Targeting Ideal Dual‐Absorber Tandem Water Splitting Using Perovskite Photovoltaics and CuInxGa1‐xSe2 Photocathodes

Efficient sunlight‐driven water splitting devices can be achieved by pairing two absorbers of different optimized bandgaps in an optical tandem design. With tunable absorption ranges and cell voltages, organic–inorganic metal halide perovskite solar cells provide new opportunities for tailoring top absorbers for such devices. In this work, semitransparent perovskite solar cells are developed for use as the top cell in tandem with a smaller bandgap photocathode to enable panchromatic harvesting of the solar spectrum. A new CuIn_xGa_1‐xSe₂ multilayer photocathode is designed, exhibiting excellent performance for photoelectrochemical water reduction and representing a near‐ideal bottom absorber. When pairing it below a semitransparent CH₃NH₃PbBr₃‐based solar cell, a solar‐to‐hydrogen efficiency exceeding 6% is achieved, the highest value yet reported for a photovoltaic–photoelectrochemical device utilizing a single‐junction solar cell as the bias source under one sun illumination. The analysis shows that the efficiency can reach more than 20% through further optimization of the perovskite top absorber.     

Water Splitting Progress in Tandem Devices: Moving Photolysis beyond Electrolysis

Water photolysis is a sustainable technology to convert natural solar energy and water into chemical fuels and is thus considered a thorough solution to the forthcoming energy crises. Unassisted water splitting that could directly harvest solar light and subsequently split water in a single device has become an important research theme. Three types of tandem devices including photoelectrochemical (PEC), photovoltaic (PV) cell/PEC and PV/electrolyser tandem cells are proposed to realize water photolysis at different levels of integration and component. Recent progress in tandem water splitting devices is summarized, and crucial issues on device optimization from the perspective of each photo‐absorber functionalities in band edge potential, light absorptivity and transmittance are discussed. By increasing the performances of stand‐alone PEC or PV devices, a 20% solar to hydrogen efficiency is predicted that is a significant value towards further application in practice. Accordingly, the challenges for materials development and configuration optimization are further outlined.     

Oxygenated CdS Buffer Layers Enabling High Open‐Circuit Voltages in Earth‐Abundant Cu2BaSnS4 Thin‐Film Solar Cells

Earth‐abundant Cu₂BaSnS₄ (CBTS) thin films exhibit a wide bandgap of 2.04–2.07 eV, a high absorption coefficient > 10⁴ cm^?1, and a p‐type conductivity, suitable as a top‐cell absorber in tandem solar cell devices. In this work, sputtered oxygenated CdS (CdS:O) buffer layers are demonstrated to create a good p–n diode with CBTS and enable high open‐circuit voltages of 0.9–1.1 V by minimizing interface recombination. The best power conversion efficiency of 2.03% is reached under AM 1.5G illumination based on the configuration of fluorine‐doped SnO₂ (back contact)/CBTS/CdS:O/CdS/ZnO/aluminum‐doped ZnO (front contact).     

Over 17% Efficiency Stand‐Alone Solar Water Splitting Enabled by Perovskite‐Silicon Tandem Absorbers

Realizing solar‐to‐hydrogen (STH) efficiencies close to 20% using low‐cost semiconductors remains a major step toward accomplishing the practical viability of photoelectrochemical (PEC) hydrogen generation technologies. Dual‐absorber tandem cells combining inexpensive semiconductors are a promising strategy to achieve high STH efficiencies at a reasonable cost. Here, a perovskite photovoltaic biased silicon (Si) photoelectrode is demonstrated for highly efficient stand‐alone solar water splitting. A p⁺nn⁺ ‐Si/Ti/Pt photocathode is shown to present a remarkable photon‐to‐current efficiency of 14.1% under biased condition and stability over three days under continuous illumination. Upon pairing with a semitransparent mixed perovskite solar cell of an appropriate bandgap with state‐of‐the‐art performance, an unprecedented 17.6% STH efficiency is achieved for self‐driven solar water splitting. Modeling and analysis of the dual‐absorber PEC system reveal that further work into replacing the noble‐metal catalyst materials with earth‐abundant elements and improvement of perovskite fill factor will pave the way for the realization of a low‐cost high‐efficiency PEC system.     

