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Ultraviolet photoelectron spectroscopy was used to study energy levels of (0001) and (000 1 _ ) surfaces of bare CdS crystal terminated with Cd and S atoms, respectively, as well as energy level alignment at hybrid interfaces of CdS crystal and donor zinc phthalocyanine (PcZn) or acceptor fluoro-substituted zinc phtalocyanine (F-PcZn) layers, respectively. The data allowed us to distinguish a slight difference between ionization potential of the Cd- and S-terminated facets of the crystal and different contribution of these surfaces to formation of the interfacial dipole at the hybrid interfaces. Ionization potential for the S-terminated surface was slightly higher as compared to the Cd-terminated one for the same crystal, and a more positive dipole was always created on the S-terminated surface independent of whether the donor or acceptor phthalocyanine was used. The results showed that PcZn and F-PcZn render a dual effect at the CdS surface. First, the molecules created a dipole at the interface, however, the sign of this dipole was opposite for PcZn and F-PcZn, respectively. Second, the both molecules contributed to the formation of a depletion layer near the crystal surface. The role of the surface states of the crystal in the above effects has been elucidated. Interaction of PcZn and CdS surface was associated with the pinning of the upper occupied level of the surface states to the positive charge transfer state corresponding to the oxidized HOMO level of the molecule at the interface, whereas interaction of F-PcZn and CdS surface with the pinning of the upper occupied level of the surface states to the negative charge transfer corresponding to the reduced LUMO level of the molecule at the interface, i.e., similar to what is observed for the metal-organic interfaces, where an upper occupied level of semiconductor surface states in our case plays the role of Fermi level in metal. [ABSTRACT FROM AUTHOR]

Abstract: In this short review, we will give examples on how photoelectron spectroscopy (PES) assisted by models on interface energetics can be used to study properties important to bulk heterojunction type organic photovoltaic devices focusing on the well-known bulk heterojunction blend of poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) and its model system P3HT:C60. We also will discuss some of the limitations of PES as applied to organic semiconductors (OS) and photovoltaic devices and finish with reviewing recent theoretical advances that now enable calculation of relevant parameters at (hybrid) interfaces measured by PES. [Copyright &y& Elsevier]

An overview is given on recent results in organic spintronic research. In particular, so-called spinterfaces, spin-injecting interfaces involving organic semiconductor (OSC) molecules and ferromagnetic metals, are discussed. The interfaces are classified in different categories depending on the type and strength of interface interaction and the relevant physics concerning energy level alignment and spin polarization of interface states are explained. Examples are given on characterization of both interface energetics and spin-related properties obtained from a wide variety of experimental techniques, highlighting the different ways contacting can modify the electronic and magnetic properties of the OSC molecules and the ferromagnetic metals at the resulting spinterfaces. Finally, models for spin injection at spinterfaces are presented and discussed, followed by some speculations on consequences for device design and performance. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012 [ABSTRACT FROM AUTHOR]

Lead‐free halide double perovskites (HDPs) have emerged as a new generation of thermochromic materials. However, further materials development and mechanistic understanding are required. Here, a highly stable HDP Cs2NaFeCl6 single crystal is synthesized, and its remarkable and fully reversible thermochromism with a wide color variation from light‐yellow to black over a temperature range of 10 to 423 K is investigated. First‐principles, density functional theory (DFT)‐based calculations indicate that the thermochromism in Cs2NaFeCl6 is an effect of electron–phonon coupling. The temperature sensitivity of the bandgap in Cs2NaFeCl6 is up to 2.52 meVK−1 based on the Varshni equation, which is significantly higher than that of lead halide perovskites and many conventional group‐IV, III–V semiconductors. Meanwhile, this material shows excellent environmental, thermal, and thermochromic cycle stability. This work provides valuable insights into HDPs' thermochromism and sheds new light on developing efficient thermochromic materials. [ABSTRACT FROM AUTHOR]

Terahertz (THz) technologies provide opportunities ranging from calibration targets for satellites and telescopes to communication devices and biomedical imaging systems. A main component will be broadband THz absorbers with switchability. However, optically switchable materials in THz are scarce and their modulation is mostly available at narrow bandwidths. Realizing materials with large and broadband modulation in absorption or transmission forms a critical challenge. This study demonstrates that conducting polymer‐cellulose aerogels can provide modulation of broadband THz light with large modulation range from ≈ 13% to 91% absolute transmission, while maintaining specular reflection loss < −30 dB. The exceptional THz modulation is associated with the anomalous optical conductivity peak of conducting polymers, which enhances the absorption in its oxidized state. The study also demonstrates the possibility to reduce the surface hydrophilicity by simple chemical modifications, and shows that broadband absorption of the aerogels at optical frequencies enables de‐frosting by solar‐induced heating. These low‐cost, aqueous solution‐processable, sustainable, and bio‐friendly aerogels may find use in next‐generation intelligent THz devices. [ABSTRACT FROM AUTHOR]

