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Semiconductors with multiple anions currently provide a new materials platform from which improved functionality emerges, posing new challenges and opportunities in material science. This review has endeavored to emphasize the versatility of the emerging family of semiconductors consisting of mixed chalcogen and halogen anions, known as "chalcohalides". As they are multifunctional, these materials are of general interest to the wider research community, ranging from theoretical/computational scientists to experimental materials scientists. This review provides a comprehensive overview of the development of emerging Bi- and Sb-based as well as a new Cu, Sn, Pb, Ag, and hybrid organic-inorganic perovskite-based chalcohalides. We first highlight the high-throughput computational techniques to design and develop these chalcohalide materials. We then proceed to discuss their optoelectronic properties, band structures, stability, and structural chemistry employing theoretical and experimental underpinning toward high-performance devices. Next, we present an overview of recent advancements in the synthesis and their wide range of applications in energy conversion and storage devices. Finally, we conclude the review by outlining the impediments and important aspects in this field as well as offering perspectives on future research directions to further promote the development of chalcohalide materials in practical applications in the future.
Assuntos
Halogênios , Ciência dos Materiais , SemicondutoresRESUMO
The photoelectrochemical (PEC) cell that collects and stores abundant sunlight to hydrogen fuel promises a clean and renewable pathway for future energy needs and challenges. Monoclinic bismuth vanadate (BiVO4 ), having an earth-abundancy, nontoxicity, suitable optical absorption, and an ideal n-type band position, has been in the limelight for decades. BiVO4 is a potential photoanode candidate due to its favorable outstanding features like moderate bandgap, visible light activity, better chemical stability, and cost-effective synthesis methods. However, BiVO4 suffers from rapid recombination of photogenerated charge carriers that have impeded further improvements of its PEC performances and stability. This review presents a close look at the emerging surface, bulk, and interface engineering strategies on BiVO4 photoanode. First, an effective approach of surface functionalization via different cocatalysts to improve the surface kinetics of BiVO4 is discussed. Second, state-of-the-art methodologies such as nanostructuring, defect engineering, and doping to further enhance light absorption and photogenerated charge transport in bulk BiVO4 are reviewed. Third, interface engineering via heterostructuring to improve charge separation is introduced. Lastly, perspectives on the foremost challenges and some motivating outlooks to encourage the future research progress in this emerging frontier are offered.
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Herein, bimetallic iron (Fe)-manganese (Mn) oxyhydroxide ((Fe1-x, Mnx )OOH, FeMnOOH) nanosheets on fluorine-doped tin oxide conducting substrates and on semiconductor photoanodes are synthesized by a facile, room temperature, electroless deposition method as catalysts for both electrochemical and photo-electrochemical (PEC) water splitting, respectively. Surprisingly, Mn-doped FeOOH can significantly modulate the nanosheet morphology to increase the active surface area, boost more active sites, and augment the intrinsic activity by tuning the electronic structure of FeOOH. Due to the 2D nanosheet architecture, the optimized FeMnOOH exhibits superior electrochemical activity and outstanding durability for the oxygen evolution reaction with a low overpotential of 246 mV at 10 mA cm-2 and 414 mV at 100 mA cm-2 , and long-term stability for 40 h without decay, which is comparable to the best electrocatalysts for water oxidation reported in the literature. By integrating with semiconductor photoanodes (such as α-Fe2 O3 nanorod (NR) arrays), bimetallic FeMnOOH catalysts achieve solar-driven water splitting with a significantly enhanced PEC performance (3.36 mA cm-2 at 1.23 V vs reversible hydrogen electrode (RHE)) with outstanding long-term stability (≈8 h) compared to that of the bare Fe2 O3 NR (0.92 mA cm-2 at 1.23 V vs RHE).
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A quaternary indium- and gallium-free kesterite (KS)-based compound, copper zinc tin sulfide (Cu2ZnSnS4, CZTS), has received significant attention for its potential applications in low cost and sustainable solar cells. It is well known that the reaction time, reactivity of the precursors, and types of capping ligands used during the synthesis of colloidal nanocrystals (NCs) strongly influence the crystallographic phase of the NCs. In this research, a non-toxic and green synthetic strategy for both the synthesis of CZTS NCs and the fabrication of a highly efficient CZTS absorber layers using an ink formulation without a toxic solvent, which meets the comprehensive framework for green chemistry that covers major aspects of the environmental strain, is demonstrated. In particular, pure metastable wurtzite (WZ) CZTS NCs are synthesized using the environmentally harmless, polyol mediated hot-injection (HI) technique at a low reaction temperature. The influence of the reaction time on the properties of the CZTS NCs is investigated in detail. Based on detailed reaction time dependent phase evolution, a possible growth and formation mechanism is proposed. Furthermore, a scalable, low cost, binder free ink formulation process without ligand exchange is developed using ethanol as the dispersal solvent. The as-prepared WZ-derived CZTS NC thin films are observed to undergo a phase transformation to KS during annealing in a sulfur vapor atmosphere via rapid thermal annealing above 500 °C, and surprisingly, this process results in fully sintered, compact and uniform CZTS thin films with large sized grains. The best solar cell device fabricated using a CZTS absorber that was sulfurized at an optimized temperature exhibits a power conversion efficiency of 2.44%, which is the highest efficiency obtained using the polyol-based HI route.
