The effect of random copolymer on the characteristic dimensions of cylinder-forming PS-b-PMMA thin films

The block copolymer self-assembly approach has received great attention in recent years as a possible way to overcome the limits of conventional lithography and to fabricate sub-22 nm structures. At this level, precise nanometric control is crucial for technological applications and the search for a flexible and reproducible protocol is a great challenge. The polystyrene-b-poly(methylmethacrylate) (PS-b-PMMA) system, with a styrene fraction of 0.71, spontaneously separates into a periodic array of hexagonally packed PMMA cylinders embedded in a matrix of PS and, under suitable processing conditions, this is perpendicularly oriented with respect to the underlying substrate. The selective removal of the PMMA allows us to obtain a nanoporous PS matrix with well-defined pore dimensions. Perpendicular orientation of the PMMA cylinders requires surface neutralization by means of a suitable PS-r-PMMA random copolymer. The choice of the random copolymer is not trivial, because different PS-r-PMMA copolymers strongly affect the characteristics of the PS-b-PMMA film deposited on it. In this paper the effects of the selected PS-r-PMMA on the arrangement as well as on the peculiar dimensions (pore diameter, pore to pore distance) of the final nanoporous PS thin film are studied. Reliable protocols for the fabrication of a disposable polymeric mask are proposed in view of its application in advanced lithographic processes.     

嵌段共聚物PS-b-PMMA在PCHMA/PMMA共混体系中增容效果的研究:嵌段比、分子量及粘度的影响

采用熔融共混方式,利用两嵌段共聚物聚苯乙烯-b-聚甲基丙烯酸甲酯(PS-b-PMMA)来增容聚甲基丙烯酸环己酯(PCHMA)/聚甲基丙烯酸甲酯(PMMA)共混体系,主要研究PS-b-PMMA嵌段比、均聚物的分子量以及体系粘度对增容效果的影响。研究发现,非对称结构的嵌段共聚物较对称结构的嵌段共聚物更容易在体相形成胶束,胶束的形成减少了嵌段共聚物在界面的利用率。均聚物分子量增大,嵌段共聚物的胶束均增加。分散相分子量增大,造成了界面的嵌段共聚物稳定性减弱,容易扩散至分散相内部,形成胶束。连续相分子量增大致使链段溶胀力减小,嵌段共聚物胶束外围的乳化效果降低,而且连续相粘度增大,使得嵌段共聚物胶束滞留在连续相,难以迁移至界面。共混体系的混合剪切增加,粘度变小,嵌段共聚物的扩散速率加快。通过调控均聚物分子量和体系粘度,能有效地减少体相胶束的形成,增大嵌段共聚物在界面的利用率。通过Leibler干湿刷理论、焓驱溶胀聚合物刷以及Stokes-Einstein扩散理论可以解释相关的结论。     

不同共混方式下非对称嵌段共聚物PS-b-PMMA对PCHMA/PMMA体系增容效果的研究:界面与胶束的竞争

采用熔融共混方式,利用非对称两嵌段共聚物聚苯乙烯-b-聚甲基丙烯酸甲酯(PS-b-PMMA)对聚甲基丙烯酸环己酯(PCHMA)/聚甲基丙烯酸甲酯(PMMA)共混体系进行增容。重点研究了嵌段比、共混方式以及分散相PMMA分子量对共混体系中非对称嵌段共聚物分布的影响,即嵌段共聚物稳定相界面与所形成胶束数量、位置之间的竞争关系。结果表明,在低分子量PMMA情况下共混方式对非对称嵌段共聚物的分布影响显著,改变共混方式可以有效减少分散相中的胶束数量,使嵌段共聚物主要分布在二元不相容增容体系两相界面。另一方面,增大PMMA分子量会改变非对称嵌段共聚物在两相界面的界面曲率,导致其在分散相中的溶解性增大,在界面上的稳定性减小,从而迁移至分散相内部并最终形成胶束。     

