Suchergebnisse

Interface dipoles formed at an electrolyte/electrode interface have been widely studied and interpreted using the "double dipole step" model, where the dipole vector is determined by the size and/or range of motion of the charged ions. Some electron transport materials (ETMs) with lone pairs of electrons on heteroatoms exhibit a similar interfacial behavior. However, the origin of the dipoles in such materials has not yet been explored in great depth. Herein, we systematically investigate the influence of the lone pair of electrons on the interface dipole through three pyridine derivatives B2-B4PyMPM. Experiments show that different positions of nitrogen atoms in the three materials give rise to different hydrogen bonds and molecular orientations, thereby affecting the areal density and direction of the lone pair of electrons. The interface dipoles of the three materials predicted by the "double dipole step" model are in good agreement with the ultraviolet photoelectron spectroscopy results both in spin-coated and vacuum-deposited films. These findings help to better understand the ETMs/electrode interfacial behaviors and provide new guidelines for the molecular design of the interlayer. ; Funding agencies: The Swedish Research Council (project grants no. 2016-05498, 2016-05990, and 2020-04538), The Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO Mat LiU no. 2009 00971), The Open Fund of the State Key Laboratory of Luminescent Materials and Devices (South China University of Technology)

Polyvinylpyrrolidone (PVP) has been successfully used as the cathode interfacial layer (CIL) in organic solar cells (OSCs) for work function (W-F) modification. However, detailed insight into the effect of a PVP interlayer on the physicochemical properties of the indium tin oxide (ITO) electrode in inverted OSCs (I-OSCs) is still largely absent. Herein, the ITO/PVP interface is investigated by photoelectron spectroscopy and the mechanisms for the energy level alignment of PVP on different substrates in general are unraveled. The results indicate that the dipole formation that reduces the W-F is driven by not only the directional intrinsic molecular dipole moments associated with the gamma-lactam of PVP, but also an additional dipole step with the same direction created by the image charges in the contacting (semi-)conductor layer. In addition, high-performance inverted OSCs (I-OSCs) are achieved by introducing a self-assembled ultrathin PVP layer using a simple immersion method. This work provides enhanced understanding of the PVP-based CIL and demonstrates its great potential in I-OSC fabrication, which can pave the way to simplified manufacturing of low-cost and large-area devices in organic electronic technologies. ; Funding Agencies|Swedish Energy AgencySwedish Energy Agency [45411-1]; Swedish Research CouncilSwedish Research Council [2016-05498, 2016-05990]; STINT grant [CH2017-7163]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; Wallenberg Wood Science Center (WWSC) [KAW 2018.0452]

Persistent photoconductivity (PPC) behavior in organic phototransistors has fascinating potentials in applications of photoelectronic devices. A key issue is how the presence of air affects the PPC behavior. Here, combining with the theoretical and experimental results, the PPC behavior is associated with photogenerated electrons trapped in oxygen atom-induced the reduced Lowest Unoccupied Molecular Orbitals or oxygen molecule-induced new trap state within energy bandgap of organic semiconductor. Inspired by the potential applications arising from the PPC behavior, organic memory phototransistors (OMPTs) are achieved by light programming and electrical erasing. The OMPTs show bistable current states as well as long retention times. Our results suggested that oxygen in air plays a key role in PPC behavior and provides a guidance for controlling the PPC behavior toward integrated multifunctional optoelectronic devices. ; Funding Agencies|Swedish Research CouncilSwedish Research CouncilEuropean Commission [2016-05498, 2016-05990, 2020-04538]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Link odping University (Faculty Grant SFO Mat LiU) [2009 00971]; State Key Laboratory of Luminescent Materials and Devices (South China University of Technology)

