高分子发光材料研究进展

高分子发光材料具有可溶液加工的特点,适于制备低成本、大面积发光器件,在平板显示和固体照明领域具有潜在的应用前景.近年来,高分子发光材料在发光机制、材料体系和器件性能等方面均取得了重要进展,各项性能得到了大幅度提升.本文从材料和器件角度,围绕高分子荧光材料、高分子磷光材料和高分子热活化延迟荧光材料的分子设计策略,总结和评述了高分子荧光材料的颜色调控和效率提升途径,高分子磷光材料的磷光掺杂剂、高分子主体、拓扑结构等因素对发光性能的影响规律,以及高分子热活化延迟荧光材料的设计原理和典型材料体系.同时,分析了高分子发光材料未来发展面临的机遇和挑战.     

抗植入式高分子医用材料感染的研究进展

植入式高分子医用材料表面会粘附细菌形成生物膜引发生物材料相关的感染(BRI),给高分子医用材料的广泛应用提出了重大挑战.本文从BRI发生的机制入手,综述了通过高分子医用材料表面改性减少细菌粘附与使用抗菌素-生物材料体系两个方面来抵抗BRI发生的研究进展,重点阐述了局部抗菌药物缓释体系及纳米技术在抗菌药物缓释体系中的应用,并指出高分子前药控释体系的研究和应用是抗高分子医用材料感染的发展趋势.     

高分子/单链高分子纳米粒子复合体系中的界面性质

高分子与纳米粒子复合是改善高分子材料性能的有效途径.近20年来关于高分子/纳米粒子复合物的研究引起了学术界广泛的兴趣.然而由于此类体系中的影响因素复杂,虽然学者们在相关材料性能的研究方面取得了重要进展,但是相关理论的发展却相对滞后,其中一个重要原因是实验上表征手段的缺失,导致对体系中纳米粒子与本体高分子链相互作用规律的认识(尤其是两者界面性质的认识)不够.本文总结和阐述了我们近几年利用分子动力学模拟技术研究高分子/单链高分子纳米粒子复合体系的主要结果,并围绕此类复合体系中的界面结构及动力学性质,讨论并总结了纳米粒子对本体高分子链的作用范围及影响规律,指出单链纳米粒子对熔体链的作用范围与纳米粒子的自身尺寸相当,而与熔体高分子链的分子量没有直接的关系.该结论将为纳米复合体系高分子理论的发展提供重要参考.     

展望21世纪的高分子化学

回顾了高分子合成化学方法和高分子材料的发展历史,结合高分子化学的研究现状,展望了２１世纪的高分子化学的发展前景。     

《功能高分子材料》

全书共分17章，结合功能高分子材料的结构与性能、制备方法及应用领域，对离子交换树脂，吸附树脂，离子交换纤维和活性碳纤维，高分子膜分离材料，高分子色谱固定相，高分子试剂，高分子负载催化剂，导电高分子材料，电效发光聚合物材料，非线性光学高分子材料，液晶高分子材料，感光高分子材料，医用高分子材料，环境敏感高分子材料，高分子电解质，高分子染料，淀粉，纤维素衍生物高分子等进行了详细论述。[第一段]     

《高分子近代史》本科课程教学的探索与思考

为了培养学生对高分子科学技术的专业兴趣,激发学习热情,浙江大学从2004年开始面向高分子材料专业本科生开设《高分子近代史》专业选修课。通过让同学们了解高分子科学和高分子工业的建立和发展历程,建立和加深学生对高分子科学和学科知识整体性、结构性的理解。以世界高分子发展和中国高分子发展的两条线索向同学们介绍高分子科学技术发展中的重要历史事件、涌现的著名高分子科学家、产生的具有历史性意义的研究成果与材料,给同学们展现高分子科学与技术发展的波澜壮阔的历史画卷。经过十多年的尝试和努力,《高分子近代史》课程在教学内容、授课方式和考核方式上均形成了自己的教学特色,受到了本科生的欢迎,对激发和培养同学们学习高分子的兴趣和热情,起到了积极的作用。     

基于芴的蓝色电致发光材料研究进展

新型有机及高分子光电材料的制备与器件设计是目前国际上一个十分活跃的领域。与液晶平面显示器相比,有机和高分子电致发光平面显示器（OLED和PLED）具有主动发光、无角度依赖性、对比度好、轻、薄、能耗低等显著特点,具有广阔的应用前景。红、绿、蓝3原色是实现有效全色显示的必备条件。与红光和绿光材料相比,蓝光材料的效率、稳定性和色纯度都与前两者相去甚远。开发好的蓝光材料不仅可以作为OLED或PLED中的发光层,还可作为主体来掺杂制备绿光和白光光源。在蓝光材料中,基于芴的齐聚物和高分子拥有良好的热稳定性、高荧光量子效率和优异的电致发光特性,但其存在电荷注入与传输困难、易发生聚集、C9位易被氧化等缺点,这些缺点正是导致器件效率低、色纯度低、光谱稳定性差的原因。综述了基于芴的蓝光小分子和高分子的研究进展,主要针对含有电子给体、受体的齐聚芴和聚芴的材料设计、合成及电致发光性能,结果表明,既含空穴传输又含电子传输片段的材料比相应的只含电子给体或受体的材料性能更佳。     

