Following pioneering work, solution-processable organic-inorganic hybrid perovskites-such as CH3NH3PbX3 (X = Cl, Br, I)-have attracted attention as light-harvesting materials for mesoscopic solar cells. So far, the perovskite pigment has been deposited in a single step onto mesoporous metal oxide films using a mixture of PbX2 and CH3NH3X in a common solvent. However, the uncontrolled precipitation of the perovskite produces large morphological variations, resulting in a wide spread of photovoltaic performance in the resulting devices, which hampers the prospects for practical applications. Here we describe a sequential deposition method for the formation of the perovskite pigment within the porous metal oxide film. PbI2 is first introduced from solution into a nanoporous titanium dioxide film and subsequently transformed into the perovskite by exposing it to a solution of CH3NH3I. We find that the conversion occurs within the nanoporous host as soon as the two components come into contact, permitting much better control over the perovskite morphology than is possible with the previously employed route. Using this technique for the fabrication of solid-state mesoscopic solar cells greatly increases the reproducibility of their performance and allows us to achieve a power conversion efficiency of approximately 15 per cent (measured under standard AM1.5G test conditions on solar zenith angle, solar light intensity and cell temperature). This two-step method should provide new opportunities for the fabrication of solution-processed photovoltaic cells with unprecedented power conversion efficiencies and high stability equal to or even greater than those of today’s best thin-film photovoltaic devices.
Dye-sensitized solar cells based on titanium dioxide (TiO(2)) are promising low-cost alternatives to conventional solid-state photovoltaic devices based on materials such as Si, CdTe and CuIn(1-x)Ga(x)Se(2) (refs 1, 2). Despite offering relatively high conversion efficiencies for solar energy, typical dye-sensitized solar cells suffer from durability problems that result from their use of organic liquid electrolytes containing the iodide/tri-iodide redox couple, which causes serious problems such as electrode corrosion and electrolyte leakage. Replacements for iodine-based liquid electrolytes have been extensively studied, but the efficiencies of the resulting devices remain low. Here we show that the solution-processable p-type direct bandgap semiconductor CsSnI(3) can be used for hole conduction in lieu of a liquid electrolyte. The resulting solid-state dye-sensitized solar cells consist of CsSnI(2.95)F(0.05) doped with SnF(2), nanoporous TiO(2) and the dye N719, and show conversion efficiencies of up to 10.2 per cent (8.51 per cent with a mask). With a bandgap of 1.3 electronvolts, CsSnI(3) enhances visible light absorption on the red side of the spectrum to outperform the typical dye-sensitized solar cells in this spectral region.
Silicon nanowire and nanopore arrays promise to reduce manufacturing costs and increase the power conversion efficiency of photovoltaic devices. So far, however, photovoltaic cells based on nanostructured silicon exhibit lower power conversion efficiencies than conventional cells due to the enhanced photocarrier recombination associated with the nanostructures. Here, we identify and separately measure surface recombination and Auger recombination in wafer-based nanostructured silicon solar cells. By identifying the regimes of junction doping concentration in which each mechanism dominates, we were able to design and fabricate an independently confirmed 18.2%-efficient nanostructured ‘black-silicon’ cell that does not need the antireflection coating layer(s) normally required to reach a comparable performance level. Our results suggest design rules for efficient high-surface-area solar cells with nano- and microstructured semiconductor absorbers.
Colloidal quantum dot (CQD) films allow large-area solution processing and bandgap tuning through the quantum size effect. However, the high ratio of surface area to volume makes CQD films prone to high trap state densities if surfaces are imperfectly passivated, promoting recombination of charge carriers that is detrimental to device performance. Recent advances have replaced the long insulating ligands that enable colloidal stability following synthesis with shorter organic linkers or halide anions, leading to improved passivation and higher packing densities. Although this substitution has been performed using solid-state ligand exchange, a solution-based approach is preferable because it enables increased control over the balance of charges on the surface of the quantum dot, which is essential for eliminating midgap trap states. Furthermore, the solution-based approach leverages recent progress in metal:chalcogen chemistry in the liquid phase. Here, we quantify the density of midgap trap states in CQD solids and show that the performance of CQD-based photovoltaics is now limited by electron-hole recombination due to these states. Next, using density functional theory and optoelectronic device modelling, we show that to improve this performance it is essential to bind a suitable ligand to each potential trap site on the surface of the quantum dot. We then develop a robust hybrid passivation scheme that involves introducing halide anions during the end stages of the synthesis process, which can passivate trap sites that are inaccessible to much larger organic ligands. An organic crosslinking strategy is then used to form the film. Finally, we use our hybrid passivated CQD solid to fabricate a solar cell with a certified efficiency of 7.0%, which is a record for a CQD photovoltaic device.
