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Light-Induced Nanowetting: Erasable and Rewritable Polymer Nanoarrays via Solid-to-Liquid Transitions
(2020-08-12)
Lin, Kuan-Ting
;
Chen, Yu-Jia
;
Huang, Meng-Ru
;
Karapala, Vamsi Krishna
;
Ho, Jhih-Hao
Template wetting methods have been widely applied in the preparation of one-dimensional (1D) polymer nanomaterials. The pattern control using the template wetting methods, however, still remains a great challenge, mainly due to the nonselectivity of the polymers toward the environmental triggering. In this work, we present a facile light-induced nanowetting (LIN) method to fabricate patterned nanoarrays using anodic aluminum oxide (AAO) templates. Photoresponsive azobenzene-containing polymers (azopolymers) that exhibit light-induced reversible solidto-liquid transitions are used. Upon exposure to ultraviolet lights, the azopolymer chains can wet the nanopores of the AAO templates in a liquid state via capillary force. The azopolymer chains are then solidified by illuminating them with visible lights, resulting in the formation of azopolymer nanoarrays. Notably, using designed photomasks, the patterns of the nanoarrays can be ingeniously controlled with the characteristic of erasable and rewritable nanostructures.
Reproducible and Bendable SERS Substrates with Tailored Wettability Using Block Copolymers and Anodic Aluminum Oxide Templates
(1970-01-01)
Lin, Yu-Liang
;
Karapala, Vamsi Krishna
;
Shen, Ming-Hui
;
Chen, Yi-Fan
;
He, Hung-Chieh
Surface properties are essential for substrates exhibiting high sensitivity in surface-enhanced Raman scattering (SERS) applications. In this work, novel SERS hybrid substrates using polystyrene-block-poly(methyl methacrylate) and anodic aluminum oxide templates is presented. The hybrid substrates not only possess hierarchical porous nanostructures but also exhibit superhydrophilic surface properties with the water contact angle approximate to 0 degrees. Such surfaces play an important role in providing uniform enhanced intensities over large areas (relative standard deviation approximate to 10%); moreover, these substrates are found to be highly sensitive (limit of detection approximate to 10(-12) m for rhodamine 6G (R6G)). The results show that the hybrid SERS substrates can achieve the simultaneous detection of multicomponent mixtures of different target molecules, such as R6G, crystal violet, and methylene blue. Furthermore, the bending experiments show that about 70% of the SERS intensities are maintained after bending from approximate to 30 degrees to 150 degrees.
Interplay of Template Constraints and Microphase Separation in Polymeric Nano-Objects Replicated from Novel Modulated and Interconnected Nanoporous Anodic Alumina
(2018-01-01)
Bayat, Haider
;
Lin, Chia-Hua
;
Cheng, Ming-Hsiang
;
Steuber, Marc
;
Chen, Jiun-Tai
We report on a versatile strategy to fabricate shape-controlled polymeric nano-objects with an internal compartmentalized structure by replication from pore-diameter-modulated and interconnected nanoporous anodized aluminum oxide (AAO). The AAO with modulated pore diameters is synthesized in a refined temperature-modulated hard anodization (TMHA) approach, by alternating the flow rate of an air stream cooling the electrolyte. Through pore-widening of the templates with modulated pore diameters, a stable interconnected 3D network with transversal ellipsoidal holes is fabricated as a second template structure. From these unprecedented template structures exhibiting modulated pores and an intricate 3D network structure, shape-controlled polymeric nano-objects are replicated using the melt wetting method with polystyrene homopolymer (PS) and cylinder-forming block copolymer polystyrene-block-polydimethylsiloxane (PS298-b-PDMS195). The replicated nanostructures are separated into individual anisotropically shaped nanocapsules by passing the replicas through a polycarbonate membrane followed by gentle sonication. Inside the nano-objects, the microphase separation of PS298-b-PDMS195 affords parallel aligned nanophases, in which domain sizes and morphologies are different compared to the unconfined bulk according to transmission electron microscopy analyses. These advanced AAO platforms and the nanoscale polymer replicas offer new routes for compartmentalized nano objects with potential future relevance for applications ranging from drug nanocarriers to biosensors.
