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1.
    
A recently developed water‐soluble self‐doped sodium salt of bis[3,4‐ethylenedioxythiophene]3thiophene butyric acid (ETE‐S) is electropolymerized and characterized by means of spectroelectrochemistry, electron paramagnetic resonance spectroscopy, and cyclic voltammetry, combined with the density functional theory (DFT) and time‐dependent DFT calculations. The focus of the studies is to underline the nature of the charge carriers when the electrochemically polymerized ETE‐S films undergo a reversible transition from reduced to electrically conductive oxidized states. Spectroelectrochemistry shows clear distinctions between absorption features from reduced and charged species. In the reduced state, the absorption spectrum of ETE‐S electropolymerized film shows a peak that is attributed to HOMO→LUMO transition. As the oxidation level increases, this peak diminishes and the absorption of the film is dominated by spinless bipolaronic states with some admixture of polaronic states possessing a magnetic momentum. For fully oxidized samples, the bipolaronic states fully dominate, and the features in the absorption spectra are related to the drastic changes of the band structure, exhibiting a strong decrease of the band gap when a polymeric film undergoes oxidation.  相似文献   

2.
    
The growing number of applications of doped organic semiconductors drives the development of highly conductive and stable materials. Lack of understanding about the formation and properties of mobile charges limits the ability to improve material design. Thus the largely unexplored photophysics of doped systems are addressed here to gain insights about the characteristics of doping‐induced polarons and their interactions with their surroundings. The study of the ultrafast optical processes in a self‐doped conjugated polyelectrolyte reveals that polarons not only affect their environment via Coulomb effects but also strongly couple electronically to nearby neutral sites. This is unambiguously demonstrated by the simultaneous depletion of both the neutral and polaronic transitions, as well as by correlated excited state dynamics, when either transition is targeted during ultrafast experiments. The results contrast with the conventional picture of localized intragap polaron states but agree with revised models for the optical transitions in doped organic materials, which predict a common ground level for polarons and neighboring neutral sites. Such delocalization of polarons into the frontier transport levels of their surroundings could enhance the electronic connectivity between doped and undoped sites, contributing to the formation of conductive charges.  相似文献   

3.
    
The properties of molecularly doped films of conjugated polymers are explored as the crystallinity of the polymer is systematically varied. Solution sequential processing (SqP) was used to introduce 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4TCNQ) into poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) while preserving the pristine polymer's degree of crystallinity. X‐ray data suggest that F4TCNQ anions reside primarily in the amorphous regions of the film as well as in the P3HT lamellae between the side chains, but do not π‐stack within the polymer crystallites. Optical spectroscopy shows that the polaron absorption redshifts with increasing polymer crystallinity and increases in cross section. Theoretical modeling suggests that the polaron spectrum is inhomogeneously broadened by the presence of the anions, which reside on average 6–8 Å from the polymer backbone. Electrical measurements show that the conductivity of P3HT films doped by F4TCNQ via SqP can be improved by increasing the polymer crystallinity. AC magnetic field Hall measurements show that the increased conductivity results from improved mobility of the carriers with increasing crystallinity, reaching over 0.1 cm2 V?1 s?1 in the most crystalline P3HT samples. Temperature‐dependent conductivity measurements show that polaron mobility in SqP‐doped P3HT is still dominated by hopping transport, but that more crystalline samples are on the edge of a transition to diffusive transport at room temperature.  相似文献   

4.
    
Molecular doping of organic semiconductors is a powerful tool for the optimization of organic electronic devices and organic thermoelectric materials. However, there are few redox dopants that have a sufficiently high electron affinity to allow the doping of conjugated polymers with an ionization energy of more than 5.3 eV. Here, p‐doping of a broad palette of conjugated polymers with high ionization energies is achieved by using the strong oxidant tris(4‐bromophenyl)ammoniumyl hexachloroantimonate (Magic Blue). In particular diketopyrrolopyrrole (DPP)‐based copolymers reach a conductivity of up to 100 S cm−1 and a thermoelectric power factor of 10 µW m−1 K−2. Further, both electron paramagnetic resonance (EPR) as well as a combination of spectroelectrochemistry and chronoamperometry is used to estimate the charge‐carrier density of the polymer PDPP‐3T doped with Magic Blue. A molar attenuation coefficient of 6.0 ± 0.2 × 103 m2 mol−1 is obtained for the first polaronic sub‐bandgap absorption of electrochemically oxidized PDPP‐3T. Comparison with chemically doped PDPP‐3T suggests a charge‐carrier density on the order of 1026 m−3, which yields a charge‐carrier mobility of up to 0.5 cm2 V−1 s−1 for the most heavily doped material.  相似文献   

5.
    
