Quantitative Analysis and Visualized Evidence for High Charge Separation Efficiency in a Solid‐Liquid Bulk Heterojunction

In the past few decades, some novel low‐cost nanostructured devices have been explored for converting solar energy into electrical or chemical energy, such as organic photovoltaic cells, photoelectrochemical solar cells, and solar water splitting cells. Generally, higher light absorption and/or charge separation efficiency are considered as the main reasons for improved performance in a nanostructured device versus a planar structure. However, quantitative analysis and definite experimental evidence remain elusive. Here, using BiVO₄ as an example, comparable samples with porous and dense structures have been prepared by a simple method. The porous and dense films are assembled into a solid‐electrolyte bulk and planar heterojunction, respectively. Some quantitative results are obtained by decoupling photon absorption, interfacial charge transfer, and charge separation processes. These results suggest that higher charge separation efficiency is mainly responsible for enhanced performance in a solid‐electrolyte bulk heterojunction. Moreover, we also present visualized evidence to show higher charge separation efficiency comes from a shorter photo‐generated hole diffusion distance in a bulk heterojunction. These results can deepen understanding charge transfer in a bulk heterojunction and offer guidance to design a more efficient low‐cost device for solar conversion and storage.     

Improved Optics in Monolithic Perovskite/Silicon Tandem Solar Cells with a Nanocrystalline Silicon Recombination Junction

Perovskite/silicon tandem solar cells are increasingly recognized as promi­sing candidates for next‐generation photovoltaics with performance beyond the single‐junction limit at potentially low production costs. Current designs for monolithic tandems rely on transparent conductive oxides as an intermediate recombination layer, which lead to optical losses and reduced shunt resistance. An improved recombination junction based on nanocrystalline silicon layers to mitigate these losses is demonstrated. When employed in monolithic perovskite/silicon heterojunction tandem cells with a planar front side, this junction is found to increase the bottom cell photocurrent by more than 1 mA cm^?2. In combination with a cesium‐based perovskite top cell, this leads to tandem cell power‐conversion efficiencies of up to 22.7% obtained from J–V measurements and steady‐state efficiencies of up to 22.0% during maximum power point tracking. Thanks to its low lateral conductivity, the nanocrystalline silicon recombination junction enables upscaling of monolithic perovskite/silicon heterojunction tandem cells, resulting in a 12.96 cm² monolithic tandem cell with a steady‐state efficiency of 18%.     

Physically Stable Polymer‐Membrane Electrolytes for Highly Efficient Solid‐State Dye‐Sensitized Solar Cells with Long‐Term Stability

A 3D polymer‐network‐membrane (3D‐PNM) electrolyte is described for highly stable, solid‐state dye‐sensitized solar cells (DSCs) with excellent power‐conversion efficiency (PCE). The 3D‐PNM electrolyte is prepared by using one‐pot in situ cross‐linking polymerization on the surface of dye‐sensitized TiO₂ particles in the presence of redox species. This method allows the direct connection of the 3D‐PNM to the surface of the TiO₂ particles as well as the in situ preparation of the electrolyte gel during device assembly. There are two junction areas (liquid and solid‐state junctions) in the DSCs that employ conventional polymer electrolytes, and the major interface is at the liquid‐state junction. The solid‐state junction is dominant in the DSCs that employ the 3D‐PNM electrolyte, which exhibit almost constant performance during aging at 65 °C for over 700 h (17.0 to 17.2 mA cm^–2). The best cell performance gives a PCE of 9.1%; this is slightly better than the performance of a DSC that employs a liquid electrolyte.     

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.     

A Stand‐Alone Si‐Based Porous Photoelectrochemical Cell

Wireless photoelectrochemical (PEC) devices promise easy device fabrication as well as reduced losses. Here, the design and fabrication of a stand‐alone ion exchange material‐embedded, Si membrane‐based, photoelectrochemical cell architecture with micron‐sized pores is shown, to overcome the i) pH gradient formation due to long‐distance ion transport, ii) product crossover, and iii) parasitic light absorption by application of a patterned catalyst. The membrane‐embedded PEC cell with micropores utilizes a triple Si junction cell as the light absorber, and Pt and IrO_x as electrocatalysts for the hydrogen evolution reactions and oxygen evolution reactions, respectively. The solar‐to‐hydrogen efficiency of 7% at steady‐state operation, as compared to an unpatterned η_PV of 10.8%, is mainly attributed to absorption losses by the incorporation of the micropores and catalyst microdots. The introduction of the Nafion ion exchange material ensures an intrinsically safe PEC cell, by reducing the total gas crossover to <0.1%, while without a cation exchange membrane, a crossover of >6% is observed. Only in a pure electrolyte of 1 m H₂SO₄, a pH gradient‐free system is observed thus completely avoiding the build‐up of a counteracting potential.     

