As electrode work function rises or falls sufficiently, the organic semiconductor/electrode contact reaches Fermi-level pinning, and then, few tenths of an electron-volt later, Ohmic transition. For ...organic solar cells, the resultant flattening of open-circuit voltage (V
) and fill factor (FF) leads to a 'plateau' that maximizes power conversion efficiency (PCE). Here, we demonstrate this plateau in fact tilts slightly upwards. Thus, further driving of the electrode work function can continue to improve V
and FF, albeit slowly. The first effect arises from the coercion of Fermi level up the semiconductor density-of-states in the case of 'soft' Fermi pinning, raising cell built-in potential. The second effect arises from the contact-induced enhancement of majority-carrier mobility. We exemplify these using PBDTTPD:PCBM solar cells, where PBDTTPD is a prototypal face-stacked semiconductor, and where work function of the hole collection layer is systematically 'tuned' from onset of Fermi-level pinning, through Ohmic transition, and well into the Ohmic regime.
The clinical relevance of immune landscape intratumoural heterogeneity (immune-ITH) and its role in tumour evolution remain largely unexplored. Here, we uncover significant spatial and phenotypic ...immune-ITH from multiple tumour sectors and decipher its relationship with tumour evolution and disease progression in hepatocellular carcinomas (HCC). Immune-ITH is associated with tumour transcriptomic-ITH, mutational burden and distinct immune microenvironments. Tumours with low immune-ITH experience higher immunoselective pressure and escape via loss of heterozygosity in human leukocyte antigens and immunoediting. Instead, the tumours with high immune-ITH evolve to a more immunosuppressive/exhausted microenvironment. This gradient of immune pressure along with immune-ITH represents a hallmark of tumour evolution, which is closely linked to the transcriptome-immune networks contributing to disease progression and immune inactivation. Remarkably, high immune-ITH and its transcriptomic signature are predictive for worse clinical outcome in HCC patients. This in-depth investigation of ITH provides evidence on tumour-immune co-evolution along HCC progression.
Abstract
It is widely thought that the water-oxidation reaction limits the maximum work function to about 5.25 eV for hole-doped semiconductors exposed to the ambient, constrained by the oxidation ...potential of air-saturated water. Here, we show that polymer organic semiconductors, when hole-doped, can show work functions up to 5.9 eV, and yet remain stable in the ambient. We further show that de-doping of the polymer is not determined by the oxidation of bulk water, as previously thought, due to its general absence, but by the counter-balancing anion and its ubiquitously hydrated complexes. The effective donor levels of these species, representing the edge of the ‘chemical’ density of states, can be depressed to about 6.0 eV below vacuum level. This can be achieved by raising the oxidation potential for hydronium generation, using large super-acid anions that are themselves also stable against oxidation. In this way, we demonstrate that poly(fluorene-
alt
-triarylamine) derivatives with tethered perfluoroalkyl-sulfonylimidosulfonyl anions can provide ambient solution-processability directly in the ultrahigh-workfunction hole-doped state to give films with good thermal stability. These results lay the path for design of soft materials for battery, bio-electronic and thermoelectric applications.
The presence of water strongly influences structure, dynamics and properties of ion-containing soft matter. Yet, the hydration of such matter is not well understood. Here, we show through a large ...study of monovalent π-conjugated polyelectrolytes that their reversible hydration, up to several water molecules per ion pair, occurs chiefly at the interface between the ion clusters and the hydrophobic matrix without disrupting ion packing. This establishes the appropriate model to be surface hydration, not the often-assumed internal hydration of the ion clusters. Through detailed analysis of desorption energies and O-H vibrational frequencies, together with OPLS4 and DFT calculations, we have elucidated key binding motifs of the sorbed water. Type-I water, which desorbs below 50 °C, corresponds to hydrogen-bonded water clusters constituting secondary hydration. Type-II water, which typically desorbs over 50-150 °C, corresponds to water bound to the anion under the influence of a proximal cation, or to a cation‒anion pair, at the cluster surface. This constitutes primary hydration. Type-III water, which irreversibly desorbs beyond 150 °C, corresponds to water kinetically trapped between ions. Its amount varies strongly with processing and heat treatment. As a consequence, hygroscopicity-which is the water sorption capacity per ion pair-depends not only on the ions, but also their cluster morphology.
