二维胶体晶体刻蚀法及其应用

二维胶体晶体刻蚀法合成二维有序纳米颗粒阵列具有操作简单、成本低、易于实现规模化的优点，它可方便地控制纳米颗粒阵列的形态（即颗粒的间距、尺寸、形状甚至成分等），从而实现阵列性质的大范围调制。而二维胶体晶体的合成是这种刻蚀技术的关键，文章着重介绍其形成的基本过程、影响因素及其合成技术；概述胶体晶体刻蚀技术的应用，并对此进行展望。     

胶体晶体和基于胶体晶体的纳米结构

胶体晶体及基于胶体晶体的各种纳米结构的制备和物理性质是近来物理学和材料科学共同关注的一个热点，文章简要阐述了胶体颗粒间的基本相互作用，着重介绍了各种胶体晶体的制备方法；结合我们近期的工作，综合评述了胶体晶体在二维纳米颗粒阵列、二维有序孔单层膜及三维光子晶体等纳米结构材料研究中的应用，并对未来的发展进行了展望。     

冷却速率对温敏聚N-异丙基丙烯酰胺胶体结晶过程的影响

冷却速率对结晶过程具有重要的影响. 本文采用温敏poly-N-isopropylacrylamide (PNIPAM) 胶体晶体体系实时观察了冷却速率对结晶晶粒尺寸的影响. 通过高倍透射明场观察和Bragg衍射观察研究连续冷却下的晶粒形核和生长实时演化过程, 发现随着冷却速率的增加, PNIPAM胶体晶体晶粒尺寸不断减少. 晶粒尺寸与冷却速率符合幂指数关系, 与金属体系具有相似的演化规律.     

Determination of the colloidal crystal nucleation rate density

Colloidal suspensions of charged latex microspheres in water exhibit liquid-like or crystalline ordering depending on particle interaction and concentration. By virtue of large particle spacing and slow dynamics, colloidal systems offer a unique opportunity to study interfacial structure and dynamics. This paper presents the first reported experimental study of the nucleation rate density, c, of an nonequilibrium (supercooled) colloidal liquid to colloidal crystal first order phase transition. Local and global observations of colloidal crystals growing from a metastable colloidal liquid were used to determine c. Microscopic local observations revealed homogeneous nucleation and constant interface velocity growth of quasispherical crystallites in the bulk and heterogeneous nucleation of a crystalline sheet with lower growth velocity at the cell wall. Complementary global observations of the recrystallization transition made by measuring the time dependence of the suspension transparency (the fraction of transmitted laser light) determined c by fitting this curve to a model based on an extension of Avrami's theory of crystallization.     

Fabrication of Two-Dimensional Arrays of Micron-Sized Gold Rings Based on Preferential Nucleation at Reentrant Sites

A templating method for fabricating two-dimensional （2D） arrays of micron-sized goM rings is reported. The microstructures are formed by electroless plating in a through-porous polymer membrane on a silicon substrate obtained from a closed-packed silica colloidal crystal. Our results show that the sizes of gold rings can be altered by varying electroless plating conditions for the porous polystyrene membranes. Moreover, we explain the growth mechanism of gold rings using the classical crystal growth theory that is preferential nucleation at reentrant sites.     

银纳米粒子阵列的自组装及其表面增强拉曼光谱应用

在以聚赖氨酸为表面耦联层分子的玻片基底制备了银纳米粒子阵列。ＳＥＭ表征结果表明,银粒子以亚单层的形式排列在基底表面。比较银溶胶和纳米粒子阵列的紫外可见光谱可见聚赖氨酸耦联层对银纳米粒子的粒径具有一定的选择性,甲基紫精在银纳米粒子阵列上的表面增强ＦＴ拉曼光谱表明在近红外区拉曼散射的表面增强主要来自于化学增强效应。     

紫外光引发还原制备金溶胶及其SERS活性的研究

文章报道了一种用紫外光引发还原制备金溶胶的新方法,其还原过程经历了自由基机理。用紫外可见光谱观察了不同反应时间溶胶状态的变化。结果表明,光照反应2h时明显出现金溶胶粒子,7h后氯金酸基本转化完毕。同时,研究了稳定剂聚乙烯吡咯烷酮(PVP)的加入对还原过程的影响,结果表明,PVP的加入不仅稳定了溶胶,而且降低了反应速率。用SEM观察了溶胶粒子聚集体的形貌。最后以1,4-bis(4-vinylpyridyl)phenylene为探针分子研究了这种溶胶的SERS活性。     