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.     

Interfacial Engineering of P3HT/ZnO Hybrid Solar Cells Using Phthalocyanines: A Joint Theoretical and Experimental Investigation

Atomistic simulations and experimental investigations are combined to study heterojunction interfaces of hybrid polymer solar cells, with the aim to better understand and precisely predict their photovoltaic properties. The focus is on a hybrid ternary model system based on a poly(3‐hexylthiophene) (P3HT)/zinc phthalocyanine (ZnPc)/ZnO interface, in which a ZnPc interlayer is applied to improve the performance of the hybrid interface. Theoretical predictions of the ternary system are validated against the properties of a concrete P3HT/ZnPc/ZnO planar heterojunction device. The theoretical predictions closely agree with the photovoltaic properties obtained in P3HT/ZnPc/ZnO solar cells, indicating the strength of the method for modeling hybrid heterojunction interfaces. The theoretical and experimental results reveal that: i) ZnPc molecules in direct contact with a ZnO surface insert new energy levels due to a strong ZnPc/ZnO coupling, ii) electron injection from these new energy levels of ZnPc into ZnO is highly efficient, iii) the ZnPc/ZnO coupling strongly influences the energy levels of the ZnO and P3HT leading to a reduction of the open circuit voltage, and iv) charge carrier recombination at the P3HT/ZnO interface is reduced by the ZnPc interlayer. The intercalation of ZnPc leads to an increase in photocurrent as well as to an overall increase in power conversion.     

Ti3C2Tx (MXene)‐Silicon Heterojunction for Efficient Photovoltaic Cells

A novel type of solar cell has been developed based on charge separation at the heterojunction formed by a transparent conducting MXene electrode and an n‐type silicon (n‐Si) wafer. A thin layer of the native silicon dioxide plays an important role in suppressing the recombination of charge carriers. A two‐step chemical treatment can increase the device efficiency by about 40%. Promisingly, an average power conversion efficiency of over 10% under simulated full sunlight is achieved for this novel class of solar cell with the application of an antireflection layer. The efficiencies of these novel solar cells based on a MXene‐Si heterojunction achieved in this work point to great promise in emerging photovoltaic technology. In addition to their high efficiency, the excellent reproducibility of such devices establishes a solid base for possible future commercialization.     

Decreased Recombination Through the Use of a Non‐Fullerene Acceptor in a 6.4% Efficient Organic Planar Heterojunction Solar Cell

An optimization of several aspects of planar heterojunction solar cells based on boron subnaphthalocyanine chloride (SubNc) as a donor material is presented. The use of hexachlorinated boron subphthalocyanine chloride (Cl₆SubPc) as an alternative acceptor to C₆₀ allows for the simultaneous increase of the short‐circuit current, fill factor, and open‐circuit voltage compared to cells with fullerene acceptors. This is due to the complementary absorption of Cl₆SubPc versus SubNc, reduced recombination at the heterointerface, and improved energetic alignment. Furthermore, insertion of a thin diindeno[1,2,3‐cd:1′,2′,3′‐lm]perylene (DIP) layer at the anode results in a very significant 60% increase in photocurrent owing to reduced exciton quenching at the anode. The simultaneous improvement of all three solar cell para­meters results in a power conversion efficiency of 6.4% for a non‐fullerene planar heterojunction cell.     