Laser-Assisted Nanowetting: Selective Fabrication of Polymer/Gold Nanorod Arrays Using Anodic Aluminum Oxide Templates
(1970-01-01)
He, Hung-Chieh
;
Yan, Ai-Ling
;
Karapala, Vamsi Krishna
;
Wang, Shun-Fa
;
Shen, Ming-Hui
1D polymer nanomaterials have attracted significant interest in recent years because of their unique properties and promising applications in various fields. It is, however, still a challenge to fabricate polymer nanoarrays with desired sizes and controlled morphologies. Here, an unprecedented approach, the laser-assisted nanowetting (LAN) method, to selectively fabricate polymer nanoarrays is presented. Polystyrene (PS) is blended with gold nanorods (AuNRs), which are used to absorb the energy from the laser. After the blend films are brought in contact with AAO templates, the AuNRs at regions shone by the laser beams absorb the energy and heat the surrounding polymer chains, resulting in the formation of PS/AuNRs arrays in selected areas. This work paves a new research direction for developing template-based polymer nanomaterials.
Rayleigh-Instability-Induced Transformation for Confined Polystyrene Nanotubes Prepared Using the Solvent-Vapor-Induced Wetting Method
(1970-01-01)
Fang, Zhi-Xuan
;
Chu, Chien-Wei
;
Tsai, Chia-Chan
;
Chang, Chun-Wei
;
Cheng, Ming-Hsiang
Polystyrene (PS) nanotubes prepared using the solvent-vapor-induced wetting method with anodic aluminum oxide templates are for the first time applied to study the thermal stabilities of polymer nanotubes confined in cylindrical geometries. The morphologies of the PS nanotubes and the corresponding transformed PS nanostructures driven by the Rayleigh instabilities after thermal annealing treatments are characterized by scanning electron microscopy. Morphology diagrams of the Rayleigh-instability-induced nanostructures for PS nanotubes prepared via the solvent-vapor-induced wetting method and the solution wetting method are constructed to study the differences in kinetics for samples using different wetting methods. Slower transformation kinetics for the PS samples prepared by the solvent-vapor-induced wetting method than those prepared by the solution wetting method are observed, indicating the better thermal stabilities and the relatively denser packings of the polymer chains in the nanopores for the PS samples prepared using the solvent-vapor-induced wetting method.
Porous Polyimide and Carbon Nanotubes: Solvent Vapor-Induced Transformation in the Nanochannels of Anodic Aluminum Oxide Templates
(2019-04-01)
He, Hung-Chieh
;
Tu, Yi-Hsuan
;
Li, Jia-Wei
;
Lin, Yu-Liang
;
Chen, Jiun-Tai
Polyimides (PIs) have attracted wide attention because of their exceptional thermal stability and applications in areas such as printed circuit boards and multichip modules. It remains a great challenge, however, to control the morphologies and properties of PI-based nanomaterials, especially porous PI-based nanotubes. In this work, a versatile method to fabricate porous PI nanotubes via the template method is developed, with a solvent vapor-induced transformation process. First, polyamic acid (PAA) solutions are used as precursors and infiltrated into the nanochannels of anodic aluminum oxide templates, forming PAA nanotubes. After the samples are annealed in tetrahydrofuran or dimethylformamide vapors, depression of the PAA tubes occurs, causing the formation of pores. The porous PAA nanotubes can be further converted to porous PI and carbon nanotubes by imidization and carbonization processes, respectively. The pore sizes of the porous nanomaterials can be controlled by changing the type of the annealing solvent and the solvent annealing time.
