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Electrochemical Self-Assembly of Nanostructured CuSCN/Rhodamine B Hybrid Thin Film and Its Dye-Sensitized Photocathodic Properties.

Iwamoto T, Ogawa Y, Sun L, White MS, Glowacki ED, Scharber MC, Sariciftci NS, Manseki K, Sugiura T, Yoshida T - J Phys Chem C Nanomater Interfaces (2014)

Bottom Line: High loading of RB into the film has been achieved to reach a CuSCN:RB volume ratio of approximately 2:1.The crystallographic orientation of the nanostructure with respect to the substrate can be controlled.Photoelectrochemical study on the porous crystalline CuSCN obtained after the DMA treatment and sensitized with RB revealed sensitized photocathodic action under visible light illumination, indicating the potential usefulness of the porous CuSCN electrodes for construction of tandem dye-sensitized solar cells.

View Article: PubMed Central - PubMed

Affiliation: Center of Innovative Photovoltaic Systems (CIPS), Gifu University , Yanagido 1-1, Gifu, Gifu 501-1193, Japan.

ABSTRACT
Nanostructured hybrid thin films of CuSCN and rhodamine B (RB) are electrochemically self-assembled (ESA) by cathodic electrolysis in an ethanol/water mixture containing Cu(2+), SCN(-), and RB. By selecting the solvent, Cu(2+)/SCN(-) ratio, and the concentration of RB, we demonstrate several control parameters in the film formation. High loading of RB into the film has been achieved to reach a CuSCN:RB volume ratio of approximately 2:1. The RB solid could almost completely be extracted from the hybrid film by soaking the film in dimethylacetamide (DMA), leading to a large increase of the surface area. The crystallographic orientation of the nanostructure with respect to the substrate can be controlled. Efficient quenching of fluorescence of RB has been observed for the CuSCN/RB hybrid film, implying hole injection from RB excited state to CuSCN. Photoelectrochemical study on the porous crystalline CuSCN obtained after the DMA treatment and sensitized with RB revealed sensitized photocathodic action under visible light illumination, indicating the potential usefulness of the porous CuSCN electrodes for construction of tandem dye-sensitized solar cells.

No MeSH data available.


Related in: MedlinePlus

SEM photographs of CuSCN and CuSCN/RB hybrid thin filmselectrodepositedfrom SCN– rich (a) and Cu2+ rich (b)baths containing 0 (a1 and b1), 0.3 (a2 and b2) and 1.0 mM (a3 andb3) RB. a1′–a3′ and b1′–b3′correspond to the cross section of a1–a3 and b1– b3,respectively. The films were observed after soaking them in DMA forremoval of RB.
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fig3: SEM photographs of CuSCN and CuSCN/RB hybrid thin filmselectrodepositedfrom SCN– rich (a) and Cu2+ rich (b)baths containing 0 (a1 and b1), 0.3 (a2 and b2) and 1.0 mM (a3 andb3) RB. a1′–a3′ and b1′–b3′correspond to the cross section of a1–a3 and b1– b3,respectively. The films were observed after soaking them in DMA forremoval of RB.

Mentions: CuSCN/RB hybrid thin films were electrodeposited for 5 minbothfrom SCN– rich and Cu2+ rich baths whilechanging the concentration of RB. The morphology of the pure CuSCNfilm looks totally different for those deposited from SCN– rich and Cu2+ rich baths (panels a1 and b1 of Figure 3, respectively). The former consists of large roundedhexagonal columnar particles, whereas the latter shows assembliesof spiky particles. Rhombohedral β-CuSCN has an elongated hexagonalunit cell with lattice constants of a = b = 3.857 Å and c = 16.449 Å.23 As discussed below, the XRD patterns of thefilms indicate that films of a1 and b1 are oriented for the c-axis perpendicular with the substrate. The hexagonal facesof the deposits in a1 should thus correspond to the (003) planes ofCuSCN, while those faces creating the spikes should probably be ofthe (101) planes. Such differences can be caused by the change ofthe stability of the crystal faces by the change of the chemical compositionof the bath influencing the dissolution and recrystallization of CuSCNduring the electrodeposition (eq 3).3When RB is added to the bath, purple-coloredCuSCN/RB hybrid thin films were obtained. As the concentration ofRB increased, the color of the film got deeper, indicating the increasedloading of RB into the film. At the same time, the morphology of thefilm drastically changed (panels a2, a3, b2, and b3 of Figure 3). Characteristic nanostructures are created asthe particle size becomes small. As discussed later, the loaded RBmolecules can almost completely be extracted by dipping the film shownin a3 in dimethylacetamine (DMA), making it highly porous. The shapeof the particles differs from sample to sample, especially as recognizedfrom the cross sections, indicating anisotropic crystal growth promotedby RB addition.


