Deok Yeon Lee

Enhanced photovoltaic performance of Cu-based metal-organic frameworks sensitized solar cell by addition of carbon nanotubes

In the present work, TiO2 nanoparticle and multi-walled carbon nanotubes composite powder is prepared hydrothermally. After doctor blading the paste from composite powder, the resulted composite film is sensitized with Cu-based metal-organic frameworks using a layer-by-layer deposition technique and the film is characterized using FE-SEM, EDX, XRD, UV/Visible spectrophotometry and photoluminescence spectroscopy. The influence of the carbon nanotubes in photovoltaic performance is studied by constructing a Grätzel cell with I3−/I− redox couple containing electrolyte. The results demonstrate that the introduction of carbon nanotubes accelerates the electron transfer, and thereby enhances the photovoltaic performance of the cell with a nearly 60% increment in power conversion efficiency.

Facile interfacial charge transfer across hole doped cobalt-based MOFs/TiO2 nano-hybrids making MOFs light harvesting active layers in solar cells

Efficient separation of charges and their mobility are key challenges in metal–organic-framework (MOF) based devices. In the present study, thin films of cobalt-based metal organic frameworks (MOFs) are synthesized using a layer-by-layer technique, and their electrical/optoelectronic properties are studied. The as-prepared MOF films show electrically insulating behavior, which after hole doping demonstrate p-type conduction behaviour. The measured HOMO–LUMO energy states of the MOF films are found to be well matched for sensitizing TiO2, and the photoluminescence quenching experiment demonstrates a facile photoelectron transfer path from the doped frameworks to TiO2. Consequently, the doped MOFs are employed successfully as light harvesting and charge transporting active layers in a fully devised TiO2-based solar cell. Two different organic ligands viz., benzene dicarboxylic acid and naphthalenedicarboxylic acid are used to synthesize two kinds of Co–MOFs having different geometrical dimensions of unit cells and pores, and their influence on hole doping and charge transportation is studied. Under optimized conditions, the Co–MOF based device demonstrates a solar-to-electric energy conversion efficiency of 1.12% with a short circuit current of 2.56 mA cm−2, showing promising future prospects of the application of Co–MOFs in photovoltaic devices. Further, the photovoltaic performance of the Co–MOF based device is comparatively studied with that of the previously reported Cu–MOF and Ru–MOF based similar devices, and the influence of different metal centers of MOFs on their light harvesting performance is discussed.

Layer-by-layer deposition and photovoltaic property of Ru-based metal–organic frameworks

In the present work, thin films of ruthenium based metal–organic frameworks are synthesized using a layer-by-layer (LbL) technique and the film is characterized using XRD, FE-SEM, UV/visible spectroscopy, cyclic voltammetry and photoluminance spectroscopy. Further, the feasibility of the MOF film as a sensitizer in a solar cell is investigated. The HOMO–LUMO level of the frameworks is estimated and is found to be suitable to allow the use of the frameworks as a sensitizer for TiO2. When TiO2 mesoporous film is sensitized with the LBL thin film of the frameworks and a Gratzel type liquid junction solar cell is constructed, it demonstrates the cell performance of Isc = 2.56 mA cm−2, Voc = 0.63 V, FF = 0.63, and Eff = 1.22%. Photoluminescence spectroscopy and electrochemical impedance spectroscopy show that iodine doping into the frameworks is essential to facilitate the photogenerated electron transfer from the frameworks to TiO2.

A coordination chemistry approach for shape controlled synthesis of indium oxide nanostructures and their photoelectrochemical properties

Indium oxide (In2O3) is an important wide band-gap semiconductor having applications in a variety of optoelectronic devices. We report here on the low temperature solution deposition of In(OH)3 and In(SO4)(OH)·H2O architectures with various shapes such as cubes, maize corns and giant crystals. The In2O3 nanostructures are then obtained by solid state transformation of In(OH)3 and In(SO4)(OH)·H2O architectures. Shape control is achieved by controlling the local concentration of In3+ ions available for reaction by applying the principles of coordination chemistry, thereby obviating the need of any shape controlling agents. The phase and surface composition is obtained by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements. The XPS is used to probe the defect structure of In2O3 architecture. Optical properties of the films, studied by UV-Vis absorption and photoluminescence (PL) spectroscopy measurements, show that the different morphologies have different band-gaps. Furthermore current–voltage characteristics of In2O3–CdSe photoelectrochemical cells are studied, which show that cube–CdSe samples display excellent photovoltaic behaviour, exhibiting a short circuit current density in excess of 10 mA cm−2. The charge transport properties of the In2O3–CdSe photoanodes are studied by impedance spectroscopy, which shows that cube–CdSe samples have lowest resistance to charge transfer.

Charge Transfer-Induced Molecular Hole Doping into Thin Film of Metal-Organic Frameworks.