Highly Efficient Solar‐Driven Carbon Dioxide Reduction on Molybdenum Disulfide Catalyst Using Choline Chloride‐Based Electrolyte

Conversion of CO₂ to energy‐rich chemicals using renewable energy is of much interest to close the anthropogenic carbon cycle. However, the current photoelectrochemical systems are still far from being practically feasible. Here the successful demonstration of a continuous, energy efficient, and scalable solar‐driven CO₂ reduction process based on earth‐abundant molybdenum disulfide (MoS₂) catalyst, which works in synergy with an inexpensive hybrid electrolyte of choline chloride (a common food additive for livestock) and potassium hydroxide (KOH) is reported. The CO₂ saturated hybrid electrolyte utilized in this study also acts as a buffer solution (pH ≈ 7.6) to adjust pH during the reactions. This study reveals that this system can efficiently convert CO₂ to CO with solar‐to‐fuel and catalytic conversion efficiencies of 23% and 83%, respectively. Using density functional theory calculations, a new reaction mechanism in which the water molecules near the MoS₂ cathode act as proton donors to facilitate the CO₂ reduction process by MoS₂ catalyst is proposed. This demonstration of a continuous, cost‐effective, and energy efficient solar driven CO₂ conversion process is a key step toward the industrialization of this technology.     

Ordered Nanoscale Heterojunction Architecture for Enhanced Solution‐Based CuInGaS2 Thin Film Solar Cell Performance

Nanopatterned CuInGaS₂ (CIGS) thin films synthesized by a sol‐gel‐based solution method and a nanoimprint lithography technique to achieve simultaneous photonic and electrical enhancements in thin film solar cell applications are demonstrated. The interdigitated CIGS nanopatterns in adjacent CdS layer form an ordered nanoscale heterojunction of optical contrast to create a light trapping architecture. This architecture concomitantly leads to increased junction area between the p‐CIGS/n‐CdS interface, and thereby influences effective charge transport. The electron beam induced current and capacitance–voltage characterization further supports the large carrier collection area and small depletion region of the nanopatterned CIGS solar cell devices. This strategic geometry affords localization of incident light inside and between the nanopatterns, where created excitons are easily dissociated, and it leads to the enhanced current generation of absorbed light. Ultimately, this approach improves the efficiency of the nanopatterned CIGS solar cell by 55% compared to its planar counterpart, and offers the possibility of simultaneous management for absorption and charge transport through a nanopatterning process.     

Recent Progress on Hole‐Transporting Materials for Emerging Organometal Halide Perovskite Solar Cells

In less than three years, the photovoltaic community has witnessed a rapid emergence of a new class of solid‐state heterojunction solar cells based on solution‐processable organometal halide perovskite absorbers. The energy conversion efficiency of solid‐state perovskite solar cells (PSCs) has been quickly increased to a certified value of 20.1% by the end of 2014 because of their unique characteristics, such as a broad spectral absorption range, large absorption coefficient, high charge carrier mobility and diffusion length. Here, the focus is specifically on recent developments of hole‐transporting materials (HTMs) in PSCs, which are essential components for achieving high solar cell efficiencies. Some fundamentals with regard to PSCs are first presented, including the history of PSCs, device architectures and general operational principles of PSCs as well as various techniques developed for the fabrications of uniform and dense perovskite complexes. A broad range of the state‐of‐the‐art HTMs being used in PSCs are then discussed in detail. Finally, an outlook on the design of more efficient HTMs for highly efficient PSCs is addressed.     

8.9% Single‐Stack Inverted Polymer Solar Cells with Electron‐Rich Polymer Nanolayer‐Modified Inorganic Electron‐Collecting Buffer Layers

Enhanced power conversion efficiency (PCE) is reported in inverted polymer solar cells when an electron‐rich polymer nanolayer (poly(ethyleneimine) (PEI)) is placed on the surface of an electron‐collecting buffer layer (ZnO). The active layer is made with bulk heterojunction films of poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]] (PTB7) and [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM). The thickness of the PEI nanolayer is controlled to be 2 nm to minimize its insulating effect, which is confirmed by X‐ray photoelectron spectroscopy and optical absorption measurements. The Kelvin probe and ultraviolet photoelectron spectroscopy measurements demonstrate that the enhanced PCE by introducing the PEI nanolayer is attributed to the lowered conduction band energy of the ZnO layer via the formation of an interfacial dipole layer at the interfaces between the ZnO layer and the PEI nanolayer. The PEI nanolayer also improves the surface roughness of the ZnO layer so that the device series resistance can be noticeably decreased. As a result, all solar cell parameters including short circuit current density, open circuit voltage, fill factor, and shunt resistance are improved, leading to the PCE increase up to ≈8.9%, which is close to the best PCE reported using conjugated polymer electrolyte films.     

