template-polymer interactions is significantly enhanced compared to the sum of single component contributions. These results provide valuable insights into surface-directed CP crystallization during large-area solution coating. Template dynamics is rarely studied and represents a new opportunity for guiding assembly of soft functional matter.

Tuning conformation, assembly, and charge transport properties of conjugated polymers by printing flow.

Intrachain charge transport is unique to conjugated polymers distinct from inorganic and small molecular semiconductors and is key to achieving high-performance organic electronics. Polymer backbone planarity and thin film morphology sensitively modulate intrachain charge transport. However, simple, generic nonsynthetic approaches for tuning backbone planarity and the ensuing multiscale assembly process do not exist. We first demonstrate that printing flow is capable of planarizing the originally twisted polymer backbone to substantially increase the conjugation length. This conformation change leads to a marked morphological transition from chiral, twinned domains to achiral, highly aligned morphology, hence a fourfold increase in charge carrier mobilities. We found a surprising mechanism that flow extinguishes a lyotropic twist-bend mesophase upon backbone planarization, leading to the observed morphology and electronic structure transitions.

Ion Gel Dynamic Templates for Large Modulation of Morphology and Charge Transport Properties of Solution-Coated Conjugated Polymer Thin Films.

Dynamic surfaces play a critical role in templating highly ordered complex structures in living systems but are rarely employed for directing assembly of synthetic functional materials. We design ion gel templates with widely tunable dynamics ( Tg) to template solution-coated conjugated polymers. We hypothesize that the ion gel expedites polymer nucleation by reconfiguring its surface to facilitate cooperative multivalent interactions with the conjugated polymer, validated using both experimental and computational approaches. Varying ion gel dynamics enables large modulation of alignment, molecular orientation, and crystallinity in templated polymer thin films. At the optimal conditions, ion-gel-templated films exhibit 55 times higher dichroic ratio (grazing incidence X-ray diffraction) and 49% increase in the relative degree of crystallinity compared to those templated by the neat polymer matrix. As a result, the maximum hole mobilities increase by factors of 4 and 11 along the π-π stacking and the backbone directions. Intriguingly, we observe a synergistic effect between the gel matrix and the ionic liquid that produces markedly enhanced templating effect than either component alone. Molecular dynamics simulations suggest that complementary multivalent interactions facilitated by template reconfigurability underlie the observed synergy. We further demonstrate field-effect transistors both templated and gated by ion gels with average mobility exceeding 7 cm2 V-1 s-1.

High-mobility, trap-free charge transport in conjugated polymer diodes.

Charge transport in conjugated polymer semiconductors has traditionally been thought to be limited to a low-mobility regime by pronounced energetic disorder. Much progress has recently been made in advancing carrier mobilities in field-effect transistors through developing low-disorder conjugated polymers. However, in diodes these polymers have to date not shown much improved mobilities, presumably reflecting the fact that in diodes lower carrier concentrations are available to fill up residual tail states in the density of states. Here, we show that the bulk charge transport in low-disorder polymers is limited by water-induced trap states and that their concentration can be dramatically reduced through incorporating small molecular additives into the polymer film. Upon incorporation of the additives we achieve space-charge limited current characteristics that resemble molecular single crystals such as rubrene with high, trap-free SCLC mobilities up to 0.2 cm2/Vs and a width of the residual tail state distribution comparable to kBT.

Electroluminescence from Solution-Processed Pinhole-Free Nanometer-Thickness Layers of Conjugated Polymers.

We report the formation of robust, reproducible, pinhole-free, thin layers of fluorinated polyfluorene conjugated copolymers on a range of polymeric underlayers via a simple solution processing method. This is driven by the different characters of the fluorinated and nonfluorinated sections of these polymers. Photothermal deflection spectroscopy is used to determine that these layers are 1-2 nm thick, corresponding to a molecularly thin layer. Evidence that these layers are continuous and pinhole-free is provided by electroluminescence data from polymer LED devices that incorporate these layers within the stacked LED structure. These reveal, remarkably, light emission solely from these molecularly thin layers.

Electroluminescent Pressure-Sensing Displays.

Simultaneous sensing and visualization of pressure provides a useful platform to obtain information about a pressurizing object, but the fabrication of such interactive displays at the single-device level remains challenging. Here, we present a pressure responsive electroluminescent (EL) display that allows for both sensing and visualization of pressure. Our device is based on a two-terminal capacitor with six constituent layers: top electrode/insulator/hole injection layer/emissive layer/electron transport layer/bottom electrode. Light emission upon exposure to an alternating current field between two electrodes is controlled by the capacitance change of the insulator arising from the pressure applied on top. Besides capacitive pressure sensing, our EL display allows for direct visualization of the static and dynamic information of position, shape, and size of a pressurizing object on a single-device platform. Monitoring the pressurized area of an elastomeric hemisphere on a device by EL enables quantitative estimation of the Young's modulus of the elastomer, offering a new and facile characterization method for the mechanical properties of soft materials.

Effect of Donor Building Blocks on the Charge-Transfer Characteristics of Diketopyrrolopyrrole-Based Donor-Acceptor-Type Semiconducting Copolymers.

