Jiun-Tai Chen

Conjugated polymer nanostructures for organic solar cell applications

Recently, there has been tremendous progress in the development of polymer-based organic solar cells. Polymer-based solar cells have attracted a great deal of attention because they have the potential to be efficient, inexpensive, and solution processable. New materials, nanostructures, device designs, and processing methods have been developed to achieve high device efficiencies. This review focuses on the fabrication techniques of conjugated polymer nanostructures and their applications for organic solar cells. We will first introduce the fundamental knowledge of organic solar cells and emphasize the importance of nanostructures. Then we will discuss different strategies for fabricating conjugated polymer nanostructures, including topics such as polymer nanowires, nanoparticles, block copolymers, layer-by-layer deposition, nanoimprint lithography, template methods, nanoelectrodes, and porous inorganic materials. The effects of the nanostructures on the device performance will also be presented. Efficiencies higher than 10% are expected for polymer-based solar cells by using new materials and techniques.

Thin Film Instabilities in Blends under Cylindrical Confinement

Rayleigh instabilities in bilayers of poly(methyl methacrylate) (PMMA) and polystyrene (PS) confined within the cylindrical nanoporous anodic aluminum oxide (AAO) membranes were investigated. The bilayered nanotubes were thermally annealed to induce phase separation and instabilities in the confined films. For short annealing times, the nanotubes were transformed into nanorods with periodic encapsulated air pockets. With longer annealing times, the air-pockets coalesced to form columns of air. Small air inclusions encased in periodic domains of PS were, in turn, incorporated within PMMA nanorods. Selectively removing the PMMA by exposure to UV radiation and washing with acetic acid, left PS nanospheres with an air inclusion. Gold nanoparticles having PS ligands were also incorporated within the PS phase, generating novel composite morphologies.

A Simple Route for the Preparation of Mesoporous Nanostructures Using Block Copolymers

Poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) nanostructures with multiple morphologies were fabricated by immersing PS-b-P4VP nanotubes in ethylene glycol, a nonsolvent for PS and a good solvent for P4VP, at different temperatures. Mesoporous structures were generated from uniform nanoscopic wormlike micelles due to a solvent-induced reconstruction when the spherical micellar structures were heated above the glass transition temperature of the PS block. The mesoporous nanostructures can be converted into inorganic oxide structures, like SiO(2) and TiO(2), by well-known sol-gel methods. The mesoporous inorganic oxides can be produced with tunable porosity by controlling the molecular weight of the block copolymers. Confinement also plays an important role to create the nanostructures with unusual morphologies.

Solvent-Annealing-Induced Nanowetting in Templates: Towards Tailored Polymer Nanostructures

We study the solvent-annealing-induced nanowetting in templates using porous anodic aluminum oxide membranes. The morphology of polystyrene and poly(methyl methacrylate) nanostructures can be controlled, depending on whether the swollen polymers are in the partial or complete wetting regimes, which are characterized by the spreading coefficient. When the swollen polymers are in the partial wetting regime, polymers wet the nanopores by capillary action, resulting in the formation of polymer nanorods. When the swollen polymers are in the complete wetting regime, polymers form wetting layers in the nanopores, resulting in the formation of polymer nanotubes. The solubility parameters of polymers and solvents are also used to predict the wetting behavior of swollen polymers in cylindrical geometry.

Effect of Nonsolvent on the Formation of Polymer Nanomaterials in the Nanopores of Anodic Aluminum Oxide Templates

We study the effect of nonsolvent on the formation of polymer nanomaterials in the nanopores of porous templates. Water (nonsolvent) is added into a poly (methyl methacrylate) (PMMA) solution in dimethylformamide (DMF) confined in the nanopores of an anodic aluminum oxide (AAO) template. Water forms a wetting layer on the pore wall and causes the PMMA solution to be isolated in the center of the nanopore, resulting in the formation of PMMA nanospheres or nanorods after the solvent is evaporated. The formation of the polymer nanomaterials induced by nonsolvent is found to be driven by the Rayleigh-instability-type transformation. Without adding the nonsolvent, PMMA chains precipitate on the walls of the nanopores after the solvent is evaporated, and PMMA nanotubes are obtained.

Fabrication of hierarchical structures by wetting porous templates with polymer microspheres.