Interfaces between organic electron-donating (D) and electron-accepting (A) materials have the ability to generate charge carriers on illumination. Efficient organic solar cells require a high yield for this process, combined with a minimum of energy losses. Here, we investigate the role of the lowest energy emissive interfacial charge-transfer state (CT1) in the charge generation process. We measure the quantum yield and the electric field dependence of charge generation on excitation of the charge-transfer (CT) state manifold via weakly allowed, low-energy optical transitions. For a wide range of photovoltaic devices based on polymer:fullerene, small-molecule:C60 and polymer:polymer blends, our study reveals that the internal quantum efficiency (IQE) is essentially independent of whether or not D, A or CT states with an energy higher than that of CT1 are excited. The best materials systems show an IQE higher than 90% without the need for excess electronic or vibrational energy.
Growth in biofuel production, which is meant to reduce greenhouse gas (GHG) emissions and fossil en-ergy demand, is increasingly seen as a threat to food supply and natural habitats. Using photovoltaics (PV) to directly convert solar radiation into electricity for battery electric vehicles (BEVs) is an alterna-tive to photosynthesis, which suffers from a very low energy conversion efficiency. Assessments need to be spatially explicit, since solar insolation and crop yields vary widely between locations. This paper therefore compares direct land use, life cycle GHG emissions and fossil fuel requirements of five differ-ent sun-to-wheels conversion pathways for every county in the contiguous U.S.: Ethanol from corn or switchgrass for internal combustion vehicles (ICVs), electricity from corn or switchgrass for BEVs, and PV electricity for BEVs. Even the most land-use efficient biomass-based pathway (i.e., switchgrass bio-electricity in U.S. counties with hypothetical crop yields of over 24 tonnes/ha) requires 29 times more land than the PV-based alternative in the same locations. PV BEV systems also have the lowest life cy-cle GHG emissions throughout the U.S. and the lowest fossil fuel inputs, except for locations with hypothetical switchgrass yields of 16 or more tonnes/ha. Including indirect land use effects further strengthens the case for PV.
The fovea centralis is a closely-packed vertical array of inverted-cone photoreceptor cells located in the retina that is responsible for high acuity binocular vision. The cones are operational in well-lit environments and are responsible for trapping the impinging illumination. We present the vertical light-funnel silicon array as a light-trapping technique for photovoltaic applications that is bio-inspired by the properties of the fovea centralis. We use opto-electronic simulations to evaluate the performance of light-funnel solar cell arrays. Light-funnel arrays present ~65% absorption enhancement compared to a silicon film of identical thickness and exhibit power conversion efficiencies that are 60% higher than those of optimized nanowire arrays of the same thickness although nanowire arrays consist of more than 2.3 times the amount of silicon. We demonstrate the superior absorption of the light-funnel arrays as compared with recent advancements in the field. Fabrication of silicon light-funnel arrays using low-cost processing techniques is demonstrated.
Growth of semiconducting nanostructures on graphene would open up opportunities for the development of flexible optoelectronic devices, but challenges remain in preserving the structural and electrical properties of graphene during this process. We demonstrate growth of highly uniform and well-aligned ZnO nanowire arrays on graphene by modifying the graphene surface with conductive polymer interlayers. Based on this structure, we then demonstrate graphene cathode-based hybrid solar cells using two different photoactive materials - PbS quantum dots and the conjugated polymer P3HT - with AM 1.5G power conversion efficiencies of 4.2% and 0.5%, respectively, approaching the performance of ITO-based devices with similar architectures. Our method preserves beneficial properties of graphene and demonstrates that it can serve as a viable replacement for ITO in various photovoltaic device configurations.
The energy costs associated with separating tightly bound excitons (photoinduced electron-hole pairs) and extracting free charges from highly disordered low-mobility networks represent fundamental losses for many low-cost photovoltaic technologies. We report a low-cost, solution-processable solar cell, based on a highly crystalline perovskite absorber with intense visible to near-infrared absorptivity, that has a power conversion efficiency of 10.9% in a single-junction device under simulated full sunlight. This “meso-superstructured solar cell” exhibits exceptionally few fundamental energy losses; it can generate open-circuit photovoltages of more than 1.1 volts, despite the relatively narrow absorber band gap of 1.55 electron volts. The functionality arises from the use of mesoporous alumina as an inert scaffold that structures the absorber and forces electrons to reside in and be transported through the perovskite.
We demonstrate four- and two-terminal perovskite-perovskite tandem solar cells with ideally matched band gaps. We develop an infrared-absorbing 1.2-electron volt band-gap perovskite, FA0.75Cs0.25Sn0.5Pb0.5I3, that can deliver 14.8% efficiency. By combining this material with a wider-band gap FA0.83Cs0.17Pb(I0.5Br0.5)3 material, we achieve monolithic two-terminal tandem efficiencies of 17.0% with >1.65-volt open-circuit voltage. We also make mechanically stacked four-terminal tandem cells and obtain 20.3% efficiency. Notably, we find that our infrared-absorbing perovskite cells exhibit excellent thermal and atmospheric stability, not previously achieved for Sn-based perovskites. This device architecture and materials set will enable “all-perovskite” thin-film solar cells to reach the highest efficiencies in the long term at the lowest costs.