Organic Solar Cells: Polythiophene: Perylene Diimide Solar Cells – the Impact of Alkyl‐Substitution on the Photovoltaic Performance (Adv. Energy Mater. 2/2011)

The photovoltaic parameters, i.e., the short‐circuit current, open‐circuit voltage and device fill factor, of bulk heterojunction solar cells that use perylene diimide (PDI) derivatives as electron acceptors are often far below the theoretically expected values for reasons still not entirely understood. This article demonstrates that the photovoltaic characteristics of blend films of regioregular poly(3‐hexylthiophene) (rr‐P3HT) and PDI molecules are improved upon using a core‐alkylated PDI derivative instead of the often used N‐alkylated PDI molecules. A doubling of the power conversion efficiency of P3HT:PDI solar cells by using the core‐alkylated PDI derivative is observed leading to an unprecedented power conversion efficiency of 0.5% for a P3HT:PDI solar cell under AM1.5 solar illumination. Furthermore, the optical properties of the novel PDI derivative are compared to two standard exclusively N‐alkylated PDI derivatives by steady‐state and time‐resolved photoluminescence spectroscopy in solution and solid state. The experiments reveal that aggregation in the solid state determines the photophysics of all PDI derivatives. However, the emission energy and excited state lifetime of the aggregates are clearly influenced by the alkyl‐substitution pattern through its effect on the packing of the PDI molecules. X‐ray diffraction experiments before and after thermal annealing of PDI:polystyrene and PDI:P3HT blends reveal subtle differences in the packing characteristics of the different PDI derivatives and, problematically, that P3HT ordering is suppressed by all of the PDI derivatives.     

Polythiophene:Perylene Diimide Solar Cells – the Impact of Alkyl‐Substitution on the Photovoltaic Performance

The photovoltaic parameters, i.e., the short‐circuit current, open‐circuit voltage and device fill factor, of bulk heterojunction solar cells that use perylene diimide (PDI) derivatives as electron acceptors are often far below the theoretically expected values for reasons still not entirely understood. This article demonstrates that the photovoltaic characteristics of blend films of regioregular poly(3‐hexylthiophene) (rr‐P3HT) and PDI molecules are improved upon using a core‐alkylated PDI derivative instead of the often used N‐alkylated PDI molecules. A doubling of the power conversion efficiency of P3HT:PDI solar cells by using the core‐alkylated PDI derivative is observed leading to an unprecedented power conversion efficiency of 0.5% for a P3HT:PDI solar cell under AM1.5 solar illumination. Furthermore, the optical properties of the novel PDI derivative are compared to two standard exclusively N‐alkylated PDI derivatives by steady‐state and time‐resolved photoluminescence spectroscopy in solution and solid state. The experiments reveal that aggregation in the solid state determines the photophysics of all PDI derivatives. However, the emission energy and excited state lifetime of the aggregates are clearly influenced by the alkyl‐substitution pattern through its effect on the packing of the PDI molecules. X‐ray diffraction experiments before and after thermal annealing of PDI:polystyrene and PDI:P3HT blends reveal subtle differences in the packing characteristics of the different PDI derivatives and, problematically, that P3HT ordering is suppressed by all of the PDI derivatives.     

Photoelectrochemical Behavior of Planar and Microwire‐Array Si|GaP Electrodes

Gallium phosphide exhibits a short diffusion length relative to its optical absorption length, and is thus a candidate for use in wire array geometries that allow light absorption to be decoupled from minority carrier collection. Herein is reported the photoanodic performance of heteroepitaxially grown gallium phosphide on planar and microwire‐array Si substrates. The n‐GaP|n‐Si heterojunction results in a favorable conduction band alignment for electron collection in the silicon. A conformal electrochemical contact to the outer GaP layer is produced using the ferrocenium/ferrocene (Fc⁺/Fc) redox couple in acetonitrile. Photovoltages of ～750 mV under 1 sun illumination are observed and are attributed to the barrier formed at the (Fc⁺/Fc)|n‐GaP junction. The short‐circuit current densities of the composite microwire‐arrays are similar to those observed using single‐crystal n‐GaP photoelectrodes. Spectral response measurements along with a finite‐difference‐time‐domain optical model indicate that the minority carrier diffusion length in the GaP is ～80 nm. Solid‐state current–voltage measurements show that shunting occurs through thin GaP layers that are present near the base of the microwire‐arrays. The results provide guidance for further studies of 3D multi‐junction photoelectrochemical cells.     