高分子导热复合材料结构设计及性能研究进展

近年来,电子设备的需求逐渐向集成化、微型化发展,随之带来了愈发严重的发热问题已经成为了阻碍电子设备发展的重要因素之一。作为电子设备重要组成材料之一的高分子材料对优良导热性能的要求也越来越高,导热高分子复合材料的研究已经成为当前功能复合材料的重要发展方向。本文综述了高分子导热复合材料的发展趋势,介绍了当前选用填料法来制备单一填料、混杂填料高分子导热复合材料以及双逾渗结构、隔离结构等复杂多相结构的高分子导热复合材料的研究进展。重点介绍了通过多种导热填料的组合利用来制备高性能导热高分子复合材料。最后,对填料法高导热高分子复合材料的发展方向做出了简要展望。     

跟踪高分子学科发展前沿，建设高分子物理国家精品课程

为建设高分子物理精品课程,近年来我们关注和跟踪高分子科学发展前沿,开设了"高分子材料流变学"、"高分子凝聚态物理"等新课,编著出版新教材。这些课程和教材的一个显著特点是不失时机地将学科发展的新动态、新成果引入研究生、本科生教学,提升高分子物理课教学质量。在编著新教材中,除介绍大量新知识、新思想外,还探索性地构建起新课程的理论体系和框架。     

计算材料学在高分子材料领域的研究进展与发展趋势

随着科技发展，计算机软硬件技术的提高大大增强了大规模并行运算的效率，使得科学家能够以相对廉价的方式调用大量算力解析高自由度体系的运行机制，为设计新的材料结构与性能提供了新思路.作为材料基因工程(materials genome engineering,MG)数据驱动研发体系的核心部分，计算材料学(computational materials science)为多项尖端领域的材料研发提供了巨大的助力，新材料的多元化程度超过了任何一个历史时期.本文综述了自2011年材料基因组计划(Materials Genome Initiative, MGI)发布以来，国内外学者利用计算材料学在高分子材料方面的研究进展，包括高性能弹性体材料、光学高分子材料、能源高分子材料、导热高分子材料和生物医用高分子材料.与此同时，阐述了计算材料学未来发展趋势与面临的挑战，期望为高分子材料基因组的发展方向提供指导.     

Dialing in color with rare earth metals: facile photoluminescent production of true white light

Combining polymeric architectures with metal ions produces hybrid materials with extremely rich properties. We are studying polymers containing terpyridine in the side chain. In this report, the chelation of lanthanide ions, Eu³⁺, Tb³⁺, and Dy³⁺ resulted in metal functionalized copolymers that exhibited excellent emission of red, green, and blue light respectively. The polymer architecture easily allows incorporation of all three colors into the material, which leads to the facile production of true white light in solution or the solid state. Quantum efficiencies for the polymer systems were determined. The white light system had an efficiency of 5%. Various combinations of colors were achieved from the basic RBG colors by simply varying the metal ion ratios in the polymer backbone. This easy tuning of the color makes these systems attractive. Copyright © 2007 John Wiley & Sons, Ltd.     

Upconversion multicolor fine-tuning: visible to near-infrared emission from lanthanide-doped NaYF4 nanoparticles

A general approach to fine-tuning the upconversion emission colors, based upon a single host source of NaYF4 nanoparticles doped with Yb3+, Tm3+, and Er3+, is presented. The emission intensity balance can be precisely controlled using different host-activator systems and dopant concentrations. The approach allows access to a wide range of luminescence emission from visible to near-infrared by single-wavelength excitation.     

Polymerized Thermally Activated Delayed-Fluorescence Small Molecules: Long-Axis Polymerization Leads to a Nearly Concentration-Independent Luminescence

Nowadays numerous thermally activated delayed fluorescence (TADF) polymers have been developed for PLEDs to realize high device performance and tunable emission colors. However, they often possess a strong concentration dependence on their luminescence including aggregation-caused quenching (ACQ) and aggregation-induced emission (AIE). Herein, we first report a nearly concentration-independent TADF polymer based on the strategy of polymerized TADF small molecules. It is found that when a donor-acceptor-donor (D-A-D) type TADF small molecule is polymerized through its long-axis direction, the triplet state is distributed along the polymeric backbone to effectively suppress the unwanted concentration quenching. Unlike the short-axis one with an ACQ effect, the photoluminescent quantum yield (PLQY) of the resultant long-axis polymer remains almost unchanged with the increasing doping concentration. Accordingly, a promising external quantum efficiency (EQE) up to 20 % is successfully achieved in a whole doping control window of 5–100 wt. %.     

