Orienting Periodic Organic−Inorganic Nanoscale Domains Through One-Step Electrodeposition

Abstract

One of the challenges in the synthesis of hybrid materials with nanoscale structure is to precisely control morphology across length scales. Using a one-step electrodeposition process on indium tin oxide (ITO) substrates followed by annealing, we report here the preparation of materials with preferentially oriented lamellar domains of electron donor surfactants and the semiconductor ZnO. We found that either increasing the concentration of surfactant or the water to dimethyl sulfoxide ratio of solutions used resulted in the suppression of bloom-like morphologies and enhanced the density of periodic domains on ITO substrates. Furthermore, by modifying the surface of the ITO substrate with the conductive polymer blend poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), we were able to alter the orientation of these electrodeposited lamellar domains to be perpendicular to the substrate. The long-range orientation achieved was characterized by 2D grazing incidence small angle X-ray scattering. This high degree of orientation in electronically active hybrids with alternating nanoscale p-type and n-type domains is of potential interest in photovoltaics or thermoelectric materials.

Electrodeposited Stable Binder‐Free Organic Ni(OH)2 Flexible Nanohybrid Electrodes for High‐Performance Supercapacitors

“…The layer formed over the flexible NF substrate indicates the deposition of peptide/Ni(OH) 2 ‐based nanohybrid material. The electrochemical conversion of the dipeptide and Ni(NO 3 ) 2 to peptide/Ni(OH) 2 can be expressed as follows …”

“…The NF was used as the working electrode, Pt wire as the counter electrode and Ag/AgCl as the reference electrode. The organic–inorganic hybrid material was grown on a flexible NF substrate through electrodeposition for 10–60 min by applying −0.9 V constant current and the temperature of the solution was maintained at 60 °C by water bath with continuous magnetic stirring . After the electrodeposition, the deposited thin film surface was washed with ultrapure water and ethanol and dried at 60 °C for 6 h.…”

Supramolecular Energy Materials

“…Also hydrophilic and more hydrophobic were utilized as well, indium tin oxide (ITO) surfaces and or more hydrophobic poly(2,3‐dihydrothieno‐1,4‐dioxin)‐poly(styrene sulfonate) (PEDOT:PSS), respectively. [ 127b ] Through this work, it was found that less hydrophobic chromophore amphiphiles result in similar isotropic orientation on both surfaces ( Figure a), whereas the hydrophobic linker results in parallel orientation on the hydrophilic ITO surface and perpendicular orientation on PEDOT:PSS (Figure 22b). To reveal the mechanism of this orientation, decanoic acid was used as a surfactant in place of the chromophore amphiphile.…”

“…Molecular design and substrate chemistry can be used to control the orientation of the resultant hybrid in electrodeposited chromophore amphiphile–inorganic hybrids, offering a new handle to control properties. [ 127 ] It was first observed that modulating the chemistry of the substrate can be leveraged to control the orientation of the lamellar flakes of pyrenebutyric acid zinc hydroxide hybrids where hydrophilic polystyrene sulfonate surfaces resulted in primarily parallel orientation of the hybrid layers to the surface. [ 127a ] This was investigated further with molecules containing no linker between the chromophore and binding group or a hydrophobic alkane linker.…”

“…[ 127 ] It was first observed that modulating the chemistry of the substrate can be leveraged to control the orientation of the lamellar flakes of pyrenebutyric acid zinc hydroxide hybrids where hydrophilic polystyrene sulfonate surfaces resulted in primarily parallel orientation of the hybrid layers to the surface. [ 127a ] This was investigated further with molecules containing no linker between the chromophore and binding group or a hydrophobic alkane linker. Also hydrophilic and more hydrophobic were utilized as well, indium tin oxide (ITO) surfaces and or more hydrophobic poly(2,3‐dihydrothieno‐1,4‐dioxin)‐poly(styrene sulfonate) (PEDOT:PSS), respectively.…”