高度取向的半导体聚合物薄膜的溶液浸涂法生长及其电荷传输特性研究

有效地控制有机半导体分子取向和堆积特性对实现高性能电子器件具有非常重要的意义,而发展简便高效的溶液相成膜技术是实现这一目的的重要途径.本文采用改进的溶液浸涂法,成功地成长出大面积宏观取向的半导体聚合物P(NDI2OD-T2)和PTHBDTP薄膜.偏光显微镜和极化的紫外-可见光吸收谱测量显示,薄膜中聚合物分子主链骨架沿成膜时液面下移方向择优取向.原子力显微镜观察到聚合物薄膜由纳米尺度的取向有序晶畴构成,畴的取向与分子链的取向一致.采用衬底-溶液界面处表面张力和溶剂蒸发诱导的分子自组织过程来解释浸涂法生长聚合物取向薄膜的微观机理.使用取向的P(NDI2OD-T2)薄膜制备场效应晶体管,显著地提高了电子迁移率(可达4倍),并实现高达19的迁移率各向异性度.这可归因于共轭的聚合物主链骨架择优取向引起电荷传导通路的变化.     

速度对聚四氟乙烯摩擦系数影响的分子动力学模拟

基于分子动力学方法建立了双层聚四氟乙烯(polytetrafluoroethylene,PTFE)摩擦模型,研究了不同速度下PTFE的摩擦过程.通过分析不同速度下接触区内下层PTFE分子键长、键角、分子形状的变化及接触过程中摩擦力和正压力的变化,从微观角度研究了速度对PTFE摩擦系数的影响.研究结果表明:随着速度的增加,接触区内PTFE粒子间的键长变短,键角变小,分子链沿x;方向的变形量增加.变形后的PTFE分子产生的回弹力导致上、下层PTFE分子间相互作用力增加,从而增加了摩擦力.当速度进一步增大时,接触区内下层PTFE粒子间的键长和键角多处于平衡位置,分子链沿x方向的变形量减小.这很可能是由于接触区内下层PTFE分子沿速度方向倾斜,使上、下层PTFE分子趋于平行滑动,从而降低了摩擦力.不同速度下正压力几乎保持不变.因此,当上层PTFE所受外载荷固定时,摩擦系数随着速度的增加先增大后减小,临界速度为1.2 m/s,这与实验研究结果一致.     

单个纳米粒子对聚合物结晶行为的影响

采用粗粒化模型,应用分子动力学方法研究了单个纳米粒子对聚合物结晶行为的影响.通过改变纳米粒子与聚合物单体之间作用方式(吸引作用或排斥作用)、纳米粒子与聚合物单体之间作用强度和聚合物分子链的长度,计算整个系统和局部区域的有序参数,研究了三个不同因素下纳米粒子对聚合物结晶行为的不同影响.研究表明,在聚合物基体中添加单个纳米粒子,纳米粒子对整个系统的结晶影响不明显,但是纳米粒子对其周围聚合物单体的结晶存在局部强化作用.当纳米粒子与聚合物单体之间为吸引作用且作用强度较大时,纳米粒子对聚合物结晶表现出明显的局部强化作用,聚合物分子链长度也有着一定的影响,在较大吸引作用强度下,长链样本比短链样本有着更为显著的局部强化作用.     

Langmuir-Blodgett膜摩擦分子动力学模拟和机理研究

采用分子动力学方法,模拟了在两块石英基板上由脂肪酸(C₁₅H₃₁COOH)组成的单层Langmuir-Blodgett (LB)膜间的摩擦特性,探究了超薄膜在滑动过程中的摩擦和结构机理.得出对于单层LB膜在滑动过程中,在速度小于60m/s时,随着速度的增大,其剪切压增大;在速度大于60 m/s时,剪切压随速度的增加而减小.其链的倾斜角随着滑动速度的增加而减小.单层膜内的分子之间以氢键方式形成了较大的分子簇,由此导致了剪切压呈现较长的周期性,但在单层膜之间无氢键形 关键词： 分子动力学模拟 朗缪尔布洛杰特膜 纳米摩擦 氢键     

拉伸取向聚合物2H NMR谱的键涨落模型Monte Carlo模拟

采用三维键涨落模型（BFM）的Monte Carlo计算机模拟方法,模拟了两种分别具有高取向和低取向链微观结构的拉伸取向聚合物²H NMR谱. 讨论了排除体积效应与链的均方末端距分布对²H NMR谱线的影响. 结果表明,排除体积效应对高取向和低取向聚合物²H谱劈裂的影响是不同的,较小均方末端距的链决定²H谱劈裂,而较大均方末端距的链使²H谱产生长的拖尾. 采用BFM计算机模拟与²H NMR实验的结合是研究拉伸取向聚合物网络微观结构的有力手段.     

