Energetic Control of Redox-Active Polymers toward Safe Organic Bioelectronic Materials

Avoiding faradaic side reactions during the operation of electrochemical devices is important to enhance the device stability, to achieve low power consumption, and to prevent the formation of reactive side-products. This is particularly important for bioelectronic devices, which are designed to operate in biological systems. While redox-active materials based on conducting and semiconducting polymers represent an exciting class of materials for bioelectronic devices, they are susceptible to electrochemical side-reactions with molecular oxygen during device operation. Here, electrochemical side reactions with molecular oxygen are shown to occur during organic electrochemical transistor (OECT) operation using high-performance, state-of-the-art OECT materials. Depending on the choice of the active material, such reactions yield hydrogen peroxide (H₂O₂), a reactive side-product, which may be harmful to the local biological environment and may also accelerate device degradation. A design strategy is reported for the development of redox-active organic semiconductors based on donor–acceptor copolymers that prevents the formation of H₂O₂ during device operation. This study elucidates the previously overlooked side-reactions between redox-active conjugated polymers and molecular oxygen in electrochemical devices for bioelectronics, which is critical for the operation of electrolyte-gated devices in application-relevant environments.     

Pyrazine-Functionalized Donor–Acceptor Covalent Organic Frameworks for Enhanced Photocatalytic H2 Evolution with High Proton Transport

The well-defined 2D or 3D structure of covalent organic frameworks (COFs) makes it have great potential in photoelectric conversion and ions conduction fields. Herein, a new donor–accepter (D–A) COF material, named PyPz-COF, constructed from electron donor 4,4′,4″,4′″-(pyrene-1,3,6,8-tetrayl)tetraaniline and electron accepter 4,4′-(pyrazine-2,5-diyl)dibenzaldehyde with an ordered and stable π-conjugated structure is reported. Interestingly, the introduction of pyrazine ring endows the PyPz-COF a distinct optical, electrochemical, charge-transfer properties, and also brings plentiful CN groups that enrich the proton by hydrogen bonds to enhance the photocatalysis performance. Thus, PyPz-COF exhibits a significantly improved photocatalytic hydrogen generation performance up to 7542 µmol g⁻¹ h⁻¹ with Pt as cocatalyst, also in clear contrast to that of PyTp-COF without pyrazine introduction (1714 µmol g⁻¹ h⁻¹). Moreover, the abundant nitrogen sites of the pyrazine ring and the well-defined 1D nanochannels enable the as-prepared COFs to immobilize H₃PO₄ proton carriers in COFs through hydrogen bond confinement. The resulting material has an impressive proton conduction up to 8.10 × 10⁻² S cm⁻¹ at 353 K, 98% RH. This work will inspire the design and synthesis of COF-based materials with both efficient photocatalysis and proton conduction performance in the future.     

Charge density and bare surface barrier height in GaN/AlGaN/GaN heterostructures: A modeling and simulation study

In this article, we present a physics‐based model to explain the effect of the GaN cap layers on the 2D electron gas density and the bare surface barrier height in AlGaN/GaN heterostructures. We consider that the 2DEG originates from the surface donor states present on the GaN cap top surface. The influence of a 2D hole gas, formed when the valence band crosses the Fermi energy level, has also been considered. This model agrees well with the published experimental results and TCAD simulations, and can easily be incorporated into the modeling of GaN/AlGaN/GaN‐based HEMT devices.     

Linking Glass-Transition Behavior to Photophysical and Charge Transport Properties of High-Mobility Conjugated Polymers

The measurement of the mechanical properties of conjugated polymers can reveal highly relevant information linking optoelectronic properties to underlying microstructures and the knowledge of the glass transition temperature (T_g) is paramount for informing the choice of processing conditions and for interpreting the thermal stability of devices. In this work, we use dynamical mechanical analysis to determine the T_g of a range of state-of-the-art conjugated polymers with different degrees of crystallinity that are widely studied for applications in organic field-effect transistors. We compare our measured values for T_g to the theoretical value predicted by a recent work based on the concept of effective mobility ζ. The comparison shows that for conjugated polymers with a modest length of the monomer units, the T_g values agree well with theoretically predictions. However, for the near-amorphous, indacenodithiophene–benzothiadiazole family of polymers with more extended backbone units, values for T_g appear to be significantly higher, predicted by theory. However, values for T_g are correlated with the sub-bandgap optical absorption suggesting the possible role of the interchain short contacts within materials’ amorphous domains.     

Impact of Defects on Pyrazolate Based Metal Organic Frameworks

The high strength of the metal-pyrazolate coordination bond allows the deliberate introduction of defects on pyrazolate based metal-organic frameworks without affecting the integrity of the porous crystalline network. Yet the presence of defects has a major impact on the properties of these systems which include higher pore accessibility and increased interactions with guest molecules, higher ion/electronic mobility and enhanced catalytic properties. In this review selected examples of the impact of the presence of defects in the capture of environmentally relevant gases, ion and electronic conductivity and catalytic properties of defective pyrazolate based metal organic frameworks are given.     

