Surface energies and self-assembly of block copolymers on grafted surfaces

We present a theoretical analysis of the self-assembly of diblock copolymers on surfaces grafted with random copolymers. Our results demonstrate that the surface energies of homopolymeric components on grafted surfaces differ from the corresponding values for self-assembled morphologies. Moreover, grafted random copolymers are shown to adapt their conformations in response to the morphology of the overlaying block copolymer film to create chemical inhomogeneities which modulate the interfacial interactions. Consequently, the surface energy differences between the different components on the grafted substrate do not serve as a useful measure to predict the stability of self-assembly of the diblock copolymer film.     

Influence of Grafting Density of Diblock Copolymers on Interfacial Assembly Behavior and Interfacial Shear Strength of Glass Fiber/Polystyrene Composites

To investigate the influence of the grafting density and the molecular structure of block copolymers on the interfacial assembly behavior and interfacial shear strength, macromolecular coupling agents, hydroxyl-terminated poly(n-butyl acrylate-b-styrene) (HO-P(BA-b-S)) were synthesized by atom transfer radical polymerization, and then chemically anchored on the glass fiber surfaces to form a well-defined monolayer. The phase separation and 'hemispherical' domain morphologies of diblock copolymer brushes at the polystyrene/glass fiber interface were observed. The interfacial assembly morphology differs with changes in the grafting density of diblock copolymers. When the grafting density is greatest, the highest height difference of the hemispherical domain and the largest surface roughness are achieved, as well as the best interface shear strength. It was also found that the copolymer brush with a PBA block of the polymerization degree (Xn) about 77 is the optimal option for the interfacial adhesion of PS/GF composites. Thus, the grafting density and molecular structure of diblock copolymers determines the interfacial assembly behavior of copolymer brushes, and therefore the interfacial shear strength.     

Block copolymer morphologies confined by square-shaped particle:Hard and soft confinement

The self-assembly of diblock copolymers confined around one square-shaped particle is studied systematically within two-dimensional self-consistent field theory(SCFT).In this model,we assume that the thin block copolymer film is confined in the vicinity of a square-shaped particle by a homopolymer melt,which is equivalent to the poor solvents.Multiple sequences of square-shaped particle-induced copolymer aggregates with different shapes and self-assembled internal morphologies are predicted as functions of the particle size,the structural portion of the copolymer,and the volume fraction of the copolymer.A rich variety of aggregates are found with complex internal self-assembled morphologies including complex structures of the vesicle,with one or several inverted micelle surrounded by the outer monolayer with the particle confined in the core.These results demonstrate that the assemblies of diblock copolymers formed around the square-shaped particle in poor solvents are of immediate interest to the assembly of copolymer and the morphology of biomembrane in the confined environment,as well as to the transitions of vesicles to micelles.     

Multiple patterns of diblock copolymer confined in irregular geometries with soft surface

The different confinement shapes can induce the formation of various interesting and novel morphologies, which might inspire potential applications of materials. In this paper, we study the directed self-assembly of diblock copolymer confined in irregular geometries with a soft surface by using self-consistent field theory. Two types of confinement geometries are considered, namely, one is the concave pore with one groove and the other is the concave pore with two grooves. We obtain more novel and different structures which could not be produced in other two-dimensional(2D) confinements. Comparing these new structures with those obtained in regular square confinement, we find that the range of ordered lamellae is enlarged and the range of disordered structure is narrowed down under the concave pore confinement.We also compare the different structures obtained under the two types of confinement geometries, the results show that the effect of confinement would increase, which might induce the diblock copolymer to form novel structures. We construct the phase diagram as a function of the fraction of B block and the ratio of h/L of the groove. The simulation reveals that the wetting effect of brushes and the shape of confinement geometries play important roles in determining the morphologies of the system. Our results improve the applications in the directed self-assembly of diblock copolymer for fabricating the irregular structures.     