Research on perovskites has grown exponentially in the past decade due to the potential of methyl ammonium lead iodide in photovoltaics. Although these devices have achieved remarkable and competitive power conversion efficiency, concerns have been raised regarding the toxicity of lead and its impact on scaling up the technology. Eliminating lead while conserving the performance of photovoltaic devices is a great challenge. To achieve this goal, the research has been expanded to thousands of compounds with similar or loosely related crystal structures and compositions. Some materials are "re-discovered", and some are yet unexplored, but predictions suggest that their potential applications may go beyond photovoltaics, for example, spintronics, photodetection, photocatalysis, and many other areas. This short review aims to present the classification, some current mapping strategies, and advances of lead-free halide double perovskites, their derivatives, lead-free perovskitoid, and low-dimensional related crystals. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Energy levels and energy level alignment at interfaces play a decisive role in designing efficient and stable organic solar cells (OSCs). In this review two usually used technologies in organic photovoltaic communities for measuring energy levels of organic semiconductors, photoelectron spectroscopy and electrochemical methods, are introduced, and the relationships between the values obtained from the corresponding techniques are compared. The energy level and energy level alignment across the interfaces involved in solution processed organic photovoltaics are described, and the corresponding integer charge transfer model for predicting and explaining energy level alignment is presented. The effects of the interface properties in designing efficient binary and ternary OSCs were discussed. The effects of environmental factors mainly including water vapor, oxygen gas and thermal annealing on energy levels and energy level alignment involved in photoactive layers, and the subsequent effects on the corresponding OSC properties are given. [ABSTRACT FROM AUTHOR]

Abstract: A universal method to obtain record‐high electronic Seebeck coefficients is demonstrated while preserving reasonable conductivities in doped blends of organic semiconductors through rational design of the density of states (DOSs). A polymer semiconductor with a shallow highest occupied molecular orbital (HOMO) level‐poly(3‐hexylthiophene) (P3HT) is mixed with materials with a deeper HOMO (PTB7, TQ1) to form binary blends of the type P3HTx:B1‐x (0 ≤ x ≤ 1) that is p‐type doped by F4TCNQ. For B = PTB7, a Seebeck coefficient S = 1100 µV K−1 with conductivity σ = 0.3 S m−1 at x = 0.10 is achieved, while for B = TQ1, S = 2000 µV K−1 and σ = 0.03 S m−1 at x = 0.05 is found. Kinetic Monte Carlo simulations with parameters based on experiments show good agreement with the experimental results, confirming the intended mechanism. The simulations are used to derive a design rule for parameter tuning. These results can become relevant for low‐power, low‐cost applications like (providing power to) autonomous sensors, in which a high Seebeck coefficient translates directly to a proportionally reduced number of legs in the thermogenerator, and hence in reduced fabrication cost and complexity. [ABSTRACT FROM AUTHOR]

Abstract: The spectra of conducting polymers obtained using ultraviolet photoelectron spectroscopy (UPS) exhibit a typical broadening of the tail σUPS ≈ 1 eV, which by an order of magnitude exceeds a commonly accepted value of the broadening of the tail of the density of states σDOS ≈ 0.1 eV obtained using transport measurements. In this work, an origin of this anomalous broadening of the tail of the UPS spectra in a doped conducting polymer, PEDOT (poly(3,4‐ethylenedioxythiophene)), is discussed. Based on the semiempirical approach and using a realistic morphological model, the density of valence states in PEDOT doped with molecular counterions is computed. It is shown that due to a disordered character of the material with randomly distributed counterions, the localized charge carriers in PEDOT crystallites experience spatially varying electrostatic potential. This leads to spatially varying local vacuum levels and binding energies. Taking this variation into account the UPS spectrum is obtained with the broadening of the tail comparable to the experimentally observed one. The results imply that the observed broadening of the tail of the UPS spectra in PEDOT provides information about a disordered spatially varying potential in the material rather than the broadening of the DOS itself. [ABSTRACT FROM AUTHOR]

Perovskite solar cells (PSCs) suffer from significant nonradiative recombination at perovskite/charge transport layer heterojunction, seriously limiting their power conversion efficiencies. Herein, solution‐processed chromium multioxide (CrOx) is judiciously selected to construct a MAPbI3/CrOx/Spiro‐OMeTAD hole‐selective heterojunction. It is demonstrated that the inserted CrOx not only effectively reduces defect sites via redox shuttle at perovskite contact, but also decreases valence band maximum (VBM)‐HOMO offset between perovskite and Spiro‐OMeTAD. This will diminish thermionic losses for collecting holes and thus promote charge transport across the heterojunction, suppressing both defect‐assisted recombination and interface carrier recombination. As a result, a remarkable improvement of 21.21% efficiency with excellent device stability is achieved compared to 18.46% of the control device, which is among the highest efficiencies for polycrystalline MAPbI3 based n–i–p planar PSCs reported to date. These findings of this work provide new insights into novel charge‐selective heterojunctions for further enhancing efficiency and stability of PSCs. [ABSTRACT FROM AUTHOR]

Fluorescent nanohybrids, based on π‐extended hydroxyoxophosphole ligands grafted onto ZnO nanoparticles, are designed and studied. The restriction of the intramolecular motions of the organic fluorophore, through either aggregates' formation in solution or processing into thin films, forms highly emissive materials due to a strong aggregation induced emission effect. Theoretical calculations and XPS analyses were performed to analyze the interactions between the organic and inorganic counterparts. Preliminary results on the use of these nanohybrids as solution‐processed emissive layers in organic light emitting diodes (OLEDs) illustrate their potential for lighting applications. [ABSTRACT FROM AUTHOR]

