嵌段共聚物组成对薄膜形貌影响的多体耗散粒子动力学研究

利用多体耗散粒子动力学(Multibody Dissipative Particle Dynamics, Multibody DPD)方法研究了在溶剂蒸发条件下, 嵌段共聚物在表面自组装形成薄膜的过程, 分别考虑了两嵌段共聚物和三嵌段共聚物及不同组成对薄膜形貌的影响. 模拟得到了无序状薄膜和层状薄膜, 并计算了这些薄膜的序参量和薄膜厚度随时间的演化. 结果表明, 嵌段共聚物的组成对薄膜厚度几乎没有影响, 当某种组分的链段很短时, 只能形成序参量较小的无序薄膜, 相反, 则可以得到序参量较大的层状薄膜.     

表面场诱导线性三嵌段共聚物薄膜的微结构及其转变规律

采用实空间自洽场理论研究了ABC对称线性三嵌段共聚物薄膜的自组装结构及其转变规律.选取具有特定聚合物参数的对称线性三嵌段共聚物,对无修饰条纹和有修饰条纹的两类薄膜受限表面情况,通过调节其薄膜表面场强度和薄膜厚度,获得了一系列新颖的聚合物薄膜微结构.研究结果表明,在无修饰条纹的单一薄膜受限情况下,共聚物趋向于形成规整有序的层状或穿孔层状结构;而在有条纹修饰情况下,共聚物在相应的条纹修饰区域下发生微相分离并趋于形成水平柱状结构.     

聚苯乙烯-聚甲基丙烯酸甲酯两嵌段共聚物薄膜在丙酮蒸汽退火下的形貌演化

用敲击模式原子力显微镜研究了聚苯乙烯-聚甲基丙烯酸甲酯(PS-b-PMMA)两嵌段共聚物薄膜形貌在丙酮蒸汽退火下随时间的演化过程.对于对称的嵌段共聚物薄膜(fPS≈fPMMA,fPS为PS-b-PMMA中PS的体积分数,fPMMA为PMMA的体积分数),通过控制膜厚和平衡态时相周期的比值可以使不同分子量的嵌段共聚物薄膜都实现由蠕虫状结构到孔洞再到条纹的形貌演化过程;对于非对称的嵌段共聚物薄膜,发现当聚苯乙烯组分含量较少(25%,36%)时,薄膜的形貌由无序态分别转变为规则排列的小球和直接转变为条纹结构;而当聚苯乙烯组分含量较多(70%)时,薄膜的形貌则由无序态转变为较平整的表面结构.我们对不同形貌的形成机理进行了详细的讨论.     

棒-棒二嵌段共聚物自组装行为的自洽场研究

利用格子自洽场模型, 模拟了棒-棒二嵌段共聚物熔体系统的自组装行为, 并与线-棒二嵌段共聚物系统性质进行了对比. 结果表明, 棒-棒二嵌段共聚物系统的有序无序转变临界点低于线-棒二嵌段共聚物系统的相变临界点. 通过模拟计算, 发现薄层交叠柱状相、柱状相、层状相和Z形层状相4种稳定的有序形貌. 薄层交叠柱状相和柱状相仅在有序无序转变曲线的边缘位置出现, 层状相也仅存在于有序无序转变临界点上面的一小块区域内, 而稳定的Z形层状结构则占据了相图中较强相互作用的大部分区域.     

嵌段共聚物自组装薄膜中纳米结构的形成及应用

嵌段共聚物在固体基底上可通过多种技术形成薄膜,如铸膜、涂膜、浸渍膜及旋涂膜.借助于热退火、溶剂蒸气退火或者非溶剂引起的相分离,在这些薄膜中可形成有序纳米结构,如柱状结构、层状结构、双连续结构和多孔结构等.这些结构在下一代的光刻技术、光子晶体、与锂离子电池等相关的离子传输、分离和催化等领域都有重要的潜在应用.本文介绍了近...     

