Donor-Acceptor Copolymer with a Linear Backbone Induced Ordered and Robust Doping Morphology for Efficient and Stable Organic Electrochemical Devices.

Donor (D)-acceptor (A) copolymer-based organic mixed ionic-electronic conductors (OMIECs) exhibit intrinsic environmental stability for they have tailored energy levels. However, their figure-of-merit (µC*) is still falling behind the D-D polymers because of morphology deterioration during the electrochemical doping process. Herein, we developed two D-A copolymers with precisely regulated backbone curvature, namely PTBT-P and PTTBT-P. Compared to the curved PTBT-P and previously reported copolymers, PTTBT-P better keeps its backbone linear, leading to a long-range ordered doping morphology, which is revealed by the in operando X-ray technique. This optimized doping morphology enables a significantly improved operando charge mobility (µ) of 2.44 cm2 V-1 s-1 and a µC* value of 342 F cm-1 V-1 s-1, one of the highest values in D-A copolymer based on OECTs. Besides, we fabricated PTTBT-P-based electrochemical random-access memories and achieved ideal and robust conductance modulation. This study highlights the critical role of backbone curvature control in the optimization of doping morphology for efficient and robust organic electrochemical devices.

A Versatile and Low-Cost Polymer Donor Based on 4-Chlorothiazole for Highly Efficient Polymer Solar Cells.

Benefiting from the emergence of narrow-band-gap small-molecule acceptors (SMAs), especially "Y" series, the power conversion efficiency (PCE) of polymer solar cells (PSCs) is rapidly improved. However, polymer donors with high efficiency, easy synthesis, and good universality are relatively scarce except PBDB-TF and D18. Herein, two polymer donors are designed and synthesized based on 4-chlorothiazole derivatives with simple structures, namely PTz3Cl and PBTTz3Cl. The OSCs based on PBTTz3Cl with slightly weaker intermolecular forces in comparison to PTz3Cl exhibits a decent PCE of 18.38% in blending with SMA L8-BO, owing to its strong donor/acceptor interaction with L8-BO, which shapes suitable phase separation morphology. Further research finds that PBTTz3Cl can exhibit excellent photovoltaic performances with various SMA materials, highlighting its universality. Based on this, ternary PSCs are designed where BTP-eC9 is introduced as a guest into the PBTTz3Cl:L8-BO host system. Thanks to further optimal blend morphology and more balanced charge transport, the PCE is improved up to 19.12%, which is among the highest values for PSCs. This work provides a new design of low-cost electron-deficient units for constructing highly versatile, high-performance polymer donors.

Terpolymer Donor with Inside Alkyl Substituents on Thiophene π-Bridges toward Thiazolothiazole A2 -Unit Enables 18.21% Efficiency of Polymer Solar Cells.

PM6 is a widely used D-A copolymer donor in the polymer solar cells (PSCs). Incorporating second electron-withdrawing (A2 ) units into PM6 backbone by ternary D-A1 -D-A2 random copolymerization strategy is an effective approach to further improve its photovoltaic performance. Here, the authors synthesize the PM6-based terpolymers by introducing thiazolothiazole as the A2 units connecting with thiophene π-bridges attaching alkyl substituent towards the A2 unit (PMT-CT) or towards D-unit (PMT-FT), and study the effect of the alkyl substituent position on the photovoltaic performance of them. Two terpolymers PMT-FT-10 and PMT-CT-10 are obtained by incorporating 10% A2 units in the terpolymers. The film of PMT-CT-10 shows slightly up-shifted highest occupied molecular orbital (HOMO) energy levels while better co-planar structure than that of PMT-FT-10. Meanwhile, the PMT-CT-10:Y6 blend film exhibits better molecular packing properties, more proper phase separation and more balanced hole and electron mobilities, which are beneficial to more efficient exciton dissociation, efficient charge transport and weaker bimolecular recombination. Consequently, the PMT-CT-10 based PSCs obtain the highest power conversion efficiency of 18.21%. The results indicate that side chain position on the thiophene π-bridges influence the device performance of the terpolymer donors, and PMT-CT-10 is a high efficiency polymer donor for the PSCs.