We present a simple route to prepare hierarchical structures by allowing the partial diffusion of polymer microspheres into the nanopores of anodic aluminum oxide (AAO) templates. Polystyrene (PS) microspheres were first spread onto a silicon substrate and allowed to self-assemble into well-ordered monolayers of the microspheres. Upon heating above the glass-transition temperature, diffusion of the PS into the pores of the AAO occurred only at pores of the microspheres in contact with the membrane. After the removal of the AAO membrane, ordered arrays of microspheres capped with nanorods were produced, yielding surfaces with topographies spanning multiple length scales. Control over the nanoscopic and microscopic length scales can be trivially achieved by changing the size of the microspheres and the diameter of the pores in the membranes.

Transformation of Polymer Nanofibers to Nanospheres Driven by the Rayleigh Instability

We study the thermal annealing effect of poly(methyl methacrylate) (PMMA) nanofibers made from anodic aluminum oxide (AAO) templates and their transformation to PMMA nanospheres. The PMMA nanofibers are prepared by wetting an AAO template with a 30 wt % PMMA solution, followed by the evaporation of the solvent. After the AAO template is removed by a weak base, the PMMA nanofibers are thermally annealed in ethylene glycol, a nonsolvent for PMMA. The surfaces of the nanofibers undulate and transform into nanospheres, driven by the Rayleigh instability. The driving force for the transformation process is the minimization of the interfacial energy between PMMA nanofibers and ethylene glycol. The transformation times at higher annealing temperatures are shorter than those at lower annealing temperatures. This study provides a facile route to prepare polymer nanospheres which are not accessible by other traditional methods.

Annealing Effect on Electrospun Polymer Fibers and Their Transformation into Polymer Microspheres

Electrospinning is a simple and convenient technique to produce polymer fibers with diameters ranging from several nanometers to a few micrometers. Different types of polymer fibers have been prepared by electrospinning for various applications. Among different post-treatment methods of electrospun polymer fibers, the annealing process plays a critical role in controlling the fiber properties. The morphology changes of electrospun polymer fibers under annealing, however, have been little studied. Here we investigate the annealing effect of electrospun poly(methyl methacrylate) (PMMA) fibers and their transformation into PMMA microspheres. PMMA fibers with an average size of 2.39 μm are first prepared by electrospinning a 35 wt% PMMA solution in dimethylformamide. After the electrospun fibers are thermally annealed in ethylene glycol, a non-solvent for PMMA, the surfaces of the fibers undulate and transform into microspheres driven by the Rayleigh instability. The driving force of the transformation process is the minimization of the interfacial energy between the polymer fibers and ethylene glycol. The sizes of the microspheres fit well with the theoretical predictions. Longer annealing times are found to be required at lower temperatures to obtain the microspheres.

Three-Dimensional Block Copolymer Nanostructures by the Solvent-Annealing- Induced Wetting in Anodic Aluminum Oxide Templates

Block copolymers have been extensively studied over the last few decades because they can self-assemble into well-ordered nanoscale structures. The morphologies of block copolymers in confined geometries, however, are still not fully understood. In this work, the fabrication and morphologies of three-dimensional polystyrene-block-polydimethylsiloxane (PS-b-PDMS) nanostructures confined in the nanopores of anodic aluminum oxide (AAO) templates are studied. It is discovered that the block copolymers can wet the nanopores using a novel solvent-annealing-induced nanowetting in templates (SAINT) method. The unique advantage of this method is that the problem of thermal degradation can be avoided. In addition, the morphologies of PS-b-PDMS nanostructures can be controlled by changing the wetting conditions. Different solvents are used as the annealing solvent, including toluene, hexane, and a co-solvent of toluene and hexane. When the block copolymer wets the nanopores in toluene vapors, a perpendicular morphology is observed. When the block copolymer wets the nanopores in co-solvent vapors (toluene/hexane = 3:2), unusual circular and helical morphologies are obtained. These three-dimensional nanostructures can serve as naontemplates for refilling with other functional materials, such as Au, Ag, ZnO, and TiO2 .

Rayleigh instability in polymer thin films coated in the nanopores of anodic aluminum oxide templates.

We study the Rayleigh instability of polystyrene (PS) thin films coated in the nanopores of anodic aluminum oxide (AAO) templates. After thermal annealing, the surface of the PS thin films undulates and the nanostructures transform from nanotubes to Rayleigh-instability-induced nanostructures (short nanorods with encapsulated air bubbles). With longer annealing times, the nanostructures further transform to nanorods with longer lengths. PS samples with two different molecular weights (24 and 100 kg/mol) are used, and their instability transformation processes are compared. The morphology diagrams of the nanostructures at different stages are also constructed to elucidate the mechanism of the morphology transformation.