Organic electrochemical transistors (OECTs) have the potential to revolutionize the field of organic bioelectronics. To date, most of the reported OECTs include p‐type (semi‐)conducting polymers as the channel material, while n‐type OECTs are yet at an early stage of development, with the best performing electron‐transporting materials still suffering from low transconductance, low electron mobility, and slow response time. Here, the high electrical conductivity of multi‐walled carbon nanotubes (MWCNTs) and the large volumetric capacitance of the ladder‐type π‐conjugated redox polymer poly(benzimidazobenzophenanthroline) (BBL) are leveraged to develop n‐type OECTs with record‐high performance. It is demonstrated that the use of MWCNTs enhances the electron mobility by more than one order of magnitude, yielding fast transistor transient response (down to 15 ms) and high μC* (electron mobility × volumetric capacitance) of about 1 F cm−1 V−1 s−1. This enables the development of complementary inverters with a voltage gain of >16 and a large worst‐case noise margin at a supply voltage of <0.6 V, while consuming less than 1 µW of power. [ABSTRACT FROM AUTHOR]

Systematic investigation of the contact resistance in electrolyte-gated organic field-effect transistors (OFETs) demonstrates a dependence of source charge injection versus gate electrode work function. This analysis reveals contact-limitations at the source metal-semiconductor interface and shows that the contact resistance increases as low work function metals are used as the gate electrode. These findings are attributed to the establishment of a built-in potential that is high enough to prevent the Fermi-level pinning at the metal-organic interface. This results in an unfavorable energetic alignment of the source electrode with the valence band of the organic semiconductor. Since the operating voltage in the electrolyte-gated devices is on the same order as the variation of the work functions, it is possible to tune the contact resistance over more than one order of magnitude by varying the gate metal. [ABSTRACT FROM AUTHOR]

Abstract: Polyaniline (PANI) films of different thickness have been deposited electrochemically at two different potentials of 0.8 and 1.2 V. Characterization of the surface composition of the material: oxidation states and structural changes have been performed using X-ray photoelectron spectroscopy (XPS). The main findings of this work show that the ratio of the imine to amine nitrogens for thicker films of PANI is close to unity, indicating that the surface layer of PANI is in the emeraldine form (base). On the other hand, the surface of thinner films of PANI contains ~14–20% imine nitrogen and ~60–70% amine nitrogen. This corresponds to an oxidation state close to that of protoemeraldine. Furthermore, XPS confirms a considerable amount of p-benzoquinone (BQ) as side product formed in all thin samples. The surface morphology examined by electron microscopy measurements shows that thin films have a uniform structure, whereas microporous structure with microchannels and microcaves inside, formed as a non-periodic network of microrods is characteristic for thicker PANI films. [Copyright &y& Elsevier]

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 FAPbI3, resulting in more significant hysteresis and shorter operational stability of the PeLEDs. [ABSTRACT FROM AUTHOR]

The energy level alignment at interfaces between a low band gap conjugated polymer and various electrodes is investigated using ultraviolet photoemission spectroscopy. When the electrode work function is lower (higher) than the negative (positive) polaronic level of the polymer, the Fermi level is pinned to the negative (positive) polaronic level. These Fermi level pinning regimes suggest a spontaneous electron transfer from or towards the electrode resulting in an interfacial dipole of different orientation. On the contrary, when the substrate work function is intermediate, there is no charge transfer and the energy level alignment across the interface follows the Schottky-Mott limit. [ABSTRACT FROM AUTHOR]

2D Ruddlesden–Popper perovskites (RPPs) are emerging as potential challengers to their 3D counterpart due to superior stability and competitive efficiency. However, the fundamental questions on energetics of the 2D RPPs are not well understood. Here, the energetics at (PEA)2(MA)n−1PbnI3n+1/[6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) interfaces with varying n values of 1, 3, 5, 40, and ∞ are systematically investigated. It is found that n–n junctions form at the 2D RPP interfaces (n = 3, 5, and 40), instead of p–n junctions in the pure 2D and 3D scenarios (n = 1 and ∞). The potential gradient across phenethylammonium iodide ligands that significantly decreases surface work function, promotes separation of the photogenerated charge carriers with electron transferring from perovskite crystal to ligand at the interface, reducing charge recombination, which contributes to the smallest energy loss and the highest open‐circuit voltage (Voc) in the perovskite solar cells (PSCs) based on the 2D RPP (n = 5)/PCBM. The mechanism is further verified by inserting a thin 2D RPP capping layer between pure 3D perovskite and PCBM in PSCs, causing the Voc to evidently increase by 94 mV. Capacitance–voltage measurements with Mott–Schottky analysis demonstrate that such Voc improvement is attributed to the enhanced potential at the interface. [ABSTRACT FROM AUTHOR]

Solution-based deposition, with its simplicity and possibility for upscaling through printing, is a promising process for low-cost electronics. Metal oxide semiconductor devices, especially indium oxide with its excellent electrical properties, offer high performance compared to amorphous Si-based rivals, and with a form factor conducive to flexible and wearable electronics. Here, rectifying diodes based on an amorphous spin-coated indium oxide are fabricated for high-speed applications. We report a solution-processed diode approaching the UHF range, based on indium oxide, with aluminum and gold as the electrodes. The device was spin-coated from a precursor material and configured into a half-wave rectifier. The J – V and frequency behavior of the diodes were studied, and the material composition of the diode was investigated by X-ray photoemission spectroscopy (XPS). The 3-dB point was found to be over 700 MHz. The results are promising for the development of autonomously powered wireless Internet-of-Things systems based on scalable, low-cost processes. [ABSTRACT FROM AUTHOR]

