Dry etching of colloidal crystal films

Two types of non-close-packed colloidal crystal films were prepared by etching the films made of polystyrene nanospheres using a hyperthermal neutral beam of oxygen gas. Etching without sintering above glass transition temperature of the polymer particles resulted in the non-close-packed structure of the nanospheres, in which polystyrene nanospheres in different lattice planes touched each other due to the reduction in the size of the nanospheres that occurred during the etching process. In contrast, a different non-close-packed structure with inter-connecting networks between etched nanospheres was generated by annealing of the colloidal crystal and a subsequent etching process. The photonic bandgap could be tuned during this dry etching of colloidal photonic crystals. This connected open structure could be used as a template for a silica inverse opal by chemical vapor deposition. An alternative dry etching process, reactive ion etching, mainly affected the morphology of particles near the top surface, and only a slight change in the stop band position of the colloidal crystal film was observed.     

Nonspherical colloidal crystals fabricated by the thermal pressing of colloidal crystal chips

Nonspherical colloids and their ordered arrays may be more attractive in applications such as photonic crystals than their spherical counterparts because of their lower symmetries, although such structures are difficult to achieve. In this letter, we describe the fabrication and characterization of colloidal crystals constructed from nonspherical polyhedrons. We fabricated such nonspherical colloidal crystals by pressing spherical polymer colloidal crystal chips at a temperature slightly lower than the glass-transition temperature (T(g)) of these polymer colloids. During this process, the polymer microspheres were distinctively transformed into polyhedrons according to their crystal structures, whereas the long-range order of the 3D lattice was essentially preserved. Because a working temperature lower than T(g) effectively prevented the colloidal crystals from fusing into films, the spherical colloidal crystals were transformed greatly under pressure, which lead to obvious change in the optical properties of colloidal crystals. Besides their special symmetry and optical properties, these nonspherical colloidal crystals can be used as templates for 2D or 3D structures of special symmetry, such as 2D nano-networks. We anticipate that this fabrication technique for nonspherical colloidal crystals can also be extended to nonspherical porous materials.     

流动控制沉积法制备PMMA叠层光子晶体薄膜及其光学性能研究

采用流动控制沉积法, 通过调控泵速和聚甲基丙烯酸甲酯(PMMA)胶体微球溶液的浓度, 制备出微球排列高度有序且薄膜紧密附着于基底的高质量光子晶体薄膜. 获得了制备高质量PMMA光子晶体薄膜的组装条件范围, 发现在该条件范围内, 当泵速或胶体微球溶液浓度一定时, PMMA光子晶体薄膜的厚度随胶体微球溶液浓度的增加或泵速的降低而增加. 研究了组装条件对PMMA光子晶体薄膜光学性能的影响, 发现光子禁带位置随光子晶体薄膜厚度增加或减少而红移或蓝移. 在此基础上, 控制组装条件得到了不同尺寸微球堆叠而成的叠层光子晶体薄膜, 并研究了其光学性能的变化规律. 结果显示, 叠层光子晶体薄膜的光子禁带峰为各层叠层光子晶体禁带峰的简单叠加, 且峰强度受光入射角方向影响.     

Fabrication of hollow colloidal crystal cylinders and their inverted polymeric replicas

We fabricated colloidal crystals on a fiber by a dip-coating method. The self-assembly of monodisperse colloidal particles was affected by the curvature of the fiber (the reciprocal of the fiber radius). As the fiber became smaller in diameter, fewer layers of the colloidal spheres were coated for a given lift-up speed. The hollow colloidal crystal cylinders were used as a template for creating macroporous structure having three-dimensionally interconnected air cavities. Specifically, the polymer precursor was infiltrated into the colloidal crystal template and the macroporous polymer structures were obtained after the selective etching of colloidal particles.     

Morphology of polythiophene and polyphenyl films produced via surface polymerization by ion-assisted deposition

Conducting polymer films are grown by either mass-selected or non-mass-selected, hyperthermal thiophene ions coincident on a surface with a thermal beam of organic monomers of either alpha-terthiophene (3T) or p-terphenyl (3P) neutrals. Previous experiments verified polymerization of both 3T and 3P by 200 eV C(4)H(4)S(+) during surface polymerization by ion-assisted deposition (SPIAD). A wide variety of structures are observed by scanning electron microscopy to form in the SPIAD polythiophene and polyphenyl films. These structures include microscale islands, lamellar structures, fractal-like growth patterns, and nanoscale crystallites. Some of the deposited films diffract X-rays while others show electron micrographs of crystallites. The variation of these patterns with deposition conditions clearly indicate that ion-induced polymerization mediates film morphology through control of ion energy and ion/neutral ratio. Furthermore, these ion-assisted events mediate important thermal processes such as sublimation.     