聚酰亚胺LB膜上液晶表面锚定的研究

通过测试光延迟研究了聚酰亚胺ＬＢ膜的光学各向异性，分析了在ＬＢ膜成膜过程中成膜分子的流动取向特性，并研究了液晶的表面锚定能，分析了ＬＢ膜上液晶的取向机制．聚酰亚胺ＬＢ膜的链段的取向程度较强摩擦情形的聚酰亚胺表面的链段取向要差．强摩擦的聚酰亚胺会比聚酰亚胺ＬＢ膜具有更好的排列液晶分子的能力．ＬＢ膜的流动取向模式使得聚酰亚胺成膜分子沿拉伸方向形成一定的有序排列，并诱导液晶分子定向排列，液晶和聚合物分子相互作用是液晶表面排列的主要动力 关键词：     

聚甲基丙烯酸三氟乙酯单体与分子链在金属有机框架中吸附及取向特性的理论研究

本文结合分子动力学、密度泛函理论和蒙特卡洛方法,研究了光学损耗低的氟化聚合物单体分子甲基丙烯酸三氟乙酯（TFMA）及其分子链在[Zn2(BDC)2TED]n和[Zn2(BPDC)2TED]n两种结构有序的金属有机框架（MOFs）材料中的吸附特性,得到相应的吸附数量和取向程度,以探索提高聚合物材料双折射性的有效途径。通过分析结果得出影响TFMA单体分子在这两种MOF孔道中吸附及取向特性的三个因素：a）由于MOF孔道壁是由金属离子和有机配体组成的极性表面,MOF孔壁与极性分子TFMA之间的静电相互作用对TFMA单体分子在孔道内的吸附和取向有促进作用;b）在受限空间中的聚合物单体分子之间的静电相互作用使其分子间隙更加紧密,同样也对其分子取向有促进作用;c）在这个两种孔洞与聚合物单体分子相对大小不同的MOF中,单体分子和分子链的取向度基本一致,但单体分子在孔径较大的MOF中吸附数量更多。这三个因素的重要影响,为聚合物单体或MOF的选取、对聚合物链取向及双折射性的控制提供理论预测方法。     

利用单分子光学探针测量幂律分布的聚合物动力学

研究聚合物薄膜纳米尺度的动力学特性对于高性能材料的制备具有重要的意义.本文利用尼罗红单分子作为光学探针吸附在聚丙烯酸甲酯(PMA)聚合物链上,研究该聚合物薄膜的动力学特性.通过单分子散焦宽场荧光成像显微镜技术测量了单分子随PMA聚合物链转动弛豫的三维再取向特性,当环境温度高于PMA的玻璃点温度19 K时,发现处于PMA聚合物薄膜中的单分子光学探针的转动态和非转动态的持续时间概率密度服从指数截止的幂律分布.研究结果表明该温度下PMA聚合物薄膜的纳米环境动力学仍存在空间和时间异构性.     

亲水性两性离子聚合物刷的构象与结构

本文应用分子场理论,研究暴露于水蒸气中的亲水性两性离子聚合物(HP)刷的构象与结构.理论模型考虑HP-水(P-W)氢键和水-水(W-W)氢键效应,以及HP单体之间的偶极-偶极相互作用.研究发现,P-W与W-W氢键决定着HP的水合性,P-W氢键形成,会诱导HP刷溶胀.我们通过考察HP单体间的偶极-偶极相互作用发现,随着偶极-偶极相互作用增强,HP链在垂直培基表面沿着链方向,形成了结节状结构.这是由于HP单体之间的偶极-偶极静电吸引作用导致单体间汇聚结节,这种结节在刷内产生了较强的排斥体积作用,因此,这种HP刷具有抗污性能.在较高的接枝密度环境下,由于HP链间单体之间的偶极-偶极静电吸引作用,会形成链间单体-单体的结节,在刷内形成结节网络状凝胶结构,这种结构的出现,会使得HP刷呈现极强的抗污性.另外,当体系中水蒸气浓度增加、水合相互作用增强时,增加的P-W氢键将平衡HP单体之间的偶极-偶极相互作用,使得结节解开,聚合物链伸展.我们的理论结果符合实验观测,由此表明,P-W氢键效应,以及HP单体之间的偶极-偶极相互作用决定着HP刷的构象转变和结构特性,刷内出现的两性离子聚合物链内单体间的结节和链间单体结节状凝胶结构,是两性离子聚合物刷呈现较强抗污性的本质特性.     

摩擦基板间液晶薄层的分子场理论

提出一种新的表面作用势用于描写摩擦基板对液晶分子的作用.通过分子场理论研究摩擦基板间的液晶薄层,基板作用使液晶分子沿面平行排列.采用Lebwohl Lasher模型,将分子质心固定在简单立方晶格的格点上.对20个分子层构成的液晶薄层进行了数值计算.存在3种分子优先取向方向不同的状态,优先取向方向沿摩擦方向的状态具有最低自由能,并考虑了基板作用引起的双轴对称性.     

