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In this manuscript we present a versatile platform for introducing functional redox species into tailor-made 3D redox polymer networks. Electrochemical characterization based on cyclic voltammetry is applied to verify the immobilization of the redox species within the conducting networks. Ultimately this strategy shall be extended to (photo)electrocatalytic applications which will profit from the conducting polymer matrix. Soluble precursor copolymers are synthesized via radical copolymerization of vinyltriphenylamine (VTPA) with chloromethylstyrene (CMS) in different ratios, whereas CMS is subsequently converted into azidomethylstyrene (AMS) to yield poly(VTPA-co-AMS) copolymers. Spin-coating of poly(VTPA-co-AMS) on gold electrodes yields thin films which are converted into stable polymer network structures by electrochemical crosslinking of the polymer chains via their pendant triphenylamine groups to yield N,N,N',N'-tetraphenylbenzidine (TPB) crosslinking points. Finally, the resulting redox-active, TPB-crosslinked films are functionalized with ethynylferrocene (EFc) as a representative redox probe using a click reaction. Main experimental tools are polarization modulation infrared reflection absorption spectroscopy and scan rate dependent cyclic voltammetry. Especially the latter proves the successful conversion and the immobilization of redox probes in the polymer matrix. The results are compared with the reference system of azide-terminated self-assembled monolayers on gold substrates, allowing to distinguish between free and immobilized EFc species.
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Block copolymers have a wide range of functions in advanced electrochemistry because of their ability to self-assemble into ordered nanometer-sized structures, resulting in their extensive usage as nanoporous templates that can be electrochemically manipulated. These highly ordered nanoporous templates are used as working electrodes for electrodeposition and electropolymerization to build nanoelectrode arrays and can serve as models to study the diffusion pathway of redox-active units with regard to chemical modification of pores. The block copolymer system allows different morphologies to be utilized, but the most exploited structures are standing cylinders of the minority block that are etched to expose highly aligned porous nanoelectrode array templates. This review starts with introducing alumina and track-etched membranes as pioneer porous templates transitioning to the production of block copolymer films as succeeding templates, with a particular focus on both poly(styrene)-block-poly(methylmethacrylate) (PS-b-PMMA) and poly(styrene)-block-poly(lactide) (PS-b-PLA). The aim is to give fundamental insights of electrochemistry where functionality extends beyond to applications in the nanoscience field of biosensors and plastic electronics.
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Polímeros/química , Óxido de Alumínio/química , Técnicas Biossensoriais , Técnicas Eletroquímicas/métodos , Metacrilatos/química , Nanoporos , Nanotecnologia , Poliestirenos/químicaRESUMO
We report the synthesis and characterization of a novel series of push-pull chromophores bearing 1D linear and ß-branched thiophenes as π-conjugated spacers between a 2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline electron donor unit and dicyano- and tricyanovinylene electron acceptor groups. The effect of the introduction of ß-thiophenes on the linear and nonlinear (NLO) optical properties as well as electrochemical and thermal data is studied in detail by performing a comparative study between the branched and 1D linear systems. In addition, a parallel DFT computational study is used to evaluate structure-property relationships. The non-linear optical behavior of the molecules both in solution and in solid state as electro-optic (EO) films using a guest-host approach shows very promising performance for electro-optic applications with high molecular first hyperpolarizabilities (µß) of 4840 × 10-48 esu and electro-optic coefficients r33 reaching 650 pm V-1. One highlight is that the electro-optic films of the ß-branched chromophores are superior in terms of thermal stability in device operation as measured by a transmissive modified reflective Teng-Man method. This work provides guidelines for the design of improved electro-optic materials including ß-branched chromophores which could be useful for practical EO applications, where both enhanced ß and r33 values together with chemical and thermal stability are necessary.
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The control of the morphology of semiconducting semicrystalline polymers is crucial to the performance of various electronic devices. Among other superstructures in semicrystalline polymers, spherulites stand out for various reasons. They are highly ordered, relatively easy to grow, and their underlying molecular structure provides anisotropic optical and electronic properties of the resulting polymeric material. In this feature article, a short overview of classical crystallization theory is given as well as a brief introduction to spherulites as supermolecular structures. The article then focuses on semicrystalline polymers with semiconducting properties. From classical melt crystallization toward solvent vapor annealing, different strategies of growing spherulites of these types of polymers are presented and examples of the corresponding polymers and their resulting morphology are given. Eventually, the potential application of spherulitic thin films in organic electronics such as field-effect transistors is demonstrated. Conductivity and mobility measurements are shown, particularly focusing on the anisotropy of the latter.