Electrochemical Self-Assembly of Nanostructured CuSCN/Rhodamine B Hybrid Thin Film and Its Dye-Sensitized Photocathodic Properties.

Iwamoto T, Ogawa Y, Sun L, White MS, Glowacki ED, Scharber MC, Sariciftci NS, Manseki K, Sugiura T, Yoshida T - J Phys Chem C Nanomater Interfaces (2014)

SEM photographs of CuSCN and CuSCN/RB hybrid thin filmselectrodepositedfrom SCN– rich (a) and Cu2+ rich (b)baths containing 0 (a1 and b1), 0.3 (a2 and b2) and 1.0 mM (a3 andb3) RB. a1′–a3′ and b1′–b3′correspond to the cross section of a1–a3 and b1– b3,respectively. The films were observed after soaking them in DMA forremoval of RB.
© Copyright Policy
Related In: Results  -  Collection

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Show All Figures
getmorefigures.php?uid=PMC4120671&req=5

fig3: SEM photographs of CuSCN and CuSCN/RB hybrid thin filmselectrodepositedfrom SCN– rich (a) and Cu2+ rich (b)baths containing 0 (a1 and b1), 0.3 (a2 and b2) and 1.0 mM (a3 andb3) RB. a1′–a3′ and b1′–b3′correspond to the cross section of a1–a3 and b1– b3,respectively. The films were observed after soaking them in DMA forremoval of RB.
Mentions: CuSCN/RB hybrid thin films were electrodeposited for 5 minbothfrom SCN– rich and Cu2+ rich baths whilechanging the concentration of RB. The morphology of the pure CuSCNfilm looks totally different for those deposited from SCN– rich and Cu2+ rich baths (panels a1 and b1 of Figure 3, respectively). The former consists of large roundedhexagonal columnar particles, whereas the latter shows assembliesof spiky particles. Rhombohedral β-CuSCN has an elongated hexagonalunit cell with lattice constants of a = b = 3.857 Å and c = 16.449 Å.23 As discussed below, the XRD patterns of thefilms indicate that films of a1 and b1 are oriented for the c-axis perpendicular with the substrate. The hexagonal facesof the deposits in a1 should thus correspond to the (003) planes ofCuSCN, while those faces creating the spikes should probably be ofthe (101) planes. Such differences can be caused by the change ofthe stability of the crystal faces by the change of the chemical compositionof the bath influencing the dissolution and recrystallization of CuSCNduring the electrodeposition (eq 3).3When RB is added to the bath, purple-coloredCuSCN/RB hybrid thin films were obtained. As the concentration ofRB increased, the color of the film got deeper, indicating the increasedloading of RB into the film. At the same time, the morphology of thefilm drastically changed (panels a2, a3, b2, and b3 of Figure 3). Characteristic nanostructures are created asthe particle size becomes small. As discussed later, the loaded RBmolecules can almost completely be extracted by dipping the film shownin a3 in dimethylacetamine (DMA), making it highly porous. The shapeof the particles differs from sample to sample, especially as recognizedfrom the cross sections, indicating anisotropic crystal growth promotedby RB addition.

Bottom Line: High loading of RB into the film has been achieved to reach a CuSCN:RB volume ratio of approximately 2:1.The crystallographic orientation of the nanostructure with respect to the substrate can be controlled.Photoelectrochemical study on the porous crystalline CuSCN obtained after the DMA treatment and sensitized with RB revealed sensitized photocathodic action under visible light illumination, indicating the potential usefulness of the porous CuSCN electrodes for construction of tandem dye-sensitized solar cells.

View Article: PubMed Central - PubMed

Affiliation: Center of Innovative Photovoltaic Systems (CIPS), Gifu University , Yanagido 1-1, Gifu, Gifu 501-1193, Japan.

ABSTRACT
Nanostructured hybrid thin films of CuSCN and rhodamine B (RB) are electrochemically self-assembled (ESA) by cathodic electrolysis in an ethanol/water mixture containing Cu(2+), SCN(-), and RB. By selecting the solvent, Cu(2+)/SCN(-) ratio, and the concentration of RB, we demonstrate several control parameters in the film formation. High loading of RB into the film has been achieved to reach a CuSCN:RB volume ratio of approximately 2:1. The RB solid could almost completely be extracted from the hybrid film by soaking the film in dimethylacetamide (DMA), leading to a large increase of the surface area. The crystallographic orientation of the nanostructure with respect to the substrate can be controlled. Efficient quenching of fluorescence of RB has been observed for the CuSCN/RB hybrid film, implying hole injection from RB excited state to CuSCN. Photoelectrochemical study on the porous crystalline CuSCN obtained after the DMA treatment and sensitized with RB revealed sensitized photocathodic action under visible light illumination, indicating the potential usefulness of the porous CuSCN electrodes for construction of tandem dye-sensitized solar cells.

No MeSH data available.


Related in: MedlinePlus