Fabrication of 2D/2D BiOBr/g-C3N4 with efficient photocatalytic activity and clarification of its mechanism.

Precise regulation of photoexcited charge carriers for separation and transportation is a core requirement for practical application in the photocatalysis field. Herein, a 2D/2D BiOBr/g-C3N4 heterojunction is prepared by a self-assembly method and exhibits enhanced and stable activity for photocatalytic degradation of bisphenol A (BPA) and norfloxacin (NFA) under visible light. Compared to pure g-C3N4, the kinetic constants of BPA and NFA degradation over BiOBr/g-C3N4 are enhanced by about 14.74 and 4.01 times, respectively. The separation and transportation mechanism for the photoexcited charge carriers is clarified by electron paramagnetic resonance (EPR), in situ X-ray photoelectron spectroscopy (in situ XPS), and theoretical calculations. The results show that BiOBr/g-C3N4 exhibits the feature of a relative p-n junction, in which the charges photoexcited on BiOBr/g-C3N4 with high redox potentials can be kept and spatially separated. Moreover, the built-in electric field with the direction of g-C3N4 → BiOBr and the opportune band curvature provide the driving force for charge separation and transportation. Additionally, BPA and NFA degradation intermediates are also detected by liquid chromatography-mass spectrometry. It is of great significance to fabricate efficient photocatalysts for environmental purification and other targeted reactions.

Molecular orientation and stability of poly(3-hexylthiophene) nanogratings affected by the fabricated solvent vapor.

During the nanoimprinting lithography (NIL) process, the role of solvent vapor in fabricating the pattern structure and inducing the molecular alignment of nanoimprinted polymer film has been attracting significant attention. We demonstrate here that the molecular orientation and thermal stability of poly(3-hexylthiophene) (P3HT) nanograting film can be affected obviously by the fabricated solvent vapor. A solvent-vapor nanoimprinting lithography (SV-NIL) technique based on a polydimethylsiloxane (PDMS) template is employed to fabricate a P3HT nanograting structure film successfully and solvent vapor is offered by chlorobenzene, chloroform and carbon disulphide, respectively. The molecular orientation of the polymer film is carefully characterized by grazing incidence wide angle X-ray diffraction (GIWAXD) measurements to investigate the effect of various solvent vapors on the molecular orientation of the P3HT nanograting film. For the P3HT nanograting film fabricated by chloroform and chlorobenzene solvent, the edge-on molecular orientation of the typical form II crystallographic structure is induced. However, this indicates that there are both the face-on molecular orientations of the form II and form I crystallographic conformation present for the P3HT nanograting film fabricated by carbon disulphide solvent. Therefore, the fabricated solvent vapor plays a significant role in determining the formation of the molecular orientation of the polymer nanostructure. Then, the role of thermal annealing in the stability of the molecular orientation was investigated for the P3HT nanograting film after a fixed temperature. As for the annealed nanograting film fabricated by chlorobenzene and chloroform solvent vapor, a single edge-on molecular orientation mode of the form I crystallographic structure has been obtained. However, for the annealed nanograting film fabricated by the carbon disulphide solvent, the edge-on and face-on molecular orientations of the form I crystallographic structure are still retained. This indicates that the stability of the form II crystallographic conformation is mainly dependent on the thermal annealing process. Therefore, after the annealing process, the final determining of the molecular alignment and crystallographic conformation depends significantly on the orientation type of the nanograting film before the annealing history, and it can be further inferred that the molecular orientation of the annealed polymer film is still affected by the fabricated solvent vapor significantly. Thus this will provide new understanding and guidance for the research of the topographical structure and molecular alignment of conjugated polymers.

The Fabrication of Nanoimprinted P3HT Nanograting by Patterned ETFE Mold at Room Temperature and Its Application for Solar Cell.

