Enhanced Photocurrent of Transparent CuFeO₂ Photocathodes by Self-Light-Harvesting Architecture

Efficient sunlight-driven water-splitting devices can be achieved by using an optically and energetically well-matched pair of photoelectrodes in a tandem configuration. The key for maximizing the photoelectrochemical efficiency is the use of a highly transparent front photoelectrode with a band gap below 2.0 eV. Herein, we propose two-dimensional (2D) photonic crystal (PC) structures consisting of a CuFeO₂-decorated microsphere monolayer, which serve as self-light-harvesting architectures allowing for amplified light absorption and high transparency. The photocurrent densities are evaluated for three CuFeO₂ 2D PC-based photoelectrodes with microspheres of different sizes. The optical analysis confirmed the presence of a photonic stop band that generates <i>slow light</i> and at the same time amplifies the absorption of light. The 410 nm sized CuFeO₂-decorated microsphere 2D PC photocathode shows an exceptionally high visible light transmittance of 76.4% and a relatively high photocurrent of 0.2 mA cm^–2 at 0.6 V vs a reversible hydrogen electrode. The effect of the microsphere size on the carrier collection efficiency was analyzed by in situ conductive atomic force microscopy observation under illumination. Our novel synthetic method to produce self-light-harvesting nanostructures provides a promising approach for the effective use of solar energy by highly transparent photocathodes

Molecular Chemistry-Controlled Hybrid Ink-Derived Efficient Cu₂ZnSnS₄ Photocathodes for Photoelectrochemical Water Splitting

To realize economically competitive hydrogen production through photoelectrochemical (PEC) water splitting, it is essential to develop an efficient photoelectrode consisting of earth-abundant constituents in conjunction with low-cost solution processing. Cu₂ZnSnS₄ (CZTS) has received significant attention as a promising photocathode owing to its abundance and good absorption properties. However, the efficiency of the solution-processed CZTS photocathode is not yet comparable to its counterparts. Here, a hybrid ink, obtained by careful control of precursor mixing order, was used to produce a highly efficient CZTS photocathode. The molecular chemistry-controlled hybrid ink formulation, particularly the roles of thiourea–Sn²⁺ complexation, was elucidated by liquid Raman spectroscopy. The hybrid ink-derived CZTS thin films modified with conformal coating of an n-type TiO₂/CdS double layer and a Pt electrocatalyst achieved an exceptionally high photocurrent of 13 mA cm^–2 at −0.2 V versus a reversible hydrogen electrode under 1 sun illumination. The modified photocathodes showed relatively stable H₂ production with faradaic efficiency close to unity

Retarding Crystallization during Facile Single Coating of NaCl-Incorporated Precursor Solution for Efficient Large-Area Uniform Perovskite Solar Cells

We demonstrated crystallization retardation of CH₃NH₃PbI₃ thin film during single coating of precursor solution by simple addition of NaCl. NaCl was codissolved into a precursor mixture solution containing PbI₂ and methylammonium iodide (MAI). Dissolved NaCl interacted with the PbI₂ in solution and produced a stable intermediate phase, which was converted to a full-coverage uniform perovskite absorber layer via reaction with MAI during a single spin-coating. The resulting planar-structure perovskite solar cell made from NaCl-supplemented precursor solution showed a 48% improvement in power conversion efficiency (PCE) (maximum value 15.16%) over the device fabricated without the additive. Our NaCl-supplemented single coating represents an easy approach to effectively obtain highly reproducible uniform performance at an overall position in 5 cm × 5 cm sized cells (divided into 20 subcells with an active area of 0.06 cm²) with average PCEs of 12.00 ± 0.48%

Investigating Recombination and Charge Carrier Dynamics in a One-Dimensional Nanopillared Perovskite Absorber

Organometal halide perovskite materials have become an exciting research topic as manifested by intense development of thin film solar cells. Although high-performance solar-cell-based planar and mesoscopic configurations have been reported, one-dimensional (1-D) nanostructured perovskite solar cells are rarely investigated despite their expected promising optoelectrical properties, such as enhanced charge transport/extraction. Herein, we have analyzed the 1-D nanostructure effects of organometal halide perovskite (CH₃NH₃PbI_3–<i>x</i>Cl_<i>x</i>) on recombination and charge carrier dynamics by utilizing a nanoporous anodized alumina oxide scaffold to fabricate a vertically aligned 1-D nanopillared array with controllable diameters. It was observed that the 1-D perovskite exhibits faster charge transport/extraction characteristics, lower defect density, and lower bulk resistance than the planar counterpart. As the aspect ratio increases in the 1-D structures, in addition, the charge transport/extraction rate is enhanced and the resistance further decreases. However, when the aspect ratio reaches 6.67 (diameter ∼30 nm), the recombination rate is aggravated due to high interface-to-volume ratio-induced defect generation. To obtain the full benefits of 1-D perovskite nanostructuring, our study provides a design rule to choose the appropriate aspect ratio of 1-D perovskite structures for improved photovoltaic and other optoelectrical applications