电子束辐照在POSS／环氧树脂二元体系TEM观察中的作用

本文以POSS／环氧树脂的二元体系为主体,研究了电子束辐照对该二元体系在透射电镜观察中的作用。研究表明,随着电子束辐照强度和辐照时间的增加,二元体系中POSS分散相的衬度越来越明显,得到的TEM图像也更加清晰。本文采用TEM图像的相对灰度值定量研究了电子束辐照时间对图像清晰度的影响,探索了电子束辐照对该二元体系TEM像衬度提高的原理。     

氨基改性MIL-101(Cr)用于CH4/CO2吸附分离的研究

采用浸渍法合成氨基改性金属有机骨架材料MIL-101(Cr),并用XRD、N2吸附和脱附、FT-IR和TG等表征手段考察材料的结构和性能,测试氨基改性MIL-101(Cr)吸附剂在101.3kPa、25℃下的CO2、CH4吸附量。结果表明,氨基改性后的MIL-101(Cr)与CO2作用力显著增强,提高了CO2吸附量和CO2/CH4分离性能。 PEI/MIL-101(Cr)质量比为70的MIL-101-PEI-70吸附剂的CO2吸附量由50.55cm3/g增加到89.43cm3/g,提升76%,而CH4吸附量由10.62cm3/g下降为5.91cm3/g,降低44%,用理想吸附溶液理论预测其CH4/CO2吸附选择性由11增加到255。吸附CO2后的吸附剂可在80℃、真空下再生,脱附条件温和。     

超临界CO2在有机液体中的分散

 针对近临界、超临界CO₂如何使有机液体及石油体积膨胀、与有机液体及石油混相和如何萃取等问题,从分子结构和分子间作用力层面简要介绍了CO₂在有机液体中的分散。近期研究结果表明,在(CO₂+有机液体)体系中,近临界、超临界CO₂并不是简单地溶解在有机液体中,而是形成了CO₂-CO₂分子聚集体、有机液体 有机液体分子聚集体和CO₂-有机液体分子聚集体共存的分散体系。随着压力的增加,由于这些分子聚集体的聚集度、尺寸或聚集体之间距离(空间)的增加,导致有机液体宏观体积增加,并进一步发展形成混相。在相同温度、压力下,有机液体的分子越小,分子间作用力越弱,CO₂越易于分散在其中,且溶解度更大,体积膨胀更明显,也更易于混相。同理,CO₂更易于萃取相对分子质量较小的物质。对CO₂与有机液体或石油混相机理和CO₂对某些物质萃取原理提出了更科学的解释。     

The Effect of Gradual Fluorination on the Properties of FnZnPc Thin Films and FnZnPc/C60 Bilayer Photovoltaic Cells

Motivated by the possibility of modifying energy levels of a molecule without substantially changing its band gap, the impact of gradual fluorination on the optical and structural properties of zinc phthalocyanine (F_nZnPc) thin films and the electronic characteristics of F_nZnPc/C₆₀ (n = 0, 4, 8, 16) bilayer cells is investigated. UV–vis measurements reveal similar Q‐ and B‐band absorption of F_nZnPc thin films with n = 0, 4, 8, whereas for F₁₆ZnPc a different absorption pattern is detected. A correlation between structure and electronic transport is deduced. For F₄ZnPc/C₆₀ cells, the enhanced long range order supports fill factors of 55% and an increase of the short circuit current density by 18%, compared to ZnPc/C₆₀. As a parameter being sensitive to the organic/organic interface energetics, the open circuit voltage is analyzed. An enhancement of this quantity by 27% and 50% is detected for F₄ZnPc‐ and F₈ZnPc‐based devices, respectively, and is attributed to an increase of the quasi‐Fermi level splitting at the donor/acceptor interface. In contrast, for F₁₆ZnPc/C₆₀ a decrease of the open circuit voltage is observed. Complementary photoelectron spectroscopy, external quantum efficiency, and photoluminescence measurements reveal a different working principle, which is ascribed to the particular energy level alignment at the interface of the photoactive materials.     