Nanoimprinting lithography (NIL) is investigated as a promising method to define nanostructure; however, finding a practical method to achieve large area patterning of conjugated polymer remains a challenge. We demonstrate here that a simple and cost-effective technique is proposed to fabricate the nanoimprinted P3HT nanograting by solvent-assisted room temperature NIL (SART-NIL) method with patterned ETFE film as mold. The patterned ETFE template is produced by embossing ETFE film into a patterned silicon master and is used as template to transfer nanogratings during the SART-NIL process. It indicates that highly reproducible and well-controlled P3HT nanograting film is obtained successfully with feature size of nanogratings ranging from 130 to 700 nm, due to the flexibility, stiffness, and low surface energy of ETFE mold. Moreover, the SART-NIL method using ETFE mold is able to fabricate nanogratings but not to induce the change of molecular orientation within conjugated polymer. The conducting ability of P3HT nanograting in the vertical direction is also not damaged after patterning. Finally, we further apply P3HT nanograting for the fabrication of active layer of OBHJ solar cell device, to investigate the morphology role presented by ETFE mold in device performance. The device performance of OBHJ solar cell is preferential to that of PBHJ device obviously.

The Fabrication of Ordered Bulk Heterojunction Solar Cell by Nanoimprinting Lithography Method Using Patterned Silk Fibroin Mold at Room Temperature.

The performance of organic solar cell is greatly determined by the nanoscale heterojunction morphology, and finding a practical method to achieve advantageous nanostructure remains a challenge. We demonstrate here that ordered bulk heterojunction (OBHJ) solar cell can be fabricated assisted by a simple, cost-effective nanoimprinting lithography method using patterned silk fibroin film mold at room temperature. The P3HT nanogratings were achieved by nanoimprinting lithography (NIL) process, and phenyl-C61-butyric acid methyl ester (PCBM) was spin-coated on the top of P3HT nanogratings. The conducting capacity of P3HT nanograting film has little difference compared with the unimprinted film in the vertical direction, due to the same edge-on chain alignment. However, it can be found that the fabrication of OBHJ nanostructure using room temperature NIL technique with patterned silk fibroin mold is able to promote optical absorption, interfacial area, and bicontinuous pathway. Therefore, the ordered heterojunction morphology plays an important part in improving device performance due to efficient exciton diffusion, dissociation, and reducing charge recombination rate.

Quantitative analysis of the size effect of room temperature nanoimprinted P3HT nanopillar arrays on the photovoltaic performance.

We develop a solvent-assisted room temperature nanoimprint lithography (SART-NIL) technique to fabricate an ideal active layer consisting of poly(3-hexylthiophene) nanopillar arrays surrounded by [6,6]-phenyl-C61-butyric acid methyl ester. Characterization by scanning electron microscopy, two-dimensional grazing incidence wide angle X-rays diffraction, and conducting atomic force microscopy reveals that the SART-NIL technique can precisely control the size of P3HT nanopillar arrays. With the decrease in diameters of P3HT nanopillar arrays, the P3HT nanopillar arrays exhibit a more preferable face-on molecular orientation, enhanced UV-vis absorption and higher conducting ability along the direction perpendicular to the substrate. The ordered bulk heterojunction film consisting of P3HT nanopillar arrays with a diameter of ∼45 nm (OBHJ-45) gives face-on orientation, a high interfacial area of 2.87, a high conducting ability of ∼130 pA and efficient exciton diffusion and dissociation. The polymer solar cell (PSC) based on an OBHJ-45 film exhibits a significantly improved device performance compared with those of PSCs based on the P3HT nanoapillar arrays with diameters ∼100 nm and ∼60 nm. We believe that the SART-NIL technique is a powerful tool for fabricating an ideal active layer for high performance PSCs.

Confinement Induced Preferential Orientation of Crystals and Enhancement of Properties in Ferroelectric Polymer Nanowires.

The physical properties of polymers strongly depend on the molecular or supermolecular order and orientation. Here we demonstrate the preferential orientation of lamellar crystals and the enhancement of ferro/piezoelectric properties in individual poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) nanowires fabricated from anodic alumina oxide (AAO) templates. The crystallographic a axis of P(VDF-TrFE) was found to be aligned along the long axis of nanowires due to geometrical confinement and grapho-expitaxial crystals growth. The alignment of lamellar crystals in P(VDF-TrFE) nanowires and enhancement of crystallization translated into improved ferro/piezoelectric properties such as lower coercive field and higher piezoelectric coefficient, testified by piezoresponse force microscopy images and piezoresponse hysteresis loops.