Microdomain morphology of lamella‐forming diblock copolymer confined in a thin film

We report the self‐consistent field theory (SCFT) of the morphology of lamella‐forming diblock copolymer thin films confined in two horizontal symmetrical/asymmetrical surfaces. The morphological dependences of thin films on the polymer‐surface interactions and confinement, such as film thickness and confinement spatial structure, have been systematically investigated. Mechanisms of the morphological transitions can be understood mainly through the polymer‐surface interactions and confinement entropy, in which the plat confinement surface provides a surface‐induced effect. The confinement is expressed in the form of the ratio D/L₀, here D is film thickness, and L₀ is the period of bulk lamellar‐structure. Much richer morphologies and multiple surface‐induced morphological transitions for the lamella‐forming diblock copolymer thin films are observed, which have not been reported before. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1–10, 2009     

Monte Carlo simulation of AB diblock copolymer between surface and substrate and comparison of experimental results

The morphologies of AB diblock copolymer film between the substrate and surface were investigated via Monte Carlo simulations on simple cubic lattices. The morphological dependence of the diblock copolymer thin film on the thickness, as well as the composition and interactive intensity has been mainly studied. With the increase of A‐segments fraction, various microdomain morphologies including regular parallel stripe‐like, mesh‐like, and normal lamella near the region of the surface were generated in this work. The morphology of thin films of asymmetric diblock copolymer was found to form cylinders in a bulk system when L_z was equal to 30. The morphologies of PS‐b‐PDMS diblock copolymer films have been studied via atomic force microscopy (AFM) and transition electron microscopy (TEM) measurements. The surface morphology of the PS‐b‐PDMS copolymer thin film shows a mesh‐like microphase separated structure, and PDMS continuous phase protruded on the PS dispersed phase. The surface composition of PS‐b‐PDMS copolymer thin films was measured by means of X‐ray photoelectron spectroscopy (XPS) and ATR‐IR. The comparison results show that the experimental observations are in good agreement with the simulation results. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1835–1845, 2006     

Size asymmetry in diblock copolymers of cylindrical morphology in thin films

We calculate the free energy of an AB diblock copolymer thin film of cylindrical morphology under confined geometry and find that the size of the cylinder can be asymmetric, depending on the film thickness and surface tension. The size of the cylinder right above the surface is slightly smaller than that of the other cylinders. The equilibrium period in this thin film is different from that in the bulk because of the surface effect. The tendency toward asymmetry diminishes as the film thickness increases and the interfacial tension between the major block (A) and the substrate decreases. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2217–2224, 2001     

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.     

Surface-induced phase transition of asymmetric diblock copolymer in selective solvents

Surface-induced phase transition of asymmetric diblock copolymer in selective solvents is first theoretically investigated by using the real-space version of self-consistent field theory (SCFT). By varying the distance between two parallel hard surfaces (or the film thickness) W and the block copolymer concentration f(p), several morphologies are predicted and the phase diagram is constructed. Self-assembly morphologies of the diblock copolymer in dilute solution are found to change significantly with different film thickness. In confined systems, stable morphologies found in the bulk solution become unstable due to the loss of polymer conformation entropy. We find that in a very dilute block copolymer solution, phase separation can be induced through polymer depletion as the solution becomes more confined. Our findings provide an interesting starting point for a renewed effort in both experimental and theoretical investigations of confined block copolymer solutions.     

Strong stretching theory for diblock copolymers in thin films under application of electric fields

We investigate the microphases of asymmetric AB diblock copolymers confined to thin films in the strong segregation limit under the application of electric fields. We evaluate the free energy of a given set of possible phases and present phase diagrams for diblock copolymers with a cylindrical bulk phase in dependence of the film thickness and the attraction between the confining walls and the A or B monomers. This is done for different field strengths and volume fractions. We find that with increasing field strength structures show a preference for alignment with the field. The alignment is stronger when the permittivity of the minority monomer is larger than that of the majority monomer. Depending on the strength of the wall potential and the film thickness, the walls can become completely wetted by the minority monomer.     

Solvent-induced novel morphologies in diblock copolymer blend thin films

We report the morphology and phase behaviors of blend thin films containing two polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymers with different blending compositions induced by a selective solvent for the PMMA block, which were studied by transmission electron microscopy (TEM). The neat asymmetric PS-b-PMMA diblock copolymers employed in this study, respectively coded as a1 and a2, have similar molecular weights but different volume fractions of PS block (fPS=0.273 and 0.722). Another symmetric PS-b-PMMA diblock copolymer, coded as s, which has a PS block length similar to that of a1, was also used. For the asymmetric a1/a2 blend thin films, circular multilayered structures were formed. For the asymmetric a1/symmetric s blend thin films, inverted phases with PMMA as the dispersed domains were observed, when the weight fraction of s was less than 50%. The origins of the morphology formation in the blend thin films via solvent treatment are discussed. Combined with the theoretical prediction by Birshtein et al. (Polymer 1992, 33, 2750), we interpret the formation of these special microstructures as due to the packing frustration induced by the difference in block lengths and the preferential interactions between the solvent and PMMA block. Results obtained here suggest that diblock copolymer blend thin films treated with a selective solvent offer an alternative and attractive approach to control the self-organization of polymers.     