Poly(benzimidazole–benzophenanthroline) (BBL) is a ladder-type conjugated polymer showing remarkable charge transport properties. Upon doping it displays various conductive regimes, leading to two insulator-to-conductor transitions. Such transitions are never fully characterized, limiting understanding of its charged states. Open issues are: i) the electron/hole polaron relaxations, ii) the structure–function relationships of multiple redox states and their connection with the conductive regimes, and iii) the role of protonation. Such knowledge-gaps are tackled via a comprehensive computational investigation of multiple redox species. Polarons show polyradicaloid character, as revealed by combining broken-symmetry density functional theory, fragment orbital density, and multireference analysis. Electron/hole polaron relaxations occur on the polymer chain, the former localizing on the benzophenanthroline moieties, the latter on the benzimidazole units. Modeling of multiple charged species, up to one electron per repeat unit (1 eru), reveals a complex scenario of quasidegenerate states each featuring different spin multiplicity. Four redox states are responsible for the BBL insulator-to-conductor transitions. The two high conductive states refer to the electron polaron (0.25 eru) and the redox species with 0.75 eru. The insulating regimes refer to the bipolaron (0.50 eru) and the redox state with 1 eru. Protonation is modeled, revealing polaron-like features in the spectroscopic properties.  相似文献   

6.
    
The interactions between counterions and electronic carriers in electrically doped semiconducting polymers are important for delocalization of charge carriers, electronic conductivity, and thermal stability. The introduction of a dianions in semiconducting polymers leads to double doping where there is one counterion for two charge carriers. Double doping minimizes structural distortions, but changes the electrostatic interactions between the carriers and counterions. Polymeric ionic liquids (PIL) with croconate dianions are helpful to investigate the role of the counterion in p-type semiconducting polymers. PILs prevent diffusion of the cation into the semiconducting polymers during ion exchange. The redox-active croconate dianions undergo ion exchange with doped semiconducting polymers depending on their ionization energy. Croconate dianions are found to reduce doped films of poly(3-hexyl thiophene), but undergo ion exchange with a polythiophene with tetraethylene glycol side chains, P(g42T-T), that has a lower ionization energy. The croconate dianion maintains crystalline order in P(g42T-T) and leads to a lower activation energy for the electrical conductivity than PF6− counterions. The control of the doping level with croconate allows optimization of the thermoelectric performance of the semiconducting polymer. The thermal stability of the doped films of P(g42T-T) is found to depend strongly on the nature of the counterion.  相似文献   

7.
研究了ＴｉＯ２掺杂对ＳｒＴｉＯ３电容－压敏双功能陶瓷晶粒生长特性和电性能的作用规律。研究结果表明ＴｉＯ２添加量较小时瓷体不能实现半导化。随着ＴｉＯ２添加量的增大,烧结后的表观电阻率减小,压敏电压和非线性指数减小,表观介电常数增大。ＳＥＭ观察发现ＴｉＯ２添加量较小时晶粒内部出现裂痕,较多的ＴｉＯ２添加量利于晶粒的长大。  相似文献   

8.
    
A specific design for solution‐processed doping of active semiconducting materials would be a powerful strategy in order to improve device performance in flexible and/or printed electronics. Tetrabutylammonium fluoride and tetrabutylammonium hydroxide contain Lewis base anions, F? and OH?, respectively, which are considered as organic dopants for efficient and cost‐effective n‐doping processes both in n‐type organic and nanocarbon‐based semiconductors, such as poly[[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)] (P(NDI2OD‐T2)) and selectively dispersed semiconducting single‐walled carbon nanotubes by π‐conjugated polymers. The dramatic enhancement of electron transport properties in field‐effect transistors is confirmed by the effective electron transfer from the dopants to the semiconductors as well as controllable onset and threshold voltages, convertible charge‐transport polarity, and simultaneously showing excellent device stabilities under ambient air and bias stress conditions. This simple solution‐processed chemical doping approach could facilitate the understanding of both intrinsic and extrinsic charge transport characteristics in organic semiconductors and nanocarbon‐based materials, and is thus widely applicable for developing high‐performance organic and printed electronics and optoelectronics devices.  相似文献   

9.
    