嵌段共聚物增容共混聚合物的相形貌及胶束迁移行为研究

主要研究了对称性的聚苯乙烯-聚甲基丙烯酸甲酯嵌段共聚物(PS-b-PMMA,简称SM)对聚甲基丙烯酸甲酯/聚甲基丙烯酸环己酯(PMMA/PCHMA)熔融共混体系的增容。采用透射电子显微镜(TEM)表征了SM和PMMA分子量对共混体系微观相形态和胶束迁移行为的影响。研究表明,SM分别在PMMA与PCHMA均聚物中形成不同结构的胶束,当SM在PMMA/PCHMA界面上形成"湿刷"时,SM在PCHMA相中形成的胶束才能迁移到PMMA相中。SM的加入改善了PMMA与PCHMA之间的相容性,但其增容效果取决于SM的分子量。随着分散相PMMA分子量从19kg/mol增加到39kg/mol,PMMA粒子的平均粒径逐渐增加。     

Three-dimensional mesoporous structures fabricated by independent stacking of self-assembled films on suspended membranes

We report an original iterative method for fabricating three-dimensional mesoporous structures by independently stacking multiple self-assembled block copolymer films supported by Si membranes. A first layer is formed on the substrate by a self-assembled PS-b-PMMA (polystyrene-block-poly(methyl methacrylate)) film. A porous, permeable Si membrane deposited on top of the first block copolymer film provides mechanical support, preventing pattern collapse during the wet developing used to selectively remove the PMMA component of the PS-b-PMMA film. A second, dense Si membrane is deposited to seal the porous membrane, resulting in an impermeable coating suspended atop the self-assembled mesoporous polystyrene structures. The process can then be iterated using the sealed membrane as the new substrate to support a subsequent self-assembled block copolymer film. This multilayer approach provides a flexible three-dimensional fabrication technique where, in each layer, pattern morphology, domain orientation and degree of ordering can be designed independently. Furthermore, the process is compatible with electron-beam directed assembly, used to achieve regular patterns with feature density multiplication at any level in the stack.     

Fabrication of nanostructure and formation of nanocrystal for non-volatile memory

In this work, we have demonstrated that the nanocrystal created by combining the self-assembled block copolymer thin film with regular semiconductor processing can be applicable to non-volatile memory device with increased charge storage capacity over planar structures. Self-assembled block copolymer thin film for nanostructures with critical dimensions below photolithographic resolution limits has been used during all experiments. Nanoporous thin film from PS-b-PMMA diblock copolymer thin film with selective removal of PMMA domains was used to fabricate nanostructure and nanocrystal. We have also reported about surface morphologies and electrical properties of the nano-needle structure formed by RIE technique. The details of nanoscale pattern of the very uniform arrays using RIE are presented. We fabricated different surface structure of nanoscale using block copolymer. We also deposited Si-rich SiNx layer using ICP-CVD on the silicon surface of nanostructure. The deposited films were studied after annealing. PL studies demonstrated nanocrystal in Si-rich SiNx film on nanostructure of silicon.     

以乙基黄原酸丙酸乙酯为链转移剂的PMMA-b-PS的可逆加成断链转移自由基聚合

将乙基黄原酸丙酸乙酯作为链转移剂,进行甲基丙烯酸甲酯(MMA)的可逆加成断链转移自由基聚合(RAFT),并将得到的产物作为大分子链转移剂,加入第二单体苯乙烯(St)进行扩链反应,制备了PMMA-b-PS嵌段共聚物。通过红外光谱、核磁共振、凝胶渗透色谱、热重分析和差示扫描量热等测试手段对制备的PMMA-b-PS嵌段共聚物进行分析表征。研究表明,第二单体St与大分子链转移剂发生了共聚,形成了嵌段共聚物;制备所得PMMA-b-PS嵌段共聚物的数均相对分子质量明显增加,相对分子质量分布变宽,初始热分解温度明显提高,玻璃化转变温度介于PMMA与PS的玻璃化转变温度之间。     