Friction and normal forces of model friction modifier additives in simulations of boundary lubrication

ABSTRACT

Interaction forces between solid surfaces are often mitigated by adsorbed molecules that control normal and friction forces at nanoscale separations. Molecular dynamics simulations were conducted of opposing semi-ordered monolayers of united-atom chains on sliding surfaces to relate friction and normal forces to imposed sliding velocity and inter-surface separation. Practical examples include adsorbed friction-modifier molecules in automatic transmission fluids. Friction scenarios in the simulations had zero, one, or two fluid layers trapped between adsorbed monolayers. Sliding friction forces increased with sliding velocity at each stable separation. Lower normal forces were obtained than in most previous nanotribology molecular simulations and were relatively independent of sliding speed. Distinguishing average frictional force from its fluctuations showed the importance of system size. Uniform velocities were obtained in the sliding direction across each adsorbed film, with a gradient across the gap containing trapped fluid. The calculated friction stress was consistent with measurements reported using a surface forces apparatus, indicating that drag between an adsorbed layer and trapped fluid can account sufficiently for sliding friction in friction modifier systems. An example is shown in which changes in molecular organisation parallel to the surface led to a large change in normal force but no change in friction force.     

Frictional properties of confined polymers

We present molecular dynamics friction calculations for confined hydrocarbon solids with molecular lengths from 20 to 1400 carbon atoms. Two cases are considered: a) polymer sliding against a hard substrate, and b) polymer sliding on polymer. In the first setup the shear stresses are relatively independent of molecular length. For polymer sliding on polymer the friction is significantly larger, and dependent on the molecular chain length. In both cases, the shear stresses are proportional to the squeezing pressure and finite at zero load, indicating an adhesional contribution to the friction force. The friction decreases when the sliding distance is of the order of the molecular length indicating a strong influence of molecular alignment during run-in. The results of our calculations show good correlation with experimental work.     

Nanoscale interaction mechanism between a solid tip and a layered material while in relative motion: the boric acid case

The interaction occurring between a layered material (boric acid) and an atomic force microscope tip is discussed. It is shown that images containing the periodicity of a boric acid crystal, and the low friction occurring between the tip and the crystal surface, are caused by an effective tip composed of boric acid molecules. The friction at the sliding system decreases with an increase of the scanning velocity, suggesting that the dependence of friction on the velocity can be caused by a change of the energy dissipation regime from the nonlinear dynamics of a sliding system to phonon excitation.     

Systematic study of the effect of disorder on nanotribology of self-assembled monolayers

The adhesion and friction between pairs of ordered and disordered self-assembled monolayers on SiO2 are studied using molecular dynamics. The disorder is introduced by randomly removing chains from a well ordered crystalline substrate and by attaching chains to an amorphous substrate. The adhesion force between monolayers at a given separation increases monotonically with chain length at full coverage and with coverage for fixed chain length. Friction simulations are performed at shear velocities between 0.02-2 m/s at constant applied pressures between 200 and 600 MPa. Stick-slip motion is observed at full coverage but disappears with disorder. With random defects, the friction becomes insensitive to chain length, defect density, and substrate.     

Elastic properties of polymer networks with sliding junctions

This paper proposes simple models of polymer networks with sliding junctions for molecular simulation and reports the main results obtained by Brownian dynamics on the elastic properties of networks with tri-functional sliding junctions. The stress-strain relation for isotropic swelling and uniaxial deformation are obtained and compared with those of the conventional chemical gels. We find that mobility and distribution of sliding junctions along the polymer chains drastically change with deformation, and lead to new profiles of the stress. We also find that sliding junctions aggregate by deformation, resulting in the decrease in the number of elastically effective chains.     

聚合物飞秒激光加工的分子动力学建模与仿真

通过合理选择聚合物分子结构模型和高精度势能函数,建立了聚合物飞秒激光烧蚀加工的分子动力学仿真模型,并使用该模型研究了聚乙烯和聚苯乙烯飞秒激光烧蚀加工中的激光能量辐照和扩散过程。研究结果表明:激光烧蚀加工中聚合物材料的去除方式包括单链热激发引起的表面蒸发和单链热运动引起的内部热膨胀。聚苯乙烯单链的微观变形方式包括单链的整体移动和单链自身结构的变化。聚乙烯和聚苯乙烯的分子结构差异对聚合物单链变形行为和材料去除体积等烧蚀加工结果具有显著的影响。     