Electron transport materials (ETMs) are widely used as interlayers to lower the cathode electrode work function in organic solar cells and organic light-emitting diodes, for example. The usual interpretation for their operating principle is a chemical interaction between the ETM and the electrode, inducing partial or integer charge transfer or collectively an intrinsic dipole moment caused by preferential molecular orientation. Herein, we systematically explore the commonly used ETM bathophenanthroline (BPhen) deposited on a series of conducting substrates. The energetics at the BPhen interface follows the typical integer charge transfer (ICT) model with an extra displacement of the vacuum level by up to -1.4 eV. The extra displacement is ascribed to the "double dipole step" formed by the positive and negative charged species and their induced image charges when they are close to the surface of substrates. After n-type doping the displacement is further increased to -1.8 eV, yielding a larger work function modification than obtained using typical electrolytes and zwitterions as cathode interlayer. ; Funding Agencies|Knut and Alice Wallenberg Foundation project "Tail of the Sun; Swedish Research CouncilSwedish Research Council [2016-05498]; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research [SE13-0060]; Ministry of Science and TechnologyMinistry of Education, Culture, Sports, Science and Technology, Japan (MEXT)Ministry of Science and Technology, Government of India [2016YFA0200700]; NSFCNational Natural Science Foundation of China [21504066, 21534003]; Swedish Energy AgencySwedish Energy Agency [45411-1]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO Mat LiU) [2009 00971]

The evolution of the electronic structure and optical transition upon n-doping of poly(9,9-dioctylfluorene) (PFO) films is elucidated with photoelectron spectroscopy, optical absorption, density functional theory (DFT), and time-dependent DFT (TD-DFT) calculations. Optical absorption measurements extending into near infrared show two low-energy absorption features at low doping ratios and an additional peak at a higher energy of similar to 2.2 eV that disappears with increasing doping ratios. A gap state (i.e., polaronic state) close to the Fermi level and a significantly destabilized highest valence band appear in the experimentally measured ultraviolet photoelectron spectra. These experimental results are interpreted by the TD-DFT calculations, which show that the lower energy peaks originate from the excitation from polaronic states to the conduction band, while the higher energy peak mainly originates from the destabilized valence band to conduction band transitions and only appears at low doping ratios (c(red) <= 50%, 0.5 potassium atom per fluorene monomer). The DFT calculations further indicate that polaron pairs rather than bipolarons are preferentially formed at high doping ratios. Comparing the results of doped glassy and beta-phase films, we find that the ordered segments in the beta-phase film disappear due to the dopant (potassium) insertion, resulting in a similar polaronic structure. ; Funding Agencies|Knut and Alice Wallenberg Foundation project "Tail of the Sun"; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research [SE13-0060]; Swedish Research CouncilSwedish Research CouncilEuropean Commission [2016-05498, 2016-05990]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]

Undoped, conjugated, organic molecules and polymers possess properties of semiconductors, including the electronic structure and charge transport, which can be readily tuned by chemical design. Moreover, organic semiconductors (OSs) can be n-doped or p-doped to become organic conductors and can exhibit mixed electronic and ionic conductivity. Compared with inorganic semiconductors and metals, organic (semi)conductors possess a unique feature: no insulating oxide forms on their surface when exposed to air. Thus, OSs form clean interfaces with many materials, including metals and other OSs. OS–metal and OS–OS interfaces have been intensely investigated over the past 30 years, from which a consistent theoretical description has emerged. Since the 2000s, increased attention has been paid to interfaces in organic electronics that involve dielectrics, electrolytes, ferroelectrics and even biological organisms. In this Review, we consider the central role of these interfaces in the function of organic electronic devices and discuss how the physico-chemical properties of the interfaces govern the interfacial transport of light, excitons, electrons and ions, as well as the transduction of electrons into the molecular language of cells. ; Funding agencies: Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO Mat LiU) [2009 00971]; Wallenberg Wood Science Center; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundatio

