Ji-Hyun Cha

Photoresponse of CsPbBr3 and Cs4PbBr6 Perovskite Single Crystals

High-quality and millimeter-sized perovskite single crystals of CsPbBr3 and Cs4PbBr6 were prepared in organic solvents and studied for correlation between photocurrent generation and photoluminescence (PL) emission. The CsPbBr3 crystals, which have a 3D perovskite structure, showed a highly sensitive photoresponse and poor PL signal. In contrast, Cs4PbBr6 crystals, which have a 0D perovskite structure, exhibited more than 1 order of magnitude higher PL intensity than CsPbBr3, which generated an ultralow photoresponse under illumination. Their contrasting optoelectrical characteristics were attributed to different exciton binding energies, induced by coordination geometry of the [PbBr6]4- octahedron sublattices. This work correlated the local structures of lead in the primitive perovskite and its derivatives to PL spectra as well as photoconductivity.

Anthraquinone sulfonate modified, layered double hydroxide nanosheets for dye-sensitized solar cells.

Dye-sensitized solar cells (DSCs) have been extensively investigated for solar energy conversion by using various combinations of inorganic semiconductors and organic sensitizers because of their low cost, easy production, and high efficiency. For efficient visible-light absorption, various organic dyes have been intensively exploited because of their advantages, such as their high molar extinction coefficients and tunable optical bands, in which they are anchored on mesoscopic TiO2 semiconductors. Recently, inorganic semiconducting materials, such as quantum dots (CdSe, CdS,) and organometal perovskites, have been proposed as inorganic sensitizers in photovoltaic cells to overcome some drawbacks of the organic dyes such as their relatively low heat stability and narrow absorption bands. One possible approach to improving the inherent light-harvesting ability of the organic dyes is to hybridize them with nanosized multifunctional inorganic materials such as layered double hydroxides (LDHs), which can provide a stable chemical environment, higher heat or photostability, and are environmentally friendly. The LDHs, also known as anionic or hydrotalcite-like clays, are useful in new multifunctional systems such as biological carriers, catalysts, and hybrid optical layers. Recently, Duan et al. reported an ultrathin hybrid film consisting of LDH nanosheets and luminescent polyanions, in which the LDH nanosheets induced a welldefined photoluminescence of polymer monolayers that are individually separated by the exfoliated LDH nanosheets. Moreover, the LDHs provide a stable chemical environment to increase the photochemical function and thermal stability of the intercalated organic photochromic dyes. In this study, LDH nanosheets are suggested as the inorganic matrix in an attempt to induce an intense photochromic function of the organic photochromic dyes, anthraquinone sulfonate anion (AQS), that are chemically immobilized on the surface of the LDH nanosheets. Herein, we report a new hybrid light sensitizer for DSCs, in which the AQS anion is selected as the organic sensitizer and the LDH nanosheets as the inorganic host. This is believed to be the first example of hybrid LDH/organic nanosheets used as a light sensitizer in photovoltaic devices. The chemical structure and photochromic behavior of the LDH AQS nanosheets in formamide are shown in Figure 1a. The powder X-ray diffraction (XRD) pattern of LDH AQS microcrystals indicated a well-crystallized rhombohedral hydrotalcite-like, 3R1 phase with lattice parameters of a=3.05 and c=60.0 . An antiparallel arrangement of the AQS would be the best model by assuming that the length of the AQS anion was 12.9 . Notably, a transparent solution was obtained by ultrasound treatment for 10 min, indicating the successful exfoliation of the platelike LDH AQS microcrystals. Typical Tyndall light scattering of the resulting solution demonstrated the presence of exfoliated LDH nanosheets as shown in Figure 1a. Interestingly, the suspension showed a strong photoinduced coloration that was not seen in the AQS–formamide solution. In (4) of Figure 1b, the UV/Vis absorption spectra for the irradiated suspension of the LDH AQS nanosheets show extremely enhanced absorption bands in the range of 400–600 nm, where the absorption bands at 435 and 525 nm are characteristic signals for the reduction state of anthraquinone sulfonate (AQS ) that have a long-term stability in a high pH condition, whereas formamide (the solvent) might be oxidized during the photoreaction. Under continuous irradiation of the exfoliated LDH AQS solution shown in (2) of Figure 1b, the band intensities gradually increased as a function of the irradiation time and then decreased after the light was cut off. The rate constants for photocoloration and decay were 0.072 and 0.059 min , respectively. This may be [a] Dr. J. H. Lee, J. Chang, J.-H. Cha, Prof. D.-Y. Jung, S. S. Kim, Prof. J. M. Kim Department of Chemistry-BK21 and Sungkyunkwan Advanced Institute of Nanotechnology Institute of Basic Sciences, Sungkyunkwan University Suwon, 440-746 (Korea) Fax: (+82)31-290-7075 E-mail : dyjung@skku.edu Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/chem.201000703.

