For over two decades bulk‐heterojunction polymer solar cell (BHJ‐PSC) research was dominated by donor:acceptor BHJ blends based on polymer donors and fullerene molecular acceptors. This situation has ...changed recently, with non‐fullerene PSCs developing very rapidly. The power conversion efficiencies of non‐fullerene PSCs have now reached over 15 %, which is far above the most efficient fullerene‐based PSCs. Among the various non‐fullerene PSCs, all‐polymer solar cells (APSCs) based on polymer donor‐polymer acceptor BHJs have attracted growing attention, due to the following attractions: 1) large and tunable light absorption of the polymer donor/polymer acceptor pair; 2) robustness of the BHJ film morphology; 3) compatibility with large scale/large area manufacturing; 4) long‐term stability of the cell to external environmental and mechanical stresses. This Minireview highlights the opportunities offered by APSCs, selected polymer families suitable for these devices with optimization to enhance the performance further, and discusses the challenges facing APSC development for commercial applications.
APSCs offer all: All‐polymer solar cells have attracted great attention, owing to rational design, improved morphology, strong absorption, enhanced stability etc. This Minireview highlights the opportunities of APSCs, selected polymer families suitable for these devices with optimization to enhance the performance further, and discusses the challenges facing APSC development for commercial applications.
Constructing highly planar, extended π-electron systems is an important strategy for achieving high-mobility organic semiconductors. In general, there are two synthetic strategies for achieving ...π-conjugated systems with high planarity. The conventional strategy connects neighboring aromatic rings through covalent bonds to restrict the rotation about single bonds. However, this usually requires a complex sequence of synthetic steps to achieve this target, which can be costly and labor-intensive. More recently, noncovalent through-space intramolecular interactions, which are defined here as noncovalent conformational locks, have been employed with great success to increase the planarity and rigidity of extended π-electron systems; this has become a well-known and important strategy to design and synthesize highly planar π-conjugated systems for organic electronics. This review offers a comprehensive and general summary of conjugated systems with such noncovalent conformational locks, including O···S, N···S, X···S (where X = Cl, Br, F), and H···S through-space interactions, together with analysis by density functional theory computation, X-ray diffraction, and microstructural characterization, as well as by evaluation of charge transport in organic thin-film transistors and solar cells.
Introducing polar functional groups into widely used polyolefins can enhance polymer surface, rheological, mixing, and other properties, potentially upgrading polyolefins for advanced, value‐added ...applications. The metal catalyst‐mediated copolymerization of non‐polar olefins with polar comonomers represents the seemingly most straightforward, atom‐ and energy‐efficient approach for synthesizing polar functionalized polyolefins. However, electrophilic early transition metal (groups 3 and 4)‐catalyzed processes which have achieved remarkable success in conventional olefin polymerizations, encounter severe limitations here, largely associated with the Lewis basicity of the polar co‐monomers. In recent years, however, new catalytic systems have been developed and successful strategies have emerged. In this Minireview, we summarize the recent progress in early transition metal polymerization catalyst development, categorized by the catalytic metal complex and polar comonomer identity. Furthermore, we discuss advances in the mechanistic understanding of these polymerizations, focusing on critical challenges and strategies that mitigate them.
Catalyst design: This Minireview summarizes the recent progress in early transition metal polymerization catalyst development, categorized by the catalytic metal complex and polar comonomer identity. Advances in the mechanistic understanding of these polymerizations are discussed, focusing on critical challenges and strategies that mitigate them.
With advances in exfoliation and synthetic techniques, atomically thin films of semiconducting transition metal dichalcogenides have recently been isolated and characterized. Their two-dimensional ...structure, coupled with a direct band gap in the visible portion of the electromagnetic spectrum, suggests suitability for digital electronics and optoelectronics. Toward that end, several classes of high-performance devices have been reported along with significant progress in understanding their physical properties. Here, we present a review of the architecture, operating principles, and physics of electronic and optoelectronic devices based on ultrathin transition metal dichalcogenide semiconductors. By critically assessing and comparing the performance of these devices with competing technologies, the merits and shortcomings of this emerging class of electronic materials are identified, thereby providing a roadmap for future development.
Using a mechanism‐based solvent‐free tandem catalytic approach, commodity polyester plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate ...(PEN) are rapidly and selectively deconstructed by combining the two air‐ and moisture‐stable catalysts, Hf(OTf)4 and Pd/C, under 1 atm H2, affording terephthalic acid (or naphthalene dicarboxylic acid for PEN) and ethane (or butane for PBT) in essentially quantitative yield. This process is effective for both laboratory grade and waste plastics, and comingled polypropylene remains unchanged. Combined experimental and DFT mechanistic analyses indicate that Hf(OTf)4 catalyzes a mildly exergonic retro‐hydroalkoxylation reaction in which an alkoxy C−O bond is first cleaved, yielding a carboxylic acid and alkene, and this process is closely coupled to an exergonic olefin hydrogenation step, driving the overall reaction forward.