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Polímeros/química , Eletrônica , Tamanho da Partícula , Semicondutores , Propriedades de SuperfícieRESUMO
The molecular organization and electronic properties of dithiocarbamate (DTC) anchored self-assembled monolayers (SAMs) linked to Au(111) substrates are studied by a combination of X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and state-of-the-art density functional theory calculations. For that, several piperidine/piperazine precursors with different architecture and substitution patterns are selected. The presented data show that the DTC anchor provides a useful building block for monomolecular self-assembly on coinage metals with both sulfur atoms bonded to the substrate in a way similar to what is usually observed for the more commonly applied thiolate docking group. The combination of the DTC group with the quite flexible piperidine/piperazine cyclic linkers results in a dense molecular packing with an upright orientation of the terminal moieties. The latter comprise phenyl rings bearing various substituents, which enables tuning the interfacial dipole over a wide range. Simulations on two prototypical DTC-docked SAMs help to better understand the experimental observations and provide insight into the local origin of the SAM-induced shifts in the electrostatic energy. In particular, a comparison of measured and simulated XP spectra reveals the significant contribution of the DTC group to the interfacial dipole.
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Conjugated donor-acceptor block co-oligomers that self-organize into D-A mesomorphic arrays have raised increasing interest due to their potential applications in organic solar cells. We report here a combined experimental and computational study of charge transfer (CT) state formation and recombination in isolated donor-spacer-acceptor oligomers based on bisthiophene-fluorene (D) and perylene diimide (A), which have recently shown to self-organize to give a mesomorphic lamellar structure at room temperature. Using femtosecond transient absorption spectroscopy and Time-Dependent Density Functional Theory in combination with the Marcus-Jortner formalism, the observed increase of the CT lifetimes is rationalized in terms of a reduced electronic coupling between D and A brought about by the chemical design of the donor moiety. A marked dependence of the CT lifetime on solvent polarity is observed, underscoring the importance of electrostatic effects and those of the environment at large. The present investigation therefore calls for a more comprehensive design approach including the effects of molecular packing.
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A zoo of chemical structures is accessible when the branched unit 2,2':3',2â³-terthiophene (3T) is included both in structurally well-defined small molecules and polymer-like architectures. The first part of this review article highlights literature on all-thiophene based branched oligomers including dendrimers as well as combinations of 3T-units with functional moieties for light-harvesting systems. Motivated by the perfectly branched macromolecular dendrimers both electropolymerization as well as chemical approaches are presented as methods for the preparation of branched polythiophenes with different branching densities. Structure-function relationships between the molecular architecture and optical and electronic properties are discussed throughout the article.
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Dendrímeros/química , Substâncias Macromoleculares/química , Polímeros/química , Tiofenos/química , Dendrímeros/síntese química , Equipamentos e Provisões Elétricas , Eletrônica , Substâncias Macromoleculares/síntese química , Modelos Químicos , Estrutura Molecular , Fenômenos de Química Orgânica , Polímeros/síntese química , Tiofenos/síntese químicaRESUMO
The electrocopolymerization of 3,4-ethylenedioxythiophene (EDOT) with the branched thiophene building block 2,2':3',2â³-terthiophene (3T) is presented as a versatile route to functional polymer films. Comparisons to blend systems of the respective homopolymers PEDOT and P3T by in situ spectroelectrochemistry and Raman spectroscopy prove the successful copolymer formation and the access to tailored redox properties and energy levels. The use of EDOT-N3 as co-monomer furthermore allows modifications of the films by polymer analogous reactions. Here, we exemplarily describe the post-functionalization with ionic moieties by 1,3-dipolar cycloaddition ("click"-chemistry) which allows to tune the surface polarity of the copolymer films from water contact angles of 140° down to 40°.