基于二维胶体晶体刻蚀法的纳米颗粒阵列

悬浮液中的胶体球在一定条件下能够自组装成二维胶体晶体，以此为掩膜可合成纳米颗粒阵列体系，其颗粒形状、尺寸以及间距等参数易于控制。调整这些参数和相应的介质环境可以实现对颗粒阵列体系性质的有效控制，这也为研究尺寸效应提供了便利，且在一些具有特殊功能的纳米器件方面具有潜在的应用价值。文章重点介绍了这种阵列体系的合成过程、结构形态和性质，并展望了其应用前景。     

Mechanism of spherulitic crystallization as deduced from observations of partially crystallized glassy polystyrene

Thin films of isotactic polystyrene partially crystallized from the glassy state were studied in detail by means of transmission electron microscopy and electron diffraction. Initial nucleation and growth stages of spherulitic fibrils (or lamellae) were illustrated clearly by using novel techniques, such as Au decoration, and novel specimens such as thin films containing holes.

Spherulitic nucleation begins with the crystallization of a liquid-crystal-like nodule or a group of these nodules merging to form a spherulitic center. Fibrils or lamellae grow and fan out from the nucleus by additional incorporation of maturing nodules. Proliferation of fibrils is essentially a space-filling process through the crystallization of uncrystallized nodules or nodules that were left behind by growing fibrils which had initiated earlier. The deduced mechanism of spherulitic crystallization leads directly to the formation of interlamellar links between neighboring fibrils. However, no extended-chain-type interlamellar links were revealed by Au decoration.

The application of the mechanism of spherulitic crystallization from the glass to that from the melt is also suggested; it is based primarily on recent studies which show remarkable similarities between structures existing in the glassy and the melt states prior to crystallization.     

Miscibility,Crystallization, and Morphology of the Double-Crystalline Blends of Insulating Polyethylene and Semiconducting Poly(3-Butylthiophene)

A series of crystalline semiconducting poly(3-butylthiophene) (P3BT)/crystalline insulating polyethylene (PE) blends were prepared and the miscibility, crystallization, and structure/morphology were investigated. Even though phase separation was observed by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS), several pieces of evidence indicated that limited miscibility should be present in PE/P3BT blends: small changes in both T_m and crystallinity of PE phase and a small portion of PE being dissolved in P3BT. The study of PE isothermal crystallization kinetics revealed that the introduction of P3BT significantly influenced the nucleation mechanism and growth geometry, i.e., PE was transformed from three-dimensional (3D) spherulitic to two-dimensional (2D) disc crystals. A striking reduction of nucleation density and an obvious ringed morphology of PE spherulites (2D) in PE/P3BT blends were also observed by polarized optical microscopy; it is proposed that the limited miscibility between PE and crystalline P3BT favors the formation of ringed PE spherulite in the blends. Additionally, preferred orientation of PE lamellae, with their b-axis largely constrained to the thin film plane, was observed by X-ray diffraction in PE/P3BT blend films. It is evidenced that the PE orientation was due to the b-axis being the crystal growth direction, which can only be in film plane.     

Effects of Montmorillonite on the Nonisothermal Crystallization Behavior of the Poly(trimethylene terephthalate)/Polypropylene/Montmorillonite Nanocomposites