• With a small applied potential, we can create large concentration of S vacancies in amorphous MoS 2 structure when deposited on semimetal CoMoP 2. • As electrocatalyst for hydrogen evolution, the current density of vacancy-rich MoS 2 is increased by 221% at a given overpotential. • Both theoretical and experiment confirmed the formation energy of S vacancies can decreased significantly by using CoMoP 2 as supporting material. The presence of elemental vacancies in materials are inevitable according to statistical thermodynamics, which will decide the chemical and physical properties of the investigated system. However, the controlled manipulation of vacancies for specific applications is a challenge. Here we report a facile method for creating large concentrations of S vacancies in the inert basal plane of MoS 2 supported on semimetal CoMoP 2. With a small applied potential, S atoms can be removed in the form of H 2 S due to the optimized free energy of formation. The existence of vacancies favors electron injection from the electrode to the active site by decreasing the contact resistance. As a consequence, the catalytic current is increased by 221% with the vacancy-rich MoS 2 as electrocatalyst for hydrogen evolution reaction (HER). A small overpotential of 75 mV is needed to deliver a current density of 10 mA cm−2, which is considered among the best values achieved for MoS 2. It is envisaged that this work may provide a new strategy for utilizing the semimetal phase for structuring MoS 2 into a multi-functional material. [ABSTRACT FROM AUTHOR]

Conductivity, carrier mobility, and a suitable Gibbs free energy are important criteria that determine the performance of catalysts for a hydrogen evolution reaction (HER). However, it is a challenge to combine these factors into a single compound. Herein, we discover a superior electrocatalyst for a HER in the recently identified Dirac nodal arc semimetal PtSn4. The determined turnover frequency (TOF) for each active site of PtSn4 is 1.54 H2 s−1 at 100 mV. This sets a benchmark for HER catalysis on Pt‐based noble metals and earth‐abundant metal catalysts. We make use of the robust surface states of PtSn4 as their electrons can be transferred to the adsorbed hydrogen atoms in the catalytic process more efficiently. In addition, PtSn4 displays excellent chemical and electrochemical stabilities after long‐term exposure in air and long‐time HER stability tests. [ABSTRACT FROM AUTHOR]

Conductivity, carrier mobility, and a suitable Gibbs free energy are important criteria that determine the performance of catalysts for a hydrogen evolution reaction (HER). However, it is a challenge to combine these factors into a single compound. Herein, we discover a superior electrocatalyst for a HER in the recently identified Dirac nodal arc semimetal PtSn4. The determined turnover frequency (TOF) for each active site of PtSn4 is 1.54 H2 s−1 at 100 mV. This sets a benchmark for HER catalysis on Pt‐based noble metals and earth‐abundant metal catalysts. We make use of the robust surface states of PtSn4 as their electrons can be transferred to the adsorbed hydrogen atoms in the catalytic process more efficiently. In addition, PtSn4 displays excellent chemical and electrochemical stabilities after long‐term exposure in air and long‐time HER stability tests. [ABSTRACT FROM AUTHOR]

None-fullerene solar cells with ternary architecture have attracted much attention because it is an effective approach for boosting the device power conversion efficiency. Here, the crystalline polymer N2200 as the third component is integrated into J71:ITIC bulk heterojunction. A series of characterizations indicate that N2200 could increase photo-harvesting, balanced hole and electron mobilities, enhanced exciton dissociation, and suppressed charge recombination, which result in the comprehensive improvement of open circuit voltage, short circuit current and fill factor in the device. Moreover, after introduction of N2200, the morphology of the ternary active layer is optimized, and the film crystallinity is improved. This work demonstrates that adding a small quantity of high crystallization acceptor into non-fullerene donor: acceptor mixture is a promising strategy toward developing high-performance organic solar cells. Image 1 • The effect of the crystalline polymer N2200 as the third component into J71:ITIC bulk heterojunction was investigated. • The enhanced device efficiency was attributed to balanced charge mobilities, and enhanced exciton dissociation. • The morphology and crystallization of the ternary active layer were optimized. [ABSTRACT FROM AUTHOR]