Hybrid Perovskite‐Organic Flexible Tandem Solar Cell Enabling Highly Efficient Electrocatalysis Overall Water Splitting

Perovskite‐organic tandem solar cells are attracting more attention due to their potential for highly efficient and flexible photovoltaic device. In this work, efficient perovskite‐organic monolithic tandem solar cells integrating the wide bandgap perovskite (1.74 eV) and low bandgap organic active PBDB‐T:SN6IC‐4F (1.30 eV) layer, which serve as the top and bottom subcell, respectively, are developed. The resulting perovskite‐organic tandem solar cells with passivated wide‐bandgap perovskite show a remarkable power conversion efficiency (PCE) of 15.13%, with an open‐circuit voltage (V_oc) of 1.85 V, a short‐circuit photocurrent (J_sc) of 11.52 mA cm^?2, and a fill factor (FF) of 70.98%. Thanks to the advantages of low temperature fabrication processes and the flexibility properties of the device, a flexible tandem solar cell which obtain a PCE of 13.61%, with V_oc of 1.80 V, J_sc of 11.07 mA cm^?2, and FF of 68.31% is fabricated. Moreover, to demonstrate the achieved high V_oc in the tandem solar cells for potential applications, a photovoltaic (PV)‐driven electrolysis system combing the tandem solar cell and water splitting electrocatalysis is assembled. The integrated device demonstrates a solar‐to‐hydrogen efficiency of 12.30% and 11.21% for rigid, and flexible perovskite‐organic tandem solar cell based PV‐driven electrolysis systems, respectively.     

Efficiency Improvement of Near‐Stoichiometric CuInSe2 Solar Cells for Application in Tandem Devices

State‐of‐the‐art Cu(In,Ga)Se₂ (CIGS) solar cells are grown with considerably substoichiometric Cu concentrations. The resulting defects, as well as potential improvements through increasing the Cu concentration, have been known in the field for many years. However, so far, cells with high Cu concentrations show decreased photovoltaic parameters. In this work, it is shown that RbF postdeposition treatment of CuInSe₂ solar cells allows for capturing the benefits from the improved absorber quality with increasing Cu content. A reduced defect density and an increased doping level for cells with high Cu concentrations close to stoichiometry are demonstrated. Implementing a high mobility front transparent conductive oxide (TCO), the improved absorbers with 1.00 eV bandgap yield a solar cell efficiency of 19.2%, and combined with a perovskite top cell a 4‐terminal tandem efficiency of 25.0% are demonstrated, surpassing the record efficiency of both subcell technologies.     

Porphyrin Sensitizers with Donor Structural Engineering for Superior Performance Dye‐Sensitized Solar Cells and Tandem Solar Cells for Water Splitting Applications

Zn(II)–porphyrin sensitizers, coded as SGT‐020 and SGT‐021 , are designed and synthesized through donor structural engineering. The photovoltaic (PV) performances of SGT sensitizer‐based dye‐sensitized solar cells (DSSCs) are systematically evaluated in a thorough SM315 as a reference sensitizer. The effect of the donor ability and the donor bulkiness on photovoltaic performances is investigated for establishing the structure–performance relationship in the platform of porphyrin‐triple bond‐benzothiadiazole‐acceptor sensitizers. By introducing a more bulky fluorene unit to the amine group in the SM315 , the power conversion efficiency (PCE) is enhanced with the increased short‐circuit current (J_sc) and open‐circuit voltage (V_oc), due to the improved light‐harvesting ability and the efficient prevention of charge recombination, respectively. As a consequence, a maximum PCE of 12.11% is obtained for SGT‐021 , whose PCE is much higher than the 11.70% PCE for SM315 . To further improve their maximum efficiency, the first parallel tandem DSSCs employing cobalt electrolyte in the top and bottom cells are demonstrated and an extremely high efficiency of 14% is achieved, which is currently the highest reported value for tandem DSSCs. The series tandem DSSCs give a remarkably high V_oc value of >1.83 V. From this DSSC tandem configuration, 7.4% applied bias photon‐to‐current efficiency is achieved for solar water splitting.     