P(St-AM)核壳聚合物微球的制备及其光子晶体膜

采用一步乳液聚合法,调节引发剂用量,制备了不同粒径的具有核壳结构的功能性聚(苯乙烯-丙烯酰胺)乳胶微球.用透射电子显微镜表征了乳胶微球的核壳结构和粒径,所制微球的粒径分别为195,217,234和255 nm.用红外光谱对微球的化学成分进行了表征,证实聚丙烯酰胺已包覆在聚苯乙烯外层.通过竖直沉积自组装法制备了聚合物微球的光子晶体薄膜.扫描电子显微镜表征了所制光子晶体膜的表面形貌,反射和透射光谱表征了光子禁带.结果表明,聚合物微球以面心立方紧密堆积,其(111)面与基底平行;微球粒径不同,光子晶体的光子禁带不同.制备了不同光子禁带的光子晶体,禁带分别位于473,515,574和630 nm,相应的薄膜分别呈蓝色、绿色、黄色和红色,对于光子晶体的拓展和应用具有重要的意义.     

SiO2胶体晶体垂直沉积自组装方法的改进

采用垂直沉积技术及相应的改进方法,使用化学合成的400 nm单分散二氧化硅微球自组装制备了胶体晶体薄膜。通过扫描电镜与分光光度计对样品的微观结构与透过光谱进行了表征,并对比研究了不同的垂直沉积方法对胶体晶体的影响。结果表明,通过温度与流量控制两种改进手段,均能制备具有六方密堆结构周期排列的胶体晶体薄膜。在垂直沉积过程中适当的升高温度有利于降低胶体粒子的用量,而通过流量控制的垂直沉积技术则可以有效缩短自组装时间。通过调节蠕动泵改变液面与基板的相对运动速度,或者调控温度改变胶体溶液的蒸发速率,可在材料表面形成单层或多层的胶体晶体薄膜。改进的垂直沉积技术将有望应用于快速沉积大面积、高质量的胶体晶体材料。     

聚苯乙烯胶晶的组装

采用自然沉降法、离心法和垂直沉积法组装了聚苯乙烯胶晶。实验结果表明,所得胶晶都具有面心立方结构,结构有序性相当高。自然沉降法和离心法适用于块体胶晶的组装,自然沉降法适用于胶晶膜的组装。     

Slow vertical deposition of colloidal crystals: a Langmuir-Blodgett process?

For an evaporating colloidal suspension in which the evaporation velocity exceeds the sedimentation velocity, particles will accumulate at the solvent-air interface. If neither diffusion nor convection can disperse this accumulation, it is expected to grow into a colloidal multilayer several microns thick. We observe that the thickness of colloidal crystals vertically deposited from 1 mum diameter polystyrene latex suspensions of 0.002 < or = phi < or = 0.008 increases linearly with distance in the growth direction and that these thickness profiles are consistent with their growth from a horizontal colloidal layer accumulated beneath the solvent-air interface. We describe a means for performing vertical deposition at growth rates slower than the evaporation rate by adding solvent to the bottom of the colloidal suspension and observe that halving the growth rate of vertical deposition increases both the thickness and the reflectivity of the resulting colloidal crystals, effects indistinguishable from those of doubling the concentration of the colloidal suspension, data also consistent with the colloidal crystals' growth from a horizontal layer of particles beneath the interface. If sufficiently little reorganization is involved as particles move from this horizontal layer to the vertically deposited colloidal crystal, slow vertical deposition of polymer microspheres might be thought of as the Langmuir-Blodgett transfer of a horizontal colloidal crystal onto a vertical substrate. Colloidal crystals deposited using both high concentration and slowed growth can have peak IR reflectance in excess of 80%, exceeding most published values. These observations provide a conceptual framework for engineering vertically deposited colloidal crystals that combine thickness with good optical performance.     

