Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites
02 Nov 2012-Science (American Association for the Advancement of Science)-Vol. 338, Iss: 6107, pp 643-647
TL;DR: 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 is reported.
Abstract: 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.
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TL;DR: A sequential deposition method for the formation of the perovskite pigment within the porous metal oxide film that greatly increases the reproducibility of their performance and allows the fabrication of solid-state mesoscopic solar cells with unprecedented power conversion efficiencies and high stability.
Abstract: 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.
8,427 citations
TL;DR: In this article, transient absorption and photoluminescence-quenching measurements were performed to determine the electron-hole diffusion lengths, diffusion constants, and lifetimes in mixed halide and triiodide perovskite absorbers.
Abstract: Organic-inorganic perovskites have shown promise as high-performance absorbers in solar cells, first as a coating on a mesoporous metal oxide scaffold and more recently as a solid layer in planar heterojunction architectures. Here, we report transient absorption and photoluminescence-quenching measurements to determine the electron-hole diffusion lengths, diffusion constants, and lifetimes in mixed halide (CH3NH3PbI(3-x)Cl(x)) and triiodide (CH3NH3PbI3) perovskite absorbers. We found that the diffusion lengths are greater than 1 micrometer in the mixed halide perovskite, which is an order of magnitude greater than the absorption depth. In contrast, the triiodide absorber has electron-hole diffusion lengths of ~100 nanometers. These results justify the high efficiency of planar heterojunction perovskite solar cells and identify a critical parameter to optimize for future perovskite absorber development.
8,199 citations
Cites background from "Efficient Hybrid Solar Cells Based ..."
...Lee et al. (12) have shown that efficient solar cells can be fabricated by replacing the TiO2 photoanode with an insulating Al2O3 scaffold, implying good electron-transport properties....
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TL;DR: It is shown that perovskite absorbers can function at the highest efficiencies in simplified device architectures, without the need for complex nanostructures.
Abstract: Many different photovoltaic technologies are being developed for large-scale solar energy conversion. The wafer-based first-generation photovoltaic devices have been followed by thin-film solid semiconductor absorber layers sandwiched between two charge-selective contacts and nanostructured (or mesostructured) solar cells that rely on a distributed heterojunction to generate charge and to transport positive and negative charges in spatially separated phases. Although many materials have been used in nanostructured devices, the goal of attaining high-efficiency thin-film solar cells in such a way has yet to be achieved. Organometal halide perovskites have recently emerged as a promising material for high-efficiency nanostructured devices. Here we show that nanostructuring is not necessary to achieve high efficiencies with this material: a simple planar heterojunction solar cell incorporating vapour-deposited perovskite as the absorbing layer can have solar-to-electrical power conversion efficiencies of over 15 per cent (as measured under simulated full sunlight). This demonstrates that perovskite absorbers can function at the highest efficiencies in simplified device architectures, without the need for complex nanostructures.
7,018 citations
Journal Article•
TL;DR: In this paper, transient absorption and photoluminescence-quenching measurements were performed to determine the electron-hole diffusion lengths, diffusion constants, and lifetimes in mixed halide and triiodide perovskite absorbers.
Abstract: Organic-inorganic perovskites have shown promise as high-performance absorbers in solar cells, first as a coating on a mesoporous metal oxide scaffold and more recently as a solid layer in planar heterojunction architectures. Here, we report transient absorption and photoluminescence-quenching measurements to determine the electron-hole diffusion lengths, diffusion constants, and lifetimes in mixed halide (CH3NH3PbI(3-x)Cl(x)) and triiodide (CH3NH3PbI3) perovskite absorbers. We found that the diffusion lengths are greater than 1 micrometer in the mixed halide perovskite, which is an order of magnitude greater than the absorption depth. In contrast, the triiodide absorber has electron-hole diffusion lengths of ~100 nanometers. These results justify the high efficiency of planar heterojunction perovskite solar cells and identify a critical parameter to optimize for future perovskite absorber development.
6,454 citations
TL;DR: Two studies show, using a variety of time-resolved absorption and emission spectroscopic techniques, that perovskite materials manifest relatively long diffusion paths for charge carriers energized by light absorption, highlighting effective carrier diffusion as a fruitful parameter for further optimization.