Abstract In this work, a new covalent grafting of chitosan on titanium and Ti6Al4V alloy surfaces is reported using chloroacetic acid as linker agent. Good results were obtained both on titanium and on Ti6Al4V alloy. The effect of the surface acid pretreatments on the subsequent functionalization with chitosan is evaluated. The morphological aspect of acid etched metal surfaces before chitosan grafting has been characterized by scanning electron microscopy (SEM). The presence of carboxylic groups on metal surfaces and then the efficiency of chitosan covalent immobilization were detected by Fourier transformed infrared-Attenuated Total Reflectance (FTIR-ATR) and X-Ray photoelectron spectroscopy (XPS). Cyclic voltammetry tests, using the functionalized titanium and Ti6Al4V samples as electrodes, were conducted in different aqueous solutions, to detect the presence of the homogeneous overlayer of chitosan on the surface, and to evaluate the importance of the carboxyl groups as linker agent. Highlights • An alternative way to bond covalently the chitosan on titanium and Ti6Al4V alloy was reported. • The chloroacetic acid was used as linker agent. • The effect of surface acid pretreatments on the functionalization is evaluated. • The surface grafting is verified by cyclic voltammetry, FTIR and XPS analysis. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Abstract: The electrolysis processes such as hydrogen evolution reaction (HER) require high efficient catalysts with robust surface stability. A high conductivity is also necessary to speed up the charge transport between the catalyst and the electrolyte. Recently, the observation of exceedingly high conductivity in the topological semimetal MoP, has provided a model catalyst to investigate the correlation between the electrical transport and the electrocatalytic activity for the HER. Thus, MoP is encapsulated in a Mo, P codoped carbon layer (MoP@C). This composite material exhibits outstanding HER performance, with an extremely low overpotential of 49 mV at a current density of 10 mA cm−2 and a Tafel slope of 54 mV dec−1 in an alkaline medium. In addition, electron transport analysis indicates that MoP exhibits high conductivity and mobility due to the existence of triple‐point fermions and a complex Fermi surface. Furthermore, the presence of PC and MoC bonds at the interface between the carbon layer and the MoP particles modulates the band structure of MoP@C and facilitates fast electron transfer, accumulation, and subsequent delocalization, which are in turn responsible for the excellent HER activity. [ABSTRACT FROM AUTHOR]

Abstract Interfacial compatibility between the electrode and organic semiconductor plays a critical role in controlling the charge transport and hence efficiency of organic solar cell. Here, we introduce a novel small-molecule zwitterionic electrolyte (S1) combined with ZnO as electron transporting interlayer employed for the inverted PTB7:PC 71 BM bulk heterojunction solar cell. The resulting device with the S1/ZnO stacked interlayer achieves a high PCE of 8.59%, obtaining a 16.2% improvement over the control device performance of 7.4% without the S1 attributed to the significant increased short-circuit current density and fill factor. The interfacial properties are investigated. It is found that the S1/ZnO interlayer possess an ultralow work function of 3.6 eV, which originates from the interfacial double dipole step induced by the zwitterionic side chain electrostatic realignment at interface. The S1/ZnO interlayer exhibits the excellent charge extraction ability, suppresses the charge recombination loss and decreases the series resistance at the active layer/electrode contact. Graphical abstract Image 1 Highlights • S1 coated ZnO layer is employed as electron transporting layer for inverted organic solar cell. • S1/ZnO stacked interlayer exhibits the excellent charge extraction ability. • ZnO/S1 stacked interlayer has an ultralow work function of 3.6 eV. • The efficiency of the device with the S1/ZnO interlayer constitutes a 16.2% improvement over that of the controlled device. [ABSTRACT FROM AUTHOR]

Room temperature flexible heat harvesters based on conducting polymers are ideally suited to cover the energy demands of the modern nomadic society. The optimization of their thermoelectric efficiency is usually sought by tuning the oxidation levels of the conducting polymers, even if such methodology is detrimental to the Seebeck coefficient ( S ) as both the Seebeck coefficient and the electrical conductivity ( σ ) are antagonistically related to the carrier concentration. Here we report a concurrent increase of S and σ and we experimentally derive the dependence of Seebeck coefficient on charge carrier mobility for the first time in organic electronics. Through specific control of the conducting polymer synthesis, we enabled the formation of a denser percolation network that facilitated the charge transport and the thermodiffusion of the charge carriers inside the conducting polymer layer, while the material shifted from a Fermi glass towards a semi-metal, as its crystallinity increased. This work sheds light upon the origin of the thermoelectric properties of conducting polymers, but also underlines the importance of enhanced charge carrier mobility for the design of efficient thermoelectric polymers. [ABSTRACT FROM AUTHOR]

A new strategy for designing ternary solar cells is reported in this paper. A low-bandgap polymer named PTB7-Th and a high-bandgap polymer named PBDTTS-FTAZ sharing the same bulk ionization potential and interface positive integer charge transfer energy while featuring complementary absorption spectra are selected. They are used to fabricate efficient ternary solar cells, where the hole can be transported freely between the two donor polymers and collected by the electrode as in one broadband low bandgap polymer. Furthermore, the fullerene acceptor is chosen so that the energy of the positive integer charge transfer state of the two donor polymers is equal to the energy of negative integer charge transfer state of the fullerene, enabling enhanced dissociation of all polymer donor and fullerene acceptor excitons and suppressed bimolecular and trap assistant recombination. The two donor polymers feature good miscibility and energy transfer from high-bandgap polymer of PBDTTS-FTAZ to low-bandgap polymer of PTB7-Th, which contribute to enhanced performance of the ternary solar cell. [ABSTRACT FROM AUTHOR]

ABSTRACT Poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate) (PEDOT:PSS) has been reported as a successful functional material in a broad variety of applications. One of the most important advantages of PEDOT:PSS is its water-solubility, which enables simple and environmental friendly manufacturing processes. Unfortunately, this also implies that pristine PEDOT:PSS films are unsuitable for applications in aqueous environments. To reach stability in polar solvents, (3-glycidyloxypropyl)trimethoxysilane (GOPS) is typically used to cross-link PEDOT:PSS. Although this strategy is widely used, its mechanism and effect on PEDOT:PSS performance have not been articulated yet. Here, we present a broad study that provides a better understanding of the effect of GOPS on the electrical and electronic properties of PEDOT:PSS. We show that the GOPS reacts with the sulfonic acid group of the excess PSS, causing a change in the PEDOT:PSS film morphology, while the oxidation level of PEDOT remains unaffected. This is at the origin of the observed conductivity changes. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 814-820 [ABSTRACT FROM AUTHOR]