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Reducing voltage losses while maintaining high photocurrents is the holy grail of current research on non-fullerene acceptor (NFA) based organic solar cell. Recent focus lies in understanding the various fundamental mechanisms in organic blends with minimal energy offsets - particularly the relationship between ionization energy offset (ΔIE) and free charge generation. Here, we quantitatively probe this relationship in multiple NFA-based blends by mixing Y-series NFAs with PM6 of different molecular weights, covering a broad power conversion efficiency (PCE) range: from 15% down to 1%. Spectroelectrochemistry reveals that a ΔIE of more than 0.3 eV is necessary for efficient photocurrent generation. Bias-dependent time-delayed collection experiments reveal a very pronounced field-dependence of free charge generation for small ΔIE blends, which is mirrored by a strong and simultaneous field-dependence of the quantified photoluminescence from the NFA local singlet exciton (LE). We find that the decay of singlet excitons is the primary competition to free charge generation in low-offset NFA-based organic solar cells, with neither noticeable losses from charge-transfer (CT) decay nor evidence for LE-CT hybridization. In agreement with this conclusion, transient absorption spectroscopy consistently reveals that a smaller ΔIE slows the NFA exciton dissociation into free charges, albeit restorable by an electric field. Our experimental data align with Marcus theory calculations, supported by density functional theory simulations, for zero-field free charge generation and exciton decay efficiencies. We conclude that efficient photocurrent generation generally requires that the CT state is located below the LE, but that this restriction is lifted in systems with a small reorganization energy for charge transfer.
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The potential of 2,2';3,2â³-terthiophene (3T) as branching units in 3D copolymers is presented with EDOT as an example comonomer. Branched EDOT/3T polythiophenes were prepared by electropolymerization, and their electrochemical and optical properties are discussed. Two different approaches were employed: (i) the direct electropolymerization of a novel branched thiophene monomer (3TE3) consisting of a 3T core that contains three outer EDOT end groups and (ii) the electrochemical copolymerization of a EDOT/3T mixture in different ratios from [1:1] to [1:10]. Cyclic voltammetric and vis spectrometric experiments show that the EDOT content within the polymer has a strong influence on the electronic properties of the material: with increasing EDOT content, the HOMO-LUMO gap is decreased. To prove copolymer formation of EDOT and 3T, chemically synthesized reference copolymers of EDOT and 3T were prepared by oxidative coupling using FeCl3, and their optical and electronic properties were compared to those of the electrodeposited films. In addition, the copolymer formation is indicated by the comparison of the electrochemical and spectroscopic results with those of the homopolymers P3T and PEDOT.
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The intricate process of biomineralization, e.g. in sea urchins, involves the precise interplay of highly regulated mineralization proteins and the spatiotemporal coordination achieved through compartmentalization. However, the investigation of biomineralization effector molecules, e.g. proteins, is challenging, due to their very low abundance. Therefore, we investigate the functional mimicry in the bioinspired precipitation of calcium carbonate (CaCO3) with artificial peptides selected from a peptide library by phage display based on peptide-binding to calcite and aragonite, respectively. The structure-directing effects of the identified peptides were compared to those of natural protein mixes isolated from skeletal (test) structures of two sea urchin species (Arbacia lixula and Paracentrotus lividus). The calcium carbonate samples deposited in the absence or presence of peptides were analyzed with a set of complementary techniques with regard to morphology, polymorph, and nanostructural motifs. Remarkably, some of the CaCO3-binding peptides induced morphological features in calcite that appeared similar to those obtained in the presence of the natural protein mixes. Many of the peptides identified as most effective in exerting a structure-directing effect on calcium carbonate crystallization were rich in basic amino acid residues. Hence, our in vitro mineralization study further highlights the important, but often neglected, role of positively charged soluble organic matrices associated with biological and bioinspired CaCO3 deposition.
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Bacteriófagos , Biomineralização , Animais , Carbonato de Cálcio/química , Peptídeos/química , Ouriços-do-Mar/metabolismo , Bacteriófagos/metabolismoRESUMO
We present an electrically switchable, compact metasurface device based on the metallic polymer PEDOT:PSS in combination with a gel polymer electrolyte. Applying square-wave voltages, we can reversibly switch the PEDOT:PSS from dielectric to metallic. Using this concept, we demonstrate a compact, standalone, and CMOS compatible metadevice. It allows for electrically controlled ON and OFF switching of plasmonic resonances in the 2-3 µm wavelength range, as well as electrically controlled beam switching at angles up to 10°. Furthermore, switching frequencies of up to 10 Hz, with oxidation times as fast as 42 ms and reduction times of 57 ms, are demonstrated. Our work provides the basis towards solid state switchable metasurfaces, ultimately leading to submicrometer-pixel spatial light modulators and hence switchable holographic devices.