Organic montmorillonite (MMT) reinforced poly(trimethylene terephthalate) (PTT)/ polypropylene (PP) nanocomposites were prepared by melt blending. The effects of MMT on the nonisothermal crystallization of the matrix polymers were investigated using differential scanning colorimetry (DSC) and analyzed by the Avrami equation. The DSC results indicated that the effects of MMT on the crystallization processes of the two polymers exhibited great disparity. The PTT's crystallization was accelerated significantly by MMT no matter whether PTT was the continuous phase or not, but the thermal nucleation mode and three-dimensional growth mechanism remained unchanged. However, in the presence of MMT, the PP's crystallization was slightly retarded with PP as the dispersed phase, and was influenced little with PTT as the dispersed phase. When the MMT content was increased from 2_wt% to 7_wt%, the crystallization of the PTT phase was slightly accelerated, whereas the crystallization of the PP phase was severely retarded, especially at lower temperatures. Moreover, the nucleation mechanism for the PP's crystallization changed from a thermal mode to an athermal one. In the polypropylene-graft-maleic anhydride (PP-g-MAH) compatibilized PTT/PP blends, with the addition of 2_wt% MMT during melt blending, the T _c (PTT) shifted 7.8°C to lower temperature and had a broadened exotherm, whereas the T _c (PP) shifted 17.1°C to higher temperature, with a narrowed exotherm. TEM analysis confirmed that part of the PP-g-MAH was combined with MMT during blending.     

Scaling in colloidal crystallization

Summary The process of colloidal crystallization has already been separately investigated by light scattering mearurements of the crystalline order (Bragg peaks) and of long-ranged density fluctuations (small-angle scattering). We present the firstsimultaneous small- and large-angle light scattering experiment. Our measurements have been performed on hard-sphere colloids of different particle densities. We show results for the temporal evolution of crystallization and find two distinct regimes: homogeneous nucleation and diffusion- or reaction-limited growth at early times, followed by ripening of the Lifshitz-Slyozov or Lifshitz-Allen-Cahn type. To our preliminary experience, we can already state that the results are always consistent in both partial experiments. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994. With deep regret we have to announce that Prof. Klaus Sch?tzel, who inspired and guided the work presented here, has died in October 1994.     

Regular array of InGaAs quantum dots with 100-nm-periodicity formed on patterned GaAs substrates

Regular arrays of InGaAs quantum dots (QDs) with a 100-nm-periodicity have been successfully fabricated by controlling the nucleation sites on artificially prepared nano-hole arrays. The nucleation probability of a single QD at each nano-hole reached 100% by depositing InGaAs at low temperature and subsequent annealing. Four InGaAs QD layers were vertically stacked while conserving the regularity, and the stacked QD array has shown a clear photoluminescence peak at room temperature. We discuss the effects of several growth conditions on the nucleation probability of QDs.     

Colloidal crystal growth at externally imposed nucleation clusters

We study the conditions under which and how an imposed cluster of fixed colloidal particles at prescribed positions triggers crystal nucleation from a metastable colloidal fluid. Dynamical density functional theory of freezing and Brownian dynamics simulations are applied to a two-dimensional colloidal system with dipolar interactions. The externally imposed nucleation clusters involve colloidal particles either on a rhombic lattice or along two linear arrays separated by a gap. Crystal growth occurs after the peaks of the nucleation cluster have first relaxed to a cutout of the stable bulk crystal.     

Crystallization Behavior of Poly(Trimethylene Terephthalate)/Polycarbonate Blends

The crystallization behavior of poly(trimethylene terephthalate (PTT) in compatibilized and uncompatibilized PTT/polycarbonate (PC) blends are investigated in the research reported in this paper. The differential scanning calorimetry (DSC) results showed that the crystallization behaviors of PTT/PC blends were very sensitive to PC content. The onset (T_ci) and the peak (T_c) crystallization temperatures shifted to lower temperatures whereas the area of the exotherm decreased quickly as the PC content was increased. The Avrami exponent, n, decreased from 4.32 to 3.61 as the PC content was increased from 0 to 20 wt %, and the growth rate constant, Z _c , decreased gradually as well. This suggests that the nucleation mechanism exhibits the tendency of changing gradually from a thermal nucleation to an athermal mode although the growth mechanism still remains three‐dimensional. When epoxy (2.7 phr) was added as a compatibilizer during melt blending, the T_ci and T_c shifted slightly to higher temperature (≤2°C), and the crystallization enthalpy, however, exhibited an increased crystallinity with the exception of the 90/10/2.7 phr PTT/PC/Epoxy. This suggests that the epoxy make a positive contribution to the PTT crystallization. Moreover, the influences of epoxy on the crystallization behaviors of PTT/PC blends are related to the epoxy content. By contrast, the compatibilizer of ethylene‐propylene‐diene copolymer graft glycidyl methacrylate (EPDM‐g‐GMA, ≤6.3 phr) had little effect on the crystallization behavior of PTT/PC blends. For PTT/PC/Epoxy (2.7 phr) blends, the Avrami exponent, n, decreased to near 3, while the growth rate constant, Z _c , increased slightly as PC content was increased from 0 to 20 wt %. It is suggested that epoxy accelerated the process of the nucleation mechanism changing from thermal nucleation to an athermal mode. The EPDM‐g‐GMA had little effect on the nucleation mode and spherical growth mechanism. The PTT spherulite morphologies in PTT/PC blends were very sensitive to blend composition. Completely different morphologies were observed in pure PTT, PTT/PC, PTT/PC/Epoxy, and PTT/PC/EPDM‐g‐GMA blends.     