Autophobicity-driven surface segregation and patterning of core-shell microgel nanoparticles

Core-shell microgel (CSMG) nanoparticles, also referred to as core-cross-linked star (CCS) polymers, can be envisaged as permanently cross-linked block copolymer micelles and, as such, afford novel opportunities for chemical functionalization, templating, and encapsulation. In this study, we explore the behavior of CSMG nanoparticles comprising a poly(methyl methacrylate) (PMMA) shell in molten PMMA thin films. Because of the autophobicity between the densely packed, short PMMA arms of the CSMG shell and the long PMMA chains in the matrix, the nanoparticles migrate to the film surface. They cannot, however, break through the surface because of the inherently high surface energy of PMMA. Similar thermal treatment of CSMG-containing PMMA thin films with a polystyrene (PS) capping layer replaces surface energy at the PMMA/air interface by interfacial energy at the PMMA/PS interface, which reduces the energy barrier by an order of magnitude, thereby permitting the nanoparticles to emerge out of the PMMA bulk. This nanoscale process is reversible and can be captured at intermediate degrees of completion. Moreover, it is fundamentally general and can be exploited as an alternative means by which to reversibly pattern or functionalize polymer surfaces for applications requiring responsive nanolithography.     

RAFT聚合方法在碳纳米管表面接枝嵌段共聚物

首先在碳纳米管表面接上可用做RAFT聚合的链转移剂——二硫代碳酸酯,然后用这些管壁接有二硫代碳酸酯的碳纳米管作为链转移剂引发甲基丙烯酸甲酯和苯乙烯单体进行可控的嵌段聚合反应,首次报道了采用二步加料方式在碳纳米管的管壁上接枝上嵌段共聚物链。对嵌段共聚物的结构进行了红外光谱(FT-IR)、热重分析(TGA)、透射电镜(TEM)表征。     

Liquid crystal alignment in electro-responsive nanostructured thermosetting materials based on block copolymer dispersed liquid crystal

Novel well-defined nanostructured thermosetting systems were prepared by modification of a diglicydylether of bisphenol-A epoxy resin (DGEBA) with 10 or 15?wt% amphiphilic poly(styrene-b-ethylene oxide) block copolymer (PSEO) and 30 or 40?wt% low molecular weight liquid crystal 4'-(hexyl)-4-biphenyl-carbonitrile (HBC) using m-xylylenediamine (MXDA) as a curing agent. The competition between well-defined nanostructured materials and the ability for alignment of the liquid crystal phase in the materials obtained has been studied by atomic and electrostatic force microscopy, AFM and EFM, respectively. Based on our knowledge, this is the first time that addition of an adequate amount (10?wt%) of a block copolymer to 40?wt% HBC-(DGEBA/MXDA) leads to a well-organized nanostructured thermosetting system (between a hexagonal and worm-like ordered structure), which is also electro-responsive with high rate contrast. This behavior was confirmed using electrostatic force microscopy (EFM), by means of the response of the HBC liquid crystal phase to the voltage applied to the EFM tip. In contrast, though materials containing 15?wt% PSEO and 30?wt% HBC also form a well-defined nanostructured thermosetting system, they do not show such a high contrast between the uncharged and charged surface.     

尼龙6／“壳—核”型聚合物共混合金的力学性能与亚微形态

采用以ＰＭＭＡ为壳，聚丙烯酸丁酯为核心的“壳－核”型聚合物作为冲击性剂，并以双酚Ａ型环氧树脂（ＤＧＥＢＡ）为增容剂，通过反应挤出法制备了尼龙６／“壳－核”型聚合物共混合金。对合金力学性能与亚微形态的研究表明，在合金中添加ＤＧＥＢＡ可以显著改善尼龙６与“壳－核”型聚合物的界面粘接性和相容性，从而大幅度地提高了合金的缺口冲击强度，同时合金的断理解伸长率与显著提高。Ｂｒａｂｅｎｄｅｒ动态扭矩显示，ＤＧＥ     

