Lithium Phenolate Complexes with a Pyridine‐Containing Polymer for Solution‐Processable Electron Injection Layers in PLEDs

A series of (vinylphenyl)pyridine‐based polymer binders, PVPh2Py, PVPh3Py, and PVPh4Py, are designed and synthesized and it is found that mixtures of Liq and the polymers exhibit superior electron injection characteristics as ultrathin (1.6 nm) electron injection layer (EIL) films. They are comparable to those of EILs composed only of Liq. The addition of the polymers does not deteriorate the performance of Liq EILs. Additionally, when the EIL thickness is increased from 1.6 nm to 16 nm, the driving voltages increase and the external quantum efficiencies decrease. The increase in the voltage and decrease in the EQE are suppressed in the device with mixed EILs compared to those observed for the device composed of 100 wt% Liq. Furthermore, the position of the nitrogen in the pyridine ring is considered to influence the electron transport properties of the EILs. The mixing PVPh4Py with Liq improves the driving voltage of the fabricated devices, even with a thick mixed EIL. This reduced dependence of the performance of EILs on their thickness will be advantageous for the coating of large areas using solution processes.     

Stable Light-Emitting Electrochemical Cells Using Hyperbranched Polymer Electrolyte

The choice of an adequate electrolyte is a fundamental aspect in polymer light-emitting electrochemical cells (PLECs) as it provides the in situ electrochemical doping and influences the performance of these devices. In this study, a hyperbranched polymer (Hybrane DEO750 8500) blended with a Li salt is used as a novel electrolyte in state-of-the-art Super Yellow (a polyphenylenevinylene) based LECs. Due to the desirable properties of the hyperbranched polymer and the homogeneous and smooth films that it forms with the emitting polymer, PLEC with excellent electroluminescent properties are obtained using a pulsed current bias scheme. The devices are very stable, with lifetimes in excess of 2000 h with initial luminance values above 450 cd m⁻², a peak efficiency of 12.6 lm W⁻¹, and sub-minute turn-on times. The stability of the devices is also studied by measuring the photoluminescence (PL) of the semiconductor during electroluminescent operation. The findings suggest that it is possible to observe the quenching of the PL in vertically stacked devices due to the advancement of the doped fronts in the film and an immediate PL recovery when the bias is removed.     

Activation Energy Spectra: Insights into Transport Limitations of Organic Semiconductors and Photovoltaic Cells

Some mechanisms of charge transport in organic semiconductors and organic photovoltaic (OPV) cells can be distinguished by their predicted change in activation energy for the current, E_a, versus applied field, F. E_a versus F is measured first in pure films of commercially available regioregular poly(3‐hexylthiophene) (P3HT) and in the same P3HT treated to reduce its charged defect density. The former shows a Poole–Frenkel (PF)‐like decrease in E_a at low F, which then plateaus at higher F. The low defect material does not exhibit PF behavior and E_a remains approximately constant. Upon addition of [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM), however, both materials show a large increase in E_a and exhibit PF‐like behavior over the entire field range. These results are explained with a previously proposed model of transport that considers both the localized random disorder in the energy levels and the long‐range electrostatic fluctuations resulting from charged defects. Activation energy spectra in working OPV cells show that the current is injection‐limited over most of the voltage range but becomes transport‐limited, with a large peak in E_a, near the open circuit photovoltage. This causes a decrease in fill factor, which may be a general limitation in such solar cells.     

Polylactic acid as a biodegradable material for all-solution-processed organic electronic devices

In this paper we report on the fabrication of spin-coated biodegradable polylactic acid (PLA) thin films to be used as substrates for the realisation of all-solution-processed organic electronic devices. The full mechanical and electrical characterisation of these substrates shows that they exhibit good mechanical and dielectric properties and are therefore suitable for the fabrication of disposable electronics. To demonstrate practically the functionality of such PLA thin films, organic electronic devices were realised on the top of them, exclusively by means of solution-process fabrication techniques and in particular inkjet-printing. Also, a photonic curing procedure is here presented as a means for sintering the conductive inks without heating up the PLA substrates. Two types of organic transistors were fabricated on the top of PLA: organic field-effect transistors (OFETs), where the PLA film was used not only as a substrate but also as the gate dielectric, and all-inkjet-printed organic electrochemical transistors (OECTs). The second typology of transistors exhibited one of the highest transconductance reported so far in the literature (up to 2.75 mS). This study opens an avenue for the fabrication of disposable, low-cost organic electronic devices.     

Electron correlation effects on polarons recombination in coupled polymer chains

The recombination dynamics of singlet and triplet oppositely charged polarons under the influence of electron–electron (e–e) interactions in coupled polymer chains are investigated using a multi-configurational time-dependent Hartree–Fock (MCTDHF) method. During recombination processes, singlet and triplet intrachain excitons are important products. By calculating the yields of the singlet and triplet intrachain excitons as a function of the on-site and long-range e–e interactions, it is found that the yields of the singlet and triplet intrachain excitons both decrease with increasing on-site e–e interactions. On the other hand, as the long-range e–e interactions increase, the yields of singlet intrachain excitons initially increase and then maintain a constant value, while the yields of the triplet intrachain excitons decrease. Our results show that the long-range e–e interaction is of fundamental importance and improves the luminescence efficiency in coupled polymer chains. Finally, the influence of the polymer chain length on the yields of singlet and triplet intrachain excitons is discussed.     