脉冲高能量密度等离子体法制备TiN薄膜及其摩擦磨损性能研究

利用脉冲高能量密度等离子体技术在室温条件下在45号钢基材上制备出了超硬耐磨TiN薄膜.利用XRD，XPS，AES，SEM等手段分析了薄膜的成分及显微组织结构，并测试了薄膜的硬度分布及摩擦磨损性能.结果表明：薄膜主要组成相为TiN，薄膜组织致密、均匀，与基材之间存在较宽的混合界面；薄膜硬度高，在干滑动磨损实验条件下具有优异的耐磨性及较低的摩擦系数. 关键词： 脉冲高能量密度等离子体 TiN膜 显微组织 耐磨性     

Microscopic degradation mechanism of polyimide film caused by surface discharge under bipolar continuous square impulse voltage

Polyimide （PI） film is an important type of insulating material used in inverter-fed motors. Partial discharge （PD） under a sequence of high-frequency square impulses is one of the key factors that lead to premature failures in insulation systems of inverter-fed motors. In order to explore the damage mechanism of PI film caused by discharge, an aging system of surface discharge under bipolar continuous square impulse voltage （BCSIV） is designed based on the ASTM 2275 01 standard and the electrical aging tests of PI film samples are performed above the partial discharge inception voltage （PDIV）. The chemical bonds of PI polymer chains are analyzed through Fourier transform infrared spectroscopy （FTIR） and the dielectric properties of unaged and aged PI samples are investigated by LCR testers HIOKI 3532-50. Finally, the micro-morphology and micro-structure changes of PI film samples are observed through scanning electron microscopy （SEM）. The results show that the physical and chemical effects of discharge cut off the chemical bonds of PI polymer chains. The fractures of ether bond （C-O-C） and imide ring （C-N-C） on the backbone of a PI polymer chain leads to the decrease of molecular weight, which results in the degradation of PI polymers and the generation of new chemical groups and materials, like carboxylic acid, ketone, aldehydes, etc. The variation of microscopic structure of PI polymers can change the orientation ability of polarizable units when the samples are under an AC electric field, which would cause the dielectric constant e to increase and dielectric loss tan ~ to decrease. The SEM images show that the degradation path of PI film is initiated from the surface and then gradually extends to the interior with continuous aging. The injection charge could result in the PI macromolecular chain degradation and increase the trap density in the PI oolvmer bulk.     

Friction,adhesion and wear durability of an ultra-thin perfluoropolyether-coated 3-glycidoxypropyltrimethoxy silane self-assembled monolayer on a Si surface

The tribological properties, such as coefficient of friction, adhesion and wear durability of an ultra-thin (<10?nm) dual-layer film on a silicon surface were investigated. The dual-layer film was prepared by dip-coating perfluoropolyether (PFPE), a liquid polymer lubricant, as the top layer onto a 3-glycidoxypropyltrimethoxy silane self-assembled monolayer (epoxy SAM)-coated Si substrate. PFPE contains hydroxyl groups at both ends of its backbone chain, while the SAM surface contains epoxy groups, which terminate at the surface. A combination of tests involving contact angle measurements, ellipsometry, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) was used to study the physical and chemical properties of the film. The coefficient of friction and wear durability of the film were investigated using a ball-on-disk tribometer (4?mm diameter Si₃N₄ ball as the counterface at a nominal contact pressure of ～330?MPa). AFM was used to investigate the adhesion forces between a sharp Si₃N₄ tip and the film. This dual-layer film had a very low coefficient of friction, adhesion and wear when compared to epoxy SAM-coated Si only or bare Si surface. The reasons for the improved tribological performance are explained in terms of the lubrication characteristics of PFPE molecules, low surface energy of PFPE, covalent bonding between PFPE and epoxy SAM coupled with reduced mobile PFPE. The low adhesion forces coupled with high wear durability show that the film has applications as a wear resistant and anti-stiction film for microcomponents made from Si.     

The phase behaviour of single polyethylene chains with and without fixing one end

The phase behaviour of a single polyethylene chain is studied by using molecular dynamics simulations. A free chain and a chain with fixing one end are considered here, since the atomic force microscope （AFM） tip can play a significant role in polymer crystallization in experiment. For a free chain, it is confirmed in our calculation that the polymer chain exhibits an extended coil state at high temperatures, collapses into a condensed state at low temperatures, i.e. the coil-to-globule transition that is determined by a high temperature shoulder of the heat capacity curve, and an additional liquid-to-solid transition that is described by a low temperature peak of the same heat curve. These results accord with previous studies of square-well chains and Lennard-Jones homopolymers. However, when one of the end monomers of the same chain is fixed the results become very different, and the chain cannot reach an extended coil-like state as a free chain does at high temperatures, i.e. there exists no coil-to-globule-like transition. These results may provide some insights into the influence of AFM tip when it is used to study the phase behaviour of polymer chains. If the interaction force between AFM tip and polymer monomers is strong, some monomers or one of them can be seen as being fixed by the tip, which is similar to our simulation model, and it is also found that AFM tip could induce polymer crystallization.