Synthesis and Nanostructures of Metal Selenide Precursors for Cu(In,Ga)Se2 Thin‐Film Solar Cells

A nanoink solution-based process was developed as a low-costing method for the fabrication of Cu(In,Ga)Se2 (CIGSe) thin-film photovoltaic cells. The sonochemical synthesis of CIGSe nanocrystals of the nanoink through step-by-step mixing of the reactants was investigated. To achieve the ideal stoichiometry of Cu(In0.7 Ga0.3 )Se2 to tune the bandgap and to fabricate high-efficiency photovoltaic cells, the synthetic parameters, the concentration of hydrazine, and the amount used of the gallium precursor were investigated. As the hydrazine concentration increased, gallium loss was observed in the CIGSe product. The gallium content in the reactant mixture strongly affected the metal stoichiometry of the prepared CIGSe nanocrystals. The nanoink solution based fabrication of thin-film photovoltaic cells was also explored, and the resulting device showed a conversion efficiency of 5.17 %.

CuGaS2 hollow spheres from Ga-CuS core-shell nanoparticles.

A liquid gallium emulsion was prepared as a starting material using ultrasound treatment in ethylene glycol. Core-shell particles of Ga@CuS were successfully synthesized by deposition of a CuS layer on gallium droplets through sonochemical deposition of copper ions and thiourea in an alcohol media. The core and shell of Ga@CuS products were composed of amorphous gallium metal and covellite phase CuS, which transformed into chalcopyrite CuGaS2 hollow spheres after sulfurization at 450°C, which was the lowest crystallization temperature. The formation of hollow nanostructures was ascribed to the Kirkendall mechanism, in which liquid gallium particles play an important role as reactive templates. In conclusion, we obtained CuGaS2 hollow spheres with a 430 nm outer diameter and 120 nm shell thickness that had the same crystal structure and electrical properties as bulk CuGaS2.

Air-Stable Transparent Silver Iodide–Copper Iodide Heterojunction Diode

Transparent AgI-CuI heterojunctions with high rectifying diode behavior were prepared via vapor-phase iodization of metal thin films on transparent conducting oxide substrates. At room temperature, Ag and Cu metal thin films were quickly transformed into the transparent and well-crystallized β-phase of AgI and the γ-phase of CuI, respectively. The AgI and CuI films exhibited n-type and p-type semiconductor properties, respectively, with wide band gaps. The heterojunctions were obtained by applying the CuI film to the AgI film in a sequential iodization process. AgI compounds generally have poor air-stability under light, making them suboptimal for use in electronic applications. Here, we used a CuI top layer to inhibit the photodecomposition of the AgI bottom layer, resulting in an air-stable and smooth AgI-CuI film. We also propose a simple patterning method for the AgI-CuI layer using selective decomposition of AgI without the need for lithography equipment or toxic chemicals. Although there is metal ion exchange between the two layers, each layer has a different chemical composition and crystal structure; therefore, the AgI-CuI heterojunction exhibits pn-diode behavior with a rectifying ratio of 9.4 × 104, which is comparable to that of other transparent pn-diodes. These findings open a new path for electronic application of AgI materials.