One of the factors limiting the performance of organic solar cells (OSCs) is their large energy losses ( Eloss) in the conversion from photons to electrons, typically believed to be around 0.6 eV and often higher than those of inorganic solar cells. In this work, a novel low band gap polymer PIDTT-TID with a optical gap of 1.49 eV is synthesized and used as the donor combined with PC71BM in solar cells. These solar cells attain a good power conversion efficiency of 6.7% with a high open-circuit voltage of 1.0 V, leading to the Eloss as low as 0.49 eV. A systematic study indicates that the driving force in this donor and acceptor system is sufficient for charge generation with the low Eloss. This work pushes the minimal Eloss of OSCs down to 0.49 eV, approaching the values of some inorganic and hybrid solar cells. It indicates the potential for further enhancement of the performance of OSCs by improving their Voc since the Eloss can be minimized. [ABSTRACT FROM AUTHOR]

In electronics, the field-effect transistor (FET) is a crucial cornerstone and successful integration of this semiconductor device into circuit applications requires stable and ideal electrical characteristics over a wide range of temperatures and environments. Solution processing, using printing or coating techniques, has been explored to manufacture organic field-effect transistors (OFET) on flexible carriers, enabling radically novel electronics applications. Ideal electrical characteristics, in organic materials, are typically only found in single crystals. Tiresome growth and manipulation of these hamper practical production of flexible OFETs circuits. To date, neither devices nor any circuits, based on solution-processed OFETs, has exhibited an ideal set of characteristics similar or better than today's FET technology based on amorphous silicon. Here, bar-assisted meniscus shearing of dibenzo-tetrathiafulvalene to coat-process self-organized crystalline organic semiconducting domains with high reproducibility is reported. Including these coatings as the channel in OFETs, electric field and temperature-independent charge carrier mobility and no bias stress effects are observed. Furthermore, record-high gain in OFET inverters and exceptional operational stability in both air and water are measured. [ABSTRACT FROM AUTHOR]

The semiconductor-electrode interface impacts the function and the performance of (opto)electronic devices. For printed organic electronics the electrode surface is not atomically clean leading to weakly interacting interfaces. As a result, solution-processed organic ultrathin films on electrodes typically form islands due to dewetting. It has therefore been utterly difficult to achieve homogenous ultrathin conjugated polymer films. This has made the investigation of the correct energetics of the conjugated polymer-electrode interface impossible. Also, this has hampered the development of devices including ultrathin conjugated polymer layers. Here, Langmuir-Shäfer-manufactured homogenous mono- and multilayers of semiconducting polymers on metal electrodes are reported and the energy level bending using photoelectron spectroscopy is tracked. The amorphous films display an abrupt energy level bending that does not extend beyond the first monolayer. These findings provide new insights of the energetics of the polymer-electrode interface and opens up for new high-performing devices based on ultrathin semiconducting polymers. [ABSTRACT FROM AUTHOR]

The color of polymer solar cells using an opaque electrode is given by the reflected light, which depends on the composition and thickness of each layer of the device. Metal-oxide-based optical spacers are intensively studied in polymer solar cells aiming to optimize the light absorption. However, the low conductivity of materials such as ZnO and TiO2 limits the thickness of such optical spacers to tenths of nanometers. A novel synthesis route of cluster-free Al-doped ZnO (AZO) nanocrystals (NCs) is presented for solution processing of highly conductive layers without the need of temperature annealing, including thick optical spacers on top of polymer blends. The processing of 80 nm thick optical spacers based on AZO nanocrystal solutions on top of 200 nm thick polymer blend layer is demonstrated leading to improved photocurrent density of 17% compared to solar cells using standard active layers of 90 nm in combination with thin ZnO-based optical spacers. These AZO NCs also open new opportunities for the processing of high-efficiency color tuned solar cells. For the first time, it is shown that applying solution-processed thick optical spacer with polymer blends of different thicknesses can process solar cells of similar efficiency over 7% but of different colors. [ABSTRACT FROM AUTHOR]

The color of polymer solar cells using an opaque electrode is given by the reflected light, which depends on the composition and thickness of each layer of the device. Metal-oxide-based optical spacers are intensively studied in polymer solar cells aiming to optimize the light absorption. However, the low conductivity of materials such as ZnO and TiO2 limits the thickness of such optical spacers to tenths of nanometers. A novel synthesis route of cluster-free Al-doped ZnO (AZO) nanocrystals (NCs) is presented for solution processing of highly conductive layers without the need of temperature annealing, including thick optical spacers on top of polymer blends. The processing of 80 nm thick optical spacers based on AZO nanocrystal solutions on top of 200 nm thick polymer blend layer is demonstrated leading to improved photocurrent density of 17% compared to solar cells using standard active layers of 90 nm in combination with thin ZnO-based optical spacers. These AZO NCs also open new opportunities for the processing of high-efficiency color tuned solar cells. For the fi rst time, it is shown that applying solution-processed thick optical spacer with polymer blends of different thicknesses can process solar cells of similar efficiency over 7% but of different colors. [ABSTRACT FROM AUTHOR]