Exploring Microstructures and Interphase Properties of Surface- Grafted Diblock Copolymers in a Homopolymer Melt by Self-Consistent Field Theory Simulations

Polymeric self-consistent field theory is used to investigate microstructures and interphase properties of diblock copolymers grafted onto solid surfaces in a homopolymer melt. The calculations show that the grafted diblock copolymers can self-assemble into hemispherical microstructures at low grafting densities of the diblock copolymers. The morphology transforms into hemicylinder-like and sandwich-like lamellar microstructures with an increase in the chain-grafting density. The effective thickness of the grafted block layer and the interphase width between the homopolymer melt and the grafted copolymers strongly depend on the physicochemical parameters of the system, such as the composition of the grafted copolymer, the chemical incompatibility between the different components, the length ratio of grafted copolymer to homopolymer, and the grafting density of the diblock copolymers. In addition, the above computational results of microphase-separated structures and interphase properties are qualitatively compared with our previous experimental observations. The comparison indicates that our theoretical results not only reproduce the general feature of the experimental observations, but also elucidate the internal structural information and complement the findings in the region of high grafting densities of diblock copolymers.     

Diblock and triblock copolymer thin films on a substrate with controlled selectivity

Using self-consistent field theory (SCFT), morphology development in symmetric linear ABC triblock copolymer films on neutral and selective substrates has been studied, and it is compared with the triblock copolymer morphologies in bulk. In particular, the effects of the substrate preferable to B (interior) block on nanopattern formation of the copolymer films are of our central interest. Here, we report various nanopatterns with tunable square morphologies. The domain patterns are much more diverse than those parallel to the substrate with substrate selectivity for end-block or those vertical to the substrate without substrate selectivity. Furthermore, in order to figure out an economical and efficient way to fabricate useful passive pattern transfer layers, which have potential applications in microelectronic processes and ultrahigh density storage media, we propose a two-step strategy and scrutinize the conditions for generating square symmetries using cylinder-forming or lamella-forming AB diblock copolymers deposited on substrates created from ABC triblock copolymer films. It is found that a thinner film with weak incompatibility can produce square patterns.     

Self-assembly of lamella-forming diblock copolymers confined in nanochannels: Effect of confinement geometry

The self-assembly of symmetric diblock copolymers confined in the channels of variously shaped cross sections(regular triangles, squares, and ellipses) is investigated using a simulated annealing technique. In the bulk, the studied symmetric diblock copolymers form a lamellar structure with period LL. The geometry and surface property of the confining channels have a large effect on the self-assembled structures and the orientation of the lamellar structures. Stacked perpendicular lamellae with period LLare observed for neutral surfaces regardless of the channel shape and size, but each lamella is in the shape of the corresponding channel’s cross section. In the case of triangle-shaped cross sections, stacked parallel lamellae are the majority morphologies for weakly selective surfaces, while morphologies including a triangular-prism-shaped B-cylinder and multiple tridentate lamellae are obtained for strongly selective surfaces. In the cases of square-shaped and ellipse-shaped cross sections, concentric lamellae are the signature morphology for strongly selective surfaces, whereas for weakly selective surfaces, stacked parallel lamellae, and several types of folding lamellae are obtained in the case of square-shaped cross sections, and stacked parallel lamellae are the majority morphologies in the case of ellipse-shaped cross sections when the length of the minor axis is commensurate with the bulk lamellar period. The mean-square endto-end distance, the average contact number between different species and the surface concentration of the A-monomers are computed to elucidate the mechanisms of the formation of the different morphologies. It is found that the resulting morphology is a consequence of competition among the chain stretching, interfacial energy, and surface energy. Our results suggest that the self-assembled morphology and the orientation of lamellae can be manipulated by the shape, the size, and the surface property of the confining channels.     