We investigate the effect of donor (D) building blocks on the charge transportation characteristics of donor (D)-acceptor (A)-type semiconducting copolymers with alternating electron-donating and electron-accepting units to provide a basis for the rational design of high-performance semiconducting polymers. For this purpose, we studied three different diketopyrrolopyrrole (DPP)-based semiconducting copolymers comprising a common dithienyl-DPP [3,6-dithienyl-2,5-diketopyrrolo(3,4-c)pyrrole] and variable donor moieties: phenylene (P)-PDPPTPT, thiophene (T)-PDPP3T, and thienothiophene (TT)-PDPP2T-TT. Structural analysis using grazing incidence X-ray diffraction indicates that all three DPP-based copolymer films have edge-on phases but poor crystallinity of the films, except the PDPP2T-TT copolymer with branched alkyl side chains that are relatively long. The electrical measurements show that the DPP-based copolymer with a TT donor unit has the highest field-effect mobility value of 0.30 cm2/V s. To understand the role of the donor units in DPP-based D-A copolymers, further insight into the charge transportation behavior is realized by analyzing the temperature-dependent transfer curves of the DPP semiconducting copolymer-based field-effect transistors using the Gaussian disorder model. Compared to the DPP-based D-A-type semiconducting copolymer with a P-moiety and shorter-branched alkyl side chains that exhibit a broad distribution in the density of localized states (DOS) and a higher thermal-activated energy for charge hopping, the DPP copolymers with a TT-moiety and longer branched side chains have the narrowest DOS, the lowest activation energy, and thus the highest hole mobility. These results suggest that the higher mobilities obtained from PDPP2T-TT with a TT donor unit can be attributed to the suppressed DOS distribution near the transport level, which mainly originates from the narrowest energy band gap tuned with the orbital couplings of the DPP acceptor and TT donor units.

Integration of Flexible and Microscale Organic Nonvolatile Resistive Memory Devices Using Orthogonal Photolithography.

We present the integration of flexible and microscale organic nonvolatile resistive memory devices fabricated in a cross-bar array structure on plastic substrates. This microscale integration was made via orthogonal photolithography method using fluorinated photoresist and solvents and was achieved without causing damage to the underlying organic memory materials. Our flexible microscale organic devices exhibited high ON/OFF ratio (I(ON/I(OFF) > 10(4)) under bending conditions. In addition, the ON and OFF states of our flexible and microscale memory devices were maintained for 10,000 seconds without any serious degradation.

Charge-Transport Anisotropy in a Uniaxially Aligned Diketopyrrolopyrrole-Based Copolymer.

Aligned films of a semiconducting DPP-based copolymer exhibit highly anisotropic charge transport with a band-like temperature dependence along the alignment direction and hole mobilities of up to 6.7 cm(2) V(-1) s(-1) . X-ray diffraction measurements reveal an exceptional degree of in-plane alignment, high crystallinity, and a dominant face-on orientation of the polymer backbones. The surprising charge-transport properties are interpreted in a tie-chain model consistent with anisotropic activation energies.

Enabling high-mobility, ambipolar charge-transport in a DPP-benzotriazole copolymer by side-chain engineering.

In this article we discuss the synthesis of four new low band-gap co-polymers based on the diketopyrrolopyrrole (DPP) and benzotriazole (BTZ) monomer unit. We demonstrate that the BTZ unit allows for additional solubilizing side-chains on the co-monomer and show that the introduction of a linear side-chain on the DPP-unit leads to an increase in thin-film order and charge-carrier mobility if a sufficiently solubilizing, branched, side chain is attached to the BTZ. We compare two different synthetic routes, direct arylation and Suzuki-polycondensation, by a direct comparison of polymers obtained via the two routes and show that direct arylation produces polymers with lower electrical performance which we attribute to a higher density of chain Furthermore we demonstrate that a polymer utilizing this design motif and synthesized via Suzuki-polycondensation ((l-C18)-DPP-(b-C17)-BTZ) exhibits exceptionally high and near balanced average electron and hole mobilities >2 cm2 V-1 s-1 which are among the highest, robustly extracted mobility values reported for DPP copolymers in a top-gate configuration to date. Our results demonstrate clearly that linear side chain substitution of the DPP unit together with co-monomers that allow for the use of sufficiently long or branched solubilizing side chains can be an attractive design motif for solution processable, high mobility DPP copolymers.

Extremely bright full color alternating current electroluminescence of solution-blended fluorescent polymers with self-assembled block copolymer micelles.

Electroluminescent (EL) devices operating at alternating current (AC) electricity have been of great interest due to not only their unique light emitting mechanism of carrier generation and recombination but also their great potential for applications in displays, sensors, and lighting. Despite great success of AC-EL devices, most device properties are far from real implementation. In particular, the current state-of-the art brightness of the solution-processed AC-EL devices is a few hundred candela per square meter (cd m(-2)) and most of the works have been devoted to red and white emission. In this manuscript, we report extremely bright full color polymer AC-EL devices with brightness of approximately 2300, 6000, and 5000 cd m(-2) for blue (B), green (G), and red (R) emission, respectively. The high brightness of blue emission was attributed to individually networked multiwalled carbon nanotubes (MWNTs) for the facile carrier injection as well as self-assembled block copolymer micelles for suppression of interchain nonradiative energy quenching. In addition, effective FRET from a solution-blended thin film of B-G and B-G-R fluorescent polymers led to very bright green and red EL under AC voltage, respectively. The solution-processed AC-EL device also worked properly with vacuum-free Ag paste on a mechanically flexible polymer substrate. Finally, we successfully demonstrated the long-term operation reliability of our AC-EL device for over 15 h.