We explore the different mechanisms through which self-assembled monolayers can tailor energy level alignment at metal–organic semiconductor interfaces. We show that the large work function variation that can be induced by the self-assembled monolayer on gold has limited ability to tailor the interface energy level alignment of a subsequent organic semiconductor overlayer. [ABSTRACT FROM AUTHOR]

Optical spacers based on metal oxide layers have been intensively studied in poly(3-hexylthiophene) (P3HT) based polymer solar cells for optimizing light distribution inside the device, but to date, the potential of such a metal oxide spacer to improve the electronic performance of the polymer solar cells simultaneously has not yet be investigated. Here, a detailed study of performance improvement in high efficient polymer solar cells by insertion of solution-processed ZnO optical spacer using ethanolamine surface modification is reported. Insertion of the modified ZnO optical spacer strongly improves the performance of polymer solar cells even in the absence of an increase in light absorption. The electric improvements of the device are related to improved electron extraction, reduced contact barrier, and reduced recombination at the cathode. Importantly, it is shown for the first time that the morphology of optical spacer layer is a crucial parameter to obtain highly efficient solar cells in normal device structures. By optimizing optical spacer effects, contact resistance, and morphology of ZnO optical spacers, poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6diyl] [3-fluoro-2-[(2-ethylhexyl)carbonyl] thieno[3,4-b]thiophenediyl]] (PTB7):[6,6]-phenyl-C71-butyric acid (PC70BM) bulk heterojunction solar cells with conversion efficiency of 7.6% are obtained in normal device structures with all-solution-processed interlayers. [ABSTRACT FROM AUTHOR]

Organic photovoltaics are under intense development and significant focus has been placed on tuning the donor ionization potential and acceptor electron affinity to optimize open circuit voltage. Here, it is shown that for a series of regioregular-poly(3-hexylthiophene):fullerene bulk heterojunction (BHJ) organic photovoltaic devices with pinned electrodes, integer charge transfer states present in the dark and created as a consequence of Fermi level equilibrium at BHJ have a profound effect on open circuit voltage. The integer charge transfer state formation causes vacuum level misalignment that yields a roughly constant effective donor ionization potential to acceptor electron affinity energy difference at the donor-acceptor interface, even though there is a large variation in electron affinity for the fullerene series. The large variation in open circuit voltage for the corresponding device series instead is found to be a consequence of trap-assisted recombination via integer charge transfer states. Based on the results, novel design rules for optimizing open circuit voltage and performance of organic bulk heterojunction solar cells are proposed. [ABSTRACT FROM AUTHOR]

Preparation of size-tunable ultrathin W18O49 nanowires by an alcohol-assisted solvothermal decomposition of tungstic acid is reported. The synthesis of ultrathin W18O49 nanowires can be achieved at large scale and low cost, while changing the molecular size of the used alcohols can control the nanowire morphology. With increasing the molecular size of the alcohol, the synthesized W18O49 nanowires have smaller diameters and longer lengths. The as-prepared blue W18O49 nanomaterials show a very strong visible light absorption caused by oxygen defects and an aspect ratio-dependent photocatalytic activity on the degradation of pollutant rhodamine B (RhB) under simulated solar light irradiation. It is found that the W18O49 nanowires with highest aspect ratio show the highest activity in the photodegradation of RhB, which could be related to their higher density of oxygen surface defects in combination with a higher adsorption capability of RhB. This new synthetic route of size tunable ultrathin W18O49 nanomaterials will enlarge their potential applications and can be possibly used in the pyrolyzing synthesis of other metal oxide nanomaterials. [ABSTRACT FROM AUTHOR]

Energy level alignment and spin polarization at tetracyanoquinodimethane/Fe and acridine orange base/Fe interfaces are investigated by means of photoelectron spectroscopy and X-ray magnetic circular dichroism (XMCD), respectively, to explore their potential application in organic spintronics. Interface dipoles are observed at both hybrid interfaces, and the work function of Fe is increased by 0.7eV for the tetracyanoquinodimethane (TCNQ) case, while it is decreased by 1.2eV for the acridine orange base (AOB) case. According to XMCD results, TCNQ molecule has little influence on the spin polarization of Fe surface. In contrast, AOB molecule reduces the interfacial spin polarization of Fe significantly. Induced spin polarization of the two organic molecules at the interfaces is not observed. The results reveal the necessity of investigating the magnetic property changes of both the OSC and the FM during the process of energy level alignment engineering. [ABSTRACT FROM AUTHOR]

Printed electronics are considered for wireless electronic tags and sensors within the future Internet-of-things (loT) concept. As a consequence of the low charge carrier mobility of present printable organic and inorganic semiconductors, the operational frequency of printed rectifiers is not high enough to enable direct communication and powering between mobile phones and printed e-tags. Here, we report an all-printed diode operating up to 1.6 GHz. The device, based on two stacked layers of Si and NbSi2 particles, is manufactured on a flexible substrate at low temperature and in ambient atmosphere. The high charge carrier mobility of the Si microparticles allows device operation to occur in the charge injection-limited regime. The asymmetry of the oxide layers in the resulting device stack leads to rectification of tunneling current. Printed diodes were combined with antennas and electrochromic displays to form an all-printed e-tag. The harvested signal from a Global System for Mobile Communications mobile phone was used to update the display. Our findings demonstrate a new communication pathway for printed electronics within loT applications. [ABSTRACT FROM AUTHOR]