受限壁的选择性对软受限下星形三嵌段共聚物形貌的影响

基于嵌段共聚物在软受限条件下能够自组装形成很多有序结构,在催化、电子器件、光学传感等领域有广泛的应用价值,目前只对线性三嵌段共聚物在软受限下的自组装形貌做了分析,对星形三嵌段共聚物在软受限下的自组装行为还未有一个统一的定论.在这项研究中,应用模拟退火来研究ABC星形三嵌段共聚物在软受限下的自组装行为,嵌段与溶剂没有选择性下(中性壁),通过调整三个嵌段(f_A、f_B和f_C)的体积分数来构建相图,我们的模拟预测了各种独特的自组装纳米结构,包括薄片+球形、圆柱状,穿孔层,薄片+圆柱体,核壳补丁.然后通过改变嵌段与溶剂的选择性预测了链长度比为1:x:1的共聚物粒子形貌.通过计算接触数、均方根末端距与平均链长的比值以及平均键长随x的变化,验证了形貌转变机制.     

Morphology of lamellae-forming block copolymer films between two orthogonal chemically nanopatterned striped surfaces

The structure of block copolymers results from the interplay between weak intermolecular forces, typically in the order of k(B)T per molecule. This is particularly true for block copolymer thin films in the presence of chemically patterned surfaces, where the different contributions to the total free energy, the interfacial and bulklike terms, have comparable magnitudes. Here, we report on the structures formed by block copolymers films equilibrated between two chemically patterned surfaces with orthogonal stripes. Our experiments and simulations reveal that the domains are continuous through the film and the interface between domains resembles the Scherk's first minimal surface. The impact of chemical patterns on block copolymer morphologies and the underlying physics gives insight into the nanofabrication of complex nanostructures with directed self-assembly using two engineered boundary conditions, as opposed to only one.     

Self-assembled pattern formation of block copolymers on the surface of the sphere using self-consistent field theory

The spherical surface is spatially discretized with triangular lattices to numerically calculate the Laplace-Beltrami operator contained in the self-consistent field theory (SCFT) equations using a finite volume method. Based on this method we have developed a spherical alternating-direction implicit (ADI) scheme for the first time to help extend real-space implementation of SCFT in 2D flat space to the surface of the sphere. By using this method, we simulate the equilibrium microphase separation morphology of block copolymers including AB diblocks, ABC linear triblocks and ABC star triblock copolymers occurred on the spherical surface. In general, two classes of microphase separation morphologies such as striped patterns for compositionally symmetric block copolymers and spotted patterns for asymmetric compositions have been found. In contrast to microphase separation morphology in 2D flat space, the geometrical characteristics of a sphere has a large influence on the self-assembled morphology. For striped patterns, several of spiral-form and ring-form patterns are found by changing the ratio of the radius of a sphere to the averaging width of the stripes. The specific pattern such as the striped and spotted pattern with intrinsic dislocations or defects stems from formed periodic patterns due to microphase separation of block copolymers arranged on the curved surface.     

Scaling theory of mixed amphiphilic monolayers

We predict the elastic properties of mixed amphiphilic monolayers in the swollen state within the blob model using scaling arguments. First the elastic moduli and the spontaneous curvature of a bimodal brush are determined as a function of the composition and the relative chain length. We obtain simple and useful scaling functions which interpolate between the elastic moduli of a pure short-chain brush and a pure long-chain brush. By using the analogy between block copolymer interfaces and polymeric brushes, the effect of mixing on self-assembled diblock copolymer monolayers is investigated in the swollen state. We calculate various interfacial properties, such as the equilibrium surface coverage, interface curvature, and the mixing free energy as a function of the composition. In general, we find a nonlinear dependence on the composition, which deviates from the simple linear averaging of the properties of pure components. Our results are used to discuss a recent experiment on the effect of amphiphilic block copolymers on the efficiency of microemulsions. Received 29 December 2000 and Received in final form 19 March 2001     

Molecular mobility of confined phases in model mesoporous (MCM-41) and microporous (AlPO4-5 zeolite) host materials