Orientation Preferences of Interchain Stackings for Poly(3-hexylthiophene) Nanowires Prepared Using Template-Based Wetting Methods
(2018-06-01)
Jeng, Kai-Sheng
;
Chu, Chien-Wei
;
Liu, Chien-Liang
;
Jean, Woan-Mei
;
Chen, Hsin-Lung
Poly(3-hexylthiophene) (P3HT) nanowires have drawn great attention recently because of their unique properties that can be applied to optoelectronic devices such as conjugated polymer solar cells and organic field-effect transistors. There is still an urgent need, however, to study the fabrication and characterization of P3HT nanowires with controllable morphologies and molecular orientations. In this work, feasible routes are presented to fabricate P3HT nanowires using the solution wetting template method and the solvent-annealing-induced nanowetting in template (SAINT) method. The morphologies and chemical compositions of the P3HT nanowires prepared using these two methods are confirmed by scanning electron microscopy, transmission electron microscopy (TEM), and Raman spectroscopy. From the ultraviolet-visible spectroscopy and wide-angle X-ray scattering results, it is concluded that the degrees of the crystallinity and the orientation preferences of interchain stackings along the pore axis for the P3HT nanowires prepared by the SAINT method are higher than those prepared by the solution wetting template method.
Shaping the Light: The Key Factors Affecting the Photophysical Properties of Fluorescent Polymer Nanostructures
(2016-12)
Chi, Mu-Huan
;
Su, Chun-Hsien
;
Cheng, Ming-Hsiang
;
Chung, Pei-Yun
;
Peng, Chi-How
To manipulate the functions of nanomaterials more precisely for diverse applications, the controllability and critical influencing factors of their properties must be thoroughly investigated. In this work, the macroscopic and microscopic effects are studied on the photophysical properties of various pyrene-ended poly(styrene-block-methyl methacrylate) nanostructures. Fluorescent polymer nanospheres, nanorods, and nanotubes are prepared by different template-based methods using anodic aluminum oxide membranes. Chain arrangements and conformations are determined as the key factors affecting the photophysical properties of the fluorescent polymer nanostructures. This work not only gives a deeper understanding of the effects on the photophysical properties of polymer nanomaterials influenced by morphologies, chain arrangements, and chain conformations, but also provides a reference for designing proper fluorescent nanostructures for specific applications.
Confinement Effects on the Optical Properties and Chain Conformations of Poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) Nanotubes
(2016-09)
Chu, Chien-Wei
;
Jeng, Kai-Sheng
;
Chi, Mu-Huan
;
Tsai, Chia-Chan
;
Cheng, Ming-Hsiang
Although many fabrication methods of conjugated polymer nanostructures have been developed, the effects of confinement on the morphologies, chain conformations, and optical properties of conjugated polymers are still not well understood. In this work, poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT), a light-emitting conjugated polymer, is used to fabricate nanotubes by a solution wetting method using anodic aluminum oxide templates. The property changes under the nanoscale confinement have been investigated. The morphologies of F8BT nanostructures are characterized by scanning electron microscope, transmission electron microscope, and laser scanning confocal microscope. The data show the hollow morphologies and no or low crystallinity of the nanostructures. The optical properties are also measured using UV-vis absorption, photoluminescence, and confocal Raman spectroscopy. The spectroscopy data indicate that F8BT polymer chains have less intermolecular interactions and coplanarity under the confinement effect.
Fabrication of Multicomponent Polymer Nanostructures Containing PMMA Shells and Encapsulated PS Nanospheres in the Nanopores of Anodic Aluminum Oxide Templates
(2015-03-01)
Ko, Hao-Wen
;
Chi, Mu-Huan
;
Chang, Chun-Wei
;
Su, Chun-Hsien
;
Wei, Tzu-Hui
Multi-component polymer nanomaterials have attracted great attention because of their applications in areas such as biomedicine, tissue engineering, and organic solar cells. The precise control over the morphologies of multi-component polymer nanomaterials, however, is still a great challenge. In this work, the fabrication of poly(methyl methacrylate)(PMMA)/polystyrene (PS) nanostructures that contain PMMA shells and encapsulated PS nanospheres is studied. The nanostructures are prepared using a triple solution wetting method with anodic aluminum oxide (AAO) templates. The nanopores of the templates are wetted sequentially by PS solutions in dimethylformamide (DMF), PMMA solutions in acetic acid, and water. The compositions and morphologies of the nanostructures are controlled by the interactions between the polymers, solvents, and AAO walls. This work not only presents a feasible method to prepare multi-component polymer nanomaterials, but also leads to a better understanding of polymer-solvent interactions in confined geometries.

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