Conjugated polymers (CPs) play a central role in electronic applications due to their easily tuned electronic and ionic conductivities via chemical or electrochemical doping. Although doping improves charge conduction by introducing high densities of carriers into the CP, the accompanying structural changes and their impact on carrier mobility remain elusive. Methods capable of probing carrier distributions and their dependence on polymer morphology are needed to better understand how to improve conductivity. Here, a transient absorption (TA) spectroscopy approach is demonstrated, capable of directly probing mobile and trapped carriers in doped CPs and that is also sensitive to polymer nanostructure by using a model polythiophene system with tuned crystallinity. Exciting polarons in the polymer films produces distinct photoinduced absorption signals in the near-infrared spectrum that decay during the picosecond timescale in the form of biphasic, stretched exponential kinetics, which reflect a distribution of mobile (free) and trapped polarons. The kinetic analysis provides evidence for mobile polarons irrespective of polymer film crystallinity, whereas polarons located in impure amorphous phases with reduced chain ordering exist within a deeper distribution of trap states. Altogether, these observations suggest a stronger correlation of carrier trapping with local chain ordering (planarity or aggregation) rather than polymer crystallinity.  相似文献   

10.
    
One grand challenge for printed organic electronics is the development of a knowledge platform that describes how polymer semiconductors assemble from solution, which requires a unified picture of the complex interplay of polymer solubility, mass transport, nucleation and, e.g., vitrification. One crucial aspect, thereby, is aggregate formation, i.e., the development of electronic coupling between adjacent chain segments. Here, it is shown that the critical aggregation temperatures in solution (no solvent evaporation allowed) and during film formation (solvent evaporation occurring) are excellent pointers to i) establish reliable criteria for polymer assembly into desired aggregates, and ii) advance mechanistic understanding of the overall polymer assembly. Indeed, important insights are provided on why aggregation occurs via a 1- or 2-step process depending on polymer solubility, deposition temperature and solvent evaporation rate; and the selection of deposition temperatures for specific scenarios (e.g., good vs bad solvent) is demystified. Collectively, it is demonstrated that relatively straightforward, concurrent in situ time-resolved absorbance and photoluminescence spectroscopies to monitor aggregate formation lead to highly useful and broadly applicable criteria for processing functional plastics. In turn, improved control over their properties and device performance can be obtained toward manufacturing sensors, energy-harvesting devices and, e.g., bioelectronics systems at high yield.  相似文献   

11.
    
Organic mixed ionic-electronic conductors (OMIECs) have emerged as promising materials for a wide range of next-generation technologies, including bioelectronics and neuromorphic computing. The performance of these materials depends on the transport of ions through the polycrystalline polymer matrix as well as how the distribution of ions and polarons in crystalline and amorphous regions impacts electronic transport. However, it is often challenging to distinguish whether ions enter crystalline or amorphous regions. In this work, steady-state and time-resolved photoluminescence (PL) spectroelectrochemistry is used to probe initial ion insertion in crystalline and amorphous regions of the OMIEC material poly(3-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]thiophene -2,5-diyl) (P3MEEET) as a function of applied voltage. It is found that PL spectroelectrochemistry reports on the initial stages of electrochemical doping through the quenching of PL emission. By distinguishing between amorphous and crystalline contributions to the PL spectrum, ion insertion in crystalline and amorphous regions as a function of voltage is tracked. It is found that PL spectroelectrochemistry is much more sensitive to the initial injection of ions than complementary methods, highlighting its potential as a sensitive tool for interrogating ion injection in OMIECs.  相似文献   

12.
    
A novel method making use of block copolymer self‐assembly in nematic liquid crystals (LCs) is described for preparing macroscopically oriented nanofibrils of π‐conjugated semiconducting polymers. Upon cooling, a diblock copolymer composed of regioregular poly(3‐hexylthiophene) (P3HT) and a liquid crystalline polymer (LCP) in a block‐selective LC solvent can self‐assemble into oriented nanofibrils exhibiting highly anisotropic absorption and polarized photoluminescence emission. An unusual feature of the nanofibrils is that P3HT chains are oriented along the fibrils' long axis. This general method makes it possible to use LCs as an anisotropic medium to grow oriented nanofibrils of many semiconducting polymers insoluble in LCs.  相似文献   

13.
    