Donor Atom‐Stabilized Aluminum Alkyls as Cocatalysts for the Ziegler–Natta Polymerization of Propene

A number of organoaluminum compounds, stabilized with intramolecular nitrogen‐ or oxygen‐donor functions, have been used as cocatalysts for the MgCl₂/TiCl₄‐catalyzed homopolymerization of propene as well as for the copolymerization of ethene with propene. The polymerization behavior of these aluminum alkyls was examined at different Al/Ti ratios within the range of 2 to 50 and compared with the reference of triethylaluminum (TEA). Especially the alkyls [2‐(N,N‐dimethylaminomethyl)phenyl]dimethylaluminum ( 1 ) and [2‐(N,N‐dimethylaminomethyl)phenyl]diethylaluminum ( 2 ) show the highest activities at very low Al/Ti ratios in the homopolymerization of propene, whereas TEA is almost inactive. The species [8‐(N,N‐dimethylamino)naphthyl]dimethylaluminum ( 4 ) reaches the highest activity of all examined alkyls and is very close to the highest value obtained with TEA. Bulky iso‐butyl groups at the aluminum center are responsible for the very poor performance of the nitrogen stabilized cocatalysts [8‐(N,N‐dimethylamino)naphthyl]diisobutylaluminum ( 5 ) and [2‐(N,N‐dimethylaminomethyl)phenyl]diisobutylaluminum ( 3 ). The properties of the polypropenes synthesized with the stabilized organoaluminum species are similar to those produced with TEA but with a distinctly higher molar mass. In the case of 1 , it was possible to increase the molar mass by a factor of three. For the copolymerizations, the compounds [2‐(N,N‐diethylaminomethyl)phenyl]diethylaluminum ( 7 ) and (2‐methoxybenzyl)diisobutylaluminum ( 8 ) were found to be most suitable, producing polymers with significantly higher activities than TEA. For all copolymers two fractions were obtained, one crystalline fraction with a low and an amorphous part with a high amount of comonomer. In both fractions, 7 and 8 provide a higher comonomer incorporation than TEA.     

Precious‐Metal‐Free Electrocatalysts for Activation of Hydrogen Evolution with Nonmetallic Electron Donor: Chemical Composition Controllable Phosphorous Doped Vanadium Carbide MXene

The insufficient strategies to improve electronic transport, the poor intrinsic chemical activities, and limited active site densities are all factors inhibiting MXenes from their electrocatalytic applications in terms of hydrogen production. Herein, these limitations are overcome by tunable interfacial chemical doping with a nonmetallic electron donor, i.e., phosphorization through simple heat‐treatment with triphenyl phosphine (TPP) as a phosphorous source in 2D vanadium carbide MXene. Through this process, substitution, and/or doping of phosphorous occurs at the basal plane with controllable chemical compositions (3.83–4.84 at%). Density functional theory (DFT) calculations demonstrate that the P? C bonding shows the lowest surface formation energy (ΔG_Surf) of 0.027 eV Å^?2 and Gibbs free energy (ΔG_H) of –0.02 eV, whereas others such as P‐oxide and P? V (phosphide) show highly positive ΔG_H. The P3–V₂CT_x treated at 500 °C shows the highest concentration of P? C bonds, and exhibits the lowest onset overpotential of –28 mV, Tafel slope of 74 mV dec^?1, and the smallest overpotential of ‐163 mV at 10 mA cm^?2 in 0.5 m H₂SO₄. The first strategy for electrocatalytically accelerating hydrogen evolution activity of V₂CT_x MXene by simple interfacial doping will open the possibility of manipulating the catalytic performance of various MXenes.     

高压热处理对氧沉淀低温形核的影响

研究了外加高压(1GPa)下对450℃热处理硅片中氧沉淀行为的影响.透射电镜观察表明相对于大气压下热处理的样品,高压处理的样品会产生密度更高、尺寸更小的氧沉淀,表明高压有利于小直径氧沉淀的生成.电学性能测试表明,高压下处理的样品其热施主生成浓度和生成速率远远高于常压下处理的样品,这表明热施主与低温热处理过程中生成的高浓度氧沉淀核心有密切的关系.     

有机太阳能电池研究进展

有机太阳能电池与无机太阳能电池相比,还存在许多关键性问题。为了改善有机太阳能电池的性能,各种研究工作正在进行,这些研究主要是为了寻找新的材料,优化器件结构。对电池原理、部分表征方法、效率损失机制、典型器件结构、最近的发展、以及未来的发展趋势作了简要描述。