Recent advances in chemical vapour deposition have led to the fabrication of large graphene sheets on metal foils for use in research and development. However, further breakthroughs are required in ...the way these graphenes are transferred from their growth substrates onto the final substrate. Although various methods have been developed, as yet there is no general way to reliably transfer graphene onto arbitrary surfaces, such as 'soft' ones. Here, we report a method that allows the graphene to be transferred with high fidelity at the desired location on almost all surfaces, including fragile polymer thin films and hydrophobic surfaces. The method relies on a sacrificial 'self-releasing' polymer layer placed between a conventional polydimethylsiloxane elastomer stamp and the graphene that is to be transferred. This self-releasing layer provides a low work of adhesion on the stamp, which facilitates delamination of the graphene and its placement on the new substrate. To demonstrate the generality and reliability of our method, we fabricate high field-strength polymer capacitors using graphene as the top contact over a polymer dielectric thin film. These capacitors show superior dielectric breakdown characteristics compared with those made with evaporated metal top contacts. Furthermore, we fabricate low-operation-voltage organic field-effect transistors using graphene as the gate electrode placed over a thin polymer gate dielectric layer. We finally demonstrate an artificial graphite intercalation compound by stacking alternate monolayers of graphene and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ). This compound, which comprises graphene sheets p-doped by partial hole transfer from the F4TCNQ, shows a high and remarkably stable hole conductivity, even when heated in the presence of moisture.
While thermodynamic detailed balance limits the maximum power conversion efficiency of a solar cell, the quality of its contacts can further limit the actual efficiency. The criteria for good ...contacts to organic semiconductors, however, are not well understood. Here, by tuning the work function of poly(3,4-ethylenedioxythiophene) hole collection layers in fine steps across the Fermi-level pinning threshold of the model photoactive layer, poly(3-hexylthiophene):phenyl-C
-butyrate methyl ester, in organic solar cells, we obtain direct evidence for a non-ohmic to ohmic transition at the hole contact that lies 0.3 eV beyond its Fermi-level pinning transition. This second transition corresponds to reduction of the photocurrent extraction resistance below the bulk resistance of the cell. Current detailed balance analysis reveals that this extraction resistance is the counterpart of injection resistance, and the measured characteristics are manifestations of charge carrier hopping across the interface. Achieving ohmic transition at both contacts is key to maximizing fill factor without compromising open-circuit voltage nor short-circuit current of the solar cell.
Surface‐functionalised graphene oxide nanosheets are obtained from substoichiometric oxidation of graphite, exfoliation, and in situ functionalization. Subsequent deoxidation produces zero‐gap ...imperfect graphenites with carrier mobilities of 10 cm2V−1s−1. These nanosheets exhibit trap‐free band‐like transport with sub‐meV carrier mobility activation energies at low temperatures for electrons and holes. Field‐effect transistors with zero gate‐voltage threshold have been demonstrated.
Polymeric metal coagulants are increasingly being used to improve coagulation efficiency, yet the research on the development of titanium and particularly polytitanium salts remains limited. This ...study is the first attempt in the synthesis, characterization, and application of polytitanium salts as coagulants. Polytitanium tetrachloride (PTC) solutions with different basicity values B (OH/Ti molar ratio) were prepared using a slow alkaline titration method. Jar tests were conducted to assess coagulation performance using both synthetic and real raw water samples, and the floc characteristics were monitored online using a laser diffraction particle size analyzer. Electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) was utilized to identify various Ti species, with the results providing strong evidence of the presence of various hydrolyzed Ti species in the titanium aqueous phase. Compared to titanium tetrachloride (TiCl4), higher or comparable turbidity and organic matter removal efficiency could be achieved by PTC with improved floc characteristics in terms of size, growth rate, and structure. Besides, the water pH after PTC coagulation was significantly improved toward neutral pH. This study indicates that PTC is an effective and promising coagulant for water purification. Besides, the PTC flocculated sludge was able to recycle and produce functional TiO2 photocatalyst.