Back Contact Engineering for Increased Performance in Kesterite Solar Cells

The thin‐film photovoltaic absorber Cu₂ZnSn(S,Se)₄ (CZTSSe) holds considerable promise for large scale conversion of sunlight into electricity. CZTSSe is composed of Earth‐abundant elements that exhibit low‐toxicities, but improvements in device efficiency have been hampered by difficulties in increasing open circuit voltages (V_OC) due, at least in part, to disorder induced band tailing. We present a method to increase V_OC through direct modification of the back contact; our approach involves the separation of fully functioning devices from their Mo/glass substrate to reveal the back CZTSSe surface. Formation of a new back contact consisting of a thermally deposited high work function material (MoO₃), together with a higly reflective (Au) capping layer, creates an electrostatic field that drives electrons to the front p‐n junction and leads to a decrease in electron‐hole recombination. Model simulations indicating an increase in V_OC with decreasing absorber thickness are borne out by experiments with devices of varying thicknesses (0.7–2.0 μm). We report V_OC increases of up to 49 mV for a 1 μm thick absorber, with even greater increases up to 61 mV when the back CZTSSe surface is etched with bromine‐methanol.     

Full‐Spectrum Liquid‐Junction Quantum Dot–Sensitized Solar Cells by Integrating Surface Plasmon–Enhanced Electrocatalysis

Full‐spectrum solar energy utilization is the ultimate goal of high‐performance photovoltaic devices. However, the present approaches to enhance sunlight harvesting in the cost‐effective quantum dot–sensitized solar cells mainly focus on the use of high‐frequency photons with the long‐wavelength sunlight being left behind. Here, a full‐spectrum solar cell architecture is proposed and the near‐infrared light–enhanced cell performance is demonstrated with a plasmonic and electrocatalytic dual‐function CuS nanostructure electrode. In the CdS/CdSe quantum dot–sensitized solar cells, an enhancement factor as high as 15% in power conversion efficiency is obtained for the device with near‐infrared part of 1‐sun light irradiating from the counter electrode side and ultraviolet–visible part incidence from the photoanode side. Electrochemical characterizations show that the enhanced electrocatalytic activity toward polysulfide reduction is attributed to the better device performance. This may be due to the plasmon‐induced photothermal effect and interfacial energy transfer from the counter electrode under the near‐infrared light, which accelerate the preceding chemical reactions for polysulfide reduction and improve the charge transfer at the electrode–electrolyte interface. This strategy provides an alternative way to achieve a full‐spectrum liquid‐junction solar cell via the integration of plasmon‐enhanced electrocatalysis into photovoltaics.     

High‐Performance Semitransparent Tandem Solar Cell of 8.02% Conversion Efficiency with Solution‐Processed Graphene Mesh and Laminated Ag Nanowire Top Electrodes

A high‐performance semitransparent tandem solar cell that uses solution‐processed graphene mesh and laminated Ag NW as a transparent anode and cathode, respectively, is demonstrated. The laminated top electrode can be deposited without causing any damage to the underneath organic solar cells. Power conversion efficiencies of 8.02% and 6.47% are obtained when the light is projected from the solution‐processed graphene mesh and laminated AgNW, respectively. The performance of the tandem cell is found to be comparable to a tandem solar cell fabricated using commercially available indium tin oxide. These findings offer a high‐performance device and open a new pathway in searching for a potential replacement to the frequently used transparent conducting electrodes.     