Two-step crystallization kinetics in colloidal hard-sphere systems

The crystallization kinetics of colloidal hard spheres was studied using a special Bragg spectrometer with high sensitivity. In contrast with the classical scenario we observe a two-step nucleation process: the number of crystallites increases slowly at early times, followed by a dramatic reduction at intermediate times, prior to undergoing a rapid increase at late times. We explain these results in terms of a polydispersity limited growth of crystallites, where the crystallization at early times is governed by local fractionation processes, leading to a long delay prior to final crystallization.     

Colloids as model systems for metals and alloys: a case study of crystallization

Metallic systems are widely used as materials in daily human life. Their properties depend very much on the production route. In order to improve the production process and even develop novel materials a detailed knowledge of all physical processes involved in crystallization is mandatory. Atomic systems like metals are characterized by very high relaxation rates, which make direct investigations of crystallization very difficult and in some cases impossible. In contrast, phase transitions in colloidal systems are very sluggish and colloidal suspensions are optically transparent. Therefore, colloidal systems are often discussed as model systems for metals. In the present work, we study the crystallization process of charged colloidal systems from the very beginning. Charged colloids offer the advantage that the interaction potential can be systematically tuned by a variation of the particle number density and the salt concentration. We apply light scattering and ultra-small angle x-ray scattering to investigate the formation of short-range order in the liquid state even far from equilibrium, crystal nucleation and crystal growth. The results are compared with equivalent studies on metallic systems.     

Isothermal Crystallization and Subsequent Melting Behavior of Poly(ethylene terephthalate)/Silica Nanocomposites

The crystallization process of poly(ethylene terephthalate)/silica nanocomposites were investigated by differential scanning calorimetry (DSC) and then analyzed using the Avrami method. The results indicated that the crystallization of pure poly(ethylene terephthalate) (PET) was fitted for thermal nucleation and three‐dimensional spherical growth throughout the whole process, whereas the crystallization of PET/silica nanocomposites exhibits two stages. The first stage corresponds to athermal nucleation and three‐dimensional spherical growth, and the second stage corresponds to recrystallization caused by the earlier spherulites impingement. The crystallization rate increases remarkably and the activation energies decrease considerably when silica nanoparticles are added. The subsequent melting behavior of the crystallized samples shows that the melting point (T _m) of nanocomposites is higher than that of pure PET, which might be caused by two factors: (1) The higher melting point might be due to some hindrance to the PET chains caused by the nanoparticles at the beginning of the melting process; (2) it might also be the case that more perfect crystals can be formed due to the higher crystallization temperatures and lower activation energies of PET/silica nanocomposites.     

Self-Assembling Process of Colloidal Particles into Two-Dimensional Arrays Induced by Capillary Immersion Force: A Simulation Study With Discrete Element Method

This paper presents a simulation study for self-assembling process of colloidal particles into two-dimensional arrays due to capillary immersion force. Discrete element method is used to simulate the dynamics of colloidal particles trapped in a thin liquid film. The previous model is improved in the following two points: a modification of the screening effect of capillary immersion force and introduction of periodic boundary condition. Snapshots provided by the simulations agree well with experimental images taken by atomic force microscopy. The self-assembling process is quantified with pair correlation function and coordination number. At lower coverage, colloidal particles rapidly form small clusters that consist of several particles in the early stage. Subsequently, chain-like structures with some branches are mainly generated. On the other hand, at higher coverage, large domains of hexagonal close-packed (HCP) structures are gradually generated. The rate of the growth of HCP domains is much slower than that of the generation of the small clusters and the chain-like structures.