Synthesis and photovoltaic properties of D-A copolymers based on alkylthio-thiophene or alkylthio-selenophene-BDT donor unit and DPP acceptor unit

Two new 2D-conjugated D-A copolymers, PBDTT-S-DPP and PBDTSe-S-DPP, based on benzodithiophene (BDT) donor unit with alkylthio-thiophene or alkylthio-selenophene conjugated side chains and 2,5-bis(2-butyloctyl)-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione) (DPP) acceptor unit, were synthesized for the application as donor materials in polymer solar cells (PSCs). The two polymers were characterized by absorption spectroscopy, cyclic voltammetry, thermogravimetric analysis, theoretical calculation with density functional theory, X-ray diffraction and photovoltaic measurements. The results show that the alkylthio-thiophene/selenophene side groups on BDT unit and intramolecular hydrogen bonding interaction in DPP acceptor unit play important roles in affecting the absorption, HOMO energy levels, molecular planarity and the crystallinity of the polymers. The PSCs based on PBDTT-S-DPP or PBDTSe-S-DPP as donor and PC₇₁BM as acceptor demonstrate power conversion efficiency (PCE) of 5.62% and 5.01%, with relatively higher V_oc of 0.79 V and 0.76 V, respectively.     

An accurate method to determine the through-plane electrical conductivity and to study transport properties in film samples

The through-plane conductivity of a film sample is critically important because it largely affects the performance of batteries, capacitors, and thermoelectric devices. In this study, we developed a modified four-probe through-plane electrical conductivity measurement method using a coaxial structure. This method is general and works for free-standing film samples. We studied different samples including a steel sheet, highly oriented pyrolytic graphite, and conducting polymers. We confirmed metallic transportation in the steel sheet and hopping transportation in graphite in the through-plane direction by conducting low temperature measurements at 100 K. In the case of a conducting polymer poly(3,4-ethylenedioxythiophene)/polystyrene sulfonate, the conductivity anisotropic ratio decreases with increasing in-plane conductivity. Temperature dependent measurements show two distinct activation energy regimes in the through-plane direction in PEDOT/PSS but almost no change in the in-plane electrical conductivity activation energy. This could be due to additional carrier paths that occur through the more disordered region (the PSS-rich region) in the through-plane direction. We also examined the Meyer–Neldel rule in PEDOT/PSS and concluded that PEDOT/PSS follows the anti-Meyer–Neldel rule, likely due to the high carrier density in the film.     

Vitamins as Active Agents for Highly Emissive and Stable Nanostructured Halide Perovskite Inks and 3D Composites Fabricated by Additive Manufacturing

The use of non-toxic and low-cost vitamins like α-tocopherol (α-TCP, vitamin E) to improve the photophysical properties and stability of perovskite nanocrystals (PNCs), through post-synthetic ligand surface passivation, is demonstrated for the first time. Especially interesting is its effect on CsPbI₃ the most unstable inorganic PNC. Adding α-TCP produces that the photoluminescence quantum yield (PLQY) of freshly prepared and aged PNCs achieves values of ≈98% and 100%, respectively. After storing 2 months under ambient air and 60% relative humidity, PLQY is maintained at 85% and 67%, respectively. α-TCP restores the PL features of aged CsPbI₃ PNCs, and mediates the radiative recombination channels by reducing surface defects. In addition, the combination of α-TCP and PNCs facilitates the chemical formulation to prepare PNCs-acrylic polymer composites processable by additive manufacturing. This enables the development of complex shaped parts with improved luminescent features and long-term stability for 4 months, which is not possible for non-modified PNCs. A PLQY ≈92% is reached in the 3D printed polymer/PNC composite, the highest value obtained for a red-emitting composite solid until now as far as it is known. The passivation shell provided by α-TCP makes that PNCs inks do not suffer any degradation process avoiding the contact with the environment and preserve their properties after reacting with polar monomers during composite polymerization.     

State‐of‐the‐Art Neutral Tint Multichromophoric Polymers for High‐Contrast See‐Through Electrochromic Devices

Two new multichromophoric electrochromic polymers featuring a conjugated EDOT/ProDOT copolymer backbone (PXDOT) and a reversible Weitz‐type redox active small molecule electrochrome (WTE) tethered to the conjugated chain are reported here. The careful design of the WTEs provides a highly reversible redox behavior with a colorless red switching that complements the colorless blue switching of the conjugated backbone. Subtractive color mixing successfully provides high performing solution processable polymeric layers with colorless neutral tint switchable limiting states for application in see‐through electrochromic devices. Design, synthesis, comprehensive chemical and spectroelectrochemical characterization as well as the preparation of a proof‐of‐concept device are discussed.     

Open‐Shell Donor–Acceptor Conjugated Polymers with High Electrical Conductivity

Conductive polymers largely derive their electronic functionality from chemical doping, processes by which redox and charge‐transfer reactions form mobile carriers. While decades of research have demonstrated fundamentally new technologies that merge the unique functionality of these materials with the chemical versatility of macromolecules, doping and the resultant material properties are not ideal for many applications. Here, it is demonstrated that open‐shell conjugated polymers comprised of alternating cyclopentadithiophene and thiadiazoloquinoxaline units can achieve high electrical conductivities in their native “undoped” form. Spectroscopic, electrochemical, electron paramagnetic resonance, and magnetic susceptibility measurements demonstrate that this donor–acceptor architecture promotes very narrow bandgaps, strong electronic correlations, high‐spin ground states, and long‐range π‐delocalization. A comparative study of structural variants and processing methodologies demonstrates that the conductivity can be tuned up to 8.18 S cm^?1. This exceeds other neutral narrow bandgap conjugated polymers, many doped polymers, radical conductors, and is comparable to commercial grades of poly(styrene‐sulfonate)‐doped poly(3,4‐ethylenedioxythiophene). X‐ray and morphological studies trace the high conductivity to rigid backbone conformations emanating from strong π‐interactions and long‐range ordered structures formed through self‐organization that lead to a network of delocalized open‐shell sites in electronic communication. The results offer a new platform for the transport of charge in molecular systems.