Structure and dynamics of thin colloidal films

This thesis begins by studying the thickness of evaporative spin coated colloidal crystals and demonstrates the variation of the thickness as a function of suspension concentration and spin rate. Particularly, the films are thicker with higher suspension concentration and lower spin rate. This study also provides evidence for the reproducibility of spin coating in terms of the thickness of the resulting colloidal films. These colloidal films, as well as the ones obtained from various other methods such as convective assembly and dip coating, usually possess a crystalline structure. Due to the lack of a comprehensive method for characterization of order in colloidal structures, a procedure is developed for such a characterization in terms of local and longer range translational and orientational order. Translational measures turn out to be adequate for characterizing small deviations from perfect order, while orientational measures are more informative for polycrystalline and highly disordered crystals. Finally, to obtain an understanding of the relationship between dynamics and structure, the dynamics of colloids in a quasi-2D suspension as a function of packing fraction is studied. The tools that are used are mean square displacement (MSD) and the self part of the van Hove function. The slow down of dynamics is observed as the packing fraction increases, accompanied with the emergence of 6-fold symmetry within the system. The dynamics turns out to be non-Gaussian at early times and Gaussian at later times for packing fractions below 0.6. Above this packing fraction, the dynamics is non-Gaussian at all times. Also the diffusion coefficient is calculated from MSD and the van Hove function. It goes down as the packing fraction is increased.

Swellable polymer films containing Au nanoparticles for point-of-care therapeutic drug monitoring using surface-enhanced Raman spectroscopy

Large (10 × 10 cm) sheets of surface-enhanced Raman spectroscopy (SERS) active polymer have been prepared by stabilising metal nanoparticle aggregates within dry hydroxyethylcellulose (HEC) films. In these films the aggregates are protected by the polymer matrix during storage but in use they are released when aqueous analyte droplets cause the films to swell to their gel form. The fact that these "Poly-SERS" films can be prepared in bulk but then cut to size and stored in air before use means that they provide a cost effective and convenient method for routine SERS analysis. Here we have tested both Ag and Au Poly-SERS films for use in point-of-care monitoring of therapeutic drugs, using phenytoin as the test compound. Phenytoin in water could readily be detected using Ag Poly-SERS films but dissolving the compound in phosphate buffered saline (PBS) to mimic body fluid samples caused loss of the drug signal due to competition for metal surface sites from Cl^- ions in the buffer solution. However, with Au Poly-SERS films there was no detectable interference from Cl^- and these materials allowed phenytoin to be detected at 1.8 mg L^-1, even in PBS. The target range of detection of phenytoin in therapeutic drug monitoring is 10-20 mg L^-1. With the Au Poly-SERS films, the absolute signal generated by a given concentration of phenytoin was lower for the films than for the parent colloid but the SERS signals were still high enough to be used for therapeutic monitoring, so the cost in sensitivity for moving from simple aqueous colloids to films is not so large that it outweighs the advantages which the films bring for practical applications, in particular their ease of use and long shelf life.

Verification and Operation of Adaptive Materials in Space

Piezoelectric polymers based on polyvinylidene fluoride (PVDF) are of interest as smart materials for novel space-based telescope applications. Dimensional adjustments of adaptive thin polymer films are achieved via controlled charge deposition. Predicting their long-term performance requires a detailed understanding of the piezoelectric property changes that develop during space environmental exposure. The overall materials performance is governed by a combination of chemical and physical degradation processes occurring in low Earth orbit as established by our past laboratory-based materials performance experiments (see report SAND 2005-6846). Molecular changes are primarily induced via radiative damage, and physical damage from temperature and atomic oxygen exposure is evident as depoling, loss of orientation and surface erosion. The current project extension has allowed us to design and fabricate small experimental units to be exposed to low Earth orbit environments as part of the Materials International Space Station Experiments program. The space exposure of these piezoelectric polymers will verify the observed trends and their degradation pathways, and provide feedback on using piezoelectric polymer films in space. This will be the first time that PVDF-based adaptive polymer films will be operated and exposed to combined atomic oxygen, solar UV and temperature variations in an actual space environment. The experiments are designed to be fully autonomous, involving cyclic application of excitation voltages, sensitive film position sensors and remote data logging. This mission will provide critically needed feedback on the long-term performance and degradation of such materials, and ultimately the feasibility of large adaptive and low weight optical systems utilizing these polymers in space.

Magnetically-actuated artificial cilia for microfluidic propulsion.

In this paper we quantitatively analyse the performance of magnetically-driven artificial cilia for lab-on-a-chip applications. The artificial cilia are fabricated using thin polymer films with embedded magnetic nano-particles and their deformation is studied under different external magnetic fields and flows. A coupled magneto-mechanical solid-fluid model that accurately captures the interaction between the magnetic field, cilia and fluid is used to simulate the cilia motion. The elastic and magnetic properties of the cilia are obtained by fitting the results of the computational model to the experimental data. The performance of the artificial cilia with a non-uniform cross-section is characterised using the numerical model for two channel configurations that are of practical importance: an open-loop and a closed-loop channel. We predict that the flow and pressure head generated by the artificial cilia can be as high as 18 microlitres per minute and 3 mm of water, respectively. We also study the effect of metachronal waves on the flow generated and show that the fluid propelled increases drastically compared to synchronously beating cilia, and is unidirectional. This increase is significant even when the phase difference between adjacent cilia is small. The obtained results provide guidelines for the optimal design of magnetically-driven artificial cilia for microfluidic propulsion.