Electrochemistry is an old but still flourishing field of research due to the importance of the efficiency and kinetics of electrochemical reactions in industrial processes and (bio-)electrochemical devices. The heterogeneous electron transfer from an electrode to a reactant in the solution has been well studied for metal, semiconductor, metal oxide, and carbon electrodes. For those electrode materials, there is little correlation between the electronic transport within the electrode material and the electron transfer occurring at the interface between the electrode and the solution. Here, we investigate the heterogeneous electron transfer between a conducting polymer electrode and a redox couple in an electrolyte. As a benchmark system, we use poly(3,4-ethylenedioxythiophene) (PEDOT) and the Ferro/ferricyanide redox couple in an aqueous electrolyte. We discovered a strong correlation between the electronic transport within the PEDOT electrode and the rate of electron transfer to the organometallic molecules in solution. We attribute this to a percolation-based charge transport within the polymer electrode directly involved in the electron transfer. We show the impact of this finding by optimizing an electrochemical thermogalvanic cell that transforms a heat flux into electrical power. The power generated by the cell increased by four orders of magnitude on changing the morphology and conductivity of the polymer electrode. As all conducting polymers are recognized to have percolation transport, we believe that this is a general phenomenon for this family of conductors. ; Funding agencies: Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University Faculty Grant [SFO-Mat-LiU 2009-00971]

Doping has been proved to be one of the powerful technologies to achieve significant improvement in the performance of organic electronic devices. Herein, we systematically map out the interface properties of solution-processed air-stable n-type (4(1,3-dimethyl-2,3-dihydro-1H-benzoimidazol-2-yl)phenyl) doping fullerenes and fullerene derivatives and establish a universal energy level alignment scheme for this class of n-doped system. At low doping levels at which the charge-transfer doping induces mainly bound charges, the energy level alignment of the n-doping organic semiconductor can be described by combining integer charger transfer-induced shifts with a so-called double-dipole step. At high doping levels, significant densities of free charges are generated and the charge flows between the organic film and the conducting electrodes equilibrating the Fermi level in a classic "depletion layer" scheme. Moreover, we demonstrate that the model holds for both n- and p-doping of pi-backbone molecules and polymers. With the results, we provide wide guidance for identifying the application of the current organic n-type doping technology in organic electronics. ; Funding Agencies|National Science Foundation of China [11604099]; East China Normal Univeristy; Swedish Foundation for Strategic Research [SE13-0060]; Swedish Research Council [2016-05498]; Goran Gustafsson Foundation; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]

Nanostructures of conventional metals offer manipulation of light at the nanoscale but are largely limited to static behavior due to fixed material properties. To develop the next frontier of dynamic nano-optics and metasurfaces, this study utilizes the redox-tunable optical properties of conducting polymers, as recently shown to be capable of sustaining plasmons in their most conducting oxidized state. Electrically tunable conducting polymer nano-optical antennas are presented, using nanodisks of poly(3,4-ethylenedioxythiophene:sulfate) (PEDOT:Sulf) as a model system. In addition to repeated on/off switching of the polymeric nanoantennas, the concept enables gradual electrical tuning of the nano-optical response, which was found to be related to the modulation of both density and mobility of the mobile polaronic charge carriers in the polymer. The resonance position of the PEDOT:Sulf nanoantennas can be conveniently controlled by disk size, here reported down to a wavelength of around 1270 nm. The presented concept may be used for electrically tunable metasurfaces, with tunable farfield as well as nearfield. The work thereby opens for applications ranging from tunable flat meta-optics to adaptable smart windows. ; Funding Agencies|Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation; Swedish Research Council (VR)Swedish Research Council [2020-00287]; Swedish Foundation for Strategic Research (SSF)Swedish Foundation for Strategic Research; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]