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The quest for developing quantum technologies is driven by the promise of exponentially faster computations, ultrahigh performance sensing, and achieving thorough understanding of many-particle quantum systems. Molecular spins are excellent qubit candidates because they feature long coherence times, are widely tunable through chemical synthesis, and can be interfaced with other quantum platforms such as superconducting qubits. A present challenge for molecular spin qubits is their integration in quantum devices, which requires arranging them in thin films or monolayers on surfaces. However, clear proof of the survival of quantum properties of molecular qubits on surfaces has not been reported so far. Furthermore, little is known about the change in spin dynamics of molecular qubits going from the bulk to monolayers. Here, a versatile bottom-up method is reported to arrange molecular qubits as functional groups of self-assembled monolayers (SAMs) on surfaces, combining molecular self-organization and click chemistry. Coherence times of up to 13 µs demonstrate that qubit properties are maintained or even enhanced in the monolayer.
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n-Type organic electrochemical transistors (OECTs) and organic field-effect transistors (OFETs) are less developed than their p-type counterparts. Herein, polynaphthalenediimide (PNDI)-based copolymers bearing novel fluorinated selenophene-vinylene-selenophene (FSVS) units as efficient materials for both n-type OECTs and n-type OFETs are reported. The PNDI polymers with oligo(ethylene glycol) (EG7) side chains P(NDIEG7-FSVS), affords a high µC* of > 0.2 F cm-1 V-1 s-1 , outperforming the benchmark n-type Pg4NDI-T2 and Pg4NDI-gT2 by two orders of magnitude. The deep-lying LUMO of -4.63 eV endows P(NDIEG7-FSVS) with an ultra-low threshold voltage of 0.16 V. Moreover, the conjugated polymer with octyldodecyl (OD) side chains P(NDIOD-FSVS) exhibits a surprisingly low energetic disorder with an Urbach energy of 36 meV and an ultra-low activation energy of 39 meV, resulting in high electron mobility of up to 0.32 cm2 V-1 s-1 in n-type OFETs. These results demonstrate the great potential for simultaneously achieving a lower LUMO and a tighter intermolecular packing for the next-generation efficient n-type organic electronics.
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The synthesis of ionically functionalized branched polythiophenes with either carboxylic acid (anionic, P3T-COOH) or methylimidazolium (cationic, P3T-MIM) end groups is presented. Due to the large number of end groups present in the polymer, the functionalization has a major impact on the solubility of the polymers. In the case of P3T-COOH, the polymer shows a fully reversible phase transfer between organic solvents and water, depending on the pH. Remarkably, the ionic-liquid-modified polymer P3T-MIM is soluble in a room-temperature ionic liquid. The absorption properties are unaffected by the functional end groups.
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To take full advantage of recent and anticipated improvements in the performance of organic semiconductors employed in organic transistors, the high contact resistance arising at the interfaces between the organic semiconductor and the source and drain contacts must be reduced significantly. To date, only a small portion of the accumulated research on organic thin-film transistors (TFTs) has reported channel-width-normalized contact resistances below 100 Ωcm, well above what is regularly demonstrated in transistors based on inorganic semiconductors. A closer look at these cases and the relevant literature strongly suggests that the most significant factor leading to the lowest contact resistances in organic TFTs so far has been the control of the thin-film morphology of the organic semiconductor. By contrast, approaches aimed at increasing the charge-carrier density and/or reducing the intrinsic Schottky barrier height have so far played a relatively minor role in achieving the lowest contact resistances. Herein, the possible explanations for these observations are explored, including the prevalence of Fermi-level pinning and the difficulties in forming optimized interfaces with organic semiconductors. An overview of the research on these topics is provided, and potential device-engineering solutions are discussed based on recent advancements in the theoretical and experimental work on both organic and inorganic semiconductors.