表面富含羧基的单分散交联聚合物微球的快速自组装制备胶体晶的研究

在20～70℃范围内,用垂直沉积的方法可使表面富含羧基的单分散交联聚合物微球在不同的基底上快速自组装成三维有序的胶体晶.不同粒径的微球形成的胶体晶其光禁带峰位不同,因此可调控不同波长的光在胶体晶中的传播.利用紫外-可见光谱研究了胶体晶的光禁带峰位与组成其微球粒径之间的关系.结果表明,随着构成胶体晶微球粒径的增大,胶体晶光禁带峰位发生了红移,而随着入射光角度的增大,胶体晶的光禁带峰位发生了蓝移.利用原子力显微镜和扫描电子显微镜研究了其它条件对聚合物微球有序排列的影响,发现聚合物微球在pH值为3.0～13.0范围内可以形成三维有序自组装胶体晶.这是由于在不同的pH值下,聚合物微球表面发生羧基化及去羧基化反应,导致在自组装过程中微球之间和微球与介质之间作用力的变化     

Nanoparticle-mediated epitaxial assembly of colloidal crystals on patterned substrates

We have studied the assembly of 3-D colloidal crystals from binary mixtures of colloidal microspheres and highly charged nanoparticles on flat and epitaxially patterned substrates created by focused ion beam milling. The microspheres were settled onto these substrates from dilute binary mixtures. Laser scanning confocal microscopy was used to directly observe microsphere structural evolution during sedimentation, nanoparticle gelation, and subsequent drying. After microsphere settling, the nanoparticle solution surrounding the colloidal crystal was gelled in situ by introducing ammonia vapor, which increased the pH and enabled drying with minimal microsphere rearrangement. By infilling the dried colloidal crystals with an index-matched fluorescent dye solution, we generated full 3-D reconstructions of their structure including defects as a function of initial suspension composition and pitch of the patterned features. Through proper control over these important parameters, 3-D colloidal crystals were created with low defect densities suitable for use as templates for photonic crystals and photonic band gap materials.     

Effect of Nano-Carbon Addition on Angle Dependence of Polystyrene Colloidal Crystal Film

Russian Journal of Physical Chemistry A - Low angle dependence single green polystyrene colloidal crystal films were prepared by vertical deposition method using polystyrene microspheres with size...     

梯度结构胶体光子晶体的制备及光子禁带调节

以改进的对流自组装方法制备层数可控的胶体光子晶体, 并通过各向同性氧等离子体(O₂ Plasma)刻蚀构造出梯度结构, 进一步通过金(Au)及无定形硅(Si)的可控沉积调节梯度结构胶体光子晶体的光子禁带, 并将该梯度结构用于罗丹明B的荧光发射增强.     

Measuring the swelling behavior of polymer microspheres with different cross-linking densities and the medium-dependent color changes of the resulting latex crystal films

We measured the size changes of cross-linked polymer microspheres of narrow size distribution with different cross-linking densities by the in situ swelling method. The swelling behavior of these cross-linked polymer microspheres revealed that their maximal swelling degree linearly decreased as a function of the cross-linker content from 6.65 at 1.36 mol% to 2.43 at 3.25 mol%. By means of UV-vis spectra, we observed the spectral changes of the latex crystal films composed of these cross-linked polymer microspheres when we filled the interstices of the latex crystal films with different fluid media. Some succeeding peak shifts were observed, which may have resulted from the movement or the swelling of the polymer microspheres in the latex crystals.     

Inverse opal photonic crystal of chalcogenide glass by solution processing

Chalcogenide opal and inverse opal photonic crystals were successfully fabricated by low-cost and low-temperature solution-based process, which is well developed in polymer films processing. Highly ordered silica colloidal crystal films were successfully infilled with nano-colloidal solution of the high refractive index As(30)S(70) chalcogenide glass by using spin-coating method. The silica/As-S opal film was etched in HF acid to dissolve the silica opal template and fabricate the inverse opal As-S photonic crystal. Both, the infilled silica/As-S opal film (Δn ~ 0.84 near λ=770 nm) and the inverse opal As-S photonic structure (Δn ~ 1.26 near λ=660 nm) had significantly enhanced reflectivity values and wider photonic bandgaps in comparison with the silica opal film template (Δn ~ 0.434 near λ=600 nm). The key aspects of opal film preparation by spin-coating of nano-colloidal chalcogenide glass solution are discussed. The solution fabricated "inorganic polymer" opal and the inverse opal structures exceed photonic properties of silica or any organic polymer opal film. The fabricated photonic structures are proposed for designing novel flexible colloidal crystal laser devices, photonic waveguides and chemical sensors.     