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.     

Dewetting behavior of a block copolymer/homopolymer thin film on an immiscible homopolymer substrate

Numerous previous studies have established that the addition of a microphase-ordered AB diblock copolymer to a thin homopolymer A (hA) film can slow, if not altogether prevent, film rupture and subsequent film dewetting on a hard substrate such as silica. However, only a few reports have examined comparable phenomena when the hA/AB blend resides on a soft B-selective surface, such as homopolymer B (hB). In this work, the dewetting kinetics of thin films composed of polystyrene (PS) and a symmetric poly(styrene-b-methyl methacrylate) (SM) diblock copolymer on a poly(methyl methacrylate) substrate is investigated by hot-stage light microscopy. Without the SM copolymer, the dewetting rate of the PS layer is constant under isothermal conditions and exhibits Arrhenius behavior with an apparent activation energy of approximately 180 kJ/mol. Addition of the copolymer promotes a crossover from early- to late-stage dewetting kinetics, as evidenced by measurably different dewetting rates. Transmission electron microscopy reveals the morphological characteristics of dewetted PS/SM films as functions of film thickness and SM concentration.     

Deviations from bulk morphologies in thin films of block copolymer/additive binary blends

Deviations from bulk morphologies in thin films of binary blends of alkyne-functionalized diblock copolymer poly(ethylene oxide)-block-poly(n-butyl methacrylate-random-propargyl methacrylate) (PEO-b-P(nBMA-r-PgMA)) and Rhodamine B azide are reported, where thermal click reaction between the two components leads to microphase separated morphologies. Both in the bulk and in thin films, increasing the azide loading ratio resulted in the transition from a lamellar microdomain morphology to a hexagonally packed cylindrical mircodomain morphology. However, in thin films the lamellae-cylinder transition was observed at a different azide loading ratio, which was determined by film thickness. As a result, significant deviations from the bulk morphology were observed. These results indicate that surface interactions and confined geometry can play an important role in dictating the morphology in thin films of BCP/additive binary blends.     

Surface-induced phase transitions in ultrathin films of block copolymers

We study theoretically the lamellar-disorder-lamellar phase transitions of AB diblock and tetrablock copolymers confined in symmetric slitlike pores where the planar surface discriminatingly adsorbs A segments but repels B segments, mimicking the hydrophobic/hydrophilic effects that have been recently utilized for the fabrication of environmentally responsive "smart" materials. The effects of film thickness, polymer volume fraction, and backbone structure on the surface morphology have been investigated using a polymer density-functional theory. The surface-induced phase transition is manifested itself in a discontinuous switch of microdomains or a jump in the surface density dictated by the competition of surface adsorption and self-aggregation of the block copolymers. The surface-induced first-order phase transition is starkly different from the thickness-induced symmetric-asymmetric or horizontal-vertical transitions in thin films of copolymer melts reported earlier.     

Ring-shaped morphology in solution-cast polystyrene-poly(methyl methacrylate) block copolymer thin films

We report observation of ring-shaped morphology formed in thin films of a cylinder-forming polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer cast from 1,1,2,2-tetrachloroethane (Tetra-CE) solution via relatively fast solvent evaporation rates, in which Tetra-CE is a good solvent for both blocks but preferential affinity for the minority PMMA block. We studied the microstructure of a set of solution-cast block copolymer films dried with different solvent evaporation rates, R. The control with different R leads to keeping microstructures in different solution concentrations (phi) and bringing mechanical strain fields with different strength in the film, for which faster evaporation rates result in microstructures of lower solution concentrations and mechanical strain fields of higher strength. As R decreases from rapid evaporation (approximately 0.1 mL/h), the film microstructure evolved from an intermediate ringlike morphology sequentially to ring-shaped morphologies including loose and tight rings and then inverted phase of PS spheres in a PMMA matrix and finally reached the equilibrium phase, namely, cylinders of PMMA in a PS matrix. In view of the influence of the film constraints, the microstructure of a film with a terraced free surface profile has been examined. The results indicate that the ring-shaped morphology can form as long as the film thickness is larger than a critical value of about one microdomain spacing. In the case where the film thickness is larger than that value, the nature of solvent and the kinetics of solvent evaporation are shown to be mainly responsible for the ring-shaped morphology formation.     

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.     