Fabrication of Fe(3)O(4) nanoparticle arrays via patterned template assisted self-assembly

Magnetic nanoparticle arrays have been fabricated by combining chemically synthesized Fe(3)O(4) nanoparticles with a diblock copolymer template substrate consisting of self-assembled polystyrene (PS) dots in a polymethylmethacrylate (PMMA) matrix. The influence of the volume fraction of the Fe(3)O(4) suspending solution and the withdrawal speed of the template on the formation of array structures was investigated. A small volume fraction of the nanoparticles and low withdrawal speed play an important role in the fabrication of the patterned arrays of nanoparticles via template assisted self-assembly. Below a withdrawal speed of 0.5?mm?s(-1) and a nanoparticle volume fraction below 0.05?vol% (in particular, at extremely high dilutions of less than 0.01?vol%), the selective deposition of one to several nanoparticles on every single PS dot becomes possible.     

Assembly of triblock copolymer brush at glass fiber/polystyrene interface and its effect on interfacial shear strength

To control the interfacial structure of glass fiber-reinforced composites, triblock copolymer coupling agents polystyrene-block-poly(n-butylacrylate)-block-poly(γ-methacryloxypropyltrimethoxysilane), (PS-b-PnBA-b-PMPS) were synthesized by atom transfer radical polymerization, then were chemically grafted on the glass fiber surfaces with a sufficiently high grafting density. When the grafted glass fibers are embedded in polystyrene (PS) matrix melt, copolymer brushes assemble at the interface of glass fiber/PS system to form the hemispherical domain morphology, where PnBA blocks form the inner core collapsing on fiber surface, while the outer layer PS blocks shield the PnBA blocks from PS homopolymer melt and entangle with the molecular chain of PS homopolymer. The influence of molecular architecture and organization of triblock copolymer coupling agents on the interfacial shear strength of glass fiber/PS system was investigated by means of Microbond Test. It is found that an increase in the PS block lengths is of advantage to the interfacial shear strength. A PnBA block length about the degree of polymerization (DPn) of 50 is desirable for the interfacial shear strength.     

ASE and photodegradation of two benzimidazole derivatives proton transfer dyes in polymeric matrices

We report the preparation and spectral characteristics of solid polymeric hosts doped with proton-transfer dyes 2-(2′-hydroxyphenyl)benzimidazole (HPBI) and 2-(2′-hydroxy-5′-chlorphenyl)benzimidazole (Cl-HPBI). The material shows amplified stimulated emission (ASE) under 337 nm pulse excitation. In comparing with PMMA, PS and a 1:1 PS/PMMA copolymer as host material the latter shows improved properties relating to efficiency and photo stability. For all samples we observed a shortening in ASE pulse width during emission due to photo degradation.     

Blends of poly(methyl methacrylate) and polyamides

The morphology of PMMA blends with different polyamides (PA-6, 6/9 and 12) was investigated by transmission electron microscopy, recognizing PA-6/PMMA as the most miscible pair. Blends of these polymers were prepared from solutions in m-cresol and formic acid and the morphology was highly dependent on the solvent. The morphology and the segregation degree of extruded PA-6/PMMA blends was investigated by scanning electron microscopy and dynamic-mechanical analysis. The compatibilization succeeded by the introduction of a block copolymer of polyamide and poly(ethylene oxide).     

