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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

Transmission absorptionspectra of as-electrodeposited CuSCN/RBhybrid thin films (solid lines) and those after soaking the filmsfor 1 h in dimethylacetamide (DMA) (dashed lines). The percentageof RB extracted by DMA treatment is also indicated. The CuSCN/RB thinfilms were electrodeposited from SCN– rich (blacklines) and Cu2+ rich (gray lines) baths containing 0.1(thin lines) or 1.0 mM (thick lines) of RB.
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fig7: Transmission absorptionspectra of as-electrodeposited CuSCN/RBhybrid thin films (solid lines) and those after soaking the filmsfor 1 h in dimethylacetamide (DMA) (dashed lines). The percentageof RB extracted by DMA treatment is also indicated. The CuSCN/RB thinfilms were electrodeposited from SCN– rich (blacklines) and Cu2+ rich (gray lines) baths containing 0.1(thin lines) or 1.0 mM (thick lines) of RB.

Mentions: When the hybrid films are soaked in dimethylacetamide (DMA), thefilms were bleached as the RB molecules were extracted, as seen fromthe change of the absorption spectra before and after the treatment(Figure 7). For the films with small RB loading,RB molecules could be only partly removed, whereas those with highRB loading allowed almost complete desorption of RB. The film withthe highest RB loading, namely, that deposited from the SCN– rich bath containing 1.0 mM RB, became nearly colorless because97% of the loaded dye was removed as estimated from the absorbancechange at the maximum of RB absorption. As discussed above, the extractionof RB should result in tiny nanopores enlarging the surface area ofthe CuSCN films. This was confirmed by Brunauer–Emmet–Telleranalysis of Kr sorption measurements (Figure 8). The surface area of about 6 m2 g–1 is already reached for the film deposited from the Cu2+ rich bath without RB. It only moderately increases by hybridizationwith RB and its extraction for the Cu2+ rich baths. Onthe other hand, that of the film deposited from the SCN– rich bath results in only about 4 m2 g–1 without RB, and it greatly increases up to 12.6 m2 g–1 when [RB] = 1.0 mM. The roughness factor (RF), definedas the ratio of the actual surface area per projected film area, ofabout 17 is reached as calculated from the amount of electrodepositedCuSCN shown in Table 1. Considering the smallfilm thickness of 0.8 μm, this roughness factor is reasonablyhigh because RF of several hundred can be reached when the thicknessis increased to a few tens of micrometers. These thicknesses and RFvalues are comparable to those of materials typically used for dye-sensitizedsolar cells. Using the reported growth conditions, we were able toextend the growth time and film thickness by roughly a factor of 5before inducing any cracking in the film. Growing thicker films wouldrequire further optimization of the growth parameters.


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)

Transmission absorptionspectra of as-electrodeposited CuSCN/RBhybrid thin films (solid lines) and those after soaking the filmsfor 1 h in dimethylacetamide (DMA) (dashed lines). The percentageof RB extracted by DMA treatment is also indicated. The CuSCN/RB thinfilms were electrodeposited from SCN– rich (blacklines) and Cu2+ rich (gray lines) baths containing 0.1(thin lines) or 1.0 mM (thick lines) of RB.
© Copyright Policy
Related In: Results  -  Collection

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

fig7: Transmission absorptionspectra of as-electrodeposited CuSCN/RBhybrid thin films (solid lines) and those after soaking the filmsfor 1 h in dimethylacetamide (DMA) (dashed lines). The percentageof RB extracted by DMA treatment is also indicated. The CuSCN/RB thinfilms were electrodeposited from SCN– rich (blacklines) and Cu2+ rich (gray lines) baths containing 0.1(thin lines) or 1.0 mM (thick lines) of RB.
Mentions: When the hybrid films are soaked in dimethylacetamide (DMA), thefilms were bleached as the RB molecules were extracted, as seen fromthe change of the absorption spectra before and after the treatment(Figure 7). For the films with small RB loading,RB molecules could be only partly removed, whereas those with highRB loading allowed almost complete desorption of RB. The film withthe highest RB loading, namely, that deposited from the SCN– rich bath containing 1.0 mM RB, became nearly colorless because97% of the loaded dye was removed as estimated from the absorbancechange at the maximum of RB absorption. As discussed above, the extractionof RB should result in tiny nanopores enlarging the surface area ofthe CuSCN films. This was confirmed by Brunauer–Emmet–Telleranalysis of Kr sorption measurements (Figure 8). The surface area of about 6 m2 g–1 is already reached for the film deposited from the Cu2+ rich bath without RB. It only moderately increases by hybridizationwith RB and its extraction for the Cu2+ rich baths. Onthe other hand, that of the film deposited from the SCN– rich bath results in only about 4 m2 g–1 without RB, and it greatly increases up to 12.6 m2 g–1 when [RB] = 1.0 mM. The roughness factor (RF), definedas the ratio of the actual surface area per projected film area, ofabout 17 is reached as calculated from the amount of electrodepositedCuSCN shown in Table 1. Considering the smallfilm thickness of 0.8 μm, this roughness factor is reasonablyhigh because RF of several hundred can be reached when the thicknessis increased to a few tens of micrometers. These thicknesses and RFvalues are comparable to those of materials typically used for dye-sensitizedsolar cells. Using the reported growth conditions, we were able toextend the growth time and film thickness by roughly a factor of 5before inducing any cracking in the film. Growing thicker films wouldrequire further optimization of the growth parameters.

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