Materials with tailored properties are crucial for high performance electronics applications. Hybrid materials composed of inorganic and organic components can possess unique merits for broad application by synergy between the advantages the respective material type offers. Here we demonstrate a novel electrochemical polymerization (EP) enabled by a 2D transition metal carbide MXene for obtaining conjugated polymer-MXene composite films deposited on conducting substrates without using traditional electrolytes, indispensable compounds for commonly electrochemical polymerization. The universality of the process provides a novel approach for EP allowing fast facile process for obtaining different new polymer/MXene composites with controlled thickness and micro-pattern. Furthermore, high performance microsupercapacitors and asymmetric microsupercapacitors are realized based on the excellent composites benefiting from higher areal capacitance, better rate capabilities and lower contact resistance than conventional electropolymerized polymers. The AMSCs exhibit a maximum areal capacitance of 69.5 mF cm(-2), an ultrahigh volumetric energy density (250.1 mWh cm(-3)) at 1.6 V, and excellent cycling stability up to 10000 cycles. The excellent electrochemical properties of the composite polymerized with MXene suggest a great potential of the method for various energy storage applications. ; Funding Agencies|Swedish Energy Agency [EM 42033-1]; Swedish Government Strategic Research Area in Material Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [200900971]; Swedish Research Council [201704123]; SSF Research Infrastructure Fellow program [RIF 14-0074]; SSF Synergy program [EM16-0004]; Knut and Alice Wallenberg (KAW) Foundation [KAW 2015.0043]; National Natural Science Foundation of China [61774077]; Open Fund of the State Key Laboratory of Luminescent Materials and Devices [2018-skllmd-12]; Fundamental Research Funds for the Central Universities

Conductive polymer PEDOT:Tos (3,4-ethylenedioxythiophene doped with molecular tosylate) gained considerable attention in various devices for bioelectronic applications, such as organic transistors and sensors. Many of these devices function upon oxidation/reduction processes in contact with aqueous electrolytes. So far, theoretical insight into morphological changes, ion injection, and water intake during these processes was rather limited. In the present work, we combined experiments and molecular dynamics simulations to study the water intake, swelling, and exchange of ions in the PEDOT:Tos film during cyclic voltammetry. We showed that the film underwent significant changes in morphology and mass during the redox processes. We observed both experimentally and in simulations that the film lost its mass during reduction, as tosylate and Na were expelled and gained mass during oxidation mainly due to the uptake of anions, i.e., tosylate and Cl. The results were in line with the UV-VIS-NIR absorption measurements and X-ray photoelectron spectroscopy (XPS) measurements, which revealed that during the redox process a portion of Tos was replaced by Cl- as the counterion for PEDOT. Also, the relative mass change between the most oxidized and reduced states was similar to 10 to 14% according to both experiments and simulations. We detected an overall material loss of the film during voltammetry cycles indicating that a portion of the material leaving the film during reduction did not return to the film during the consecutive oxidation. Our combined experimental/simulation study unraveled the underlying molecular processes in the PEDOT:Tos film upon the redox process, providing the essential understanding needed to improve and assess the performance of bioelectronic devices. ; Funding Agencies|Swedish Research CouncilSwedish Research CouncilEuropean Commission [2016-05990, 2017-04474]; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; Swedish e-Science Research Centre (SeRC)

The conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) has shown promise as air electrode in renewable energy technologies like metal-air batteries and fuel cells. PEDOT is based on atomic elements of high abundance and is synthesized at low temperature from solution. The mechanism of oxygen reduction reaction (ORR) over chemically polymerized PEDOT: Cl still remains controversial with eventual role of transition metal impurities. However, regardless of the mechanistic route, we here demonstrate yet another key active role of PEDOT in the ORR mechanism. Our study demonstrates the decoupling of conductivity (intrinsic property) from electrocatalysis (as an extrinsic phenomenon) yielding the evidence of doping of the polymer by oxygen during ORR. Hence, the PEDOT electrode is electrochemically reduced (undoped) in the voltage range of ORR regime, but O-2 keeps it conducting; ensuring PEDOT to act as an electrode for the ORR. The interaction of oxygen with the polymer electrode is investigated with a battery of spectroscopic techniques. ; Funding Agencies|European Research Council (ERC) [307596]; Knut and Alice Wallenberg foundation; Wenner-Gren Foundations; Swedish Research Council; Swedish Foundation for Strategic Research [0-3D]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]