聚苯乙烯-聚甲基丙烯酸甲酯两嵌段共聚物薄膜在超临界二氧化碳和丙酮溶剂耦合作用下的形貌演化

以聚苯乙烯-聚甲基丙烯酸甲酯(PS-b-PMMA)两嵌段共聚物薄膜为考察对象,首先对比研究了PS-b-PMMA薄膜分别在丙酮溶剂和超临界二氧化碳(scCO_2)环境中退火的形貌演变,进而提出利用scCO_2和丙酮溶剂的耦合作用调控嵌段共聚物薄膜的相转变。实验结果表明,利用scCO_2和丙酮溶剂的耦合作用,能够显著缩短嵌段共聚物薄膜的有序-无序相转变时间,得到高度有序的分相形貌。     

A Simple Top‐Down/Bottom‐Up Approach to Sectored,Ordered Arrays of Nanoscopic Elements Using Block Copolymers

A top‐down/bottom‐up approach is demonstrated by combining electron‐beam (e‐beam) lithography and a solvent annealing process. Micellar arrays of polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) with a high degree of lateral order can be produced on a surface where sectoring is defined by e‐beam patterning. The e‐beam is used to crosslink the block copolymer (BCP) film immediately after spin‐coating when the BCP is disordered or in a highly ordered solvent‐annealed film. Any patterns can be written into the BCP by crosslinking. Upon exposure to a preferential solvent for the minor component block followed by drying, cylindrical nanopores are generated within the nonexposed areas by a surface reconstruction process, while, in the exposed areas, the films remain unchanged. Nickel nanodot arrays can be placed over selected areas on a surface by thermal evaporation and lift‐off process.     

Au nanopatterns on glass substrate using block copolymer and their applications in transparent conducting electrode

High density Au nanostructures were fabricated using polystyrene-block-polymethylmethacrylate (PS-b-PMMA) copolymer on glass substrate for the preparation of electrode materials with good stability, high transparency and excellent conductivity. A 1 wt.% polymer solution in toluene was spin coated on glass substrate. Samples were baked for 48 h at 200 °C with a continuous flow of Ar. Patterned polymer film was obtained by removing the PMMA region through exposing ultraviolet irradiation and rinsing in acetic acid. Au thin films with several thicknesses were then deposited onto the patterned glass substrates by thermal evaporation or sputtering. Removing PS cylinders by sonicating in acetone resulted in Au nanopattern on glass substrates. The connecting gold film acts as conductor while the holes allow light pass through it and helps to be transparent. The transmittance with Au film thickness of 7 nm and 4 nm was found to be about 63% and 70%, respectively. The resistivity was in the range 10^− 5 Ω cm-10^− 6 Ω cm which is comparable with ITO (10^− 3 Ω cm-10^− 4 Ω cm).     

纳米铜/PMMA-b-PS的超声合成及有序组装

在超声辐射作用下,以α-溴代丙酸乙酯为引发剂,溴化亚铜/2,2-联吡啶为催化体系,通过原子转移自由基聚合(A-TRP)制备了分子链末端含有一个α-溴原子的聚甲基丙烯酸甲酯(PMMA-Br)。以此为大分子引发剂引发苯乙烯单体进行ATRP反应,制得聚甲基丙烯酸甲酯嵌段聚苯乙烯(PMMA-b-PS)共聚物。通过硼氢化钠还原聚合物体系中的溴化亚铜,从而得到纳米铜/PMMA-b-PS复合粒子。红外光谱(FT-IR)和核磁共振(1H-NMR)表征嵌段共聚物的结构;凝胶渗透色谱(GPC)测定了共聚物的相对分子量和多分散系数;X射线光电子能谱(XPS)证明纳米铜和PMMA-b-PS嵌段共聚物中PMMA之间存在一定的相互作用;通过高分辨透射电子显微镜(HTEM)观察到纳米铜具有诱导聚合物组装的现象。     

两嵌段共聚物PMMA-b-PHEMA的合成与表征

采用分步法合成了两嵌段共聚物聚甲基丙烯酸甲酯-b-聚甲基丙烯酸-2-羟乙酯.首先以AIBN为引发剂,FeCl<,3>/PPh<,为>催化体系,通过甲基丙烯酸甲酯(MMA)的反向原子转移自由基聚合,得到端基含Cl的聚合物PMMA-Cl,其分子量分布为1.36;然后以此为大分子引发剂,FeCl<,2>/PPh<,3>为催化...