环形对称两嵌段共聚物在薄膜中自组装行为的计算机模拟

采用Monte Carlo模拟方法考察了AB环形对称两嵌段共聚物受限在薄膜中的自组装行为。模拟结果表明,AB环形对称两嵌段共聚物在薄膜中自组装形成的层状结构的取向依赖于薄膜表面的选择性或膜厚。当薄膜表面无选择性或具有强选择性时,体系中层状结构的取向分别为垂直和平行于薄膜表面;当薄膜表面选择性较弱时,随着膜厚的增加层状结构的取向会发生由垂直向平行于薄膜表面的转变。这些模拟结果与文献报道中线形体系十分一致。然而值得注意的是,当薄膜表面的选择性适中时,环形体系中形成了一种在线形体系中未被观察到的具有波浪形层状结构的新颖有序结构。通过对该结构相互作用焓密度与链构象的分析发现,该结构是一种稳定态结构。此外,通过对比相同参数下环形体系与线形体系的层状结构发现,环形体系层状结构的特征尺寸明显小于线形体系。上述模拟结果表明相对于与其分子量相同的线形嵌段共聚物,环形嵌段共聚物由于其特殊的几何结构能够形成新颖的或具有更小特征尺寸的微相分离结构,而控制特征尺寸,尤其是获得尽可能小的特征尺寸,对于制备具有更小纳米结构和更高集成度的微电子器件具有重要意义。     

嵌段共聚物胶束薄膜空穴化结构形成的研究

用原子力显微镜研究了嵌段共聚物胶束薄膜的空穴化结构.结果表明,嵌段共聚物胶束薄膜的空穴化强烈地依赖于所用酸中氢离子的数目,只有使用一元酸时才能得到空穴化结构,而二元酸和三元酸都得不到空穴化结构.提出了形成空穴化结构可能的机理.运用选择性溶剂蒸气和一元酸分别处理胶束薄膜,得到了相同的表面形貌.     

外加气流法制备微相结构有序的PS-b-PEO嵌段共聚物薄膜

采用原子转移自由基聚合(ATRP)的方法合成了聚苯乙烯-聚环氧乙烷(PS-b-PEO)嵌段共聚物,并利用核磁共振波谱(1H-NMR)、傅里叶变换红外光谱(FTIR)以及凝胶渗透色谱法(GPC)对聚合物进行了表征.利用外加气流法制备了具有不同形貌的嵌段共聚物薄膜,并讨论聚合物分子组成、气流温度、气流速度以及不同基底对薄膜表面形貌以及内部结构的影响.当嵌段共聚物中聚苯乙烯嵌段的质量分数为83%~85%,气流温度为30~50℃,气流速度3~5 m/s时,有利于形成表面垂直柱状微相分离结构.当硅基底的接触角小于90°时,在合适的外加气流场作用下可以形成薄膜的表层和底层垂直有序而薄膜内部无序的非对称结构.     

单一分子量含氟嵌段共聚物的本体及薄膜自组装研究

嵌段共聚物导向自组装作为一种自下而上的图案化工艺,受到工业界和学术界的广泛关注.然而,导向自组装中缺陷率与分子参数之间的关系研究尚不清晰.本文工作基于模块化合成策略,利用迭代指数增长法并结合巯基-双键的点击反应成功制备了高χ低N的单一分子量含氟聚酯嵌段共聚物(oLA_n-FPOSS).单一分子量特征可以排除多分散性对自组装行为的影响.本体自组装研究表明聚酯嵌段和含氟嵌段具有强相分离驱动力,可以形成特征尺寸小于10 nm的六方柱状相结构(HEX).在薄膜自组装中,嵌段共聚物经过简单的热退火可以在硅片表面形成平行基底排布的柱状纳米图案.此外,通过对比研究不同链长单一分子量嵌段共聚物的薄膜组装行为,发现随着嵌段共聚物链长的增长薄膜组装图形缺陷率明显下降,初步揭示了薄膜自组装过程中缺陷形成对嵌段共聚物链长的依赖性.     

掺杂嵌段共聚物薄膜的相分离研究

采用Monte Carlo方法结合退火方法研究掺杂非对称两嵌段共聚物薄膜的相分离情况.发现随着掺杂极性粒子浓度的增加,嵌段共聚物薄膜体系由层状相逐渐转化成层状和柱状共混相,最后变成分布均匀的柱状相.当掺杂浓度增加到一定程度时,形成了如六边形(6-fold)、七边形(7-fold)和五边形柱状(5-fold)的相结构;六边形柱状相结构的比例随着浓度增加而增加,七边形(7-fold)和五边形柱状(5-fold)相结构的比例随着浓度增加而减小.同时还讨论了两嵌段共聚物大小与掺杂浓度的关系.     