The characteristic doping process in polymer light‐emitting electrochemical cells (LECs) causes a tradeoff between luminescence intensity and efficiency. Experiments and numerical modeling on thin film polymer LECs show that, on the one hand, carrier injection and transport benefit from electrochemical doping, leading to increased electron‐hole recombination. On the other hand, the radiative recombination efficiency is reduced by exciton quenching by polarons involved in the doping. Consequently, the quasi‐steady‐state luminescent efficiency decreases with increasing ion concentration. The transient of the luminescent efficiency shows a characteristic roll‐off while the current continuously increases, attributed to ongoing electrochemical doping and the associated exciton quenching. Both effects can be modeled by exciton polaron‐quenching via diffusion‐assisted Förster resonance energy transfer. These results indicate that the tradeoff between efficiency and intensity is fundamental, suggesting that the application realm of future LECs should be sought in high‐brightness, low‐production cost devices, rather than in high‐efficiency devices.  相似文献   

14.
    
The development of sensor electrode materials for the detection of metabolites will enable point-of-care diagnostic devices for the monitoring and treatment of metabolic diseases such as diabetes. Current state-of-the-art glucose sensing electrodes employ the organic salt tetrathiafulvene tetracyanoquinodimethane (TTF TCNQ) to receive electrons directly from enzymatic reactions of glucose. However, TTF TCNQ is insoluble in most solvents, making it challenging to deposit high-quality electrodes. Furthermore, its hydrophobicity hinders its interface with aqueous solutions in physiological environments. To overcome these issues, TCNQ derivatives are introduced into an electron-rich and hydrophilic conjugated polymer. Thus, a polymeric electrode is demonstrated that is easily solution processible and can undergo volumetric direct electron transfer with glucose reactions throughout its bulk. This study further elucidates the electron transfer mechanism during chemical doping and metabolite sensing reactions to inform general design rules for this new class of glucose sensing materials.  相似文献   

15.
    
Carrier mobility in doped conjugated polymers is limited by Coulomb interactions with dopant counterions. This complicates studying the effect of the dopant's oxidation potential on carrier generation because different dopants have different Coulomb interactions with polarons on the polymer backbone. Here, dodecaborane (DDB)‐based dopants are used, which electrostatically shield counterions from carriers and have tunable redox potentials at constant size and shape. DDB dopants produce mobile carriers due to spatial separation of the counterion, and those with greater energetic offsets produce more carriers. Neutron reflectometry indicates that dopant infiltration into conjugated polymer films is redox‐potential‐driven. Remarkably, X‐ray scattering shows that despite their large 2‐nm size, DDBs intercalate into the crystalline polymer lamellae like small molecules, indicating that this is the preferred location for dopants of any size. These findings elucidate why doping conjugated polymers usually produces integer, rather than partial charge transfer: dopant counterions effectively intercalate into the lamellae, far from the polarons on the polymer backbone. Finally, it is shown that the IR spectrum provides a simple way to determine polaron mobility. Overall, higher oxidation potentials lead to higher doping efficiencies, with values reaching 100% for driving forces sufficient to dope poorly crystalline regions of the film.  相似文献   

16.
    
A study of how light‐induced degradation influences the fundamental photophysical processes in the active layer of poly(3‐hexylthiophene)/[6,6]‐phenyl C61‐butyric acid methyl ester (P3HT/PCBM) solar cells is presented. Non‐encapsulated samples are systematically aged by exposure to AM 1.5 illumination in the presence of dry air for different periods of time. The extent of degradation is quantified by the relative loss in the absorption maximum of the P3HT, which is varied in the range 0% to 20%. For degraded samples an increasing loss in the number of excitons within the P3HT domains is observed with longer ageing periods. This loss occurs rapidly, within the first 15 ps after photoexcitation. A more pronounced decrease in the population of polarons than excitons is observed, which also occurs on a timescale of a few picoseconds. These observations, complemented by a quantitative analysis of the polaron and exciton population dynamics, unravel two primary loss mechanisms for the performances of aged P3HT/PCBM solar cells. One is an initial ultrafast decrease in the polaron generation, apparently not related to the exciton diffusion to the polymer/fullerene interface; the second, less significant, is a loss in the exciton population within the photoexcited P3HT domains. The steady‐state photoinduced absorption spectra of degraded samples exhibits the appearance of a signal ascribed to triplet excitons, which is absent for non‐degraded samples. This latter observation is interpreted considering the formation of degraded sites where intersystem crossing and triplet exciton formation is more effective. The photovoltaic characteristics of same blends are also studied and discussed by comparing the decrease in the overall power conversion efficiency of solar cells.  相似文献   