This paper discusses the self-assembly of block copolymers into vesicular morphology. After a brief state of art of the field, a system based on an amphiphilic poly(butadiene)-b-poly(-L-glutamic acid) (PB-b-PGA) diblock copolymer in aqueous solution is discussed in detail. The aggregation behavior of this block copolymer has been investigated by means of fluorescence spectroscopy, dynamic (DLS) and static (SLS) light scattering as well as transmission electron microscopy (TEM). The diblock copolymer was found to form well-defined vesicles in water. The size of these so-called polymersomes or peptosomes could be reversibly manipulated as a function of both pH and ion strength. Depending on the pH of the aqueous solution, the hydrodynamic radii of these vesicles were found to vary from 100 nm to 150 nm. By cross-linking the 1,2-vinyl double bonds present in the polybutadiene block, the ability to transform a transient supramolecular self-organized aggregate into a permanent “shape-persistent stimuli-responsive nanoparticle” has been demonstrated. Received 25 June 2002 and Received in final form 22 October 2002 Published online: 11 March 2003     

Two-dimensional micelle formation of polystyrene-poly(vinylpyridine) diblock copolymers on mice surfaces

We have used atomic force microscopy to study the adsorption of PolyStyrene-Poly(VinylPyridine) (PS-PVP) block copolymers from a selective solvent onto atomically smooth mica surfaces. At certain copolymer concentrations, we observe a highly regular array of spherical surface micelles covering macroscopic areas of the substrate surface. Evidence is given for a thin homogeneous layer underneath the micelles which is probably due to adsorption of free copolymer chains and brush formation prior to the formation of the micellar structures. We discuss the quality of the self-assembled structures regarding different types of defects and try to identify means for improving the long range periodicity of the structures.     

不对称二聚物粒子在两嵌段共聚物形成的支撑膜上的自组装

结合自洽场理论和密度泛函理论,研究了不对称的二聚物粒子在AB两嵌段共聚物形成的支撑膜上的自组装行为. 不对称的二聚物粒子是由两个不同的球组成的两性分子. 其中一个球与A嵌段相亲,另外一个喜欢B嵌段. 不对称粒子能在支撑膜上形成一个双层结构. 由于衬底的存在,所形成的支撑膜上下两叶的对称性被破坏,导致了二聚物粒子在膜上形成的结构也变的不对称. 随着二聚物粒子浓度的增加,在膜上的二聚物粒子的结构将发生变化,从稀四方、六角、密四方再到圆柱结构. 在一个高浓度的密堆积下,二聚物粒子将形成弯曲的圆柱结构. 在支撑膜     

Dynamics and order-disorder transitions in bidisperse diblock copolymer blends

We employ the dynamic extension of self-consistent field theory (DSCFT) to study dynamics and order-disorder transitions (ODT) in AB diblock copolymer binary mixtures of two different monodisperse chain lengths by imitating the dynamic storage modulus G′ corresponding to any given morphology in the oscillatory shear measurements. The different polydispersity index (PDI) is introduced by binary blending AB diblock copolymers with variations in chain lengths and chain number fractions. The simulation results show that the increase of polydispersity in the minority or symmetric block introduces a decrease in the segregation strength at the ODT, (χN)_ODT, whereas the increase of polydispersity in the majority block results in a decrease, then increase and final decrease again in (χN)_ODT. To the best of our knowledge, our DSCFT simulations, for the first time, predict an increase in (χN)_ODT with the PDI in the majority block, which produces the experimental results. The simulations by previous SCFT, which generally speaking, is capable of describing equilibrium morphologies, however, contradict the experimental data. The polydispersity acquired by properly tuning the chain lengths and number fractions of binary diblock copolymer blends should be a convenient and efficient way to control the microphase separation strength at the ODT.     