Effect of temperature on the morphology and kinetics of surface pattern formation in thin block copolymer films

Hole formation and growth on the top layer of thin symmetric diblock copolymer films, forming an ordered lamellar structure parallel to the solid substrate (silicon wafer) within these films, is investigated as a function of time (t), temperature (T), and film thickness (l), using a high-throughput experimental technique. The kinetics of this surface pattern formation process is interpreted in terms of a first-order reaction model with a time-dependent rate constant determined uniquely by the short-time diffusive growth kinetics characteristic of this type of ordering process. On the basis of this model, we conclude that the average hole size, lambda(h), approaches a steady-state value, lambda(h)(t-->infinity) identical with lambda(h,infinity)(T), after long annealing times. The observed change in lambda(h,infinity)(T) with temperature is consistent with a reduction of the surface elasticity (Helfrich elastic constant) of the outer block copolymer layer with increasing temperature. We also find that the time constant, tau(T), characterizing the rate at which lambda(h)(t) approaches lambda(h,infinity)(T), first decreases and then increases with increasing temperature. This temperature variation of tau(T) is attributed to two basic competing effects that influence the rate of ordering in block copolymer materials: the reduction in molecular mobility at low temperatures associated with glass formation and a slowing of the rate of ordering due to fluctuation effects associated with an approach to the block copolymer film disordering temperature (T(d)) from below.     

Evolution in surface morphology during rapid microwave annealing of PS‐b‐PMMA thin films

Microwave annealing enables rapid (60 s) ordering and orientation of block copolymer films. The developed morphology in polystyrene‐block‐poly(methyl methacrylate) (PS‐b‐PMMA) thin films depends on details of the heating rate that is controlled by microwave output energy as well as the sample location in the microwave. Over a wide heating rate (1.1–2.7 °C/s), perpendicular orientation of the cylindrical mesostructure at the surface is >50% after 60 s, but goes through a maximum at 1.8 °C/s leading to approximately 97% perpendicular cylinders at the surface. The propagation of this perpendicular surface morphology through the film thickness is also dependent upon the microwave annealing conditions. The surface structure evolves with the microwave annealing time from imperfect ordering to perpendicular cylinders to parallel cylinders as the annealing time increases. This work demonstrates the importance of controlling the heating rate during microwave annealing, which will be critical for optimizing microwave conditions for directed self‐assembly. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1499–1506     

Solvent-induced microphase separation in diblock copolymer thin films with reversibly switchable morphology

We have studied the surface morphology of symmetric poly(styrene)-block-poly(methyl methacrylate) diblock copolymer thin films after solvent vapor treatment selective for poly(methyl methacrylate). Highly ordered nanoscale depressions or striped morphologies are obtained by varying the solvent annealing time. The resulting nanostructured films turn out to be sensitive to the surrounding medium, that is, their morphologies and surface properties can be reversibly switchable upon exposure to different block-selective solvents.     

Solvent vapor annealing of block copolymer thin films: removal of processing history

The ordering processes of PS-b-P2VP block copolymer thin films with different processing histories were studied during solvent vapor annealing by in situ grazing incidence small-angle X-ray scattering (GISAXS). We compared cylinder-forming PS-b-P2VP thin films with 34 kg/mol molecular weight that were prepared in three different ways: spin coating, spin coating and subsequent solvent vapor annealing where the solvent vapor was removed instantaneously, and spin coating and subsequent solvent vapor annealing where the solvent vapor was removed slowly. Block copolymer thin films retained the morphology resulting from the different “processing histories” at smaller swelling ratios. This processing history was erased when the samples reached a higher swelling ratio (~1.4). After the solvent was slowly removed from the swollen film, the surface morphology was characterized by ex situ AFM. All samples showed the same morphology after solvent annealing regardless of the initial morphology, indicating the morphology of solvent annealed samples is determined by the polymer concentration in the swollen film and the solvent vapor removal rate, but not the processing history.     

Morphologies in solvent-annealed thin films of symmetric diblock copolymer

We have systematically studied the thin film morphologies of symmetric poly(styrene)-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer after annealing to solvents with varying selectivity. Upon neutral solvent vapor annealing, terraced morphology is observed without any lateral structures on the surfaces. When using PS-selective solvent annealing, the film exhibits macroscopically flat with a disordered micellar structure. While PMMA-selective solvent annealing leads to the dewetting of the film with fractal-like holes, with highly ordered nanoscale depressions in the region of undewetted films. In addition, when decreasing the swelling degree of the film in the case of PMMA-selective solvent annealing, hills and valleys are observed with the coexistence of highly ordered nanoscale spheres and stripes on the surface, in contrast to the case of higher swelling degree. The differences are explained qualitatively on the basis of polymer-solvent interaction parameters of the different components.     