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Peri-implantitis is the most common risk factor for dental implant failure. Nanostructured ceria (nano-CeO2) has anti-inflammatory and antibacterial functions, and different shapes of ...ceria enclosed by specific crystal planes could be an effective approach to enhance intrinsic catalysis. In the present study, the authors developed a novel implant surface-modification strategy by coating different shapes of nano-CeO2 onto titanium (Ti) surfaces to enhance their antibacterial and anti-inflammatory properties. The objectives of the study were to: (1) develop novel Ti surfaces modified with different shapes of nano-CeO2 (nanorod, nanocube and nano-octahedron) for peri-implantitis prevention; (2) investigate and compare the inhibition efficacy of different shapes of CeO2-modified surfaces against biofilms of peri-implantitis-related pathogens; and (3) evaluate the different CeO2-modified surfaces on cell inflammatory response in vitro and in vivo. The results showed that nanorod CeO2-modified Ti had more bacteria attachment of Streptococcus sanguinis in the early stage, compared with other CeO2-modified Ti (p < 0.05). They all exhibited similarly substantial CFU reductions against peri-implantitis-related biofilms (p > 0.1). Nanocube and nano-octahedron CeO2-modified Ti exerted much better anti-inflammatory effects and ROS-scavenging ability than nanorod CeO2in vitro (p < 0.05). In vivo, the mean mRNA expression of TNF-α, IL-6 and IL-1β in the tissues around Ti was decreased by the three shapes of nano-CeO2; nano-octahedron CeO2 showed the strongest anti-inflammatory effect among all groups (p < 0.05). In conclusion, all three types of CeO2-modified Ti exerted equally strong antibacterial properties; nano-octahedron CeO2-modified Ti had the best anti-inflammatory effect. Therefore, CeO2-modified Ti surfaces are highly promising for enhancing antimicrobial functions for dental implants. Novel nano-octahedron CeO2 coating on Ti had great therapeutic potential for alleviating and eliminating peri-implantitis.
Peri-implantitis is the most common risk factor for dental implant failure. Nanostructured ceria (nano-CeO2) has anti-inflammatory and antibacterial functions, and different shapes of ceria enclosed by specific crystal planes could be an effective approach to enhance intrinsic catalysis. In the present study, we developed a novel implant surface-modification strategy by coating different shapes of nano-CeO2 onto titanium surfaces to enhance their antibacterial and anti-inflammatory properties for dental implants. In addition, we found that the nano-octahedron CeO2 coating on titanium would have great therapeutic potential for alleviating and eliminating peri-implantitis.
Developing efficient earth‐abundant MoS2 based hydrogen evolution reaction (HER) electrocatalysts is important but challenging due to the sluggish kinetics in alkaline media. Herein, a strategy to ...fabricate a high‐performance MoS2 based HER electrocatalyst by modulating interface electronic structure via metal oxides is developed. All the heterostructure catalysts present significant improvement of HER electrocatalytic activities, demonstrating a positive role of metal oxides decoration in promoting the rate‐limited water dissociation step for the HER mechanism in alkaline media. The as‐obtained MoS2/Ni2O3H catalyst exhibits a low overpotential of 84 mV at 10 mA cm−2 and small charge‐transfer resistance of 1.5 Ω in 1 m KOH solution. The current density (217 mA cm−2) at the overpotential of 200 mV is about 2 and 24 times higher than that of commercial Pt/C and bare MoS2, respectively. Additionally, these MoS2/metal oxides heterostructure catalysts show outstanding long‐term stability under a harsh chronopotentiometry test. Theoretical calculations reveal the varied sensitivity of 3d‐band in different transition oxides, in which Ni‐3d of Ni2O3H is evidently activated to achieve fast electron transfer for HER as the electron‐depletion center. Both electronic properties and energetic reaction trends confirm the high electroactivity of MoS2/Ni2O3H in the adsorption and dissociation of H2O for highly efficient HER in alkaline media.
Through interfacial engineering, the earth‐abundant MoS2 based catalyst is synthesized with transition metal oxides. With the optimized electroactive interfaces with efficient electron transfer, the low overpotential for the hydrogen evolution reaction (HER) in the alkaline is realized in MoS2/Ni2O3H with long‐term durability. This indicates a new strategy of developing superior catalysts for HER in the harsh alkaline environment.
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