Solar energy, although it has the highest power density available in terms of renewable energy, has the drawback of being erratic. Integrating an energy harvesting and storage device into photovoltaic energy storage modules is a viable route for obtaining self-powered energy systems. Herein, an MXene-based all-solution processed semitransparent flexible photovoltaic supercapacitor (PSC) was fabricated by integrating a flexible organic photovoltaic (OPV) with Ti3C2Tx MXene as the electrode and transparent MXene supercapacitors with an organic ionogel as the electrolyte in the vertical direction, using Ti3C2Tx thin film as a common electrode. In the quest for a semitransparent flexible PSC, Ti3C2Tx MXene was first used as a transparent electrode for OPV with a high power conversion efficiency of 13.6%. The ionogel electrolyte-based transparent MXene supercapacitor shows a high volumetric capacitance of 502 F cm(-3) and excellent stability. Finally, a flexible PSC with a high average transmittance of over 33.5% was successfully constructed by all-solution processing and a remarkable storage efficiency of 88% was achieved. This strategy enables a simple route for fabricating MXene based high-performance all-solution-processed flexible PSCs, which is important for realizing flexible and printable electronics for future technologies. ; Funding Agencies|Swedish Energy AgencySwedish Energy Agency [EM 42033-1]; Swedish Government Strategic Research Area in Material Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [200900971]; Swedish Research CouncilSwedish Research Council [2017-04123]; SSF Research Infrastructure Fellow Program [RIF 14-0074]; SSF Synergy Program [EM16-0004]; Knut and Alice Wallenberg (KAW) FoundationKnut & Alice Wallenberg Foundation [KAW 2015.0043]; National Natural Science Foundation of ChinaNational Natural Science Foundation of China [61774077]; Open Fund of the State Key Laboratory of Luminescent Materials and Devices [2018-skllmd-12]; Fundamental Research Funds for the Central UniversitiesFundamental Research Funds for the Central Universities

Matched energy level alignment is a key requirement for efficient organic devices such as organic light-emitting diodes, photovoltaics, and field-effect transistors. The effect of thermal stress/annealing on energy level alignment and related properties of the devices are less discussed compared to the extensively explored effect on morphology and corresponding device performance. Here all polymer solar cells (all-PSCs) are employed to study thermal annealing effects on energy level alignment and the corresponding effect on the device properties of the all-PSCs. It is found that optimized energy level alignment can be achieved by thermal annealing. An interface dipole layer at the donor/acceptor interface is introduced by energy level realignment that assists charge generation by reducing geminate recombination so that the voltage loss is dramatically reduced, improving the performance of the all-PSCs. ; Funding Agencies|Knut and Alice Wallenberg Foundation project "Tail of the Sun"; Swedish Research CouncilSwedish Research Council [2016-05498]; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research [SE13-0060]; Swedish Energy AgencySwedish Energy Agency [45411-1]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO Mat LiU) [2009 00971]

Despite quick development of perovskite light-emitting diodes (PeLEDs) during the past few years, the fundamental mechanisms on how ion migration affects device efficiency and stability remain unclear. Here, it is demonstrated that the dynamic redistribution of mobile ions in the emissive layer plays a key role in the performance of PeLEDs and can explain a range of abnormal behaviours commonly observed during the device measurement. The dynamic redistribution of mobile ions changes charge-carrier injection and leads to increased recombination current; at the same time, the ion redistribution also changes charge transport and results in decreased shunt resistance current. As a result, the PeLEDs show hysteresis in external quantum efficiencies (EQEs) and radiance, that is, higher EQEs and radiance during the reverse voltage scan than during the forward scan. In addition, the changes on charge injection and transport induced by the ion redistribution also well explain the rise of the EQE/radiance values under constant driving voltages. The argument is further rationalized by adding extra formamidinium iodide (FAI) into optimized PeLEDs based on FAPbI(3), resulting in more significant hysteresis and shorter operational stability of the PeLEDs. ; Funding Agencies|ERC Starting GrantEuropean Research Council (ERC) [717026]; Swedish Energy Agency EnergimyndighetenSwedish Energy Agency [48758-1, 44651-1]; Swedish Foundation for International Cooperation in Research and Higher Education [CH2018-7736]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; NSFCNational Natural Science Foundation of China (NSFC) [61774077]; Research and Development Program in Key Areas of Guangdong Province [2019B1515120073, 2019B090921002, 2019B010132004]; China Scholarship CouncilChina Scholarship Council