17.
采用化学聚合和电化学聚合两步法制作聚吡咯(PPy)铝电解电容器,研究了电化学聚合温度对PPy的微观形貌及聚吡咯铝电解电容器的电容和等效串联电阻Res的影响,结果表明:在10～20℃聚合所得到的聚吡咯铝电解电容器的电性能都比较理想,尤以15℃电化学聚合的为最优,其电容最大为12.6μF,Res最小为32mΩ。并且在此温度条件下制备的PPy致密性高,颗粒大小均匀。  相似文献   

18.
    
A scalable and green approach to manufacture semiconducting microfibers from polymer melts has been demonstrated. The polymer chains are highly aligned along the microfiber's long axis direction and exhibit highly anisotropic optical properties. In addition, the polymer microfibers show good flexibility and stretchability with a yield point around 10% under a reversible stress and can be stretched up to 180% without breaking. These features are desired for future flexible, stretchable, and conformable electronics. The origin of this stretchability is studied with diketopyrrolopyrrole derivatives using different conjugation break spacers and side chains. In addition, stretchable conducting microfibers can be obtained by doping with FeCl3, which are further evaluated as organic conductors and source/drain electrodes in organic field‐effect transistors.  相似文献   

19.
    
Precise control of orientation and crystallinity is achieved in regioregular poly(3‐hexylthiophene) (P3HT) thin films by using high‐temperature rubbing, a fast and effective alignment method. Rubbing P3HT films at temperatures TR ≥ 144 °C generates highly oriented crystalline films with a periodic lamellar morphology with a dichroic ratio reaching 25. The crystallinity and the average crystal size along the chain axis direction, lc, are determined by high‐resolution transmission electron microscopy and differential scanning calorimetry. The inverse of the lamellar period l scales with the supercooling and can accordingly be controlled by the rubbing temperature TR. Uniquely, the observed exciton coupling in P3HT crystals is correlated to the length of the average planarized chain segments lc in the crystals. The high alignment and crystallinity observed for TR > 200 °C cannot translate to high hole mobilities parallel to the rubbing because of the adverse effect of amorphous zones interrupting charge transport between crystalline lamellae. Although tie chains bridge successive P3HT crystals through amorphous zones, their twisted conformation restrains interlamellar charge transport. The evolution of charge transport anisotropy is correlated to the evolution of the dominant contact plane from mainly face‐on (TR ≤ 100 °C) to edge‐on (TR ≥ 170 °C).  相似文献   

20.
    
Photodetectors operating across the near- to short-wave infrared (NIR–SWIR, λ = 0.9–1.8 µm) underpin modern science, technology, and society. Organic photodiodes (OPDs) based on bulk-heterojunction (BHJ) active layers overcome critical manufacturing and operating drawbacks inherent to crystalline inorganic semiconductors, offering the potential for low-cost, uncooled, mechanically compliant, and ubiquitous infrared technologies. A constraining feature of these narrow bandgap materials systems is the high noise current under an applied bias, resulting in specific detectivities (D*, the figure of merit for detector sensitivity) that are too low for practical utilization. Here, this study demonstrates that incorporating wide-bandgap insulating polymers within the BHJ suppresses noise by diluting the transport and trapping sites as determined using capacitance-frequency analysis. The resulting D* of NIR–SWIR OPDs operating from 600–1400 nm under an applied bias of −2 V is improved by two orders of magnitude, from 108 to 1010 Jones (cm Hz1/2 W−1), when incorporating polysulfone within the blends. This broadly applicable strategy can reduce noise in IR-OPDs enabling their practical operation and the realization of emerging technologies.  相似文献   

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