Formation of GaAs/AlGaAs and InGaAs/GaAs nanorings by droplet molecular-beam epitaxy

GaAs/AlGaAs lattice-matched nanorings are formed on GaAs (100) substrates by droplet epitaxy. The crucial step in the formation of nanorings is annealing Ga droplets under As flux for proper time. The observed morphologic evolution of Ga droplets during annealing does not support the hypothesis that As atoms preferentially react with Ga around the periphery of the droplets, but somehow relates to a dewetting process similar to that of unstable films. Photoluminescene (PL) test results confirm the quantum-confinement effect of these GaAs nanorings. Using similar methods, we have fabricated InGaAs/GaAs lattice-mismatched rings. (c) 2005 American Institute of Physics.

高分子薄膜微图案的构筑调控

发展不依赖于传统刻蚀技术的、图案尺寸等可以动态调控的微图案化方法是当前国际上的研究热点。高分子由于可以通过可控聚合调控其预定结构和尺寸，并且具有易于加工和可以嵌入多种化学功能团等特点，是制备不依赖于传统刻蚀技术的价廉、高产的微图案化的理想材料。因而设计具有特定结构的高分子，利用高分子的丰富的相态结构和其在外场等作用下的性质，发展高分子图案化方法、技术和原理具有重要意义。本论文利用高分子的尺度和结构特征以及对外场的响应特性，研究其自组装形成微、纳米图案的影响因素和机理，掌握了调控图案形态、尺寸、表面性质的规律，实现了稳定、有序的智能图案的动态设计。主要内容如下：（1）利用冷凝的水蒸汽液滴为模板，在PS、PMMA等均聚物薄膜上制备了微米尺寸的规则孔洞结构。研究了溶剂性质、聚合物溶液粘度、环境湿度等对规则孔洞形成的影响，观察了孔洞形成的中间过程，提出了孔洞形成的机理。（2）研究了高分子均聚物和以聚合物为基体的发光小分子薄膜在外场（电场、温度场）作用下的长程有序规则排列图案的形成条件和机理，以及外场作用对高分子有序结构的影响因素。静电力和温度梯度使薄膜变得不稳定，表面产生具有一定波长和周期的起伏波，这种波动逐渐增强使薄膜破裂最终形成规则结构。（3）通过研究发现薄膜厚度、溶剂对不同链段的选择性以及溶剂蒸汽处理时间对嵌段共聚物薄膜表面形态的演变有重要影响。对于对称双嵌段共聚物PS-b-PMMA薄膜，在PMMA的选择性溶剂蒸汽中，通过改变溶剂蒸汽对PS-b-PMMA薄膜的溶胀程度和处理时间，得到规则孔洞到条纹转变的一系列纳米结构和规则小球到条纹转变的一系列纳米结构。溶剂蒸汽改变了薄膜边界条件，使富集在基底的PMMA向薄膜表面迁移，使其表面形貌和组成发生变化。通过将此体系与均聚物和短链嵌段共聚物共混，改变链段间的界面张力，可以调控纳米结构的尺寸。更进一步，得到的纳米结构图案化的薄膜具有环境敏感性。当将其置于对PS嵌段具有选择性的溶剂蒸汽中时，变换薄膜的边界条件，表面形貌和性质发生了反转。

Dewetting behavior of polystyrene film filled with (C6H5C2H4NH3)(2)PbI4

The dewetting behavior of thin (about 30 nm) polystyrene (PS) films filled with different amount of (C6H5C2H4NH3)(2)PbI4 (PhE-PbI4) on the silicon substrate with a native oxide layer was investigated. For different additive concentrations, PhE-PbI4 showed different spatial distributions in the PS films, which had a strong influence on the film wettability, dewetting dynamics, and mechanism. With 0.5 wt % additive, PhE-PbI4 formed a noncontinuous diffusion layer, which caused a continuous hole nucleation in the film. With about 1 wt % additive, a continuous gradient distribution layer of PhE-PbI4 formed in the film, which inhibited the dewetting.

Rim instability by solvent-induced dewetting

We study the condition of the occurrence of the rim instability in the solvent-induced dewetting process. Our experimental results show that the film thickness not only greatly influences the occurrence of the rim instability, but also influences the wavelength lambda as characterized by the undulation of the deformed contact line. The molecular weight of polymer does not almost influence the occurrence of the rim instability and the wavelength lambda. The wavelength lambda is proportional to the width of the rim in the rim instability region. The receding contact angle theta of polymer solutions on substrates in the dewetting process is an important factor to influence the rim instability in the solvent-induced dewetting.

AN ACTINOMETRIC STUDY OF C2H2 PLASMA POLYMERIZATION AND FILM PROPERTIES

Thin polymer films were grown in radio frequency discharges containing C2H2. Actinometry revealed the trend in the plasma concentration of the CH species as a function of the operating pressure. The C-H bond density in the films, revealed by infrared analysis, was found to increase with the pressure of C2H2 in a similar way to that of the concentration of the CH species in the discharge. From transmission ultraviolet-visible spectroscopy data, optical parameters of the polymers, namely, the refractive index and the optical gap, were calculated. For the range of pressure studied, the refractive index decreased from 1.73 to 1.63 and the optical gap increased from 2.4 to 3.3 eV. Finally, measurements of the residual stress of the polymer films were carried out by the bending beam method, using a He-Ne laser, yielding values from 0.05 to 0.3 GPa. (C) 1995 American Vacuum Society.

A Novel Plasma Technique for Surface Treatment: The Plasma Expander

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)