Complex nanostructured materials from segmented copolymers prepared by ATRP

The development of new controlled/living radical polymerization processes, such as Atom Transfer Radical Polymerization (ATRP) and other techniques such as nitroxide mediated polymerization and degenerative transfer processes, including RAFT, opened the way to the use of radical polymerization for the synthesis of well-defined, complex functional nanostructures. The development of such nanostructures is primarily dependent on self-assembly of well-defined segmented copolymers. This article describes the fundamentals of ATRP, relevant to the synthesis of such systems. The self-assembly of block copolymers prepared by ATRP is illustrated by three examples. In the first, block copolymers of poly(butyl acrylate) with polyacrylonitrile phase separate, leading to spherical, cylindrical or lamellar morphologies, depending on the block copolymer composition. At a higher temperature, polyacrylonitrile block converts to nanostructured carbon clusters, whereas poly(butyl acrylate) block serves as a sacrificial block, aiding the development of designed nanostructures. In the second example, conductive nanoribbons of poly(n-hexylthiophene) surrounded by a matrix of organic polymers are formed from block copolymers prepared by ATRP. The third example describes an inorganic-organic hybrid system consisting of hard nanocolloidal silica particles (20 nm) grafted by ATRP with well-defined polystyrene-poly(benzyl acrylate) block copolymer chains (1000 chains per particle). Silica cores in this system are surrounded by a rigid polystyrene inner shell and softer polyacrylate outer shell. Received 9 July 2002 Published online: 11 March 2003     

The segregation of poly(styrene-b-isoprene) diblock copolymers to the surface of a polystyrene melt: the effect of the ratio of block lengths

The effect of the ratio of block lengths on the interfacial partitioning of poly(styrene-block-1,4 isoprene) diblock copolymers from their mixtures with polystyrene homopolymer melt is investigated utilizing a series of copolymers with almost constant molecular weight but different compositions. The concentration profile of the copolymer is measured directly using the nuclear reaction analysis technique; a segregation of the diblock is found at both the air/polymer surface, due to the lower surface energy of polyisoprene, and at the substrate/polymer interface. No significant effect of the block length ratio on the free-surface excess was observed. The block molecular weights have apparently led to dangling chain conformations in the non-overlapping mushroom and in the overlapping mushroom regimes whereas the brush regime was not accessible; no indications of a real border between the two former regimes was found. Received: 20 July 1998 / Received in final form and Accepted: 11 September 1998     

Preparation of well-defined polymer-silicon wafer hybrids via surface-initiated RAFT-mediated process

A simple method was developed for the immobilization of reversible addition-fragmentation chain-transfer (RAFT) initiators on the silicon surface. Well-defined polymer-silicon hybrids, including the tethered brushes of glycidyl methacrylate (GMA) polymer, poly(ethylene glycol) monomethacrylate (PEGMA) polymer and block copolymer on a silicon wafer, were prepared via surface-initiated RAFT living radical polymerization. The “living” chain ends were used as the macroinitiator for the subsequent synthesis of diblock copolymers.     

Mechanism for hierarchical self-assembly of nanoparticles on scaffolds derived from block copolymers

Lithographically patterned substrates can direct the self-assembly of block copolymer films into aligned structures that, in turn, template the self-organization of colloidal nanoparticles. Deposition on pristine diblock copolymer films does not lead to reproducible selective decoration, but films modified to have nanoscale corrugation act as scaffolds for highly selective nanoparticle adsorption. The mechanism for this selectivity relies on the lateral forces inherent to spin casting to remove all of the nanoparticle suspension not confined within the nanoscopic trenches. This technique does not rely on interactions between the surfactant capping molecules and the polymer and is therefore general to a wide class of nanoparticle materials. Prospects to obtain long-range ordering and associated potential applications are discussed.     

Multiscale coarse graining of diblock copolymer self-assembly: from monomers to ordered micelles

Starting from a microscopic lattice model, we investigate clustering, micellization, and micelle ordering in semidilute solutions of AB diblock copolymers in a selective solvent. To bridge the gap in length scales, from monomers to ordered micellar structures, we implement a two-step coarse-graining strategy, whereby the AB copolymers are mapped onto ultrasoft dumbells with monomer-averaged effective interactions between the centers of mass of the blocks. Monte Carlo simulations of this coarse-grained model yield clear-cut evidence for self-assembly into micelles with a mean aggregation number n approximately 100 beyond a critical concentration. At a slightly higher concentration the micelles spontaneously undergo a disorder-order transition to a cubic phase. We determine the effective potential between these micelles from first principles.