Spray Deposition of Silver Nanowire Electrodes for Semitransparent Solid‐State Dye‐Sensitized Solar Cells

Transparent top electrodes for solid‐state dye‐sensitized solar cells (ssDSCs) allow for fabrication of mechanically stacked ssDSC tandems, partially transparent ssDSCs for building integration, and ssDSCs on metal foil substrates. A solution‐processed, highly transparent, conductive electrode based on PEDOT:PSS [poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)] and spray‐deposited silver nanowires (Ag NWs) is developed as an effective top contact for ssDSCs. The electrode is solution‐deposited using conditions and solvents that do not damage or dissolve the underlying ssDSC and achieves high performance: a peak transmittance of nearly 93% at a sheet resistance of 18 Ω/square – all without any annealing that would harm the ssDSC. The role of the PEDOT:PSS in the electrode is twofold: it ensures ohmic contact between the ssDSC 2,2′,7,7′‐tetrakis‐(N,N‐di‐p‐methoxyphenylamine)9,9′‐spirobifluorene (Spiro‐OMeTAD) overlayer and the silver nanowires and it decreases the series resistance of the device. Semitransparent ssDSCs with D35 dye fabricated using this Ag NW/PEDOT:PSS transparent electrode show power conversion efficiencies of 3.6%, nearly as high as a reference device using an evaporated silver electrode (3.7%). In addition, the semitransparent ssDSC shows high transmission between 700–1100 nm, a necessity for use in efficient tandem devices. Such an electrode, in combination with efficient ssDSCs or hybrid perovskite‐sensitized solar cells, can allow for the fabrication of efficient, cost‐effective tandem photovoltaics.     

A Floating Sheet for Efficient Photocatalytic Water Splitting

Solar photocatalytic water splitting has been a promising way to provide clean hydrogen energy. There are two weaknesses in the typical photocatalytic process in which photocatalysts are generally dispersing in water under stir. One is the inadequate utilization of light energy and the other one is the cumbersome operation in the recycling procedure. This study demonstrates an efficient solar photocatalytic water splitting using a floating sheet with a novel WSe₂ cocatalyst. The sheet is fabricated by laser‐depositing WSe₂ film on a carbon foam (CF) substrate and drop‐casting of the synthesized nanodiamond‐embedded Cu₂O (NEC) photocatalysts. This is a new‐type artificial photocatalytic system that overcomes the above‐mentioned weaknesses of a powder‐dispersing system. The WSe₂ cocatalyst acts as an electron sink to promote electron–hole separation, resulting in the further improvement of photocatalytic performance. This floating NEC/WSe₂/CF structure achieves efficient water splitting upon simulated solar irradiation with an increased H₂ evolution rate, which is 13.2 times that of the powder‐dispersing system. This study offers a strategy for the design of new‐type photocatalytic system and discovery of alternative noble metal‐free cocatalysts.     

Efficient Hybrid Tandem Solar Cells Based on Optical Reinforcement of Colloidal Quantum Dots with Organic Bulk Heterojunctions

While colloidal quantum dot photovoltaic devices (CQDPVs) can achieve a power conversion efficiency (PCE) of ≈12%, their insufficient optical absorption in the near‐infrared (NIR) regime impairs efficient utilization of the full spectrum of visible light. Here, high‐efficiency, solution‐processed, hybrid series, tandem photovoltaic devices are developed featuring CQDs and organic bulk heterojunction (BHJ) photoactive materials for front‐ and back‐cells, respectively. The organic BHJ back‐cell efficiently harvests the transmitted NIR photons from the CQD front‐cell, which reinforces the photon‐to‐current conversion at 350–1000 nm wavelengths. Optimizing the short‐circuit current density balance of each sub‐cell and creating a near ideal series connection using an intermediate layer achieve a PCE (12.82%) that is superior to that of each single‐junction device (11.17% and 11.02% for the CQD and organic BHJ device, respectively). Notably, the PCE of the hybrid tandem device is the highest among the reported CQDPVs, including single‐junction devices and tandem devices. The hybrid tandem device also exhibits almost negligible degradation after air storage for 3 months. This study suggests a potential route to improve the performance of CQDPVs by proper hybridization with NIR‐absorbing photoactive materials.     