Electron-deficient TVT unit-based D-A polymer donor for high-efficiency thick-film OSCs.

As the power conversion efficiencies of organic solar cells (OSCs) have been improved continuously in recent years, more attention will be paid to the industrial production and practical application of OSCs. However, there are still many problems to be solved in the process of large-scale production. Among them, reducing the costs of the materials and enhancing the film-thickness tolerance of the active layer are the two key points. Therefore, it is urgent to develop organic semiconductor materials which are easy to synthesize and suitable for the construction of high-efficiency, thick-film OSCs. In this work, we have focused on the (E)-2-[2-(thiophen-2-yl)vinyl]thiophene (TVT) unit because of its unique coplanar structure. And we noticed that TVT was mostly used as an electron-donating unit in the previous reports. However, we have modified TVT into electron-withdrawing unit by the introduction of fluorine atoms/ester groups. And two new donor-acceptor (D-A) copolymers have been obtained by combining the electron-withdrawing TVT unit with benzo[2,1-b:4,5-b']dithiophene (BDT) unit. Among them, the polymer based on the ester modified TVT unit presents excellent photovoltaic performance by virtue of its good solubility and preferable molecular stacking mode, and the corresponding devices also show extraordinarily high-thickness tolerance. The emergence of this new electron-withdrawing TVT unit will undoubtedly further promote the development of low-cost, high-efficiency, thick-film OSCs.

A Quinoxaline-Based D-A Copolymer Donor Achieving 17.62% Efficiency of Organic Solar Cells.

Side-chain engineering has been an effective strategy in tuning electronic energy levels, intermolecular interaction, and aggregation morphology of organic photovoltaic materials, which is very important for improving the power conversion efficiency (PCE) of organic solar cells (OSCs). In this work, two D-A copolymers, PBQ5 and PBQ6, are designed and synthesized based on bithienyl-benzodithiophene (BDTT) as the donor (D) unit, difluoroquinoxaline (DFQ) with different side chains as the acceptor (A) unit, and thiophene as the π-bridges. PBQ6 with two alkyl-substituted fluorothiophene side chains on the DFQ units possesses redshifted absorption, stronger intermolecular interaction, and higher hole mobility than PBQ5 with two alkyl side chains on the DFQ units. The blend film of the PBQ6 donor with the Y6 acceptor shows higher and balanced hole/electron mobilities, less charge carrier recombination, and more favorable aggregation morphology. Therefore, the OSC based on PBQ6:Y6 achieves a PCE as high as 17.62% with a high fill factor of 77.91%, which is significantly higher than the PCE (15.55%) of the PBQ5:Y6-based OSC. The PCE of 17.62% is by far one of the highest efficiencies for the binary OSCs with polymer donor and Y6 acceptor.

Synthesis and Properties of Thiophene and Aniline Copolymer Using Atmospheric Pressure Plasma Jets Copolymerization Technique.

This paper investigates the properties of thiophene and aniline copolymer (TAC) films deposited by using atmospheric pressure plasma jets copolymerization technique relative to various blending ratios of aniline and thiophene monomer for synthesizing the donor-acceptor conjugated copolymers. Field emission scanning electron microscopy (FE-SEM) and atomic force microscopy are utilized to measure the surface morphology, roughness and film thickness of TAC films. Structural and chemical properties of TAC films are investigated by Fourier transforms-infrared spectroscopy (FT-IR), time of flight secondary ion mass spectrometry, and X-ray photoelectron spectroscopy. FE-SEM images show that the film thickness and nanoparticles size of the TAC films increase with an addition thiophene monomer in the aniline monomer. FE-SEM, FT-IR results show that TAC films are successfully synthesized on glass substrates in all cases. The iodine doped TAC film on the Si substrate with interdigitated electrodes shows the lowest electrical resistance at blending condition of thiophene of 25%.