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The coupling of oxygen evolution reaction (OER) catalysts with photoanodes is a promising strategy for enhancing the photoelectrochemical (PEC) performance by passivating photoanode's surface defect states and facilitating charge transfer at the photoanode/electrolyte interface. However, a serious interface recombination issue caused by poor interface and OER catalysts coating quality often limits further performance improvement of photoanodes. Herein, a rapid Fenton-like reaction method is demonstrated to produce ultrathin amorphous Ni:FeOOH catalysts with in situ-induced oxygen vacancies (Vo) to improve the water oxidation activity and stability of BiVO4 photoanodes. The combined physical characterizations, PEC studies, and density functional theory calculations revealed that the reductive environment in a Fenton-like reaction in situ produces abundant Vo in Ni:FeOOH catalysts, which significantly improves charge separation and charge transfer efficiency of BiVO4 while also offering abundant active sites and a reduced energy barrier for OER. As a result, Ni:FeOOH-Vo catalysts yielded a more than 2-fold increased photocurrent density in the BiVO4 photoanode (from 1.54 to 4.15 mA cm-2 at 1.23 VRHE), accompanied by high stability for 5 h. This work not only highlights the significance of abundant Vo in catalysts but also provides new insights into the rational design and fabrication of efficient and stable solar water-splitting systems.
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The use of flexible and highly conducting molybdenum (Mo) foil as a substrate offers several advantages such as a high thermal stability, smooth surface, and chemical inertness for the fabrication of high-efficiency thin film solar cells (TFSCs) by lowering the manufacturing costs. Here, we report a record preliminary efficiency of â¼8% for sputtered-grown Cu2ZnSn(S,Se)4 (CZTSSe) TFSCs on flexible and lightweight Mo foils. Careful studies were focused on identifying the role of preparative parameters such as annealing temperature, absorber composition, and post-preparative optimization to bridge the obtained record efficiency of â¼8% to a previous record efficiency of 7.04% for Na-incorporated CZTSSe sputter-based TFSCs. Interestingly, the preliminary record efficiency of â¼8% for our CZTSSe device grown via a scalable sputtering method was achieved by optimizing the absorber quality and post-preparative device optimization. While our preliminary results with a record efficiency demonstrate the potential of sputtering method, there is much scope for further improvement in the device efficiency by thoroughly understanding alkali element doping in the absorber layer.
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Herein, we report a facile process, i.e., controlling the initial chamber pressure during the postdeposition annealing, to effectively lower the band tail states in the synthesized CZTSSe thin films. Through detailed analysis of the external quantum efficiency derivative ( dEQE/ dλ) and low-temperature photoluminescence (LTPL) data, we find that the band tail states are significantly influenced by the initial annealing pressure. After carefully optimizing the deposition processes and device design, we are able to synthesize kesterite CZTSSe thin films with energy differences between inflection of d(EQE)/dλ and LTPL as small as 10 meV. These kesterite CZTSSe thin films enable the fabrication of solar cells with a champion efficiency of 11.8% with a low Voc deficit of 582 mV. The results suggest that controlling the annealing process is an effective approach to reduce the band tail in kesterite CZTSSe thin films.
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A facile improved successive ionic-layer adsorption and reaction (SILAR) sequence is described for the fabrication of Cu2ZnSn(S,Se)4 (CZTSSe) thin-film solar cells (TFSCs) via the selenization of a precursor film. The precursor films were fabricated using a modified SILAR sequence to overcome compositional inhomogeneity due to different adsorptivities of the cations (Cu+, Sn4+, and Zn2+) in a single cationic bath. Rapid thermal annealing of the precursor films under S and Se vapor atmospheres led to the formation of carbon-free Cu2ZnSnS4 (CZTS) and CZTSSe absorber layers, respectively, with single large-grained layers. The best devices based on CZTS and CZTSSe absorber layers showed total area (â¼0.30 cm2) power conversion efficiencies (PCEs) of 1.96 and 3.74%, respectively, which are notably the first-demonstrated efficiencies using a modified SILAR sequence. Detailed diode analyses of these solar cells revealed that a high shunt conductance (G sh), reverse saturation current density (J o), and ideality factor (n d) significantly affected the PCE, open-circuit voltage (V oc), and fill factor (FF), whereas the short-circuit current density (J sc) was dominated by the series resistance (R s) and G sh. However, the diode analyses combined with the compositional and interface microstructural analyses shed light on further improvements to the device efficiency. The facile layer-by-layer growth of the kesterite CZTS-based thin films in aqueous solution provides a great promise as an environmentally benign pathway to fabricate a variety of multielement-component compounds with high compositional homogeneities.
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A simple and eco-friendly method of solution processing of Cu2SnS3 (CTS) absorbers using an aqueous precursor solution is presented. The precursor solution was prepared by mixing metal salts into a mixture of water and ethanol (5:1) with monoethanolamine as an additive at room temperature. Nearly carbon-free CTS films were formed by multispin coating the precursor solution and heat treating in air followed by rapid thermal annealing in S vapor atmosphere at various temperatures. Exploring the role of the annealing temperature in the phase, composition, and morphological evolution is essential for obtaining highly efficient CTS-based thin film solar cells (TFSCs). Investigations of CTS absorber layers annealed at various temperatures revealed that the annealing temperature plays an important role in further improving device properties and efficiency. A substantial improvement in device efficiency occurred only at the critical annealing temperature, which produces a compact and void-free microstructure with large grains and high crystallinity as a pure-phase absorber layer. Finally, at an annealing temperature of 600 °C, the CTS thin film exhibited structural, compositional, and microstructural isotropy by yielding a reproducible power conversion efficiency of 1.80%. Interestingly, CTS TFSCs exhibited good stability when stored in an air atmosphere without encapsulation at room temperature for 3 months, whereas the performance degraded slightly when subjected to accelerated aging at 80 °C for 100 h under normal laboratory conditions.