Theoretical investigation on the white-light emission from a single-polymer system with simultaneous blue and orange emission (Part II)

We report here a theoretical investigation of the white-light emission from a single-polymer system with simultaneous blue (polyfluorene as a blue host) and orange (2,1,3-benzothiadiazole(BTD)-based derivative as an orange dopant) emission. With use of quantum-chemical approaches, our studies are focused on the variation in electronic and optical properties as a function of the chemical composition of the backbone in BTD-based derivatives. Furthermore, the results show that the electronic and optical properties of designed BTD-based derivatives can be tuned by the introduction of suitable electron-donating groups on terminal N,N-disubstituted amino groups, implying good candidates as orange dopants in WPLEDs with polyfluorene as a blue-light-emitting host. In addition, low reorganization energy values of holes or narrow differences between hole and electron transportations within the framework of the charge hopping model suggest designed BTD-based derivatives to be good hole transport or ambipolar transport materials in organic light-emitting diodes. It is also found that the designed BTD-based derivatives containing fluorene-based unit exhibit higher stability.     

Designing of the white-light emission from a single-polymer system: Quantum theoretical study

Quantum-chemical calculations are applied to study the white-light emission from a single-polymer system with simultaneous blue (polyfluorene as a blue host) and orange (2,1,3-benzothiadiazole-based derivative as an orange dopant) emissions. Particular attention is paid to the variation in electronic and optical properties upon the structure tuning in pristine 2,1,3-benzothiadiazole-based derivative. Importantly, by the introduction of electron-donating groups on terminal N,N-disubstituted amino groups, the electronic and optical properties of designed 2,1,3-benzothiadiazole-based derivative have been tuned, making them to be potential candidates as orange dopants in white organic light-emitting devices based on polymers with polyfluorene as a blue-light-emitting host. Furthermore, designed 2,1,3-benzothiadiazole-based derivatives have a possibility to be good hole or ambipolar transport materials in organic light-emitting diodes from the charge hopping model. Finally, we find that the designed 2,1,3-benzothiadiazole-based derivative exhibit improved stability.     

Control of Multicolor and White Emission by Adjusting the Equilibrium between Fluorophores,Lewis Acids,and Their Complexes in Polymers

Multicolor emissive materials consisting of a single luminophore, a Lewis acid, and their complex were developed. The emission colors can be tuned by changing the concentration of the solution and the ratio of mixed solvents. Various emission colors in the solid state were observed when the complexes were added to polymers in different amounts. The color change is due to equilibrium disruption between the single luminophore, the Lewis acid, and the complex thereof. White emission was observed by appropriately controlling the equilibrium by changing the amount of the complex in the polymer.     

Control of Multicolor and White Emission by Adjusting the Equilibrium between Fluorophores,Lewis Acids,and Their Complexes in Polymers

Multicolor emissive materials consisting of a single luminophore, a Lewis acid, and their complex were developed. The emission colors can be tuned by changing the concentration of the solution and the ratio of mixed solvents. Various emission colors in the solid state were observed when the complexes were added to polymers in different amounts. The color change is due to equilibrium disruption between the single luminophore, the Lewis acid, and the complex thereof. White emission was observed by appropriately controlling the equilibrium by changing the amount of the complex in the polymer.     

Electroluminescent Conjugated Polymers—Seeing Polymers in a New Light

A new exciting interdisciplinary research field has evolved following the discovery that conjugated polymers can emit light when put into light-emitting diodes. A myriad of light-emitting polymers (examples of which are shown below) shining in various colors have been developed through chemical intuition and structural design.     

Free radical oxidation reaction for selectively solvatochromic sensors with dynamic sensing ability

A novel BODIPY (boradiazaindacene) dye denoted as BODIPY-DT containing terpyridine unit has been designed and characterized. The dye is found to be selective and visual solvatochromic sensor toward DMF among test organic solvents. The sensing process displays time-controllable, dynamic signal outputs in the emission colors including red, purple, yellow and even white emission colors. It is presented that selective free radical oxidation reaction happens during the recognition process.     

Orthogonal Trichromatic Upconversion with High Color Purity in Core-Shell Nanoparticles for a Full-Color Display

Materials with tunable emission colors has attracted increasing interest in both fundamental research and applications. As a key member of light-emitting materials family, lanthanide doped upconversion nanoparticles (UCNPs) have been intensively demonstrated to emit light in any color upon near-infrared excitation. However, realizing the trichromatic emission in UCNPs with a fixed composition remains a great challenge. Here, without excitation pulsed modulation and three different near-infrared pumping, we report an experimental design to fine-control emission in the full color gamut from core–shell-structured UCNPs by manipulating the energy migration through dual-channel pump scheme. We also demonstrate their potential application in full-color display. These findings may benefit the future development of convenient and versatile optical methos for multicolor tuning and open up the possibility of constructing full-color volumetric display systems with high spatiotemporal resolution.