蒸发自组装法制备聚苯乙烯胶体晶体

采用乳液聚合法制得亚微米级聚苯乙烯单分散微球,并用蒸发自组装法在乳液气-液界面进行自上而下的层层组装,制得了厚度在450μm以上的三维有序胶体晶体。结果表明,影响胶体晶体有序性的关键因素是对蒸发速度的控制,促使胶体晶体规则排列的最主要作用力为溶液的毛细管力。在胶体晶体组装末期,随着溶剂量的减少,空间阻力逐渐增大,微球对流能力下降,造成胶体晶体的有序性降低。     

Colloidal lithographic nanopatterning via reactive ion etching

We report here a novel colloidal lithographic approach to the fabrication of nonspherical colloidal particle arrays with a long-range order by selective reactive ion etching (RIE) of multilayered spherical colloidal particles. First, layered colloidal crystals with different crystal structures (or orientations) were self-organized onto substrates. Then, during the RIE, the upper layer in the colloidal multilayer acted as a mask for the lower layer and the resulting anisotropic etching created nonspherical particle arrays and new patterns. The new patterns have shapes that are different from the original as a result of the relative shadowing of the RIE process by the top layer and the lower layers. The shape and size of the particles and patterns were dependent on the crystal orientation relative to the etchant flow, the number of colloidal layers, and the RIE conditions. The various colloidal patterns can be used as masks for two-dimensional (2-D) nanopatterns. In addition, the resulting nonspherical particles can be used as novel building blocks for colloidal photonic crystals.     

Crystallization of colloidal crystal on hydrogel surface

A dip-coating method to fabricate wet and dry type of colloidal crystal films was developed. The wet type of colloidal crystal film was fabricated by lifting an agarose-hydrogel-coated substrate out of an aqueous suspension containing monodisperse polymer spheres and the dry type of colloidal crystal film was derived by following desiccation of the wet film. Monodisperse spheres formed ordered structures in the both type of the films, which contributed sharp reflection peaks. Brilliant colors were observed when the reflection peaks fell in the visible region. Formation mechanism of the colloidal crystal and their optical properties were discussed.     

Formation of ordered mesoporous films from in situ structure inversion of azo polymer colloidal arrays

This work shows that mesoporous polymeric films with spherical and elliptical pores can be obtained by in situ structure inversion of the azo polymer colloid arrays through selective interaction with solvent. The epoxy-based azo polymer contained both the pseudo-stilbene-type azo chromophores and the hydrophilic carboxyl groups. The colloidal spheres of the azo polymer were prepared by gradual hydrophobic aggregation of the polymeric chains in THF-H2O media, induced by a steady increase in the water content. Ordered 2D arrays of the hexagonally close-packed colloidal spheres were obtained by the vertical deposition method. After the solvent (THF) annealing, the ordered 2D arrays were directly transformed to mesoporous films through the sphere-pore inversion. Under the same condition, the 2D arrays composed of the ellipsoidal colloids, which were obtained by the irradiation of a polarized Ar+ laser beam on the colloidal sphere arrays, could be transformed to films with ordered elliptical pores. To our knowledge, this is the first example to demonstrate that mesoporous structures can be directly formed from the colloidal arrays of a homopolymer through structure inversion. This observation can shed new light on the nature of self-assembly processes and provide a feasible approach to fabricate mesoporous structures without the infiltration-removal step. By exploring the photoresponsive properties of the materials, mesoporous film with special pore structure and properties can be expected.     

Silica colloidal crystals as three-dimensional scaffolds for supported lipid films

This report describes the assembly of laterally diffusive lipid layers within the pores of colloidal crystals for potential application in membrane-based sensing. The amount of lipid encapsulated within colloidal crystals depends upon the method used to introduce the lipid to the crystalline substrate. Relative to a planar supported lipid bilayer, lipid loading in a 6.6 microm thick crystal was 15-73 times greater, as observed by fluorescence microscopy. Protein adsorption studies indicate that the crystal pores are open and that the silica surface of the crystal is passivated with respect to adsorption of a model protein when coated with POPC. Furthermore, the mesoporous environment of the colloidal crystal is found to protect lipid films from drying and rehydration processes that destroy planar supported lipid bilayers. The potential of colloidal crystal encapsulated lipid films for chemical sensing is demonstrated by a model protein binding assay.