Commodity polyester plastics such as PET, PBT, and PEN are hydrogenolytically deconstructed to their starting monomeric carboxylic acids and light alkanes using a solventless tandem catalytic approach. These selective reactions operate near the polymer melting temperature under 1 atm H2 and are compatible with mixed plastics.
Recent advances in flexible and stretchable electronics (FSE), a technology diverging from the conventional rigid silicon technology, have stimulated fundamental scientific and technological research ...efforts. FSE aims at enabling disruptive applications such as flexible displays, wearable sensors, printed RFID tags on packaging, electronics on skin/organs, and Internet-of-things as well as possibly reducing the cost of electronic device fabrication. Thus, the key materials components of electronics, the semiconductor, the dielectric, and the conductor as well as the passive (substrate, planarization, passivation, and encapsulation layers) must exhibit electrical performance and mechanical properties compatible with FSE components and products. In this review, we summarize and analyze recent advances in materials concepts as well as in thin-film fabrication techniques for high-k (or high-capacitance) gate dielectrics when integrated with FSE-compatible semiconductors such as organics, metal oxides, quantum dot arrays, carbon nanotubes, graphene, and other 2D semiconductors. Since thin-film transistors (TFTs) are the key enablers of FSE devices, we discuss TFT structures and operation mechanisms after a discussion on the needs and general requirements of gate dielectrics. Also, the advantages of high-k dielectrics over low-k ones in TFT applications were elaborated. Next, after presenting the design and properties of high-k polymers and inorganic, electrolyte, and hybrid dielectric families, we focus on the most important fabrication methodologies for their deposition as TFT gate dielectric thin films. Furthermore, we provide a detailed summary of recent progress in performance of FSE TFTs based on these high-k dielectrics, focusing primarily on emerging semiconductor types. Finally, we conclude with an outlook and challenges section.
Organic semiconductors have unique properties compared to traditional inorganic materials such as amorphous or crystalline silicon. Some important advantages include their adaptability to ...low-temperature processing on flexible substrates, low cost, amenability to high-speed fabrication, and tunable electronic properties. These features are essential for a variety of next-generation electronic products, including low-power flexible displays, inexpensive radio frequency identification (RFID) tags, and printable sensors, among many other applications. Accordingly, the preparation of new materials based on π-conjugated organic molecules or polymers has been a central scientific and technological research focus over the past decade. Currently, p-channel (hole-transporting) materials are the leading class of organic semiconductors. In contrast, high-performance n-channel (electron-transporting) semiconductors are relatively rare, but they are of great significance for the development of plastic electronic devices such as organic field-effect transistors (OFETs). In this Account, we highlight the advances our team has made toward realizing moderately and highly electron-deficient n-channel oligomers and polymers based on oligothiophene, arylenediimide, and (bis)indenofluorene skeletons. We have synthesized and characterized a “library” of structurally related semiconductors, and we have investigated detailed structure–property relationships through optical, electrochemical, thermal, microstructural (both single-crystal and thin-film), and electrical measurements. Our results reveal highly informative correlations between structural parameters at various length scales and charge transport properties. We first discuss oligothiophenes functionalized with perfluoroalkyl and perfluoroarene substituents, which represent the initial examples of high-performance n-channel semiconductors developed in this project. The OFET characteristics of these compounds are presented with an emphasis on structure–property relationships. We then examine the synthesis and properties of carbonyl-functionalized oligomers, which constitute second-generation n-channel oligothiophenes, in both vacuum- and solution-processed FETs. These materials have high carrier mobilities and good air stability. In parallel, exceptionally electron-deficient cyano-functionalized arylenediimide derivatives are discussed as early examples of thermodynamically air-stable, high-performance n-channel semiconductors; they exhibit record electron mobilities of up to 0.64 cm2/V·s. Furthermore, we provide an overview of highly soluble ladder-type macromolecular semiconductors as OFET components, which combine ambient stability with solution processibility. A high electron mobility of 0.16 cm2/V·s is obtained under ambient conditions for solution-processed films. Finally, examples of polymeric n-channel semiconductors with electron mobilities as high as 0.85 cm2/V·s are discussed; these constitute an important advance toward fully printed polymeric electronic circuitry. Density functional theory (DFT) computations reveal important trends in molecular physicochemical and semiconducting properties, which, when combined with experimental data, shed new light on molecular charge transport characteristics. Our data provide the basis for a fundamental understanding of charge transport in high-performance n-channel organic semiconductors. Moreover, our results provide a road map for developing functional, complementary organic circuitry, which requires combining p- and n-channel transistors.
PDF