Metal Halide Perovskites for Solar‐to‐Chemical Fuel Conversion

This review article presents and discusses the recent progress made in the stabilization, protection, improvement, and design of halide perovskite‐based photocatalysts, photoelectrodes, and devices for solar‐to‐chemical fuel conversion. With the target of water splitting, hydrogen iodide splitting, and CO₂ reduction reactions, the strategies established for halide perovskites used in photocatalytic particle‐suspension systems, photoelectrode thin‐film systems, and photovoltaic‐(photo)electrocatalysis tandem systems are organized and introduced. Moreover, recent achievements in discovering new and stable halide perovskite materials, developing protective and functional shells and layers, designing proper reaction solution systems, and tandem device configurations are emphasized and discussed. Perspectives on the future design of halide perovskite materials and devices for solar‐to‐chemical fuel conversion are provided. This review may serve as a guide for researchers interested in utilizing halide perovskite materials for solar‐to‐chemical fuel conversion.     

Recent Advances and Emerging Trends in Photo‐Electrochemical Solar Energy Conversion

Photo‐electrochemical (PEC) solar energy conversion offers the promise of low‐cost renewable fuel generation from abundant sunlight and water. In this Review, recent developments in photo‐electrochemical water splitting are discussed with respect to this promise. State‐of‐the‐art photo‐electrochemical device performance is put in context with the current understanding of the necessary requirements for cost‐effective solar hydrogen generation (in terms of solar‐to‐hydrogen conversion efficiency and system durability, in particular). Several important studies of photo‐electrochemical hydrogen generation at p‐type photocathodes are highlighted, mostly with protection layers (for enhanced durability), but also a few recent examples where protective layers are not needed. Recent work with the widely studied n‐type BiVO₄ photoanode is detailed, which highlights the needs and necessities for the next big photoanode material yet to be discovered. The emerging new research direction of photo‐electrocatalytic upgrading of biomass substrates toward value‐added chemicals is then discussed, before closing with a commentary on how research on PEC materials remains a worthwhile endeavor.     

Design and Fabrication of a Precious Metal‐Free Tandem Core–Shell p+n Si/W‐Doped BiVO4 Photoanode for Unassisted Water Splitting

Tandem photoelectrochemical water splitting cells utilizing crystalline Si and metal oxide photoabsorbers are promising for low‐cost solar hydrogen production. This study presents a device design and a scalable fabrication scheme for a tandem heterostructure photoanode: p⁺n black silicon (Si)/SnO₂ interface/W‐doped bismuth vanadate (BiVO₄)/cobalt phosphate (CoPi) catalyst. The black‐Si not only provides a substantial photovoltage of 550 mV, but it also serves as a conductive scaffold to decrease charge transport pathlengths within the W‐doped BiVO₄ shell. When coupled with cobalt phosphide (CoP) nanoparticles as hydrogen evolution catalysts, the device demonstrates spontaneous water splitting without employing any precious metals, achieving an average solar‐to‐hydrogen efficiency of 0.45% over the course of an hour at pH 7. This fabrication scheme offers the modularity to optimize individual cell components, e.g., Si nanowire dimensions and metal oxide film thickness, involving steps that are compatible with fabricating monolithic devices. This design is general in nature and can be readily adapted to novel, higher performance semiconducting materials beyond BiVO₄ as they become available, which will accelerate the process of device realization.     

Semi‐Transparent Tandem Organic Solar Cells with 90% Internal Quantum Efficiency

Semi‐transparent (ST) organic solar cells with potential application as power generating windows are studied. The main challenge is to find proper transparent electrodes with desired electrical and optical properties. In this work, this is addressed by employing an amphiphilic conjugated polymer PFPA‐1 modified ITO coated glass substrate as the ohmic electron‐collecting cathode and PEDOT:PSS PH1000 as the hole‐collecting anode. For active layers based on different donor polymers, considerably lower reflection and parasitic absorption are found in the ST solar cells as compared to solar cells in the standard geometry with an ITO/PEDOT:PSS anode and a LiF/Al cathode. The ST solar cells have remarkably high internal quantum efficiency at short circuit condition (～90%) and high transmittance (～50%). Hence, efficient ST tandem solar cells with enhanced power conversion efficiency (PCE) compared to a single ST solar cell can be constructed by connecting the stacked two ST sub‐cells in parallel. The total loss of photons by reflection, parasitic absorption and transmission in the ST tandem solar cell can be smaller than the loss in a standard solar cell based on the same active materials. We demonstrate this by stacking five separately prepared ST cells on top of each other, to obtain a higher photocurrent than in an optimized standard solar cell.     