Despite the highly porous nature with significantly large surface area, metal-organic frameworks (MOFs) can be hardly used in electronic and optoelectronic devices due to their extremely poor electrical conductivity. Therefore, the study of MOF thin films that require electron transport or conductivity in combination with the everlasting porosity is highly desirable. In the present work, thin films of Co3(NDC)3DMF4 MOFs with improved electronic conductivity are synthesized using layer-by-layer and doctor blade coating techniques followed by iodine doping. The as-prepared and doped films are characterized using FE-SEM, EDX, UV/visible spectroscopy, XPS, current-voltage measurement, photoluminescence spectroscopy, cyclic voltammetry, and incident photon to current efficiency measurements. In addition, the electronic and semiconductor properties of the MOF films are characterized using Hall Effect measurement, which reveals that, in contrast to the insulator behavior of the as-prepared MOFs, the iodine doped MOFs behave as a p-type semiconductor. This is caused by charge transfer-induced hole doping into the frameworks. The observed charge transfer-induced hole doping phenomenon is also confirmed by calculating the densities of states of the as-prepared and iodine doped MOFs based on density functional theory. Photoluminescence spectroscopy demonstrates an efficient interfacial charge transfer between TiO2 and iodine doped MOFs, which can be applied to harvest solar radiations.

Anodically fabricated self-organized nanoporous tin oxide film as a supercapacitor electrode material

Self-organized nanoporous tin oxide films were fabricated by anodizing a tin substrate in an aqueous electrolyte containing oxalic or phosphoric acid. The films were characterized using FE-SEM, XRD, XPS, and TGA. In addition, the supercapacitive properties of the porous oxide films were measured using cyclic voltammetry and galvanostatic charge/discharge technique. The film demonstrated a maximum specific capacitance of 274 F g−1 with long life in electrochemical charge/discharge cycles.

Novel Solid-State Solar Cell Based on Hole-Conducting MOF-Sensitizer Demonstrating Power Conversion Efficiency of 2.1%

This work reports on designing of first successful MOF-sensitizer based solid-state photovoltaic device, perticularly with a meaningful output power conversion efficiency. In this study, an intrinsically conductive cobalt-based MOFs (Co-DAPV) formed by the coordination between Co (II) ions and a redox active di(3-diaminopropyl)-viologen (i.e., DAPV) ligand is investigated as sensitizer. Hall-effect measurement shows p-type conductivity of the Co-DAPV film with hole mobility of 0.017 cm2 V-1 s-1, suggesting its potential application as hole transporting sensitizer. Further, the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of Co-DAPV are well-matched to be suitably employed for sensitizing TiO2. Thus, by layer-by-layer deposition of hole conducting MOF-sensitizer onto mesoporous TiO2 film, a power conversion efficiency of as high as 2.1% is achieved, which exceeds the highest efficiency values of MOF-sensitized liquid-junction solar cells reported so far.

A facile approach for carburization of anodically grown titania nanotubes: towards metallization of nanotubes

The present work demonstrates a facile, low cost and environmentally friendly technique for carburization of TiO2 nanotubes. XRD and XPS investigations suggest that the anodically grown self-organized TiO2 nanotubes when annealed in an argon filled steel nut–bolt cavity working as an autogenic pressure reactor undergo carburization at 650 °C, which converts TiO2 into TiOyCz. TEM-SAED suggests that the carburized nanotubes are polycrystalline, and also contain some reduced oxides of titanium. The conductivity measurement of the carburized nanotubes shows their conductivity to be close to metals. The electrochemical investigation of the carburized nanotubes demonstrates that the material can be used as a conductive electrode material for electrochemical reactions.

Sequential chemical bath deposition of Cu(2-x)Se/CdS film by suppressing ion-exchange reaction.

Chemical bath deposition is an attractive technique to form single- and multilayered metal oxide/chalcogenide films on electrode surfaces. However, the occurrence of desorption and/or ion-exchange reaction during subsequent chemical bath deposition has so far limited preparation of multilayered metal oxide/chalcogenide films. In this paper, we report a method to prevent desorption and ion-exchange reaction of metal oxide/chalcogenide on electrode surfaces using a polyelectrolyte multilayer during sequential chemical bath deposition. By controlling the ion permeability of the polyelectrolyte multilayer, Cu(2-x)Se film was successfully deposited on the CdS film. The Cu(2-x)Se/CdS film is confirmed by UV-vis absorption spectroscopy, scanning electron microscopy, energy dispersive X-ray analysis, and X-ray powder diffractometer. Furthermore, the Cu(2-x)Se/CdS films were investigated as photoinduced charge transfer devices which showed photocurrents of 0.22 mA/cm(2) under illumination (I = 100 mW/cm(2)).