Model experiments for a molecular understanding of polymer crystallization

Time‐resolved real‐space observations of morphology and pattern formation resulting from crystallization of ultrathin films of low‐molecular‐weight poly(ethylene oxide) (PEO) or diblock copolymers containing PEO shed light on the mechanisms of how polymer crystals are formed. We used simple but restricted geometries like thin films of controlled thickness or confinement resulting from block copolymer mesotructures. Under such conditions, we were able to relate the observed morphology and its temporal evolution directly to molecular processes and the kinetics of crystal growth. We demonstrate that changes in the morphology with time are due to different thermal histories and are the consequence of the mestable nature of polymer crystals. Information about the nucleation process was obtained by examining crystal formation in 12‐nm small spherical cells of a block copolymer mesostructure. We discuss the advantages of thin‐film studies for a better understanding of polymer crystallization. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1869–1877, 2003     

Instabilities in block copolymer films induced by compressible solvents

We combine a simple lattice-gas model for fluid mixtures along with polymer mean-field theory for block copolymer melts to study the stability of thin films of diblock copolymers in the presence of compressible fluid solvents. Using a free energy analysis, the stable and unstable thicknesses of a copolymer thin film are obtained for given solvent conditions. Our results suggest that the interplay between confinement, the compressibility of the solvent, and its selectivity to polymer component can lead to significant changes on the ordering and stability of the diblock copolymer thin films. Our results are in qualitative agreement with recent experimental results.     

SELF ASSEMBLY OF ABC TRIBLOCK COPOLYMER THIN FILMS ON A BRUSH-COATED SUBSTRATE

Self assemblies of ABC triblock copolymer thin films on a densely brush-coated substrate were investigated by using the self-consistent field theory.The middle block B and the coated polymer form one phase and the alternating phase A and phase C occur when the film is very thin either for the neutral or selective hard surface(which is opposite to the brushcoated substrate).The lamellar phase is stable on the hard surface when it is neutral and interestingly,the short block tends to stay on this hard surf...     

Surface and bulk ordering in thin films of a symmetrical diblock copolymer

Amphiphilic diblock copolymers have the ability to adapt their surface's molecular composition to the hydrophilicity of their environment. In the case of about equal volume fractions of the two polymer blocks, the bulk of these polymers is known to develop a laminar ordering. We report here our investigation of the relationship between bulk ordering and surface morphology/chemical composition in thin films of such an amphiphilic diblock copolymer. Upon annealing in vacuum, the expected lamella ordering in the bulk of the film is observed and we find the morphology of the film surface to be defined by the thickness of the as‐deposited film: If the as‐deposited thickness matches the height of a lamella stack, then the film exhibits a smooth surface. Otherwise, an incomplete lamella forms at the film surface. We show that the coverage of this incomplete layer can be quantified by X‐ray reflectivity. To establish the lamella ordering in the bulk, the film needs to be annealed above the glass temperature of the two blocks. Molecular segregation at the film surface, however, is already occurring at temperatures well below the glass temperature of the two blocks. This indicates that below the glass temperature of the blocks the bulk of the thin film is “frozen,” whereas the polymer chains composing the surface lamella have an increased mobility. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys., 2013 , 51, 1282–1287     

Monte Carlo simulation on layered polymeric films

Thin films of polymer blends composed of alternating copolymer, diblock copolymer and/or homopolymer are studied using Monte Carlo simulation. A multilayer morphology is observed in the film, that is, the blended polymers assemble into individual domains arranged from interior to the surfaces of the film. The coexisting components residing throughout the neighboring domains in the film make no distinguishable interface between any neighboring domains. By this means, it forms a vertical composition gradient in the polymeric film. Being different from layer-by-layer deposition of polyelectrolyte or hydrogen bonding approach etc., the layered structure in this study is formed by polymer blending in one step. Alternating copolymers are found to be essential components to form vertical composition gradient （layered structure） in thin films.     

Effect of a solvent on self-organization in nanofilms: Modeling by the dissipative particle dynamics method

Mesoscopic simulation of processes of drying and swelling of thin copolymer films on a solid substrate is performed. Structural rearrangements in films of symmetric and asymmetric diblock copolymers are studied by the dissipative particle dynamics method in the presence of both nonselective and selective solvents. The plasticizing effect of a solvent is favorable for formation of lamellar and hexagonal mesophases. Owing to evaporation of the solvent from a film or its absorption from the external volume, flows along the normal to the film surface arise. These flows exert an orienting effect on the microdomain structure.     

THE EFFECTS OF PATTERNED SURFACES ON THE PHASE SEPARATION FOR DIBLOCK COPOLYMERS

The phase behaviors of symmetric diblock copolymer thin films confined between two hard,parallel and diversified patterned surfaces are investigated by three-dimensional dissipative particle dynamics(DPD)simulations.The induction of diversified patterned surfaces on phase separation of symmetric diblock copolymer films in snapshots,density profiles and concentration diagrams of the simulated systems are presented.The phase separations can be controlled by the patterned surfaces.In the meantime,the mean-s...