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Switchable metasurfaces can actively control the functionality of integrated metadevices with high efficiency and on ultra-small length scales. Such metadevices include active lenses, dynamic diffractive optical elements, or switchable holograms. Especially, for applications in emerging technologies such as AR (augmented reality) and VR (virtual reality) devices, sophisticated metaoptics with unique functionalities are crucially important. In particular, metaoptics which can be switched electrically on or off will allow to change the routing, focusing, or functionality in general of miniaturized optical components on demand. Here, we demonstrate metalenses-on-demand made from metallic polymer plasmonic nanoantennas which are electrically switchable at CMOS (complementary metal-oxide-semiconductor) compatible voltages of ±1 V. The nanoantennas exhibit plasmonic resonances which can be reversibly switched ON and OFF via the applied voltage, utilizing the optical metal-to-insulator transition of the metallic polymer. Ultimately, we realize an electro-active non-volatile multi-functional metaobjective composed of two metalenses, whose unique optical states can be set on demand. Overall, our work opens up the possibility for a new level of electro-optical elements for ultra-compact photonic integration.
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The understanding and applications of electron-conducting π-conjugated polymers with naphtalene diimide (NDI) blocks show remarkable progress in recent years. Such polymers demonstrate a facilitated n-doping due to the strong electron deficiency of the main polymer chain and the presence of the positively charged side groups stabilizing a negative charge of the n-doped backbone. Here, the n-type conducting NDI polymer with enhanced stability of its n-doped states for prospective "in-water" applications is developed. A combined experimental-theoretical approach is used to identify critical features and parameters that control the doping and electron transport process. The facilitated polymer reduction ability and the thermodynamic stability in water are confirmed by electrochemical measurements and doping studies. This material also demonstrates a high conductivity of 10-2 S cm-1 under ambient conditions and 10-1 S cm-1 in vacuum. The modeling explains the stabilizing effects for various dopants. The simulations show a significant doping-induced "collapse" of the positively charged side chains on the core bearing a partial negative charge. This explains a decrease in the lamellar spacing observed in experiments. This study fundamentally enables a novel pathway for achieving both thermodynamic stability of the n-doped states in water and the high electron conductivity of polymers.
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We report the synthesis of a series of block copolymers consisting of a rod-like semiconducting poly(2,5-di(2'-ethylhexyloxy)-1,4-phenylenevinylene) (DEH-PPV) block and a flexible poly(lactic acid) (PLA) block that can be selectively degraded under mild conditions. Such selectively degradable block copolymers are designed as self-assembling templates for bulk heterojunction donor-acceptor layers in organic solar cells. A lamellar microphase-separated domain structure was identified for block copolymers with PLA volume fractions between 29 and 79% in bulk and thin films using SAXS, TEM, and AFM. Depending on the ratio of the two blocks we find either lamellae oriented parallel or perpendicular to the substrate in thin films.
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Ácido Láctico/química , Transição de Fase , Polimerização , Polímeros/química , Compostos de Vinila/química , Cromatografia em Gel , Ácido Láctico/síntese química , Poliésteres , Polímeros/síntese química , Polivinil/síntese química , Polivinil/química , Semicondutores , Silício/química , Propriedades de Superfície , Temperatura de TransiçãoRESUMO
Nature will always be an endless source of bioinspiration for man-made smart materials and multifunctional devices. Impressively, even cutoff leaves from resurrection plants can autonomously and reproducibly change their shape upon humidity changes, which goes along with total recovery of their mechanical properties after being completely dried. In this work, simple bilayers are presented as autonomously moving, humidity-triggered bending actuators. The bilayers-showing reproducible bending behavior with reversible kinematics and multiway behavior-are studied in terms of their mechanical behavior upon humidity changes. The active layer consists of a highly conducting polymer film based on poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) with poly(dimethylsiloxane) (PDMS) as passive layer. The response to humidity is explored with dynamic mechanical thermal analysis and quartz crystal microbalance measurements. Introduction of a composite beam model allows to predict the curvature of the actuators with input from the rheological measurements. It is clearly demonstrated that volumetric strain and Young's modulus, both heavily influenced by the water uptake, dominate the bending behavior and therefore the curvature of the actuators. This loop of rheological characterization coupled with an analytical model allows to predict curvatures of in principle any complex geometry and material combination for moving parts in soft robotics.