Thin‐Film Solar Cells with InP Absorber Layers Directly Grown on Nonepitaxial Metal Substrates

The design and performance of solar cells based on InP grown by the nonepitaxial thin‐film vapor–liquid–solid (TF‐VLS) growth technique is investigated. The cell structure consists of a Mo back contact, p‐InP absorber layer, n‐TiO₂ electron selective contact, and indium tin oxide transparent top electrode. An ex situ p‐doping process for TF‐VLS grown InP is introduced. Properties of the cells such as optoelectronic uniformity and electrical behavior of grain boundaries are examined. The power conversion efficiency of first generation cells reaches 12.1% under simulated 1 sun illumination with open‐circuit voltage (V_OC) of 692 mV, short‐circuit current (J_SC) of 26.9 mA cm^?2, and fill factor (FF) of 65%. The FF of the cell is limited by the series resistances in the device, including the top contact, which can be mitigated in the future through device optimization. The highest measured V_OC under 1 sun is 692 mV, which approaches the optically implied V_OC of ≈795 mV extracted from the luminescence yield of p‐InP.     

Device Characteristics of an 11.4% CZTSe Solar Cell Fabricated from Sputtered Precursors

Kesterite is an attractive material for absorber layers in thin film photovoltaics. Solar cells based on kesterite have shown a substantial progress over the last decade; nevertheless, further improvements in device efficiency are pending due to the open‐circuit voltage (V_oc) deficit (i.e., difference between the maximum V _oc that can be achieved according to Shockley–Queisser limit and actual V _oc from the device). In this study, the optoelectronic properties of the author's internal record Cu₂ZnSnSe₄ solar cell, which shows a power conversion efficiency of 11.4%, are presented. The device measurements reveal a V_oc deficit of 337 mV, which is one of the lowest V _oc deficits in the literature. Moreover, an unusual behavior for kesterite is observed: (i) photon energy of the photoluminescence emission and (ii) the extrapolated V _oc for 0 K are both matching the band gap region of the absorber. These results indicate a significant improvement in the recombination characteristics and absorber quality in comparison to other kesterite devices in literature.     

Scalable Triple Cation Mixed Halide Perovskite–BiVO4 Tandems for Bias‐Free Water Splitting

Strong interest exists in the development of organic–inorganic lead halide perovskite photovoltaics and of photoelectrochemical (PEC) tandem absorber systems for solar fuel production. However, their scalability and durability have long been limiting factors. In this work, it is revealed how both fields can be seamlessly merged together, to obtain scalable, bias‐free solar water splitting tandem devices. For this purpose, state‐of‐the‐art cesium formamidinium methylammonium (CsFAMA) triple cation mixed halide perovskite photovoltaic cells with a nickel oxide (NiO_x) hole transport layer are employed to produce Field's metal‐epoxy encapsulated photocathodes. Their stability (up to 7 h), photocurrent density (–12.1 ± 0.3 mA cm^?2 at 0 V versus reversible hydrogen electrode, RHE), and reproducibility enable a matching combination with robust BiVO₄ photoanodes, resulting in 0.25 cm² PEC tandems with an excellent stability of up to 20 h and a bias‐free solar‐to‐hydrogen efficiency of 0.35 ± 0.14%. The high reliability of the fabrication procedures allows scaling of the devices up to 10 cm², with a slight decrease in bias‐free photocurrent density from 0.39 ± 0.15 to 0.23 ± 0.10 mA cm^?2 due to an increasing series resistance. To characterize these devices, a versatile 3D‐printed PEC cell is also developed.