Optical,Electrical, and Magnetic Studies of Organic Solar Cells Based on Low Bandgap Copolymer with Spin ½ Radical Additives

The charge photogeneration and recombination processes in organic photovoltaic solar cells based on blend of the low bandgap copolymer, PTB7 (fluorinated poly‐thienothiophene‐benzodithiophene) with C60‐PCBM using optical, electrical, and magnetic measurements in thin films and devices is studied. A variety of steady state optical and magneto‐optical techniques were employed, such as photoinduced absorption (PA), magneto‐PA, doping‐induced absorption, and PA‐detected magnetic resonance (PADMR); as well as picosecond time‐resolved PA. The charge polarons and triplet exciton dynamics in films of pristine PTB7, PTB7/fullerene donor–acceptor (D–A) blend is followed. It is found that a major loss mechanism that limits the power conversion efficiency (PCE) of PTB7‐based solar cell devices is the “back reaction” that leads to triplet exciton formation in the polymer donor from the photogenerated charge‐transfer excitons at the D–A interfaces. A method of suppressing this “back reaction” by adding spin½ radicals Galvinoxyl to the D–A blend is presented; this enhances the cell PCE by ≈30%. The same method is not effective for cells based on PTB7/C70‐PCBM blend, where high PCE is reached even without Galvinoxyl radical additives.     

ε‐Branched Flexible Side Chain Substituted Diketopyrrolopyrrole‐Containing Polymers Designed for High Hole and Electron Mobilities

Based on the integrated consideration and engineering of both conjugated backbones and flexible side chains, solution‐processable polymeric semiconductors consisting of a diketopyrrolopyrrole (DPP) backbone and a finely modulated branching side chain (ε‐branched chain) are reported. The subtle change in the branching point from the backbone alters the π?π stacking and the lamellar distances between polymer backbones, which has a significant influence on the charge‐transport properties and in turn the performances of field‐effect transistors (FETs). In addition to their excellent electron mobilities (up to 2.25 cm² V^?1 s^?1), ultra‐high hole mobilities (up to 12.25 cm² V^?1 s^?1) with an on/off ratio (I_on/I_off) of at least 10⁶ are achieved in the FETs fabricated using the polymers. The developed polymers exhibit extraordinarily high electrical performance with both hole and electron mobilities superior to that of unipolar amorphous silicon.     

Efficiently Releasing the Trapped Energy Flow in White Organic Light‐Emitting Diodes with Multifunctional Nanofunnel Arrays

White organic light‐emitting diodes (OLEDs) hold great promise for applications in displays and lighting due to high efficiency and superior white color balance. However, further improvement in efficiency remains a continuous and urgent demand due to limited energy flow extraction. A powerful method for drastically releasing the trapped energy flow in conventional white OLEDs is demonstrated by implementing unique quasi‐periodic subwavelength nanofunnel arrays (NFAs) via soft nanoimprinting lithography, which is ideal for enhancing light extraction without any spectral distortion or angular dependence. The resulting efficiency is over 2 times that of a conventional OLED used as a comparison. The external quantum efficiency and power efficiency are raised to 32.4% and 56.9 lm W^?1, respectively. Besides, the substantial increase in efficiency over a broad bandwidth with angular color stability, the experimental proofs show that the NFA‐based extraction structure affords the enticing capacity against scrubbing and the self‐cleaning feature, which are critical to the commercial viability in practical applications.     

Locally Welded Silver Nano‐Network Transparent Electrodes with High Operational Stability by a Simple Alcohol‐Based Chemical Approach

As an indispensable aspect of emerging flexible optoelectronics, flexible transparent electrodes, especially those comprised of metal nanowires, have attracted great attentions recently. Welding the nanowire junctions is an effective strategy for reducing the sheet resistance and improving the operational stability of flexible nanowire electrode in practical applications. Herein, a simple alcohol‐based solution approach is proposed to weld crossed silver nanowires by chemically growing silver “solder” at the junctions of the nanowires, forming transparent silver nano‐network electrodes with improved electrical conductivity and operational stability. Remarkably, silver nano‐networks can be rapidly formed by this simple approach under ambient condition and room temperature, requiring no assistance from heat, light, electrical current, or mechanical pressure. Furthermore, our results show that the nano‐network electrode formed from large diameter nanowires offers a better operational stability, whose trend is opposite to that of the untreated electrodes. To demonstrate the potential application of the highly stable silver nano‐network from large diameter nanowires, organic solar cells fabricated on the nano‐network electrode incorporated with silicon dioxide nanoparticles achieve comparable performance to the ITO control device. Consequently, strategy demonstrated in this work can contribute to low‐cost and highly stable transparent electrodes in emerging flexible optoelectronics.