Ferromagnetic metal-organic semiconductor (FM-OSC) hybrid interfaces have been shown to play an important role for spin injection in organic spintronics. Here, 11,11,12,12-tetracyanonaptho-2,6-quinodimethane (TNAP) is introduced as an interfacial layer in Co-OSCs heterojunctions with an aim to tune the spin injection. The Co/TNAP interface is investigated by use of X-ray and ultraviolet photoelectron spectroscopy (XPS/UPS), near edge X-ray absorption fine structure (NEXAFS) and X-ray magnetic circular dichroism (XMCD). Hybrid interface states (HIS) are observed at Co/TNAP interfaces, resulting from chemical interactions between Co and TNAP. The energy level alignment at the Co/TNAP/OSCs interface is also obtained, and a reduction of the hole injection barrier is demonstrated. XMCD results confirm sizeable spin polarization at the Co/TNAP hybrid interface. [ABSTRACT FROM AUTHOR]

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. [Display omitted] • 2DMCs are used as OSCs layer to rule out the influence of grain boundaries on OPTs. • PPC behavior can be obtained when OPTs measured in air compared with OPTs measured under vacuum. • Oxygen-induced trap states play a critical role in PPC behavior. • Memory characteristics arising from PPC behavior are investigated. [ABSTRACT FROM AUTHOR]

Effects of in situ oxygen/water exposure on the energetics of [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) films are presented. For oxygen exposure, the work function is downshifted by ≈0.15 eV compared to the ideal integer charge transfer (ICT) curve for pristine PCBM, which is incompatible with significant introduction of electron trap states or p‐doping. Water induces the highest occupied molecular orbital (HOMO) structure to undergo strong, irreversible modifications accompanied by a chemical interaction with PCBM. [ABSTRACT FROM AUTHOR]

Polymers are lightweight, flexible, solution-processable materials that are promising for low-cost printed electronics as well as for mass-produced and large-area applications. Previous studies demonstrated that they can possess insulating, semiconducting or metallic properties; here we report that polymers can also be semi-metallic. Semi-metals, exemplified by bismuth, graphite and telluride alloys, have no energy bandgap and a very low density of states at the Fermi level. Furthermore, they typically have a higher Seebeck coefficient and lower thermal conductivities compared with metals, thus being suitable for thermoelectric applications. We measure the thermoelectric properties of various poly(3,4-ethylenedioxythiophene) samples, and observe a marked increase in the Seebeck coefficient when the electrical conductivity is enhanced through molecular organization. This initiates the transition from a Fermi glass to a semi-metal. The high Seebeck value, the metallic conductivity at room temperature and the absence of unpaired electron spins makes polymer semi-metals attractive for thermoelectrics and spintronics. [ABSTRACT FROM AUTHOR]

The energy level alignment in metal-organic and organic-organic junctions of the widely used materials tris-(8-hydroxyquinoline)aluminum (Alq3) and 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA) is investigated. The measured alignment schemes for single and bilayer films of Alq3 and NTCDA are interpreted with the integer charge transfer (ICT) model. Single layer films of Alq3 feature a constant vacuum level shift of ∼0.2-0.4 eV in the absence of charge transfer across the interface. This finding is attributed to the intrinsic dipole of the Alq3 molecule and (partial) ordering of the molecules at the interfaces. The vacuum level shift changes the onset of Fermi level pinning, as it changes the energy needed for equilibrium charge transfer across the interface. [ABSTRACT FROM AUTHOR]

Abstract: We report a method for inkjet-printing an organic semiconductor layer on top of the electrolyte insulator layer in polyelectrolyte-gated OFETs by using a surface modification treatment to overcome the underlying wettability problem at this interface. The method includes depositing an amphiphilic diblock copolymer (P3HT-b-PDMAEMA). This material is designed to have one set of blocks that mimics the hydrophobic properties of the semiconductor (poly(3-hexylthiophene) or P3HT), while the other set of blocks include polar components that improve adhesion to the polyelectrolyte insulator. Contact angle measurements, atomic force microscopy, and X-ray photoelectron spectroscopy confirm formation of the desired surface modification film. Successful inkjet printing of a smooth semiconductor layer allows us to manufacture complete transistor structures that exhibit low-voltage operation in the range of 1V. [Copyright &y& Elsevier]

Abstract: Substantial potential steps ∼0.5eV are frequently observed in organic multilayers of donor and acceptor molecules. Often such potential steps depend on the order in which the individual layers are deposited, or on which substrate they are deposited. In this paper we outline a model for these potential steps, based upon integer charge transfer between donors and acceptors, charge equilibration across the multilayer, and simple electrostatics. Each donor, acceptor, or substrate material is characterized by a pinning level, and the potential profile can be deduced from the sequential order of the layers, and the differences between their pinning levels. For particular orderings we predict that intrinsic potential differences lead to electric fields across individual layers, which may falsely be interpreted as band bending. [Copyright &y& Elsevier]

We develop an integer charge transfer model for the potential steps observed at interfaces between donor and acceptor molecular semiconductors. The potential step can be expressed as the difference between the Fermi energy pinning levels of electrons on the acceptor material and holes on the donor material, as determined from metal-organic semiconductor contacts. These pinning levels can be obtained from simple density functional theory calculations. [ABSTRACT FROM AUTHOR]