Solar Rechargeable Batteries Based on Lead–Organohalide Electrolyte

A dye‐sensitized solar cell (DSC) with in situ energy storage capacity is demonstrated using a lead–organohalide electrolyte CH₃NH₃I·PbCl₂ (LOC) to replace the conventional I^?/I₃^? electrolyte. The coupling of lead and iodine in one electrolyte creates a dual‐function rechargeable solar battery that combines the working processes of photoelectrochemical cells with electrochemical batteries. Optimization of the H⁺ concentration in the electrolyte leads to increased photocharging efficiency and storage. The power conversion efficiency of the LOC–DSC is 8.6% under one sun illumination (AM 1.5, 100 mW cm^?2) as a DSC. When operating as a battery, Faraday efficiency can be achieved as high as 81.5% using a bromide‐based CH₃NH₃Br·PbBr₂ (LOB) electrolyte in a DSC configuration. This new cell design suggests a means of combining photovoltaic energy conversion and electrical energy storage.     

Improved Power Conversion Efficiency of P3HT:PCBM Organic Solar Cells by Strong Spin–Orbit Coupling‐Induced Delayed Fluorescence

Solution‐processed organic bulk heterojunction solar cells based on poly(3‐hexylthiophene) (P3HT) blended with [6,6]‐phenyl‐C₆₀‐butyric acid methyl ester are doped with different concentrations of iron (II,III) oxide nanoparticles (Fe₃O₄). The power conversion efficiency of the devices doped at low concentrations is improved up to 11%. The improvement finds its origin in a lower recombination current, which is a consequence of an increased effective exciton lifetime according to the J–V characteristics and the optoelectronical analysis of the films. The increase in performance cannot be attributed to changes in morphology or crystallinity according to grazing‐incidence X‐ray scattering experiments. The evolution of the solar cell short‐circuit current at low doping concentrations is related to variations in the arrangement of the crystalline regions of P3HT. For high doping concentrations (above 1.0 wt%) the performance of the solar cell decays rapidly, ascribed to the increased leakage currents in the device caused by the presence of nanoparticles.     

Safety‐Reinforced Poly(Propylene Carbonate)‐Based All‐Solid‐State Polymer Electrolyte for Ambient‐Temperature Solid Polymer Lithium Batteries

An integrated preparation of safety‐reinforced poly(propylene carbonate)‐based all‐solid polymer electrolyte is shown to be applicable to ambient‐temperature solid polymer lithium batteries. In contrast to pristine poly(ethylene oxide) solid polymer electrolyte, this solid polymer electrolyte exhibits higher ionic conductivity, wider electrochemical window, better mechanical strength, and superior rate performance at 20 °C. Moreover, lithium iron phosphate/lithium cell using such solid polymer electrolyte can charge and discharge even at 120 °C. It is also noted that the solid‐state soft‐package lithium cells assembled with this solid polymer electrolyte can still power a red light‐emitting diode lamp without suffering from internal short‐circuit failures even after cutting off one part of the battery. Considering the aspects mentioned above, the solid polymer electrolyte is eligible for practical lithium battery applications with improved reliability and safety. Just as important, a new perspective that the degree of amorphous state of polymer is also as critical as its low glass transition temperature for the exploration of room temperature solid polymer electrolyte is illustrated. In all, this study opens up a kind of new avenue that could be a milestone to the development of high‐voltage and ambient‐temperature all‐solid‐state polymer electrolytes.     

GaSb‐Based Solar Cells for Full Solar Spectrum Energy Harvesting

In this work, a multijunction solar cell is developed on a GaSb substrate that can efficiently convert the long‐wavelength photons typically lost in a multijunction solar cell into electricity. A combination of modeling and experimental device development is used to optimize the performance of a dual junction GaSb/InGaAsSb concentrator solar cell. Using transfer printing, a commercially available GaAs‐based triple junction cell is stacked mechanically with the GaSb‐based materials to create a four‐terminal, five junction cell with a spectral response range covering the region containing >99% of the available direct‐beam power from the Sun reaching the surface of the Earth. The cell is assembled in a mini‐module with a geometric concentration ratio of 744 suns on a two‐axis tracking system and demonstrated a combined module efficiency of 41.2%, measured outdoors in Durham, NC. Taking into account the measured transmission of the optics gives an implied cell efficiency of 44.5%.