Ordering evolution of block copolymer thin films upon solvent-annealing process

Morphologies of polystyrene-block-poly(2-vinylpyridine) copolymer (S2VP) thin films, which are forming poly(2-vinylpyridine) cylinders in bulk phase, were investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM) to account for their ordering behavior induced by solvent annealing. Initially, when the copolymer was dissolved in toluene, which is selective solvent for majority polystyrene (PS) blocks, and was spin-coated on Si substrates, dimple-type micellar structures of S2VP were formed. After the film was placed in a solvent-annealing chamber covered with a lid under the existence of chloroform, surface morphologies of S2VP were measured as a function of annealing time. In this study, it was found that the morphologies of S2VP thin film repeated the cycle of the creation and extinction of various morphologies on ordering process. Namely, S2VP exhibited the various transformations between different morphologies, including highly disordered state, cylinders normal to the plane, and cylinders parallel to the plane. Each of the morphologies observed here was employed as a template to synthesize gold (Au) nanoparticles or nanowires. The arrays of Au nano-objects were used to tune a surface plasmon resonance.     

Simulated annealing study of asymmetric diblock copolymer thin films

We report a simulated annealing study of the morphology of asymmetric diblock copolymer thin films confined between two homogeneous and identical surfaces. We have focused on copolymers that form a gyroidal morphology in the bulk. The morphological dependence of the confined films on the film thickness and the surface-polymer interaction has been systematically investigated. From the simulations it is found that much richer morphologies can form for the gyroid-forming asymmetric diblock copolymer thin films, in contrast to the lamella-forming symmetric and cylinder-forming asymmetric diblock copolymer films. Multiple morphological transitions induced by changing the film thickness and polymer-surface interactions are observed.     

聚苯乙烯/聚二甲基硅氧烷嵌段共聚物的表面形态研究

采用原子力显微镜(AFM)和透射电镜(TEM)研究了聚苯乙烯/聚二甲基硅氧烷嵌段共聚物(PS-b-PDMS)薄膜的相形态.结果表明,当采用甲苯作为溶剂,旋转涂膜的薄膜样品呈现网络状的形态分布在表面,而样品所对应的透射电镜照片中,PDMS相作为球状分布在PS的连续相中.退火温度对共聚物表面形态有一定的影响,当退火温度高于PDMS的玻璃化温度,表面中PDMS相增多.PS-b-PDMS嵌段共聚物的表面形态随着所用溶剂的变化而有所不同,当采用甲苯作为溶剂时,样品的PS相形成凹坑分布在PDMS的相区之中,而采用环己烷作为溶剂时,PS相作为突起分布在PDMS相区之中.另外,基底对共聚物薄膜表面形态的有较大的影响,当采用硅晶片作为基底时,样品中的PDMS相和PS相呈现近似平行于表面的层状结构.     

Microdomain Morphology of Symmetrical Diblock Copolymer Thin Films Confined in a Slit

The microphase separation and morphology of symmetric diblock copolymer thin films confined in a slit with neutral or attractive surfaces were studied by the cell dynamic system method (CDS) and Monte Carlo simulation. The size effect, especially in CDS, was carefully investigated indicating that excessively small sizes in the X‐ and Y‐directions will give incorrect results although periodic boundary conditions are imposed. When the walls are neutral, parallel ordered lamella structure only exists over a short range, while irregular microdomain morphology occurs over the whole region. When directional quenching is applied, or the walls are attractive to one of the blocks, a periodical lamellar structure of alternating A‐rich and B‐rich layers occurs over the whole region of the film. Changing the slit width and the strength of interaction will influence the period and arrangement of lamellae. Agreement between the results from CDS and those from simulation is satisfactory indicating the reliability of the CDS method. Comparisons with corresponding experimental results are also discussed.     

Effect of substrate and molecular weight on the stability of thin films of semicrystalline block copolymers

The thermal stability of the thin film morphology of two symmetric oxyethylene/oxybutylene block copolymers (E76B38 and E114B56) on mica and silicon was investigated via atomic force microscopy (AFM). It is found that morphological transition of EmBn thin films during melting is strongly dependent on the molecular weight of the diblock copolymers and their interaction with the substrate. For E76B38 on mica, a single-layered structure transforms into a double-layered structure upon melting, but the same polymer on silicon retains a single-layered structure after melting and spreads quickly to wet-out the silicon surface. Conversely a longer polymer, E114B56, has a thin film on mica that does not change much after melting of the crystalline E block. A mechanism was proposed to explain the relative stability of E76B38 and E114B56 thin films upon melting. Internal stress is produced during melting and can be released along two directions. The release along the vertical direction is restricted by the energy barrier related to the segregation strength, and the release along the horizontal direction is dependent on the mobility of block copolymer related to the interaction between the block copolymer and the substrate. Domain size affects the release rate of the internal stress along the horizontal direction and thus the thermal stability of EmBn thin films. Switching between horizontal and vertical releases can be realized by controlling the domain size of the thin films.