Abstract: Low-temperature solution-processed photovoltaics suffer from low efficiencies because of poor exciton or electron-hole diffusion lengths (typically about 10 nanometers). Recent reports of highly efficient CH3NH3PbI3-based solar cells in a broad range of configurations raise a compelling case for understanding the fundamental photophysical mechanisms in these materials. By applying femtosecond transient optical spectroscopy to bilayers that interface this perovskite with either selective-electron or selective-hole extraction materials, we have uncovered concrete evidence of balanced long-range electron-hole diffusion lengths of at least 100 nanometers in solution-processed CH3NH3PbI3. The high photoconversion efficiencies of these systems stem from the comparable optical absorption length and charge-carrier diffusion lengths, transcending the traditional constraints of solution-processed semiconductors.
5,882 citations
Cites background from "Efficient Hybrid Solar Cells Based ..."
...(12) have shown that efficient solar cells can be fabricated by replacing the TiO2 photoanode with an insulating Al2O3 scaffold – implying good electron transport properties....
[...]
...Increasing the optical thickness of these layers through light trapping architectures compensates for this slight mismatch – accounting for the high photoconversion efficiencies reported in these systems (9-14, 40)....
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...Lee et al. (12) have shown that efficient solar cells can be fabricated by replacing the TiO2 photoanode with an insulating Al2O3 scaffold, implying good electron-transport properties....
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References
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TL;DR: In this article, the authors describe a photovoltaic cell, created from low-to medium-purity materials through low-cost processes, which exhibits a commercially realistic energy-conversion efficiency.
Abstract: THE large-scale use of photovoltaic devices for electricity generation is prohibitively expensive at present: generation from existing commercial devices costs about ten times more than conventional methods1. Here we describe a photovoltaic cell, created from low-to medium-purity materials through low-cost processes, which exhibits a commercially realistic energy-conversion efficiency. The device is based on a 10-µm-thick, optically transparent film of titanium dioxide particles a few nanometres in size, coated with a monolayer of a charge-transfer dye to sensitize the film for light harvesting. Because of the high surface area of the semiconductor film and the ideal spectral characteristics of the dye, the device harvests a high proportion of the incident solar energy flux (46%) and shows exceptionally high efficiencies for the conversion of incident photons to electrical current (more than 80%). The overall light-to-electric energy conversion yield is 7.1-7.9% in simulated solar light and 12% in diffuse daylight. The large current densities (greater than 12 mA cm-2) and exceptional stability (sustaining at least five million turnovers without decomposition), as well as the low cost, make practical applications feasible.
26,457 citations
TL;DR: Two organolead halide perovskite nanocrystals were found to efficiently sensitize TiO(2) for visible-light conversion in photoelectrochemical cells, which exhibit strong band-gap absorptions as semiconductors.
Abstract: Two organolead halide perovskite nanocrystals, CH3NH3PbBr3 and CH3NH3PbI3, were found to efficiently sensitize TiO2 for visible-light conversion in photoelectrochemical cells. When self-assembled on mesoporous TiO2 films, the nanocrystalline perovskites exhibit strong band-gap absorptions as semiconductors. The CH3NH3PbI3-based photocell with spectral sensitivity of up to 800 nm yielded a solar energy conversion efficiency of 3.8%. The CH3NH3PbBr3-based cell showed a high photovoltage of 0.96 V with an external quantum conversion efficiency of 65%.
16,634 citations
"Efficient Hybrid Solar Cells Based ..." refers background in this paper
...In contrast to the methylammonium trihalogen plumbates previously reported in solar cells (i.e., CH3NH3PbI3) (21, 22), this iodidechloride mixed-halide perovskite was remarkably stable to processing in air....
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...The extremely narrow diffraction peaks suggest that the films have long range crystalline domains (greater than 200 nm, peak width limited by instrument broadening) and are highly oriented with the a-axis (21, 26)....
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...S1) (25) showed diffraction peaks at 14.20°, 28.58°, and 43.27°, which we assigned as the (110), (220), and (330) planes, respectively, of a tetragonal perovskite structure with lattice parameters a = 8.825 Å, b = 8.835 Å, c = 11.24 Å, similar to the CH3NH3PbI3 previously reported (21)....
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..., CH3NH3PbI3) (21, 22), this iodide-chloride mixed-halide perovskite was remarkably stable to processing in air....
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...24 Å, similar to the CH3NH3PbI3 previously reported (21)....
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TL;DR: In this paper, the carrier collection efficiency and energy conversion efficiency of polymer photovoltaic cells were improved by blending of the semiconducting polymer with C60 or its functionalized derivatives.
Abstract: The carrier collection efficiency (ηc) and energy conversion efficiency (ηe) of polymer photovoltaic cells were improved by blending of the semiconducting polymer with C60 or its functionalized derivatives. Composite films of poly(2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene) (MEH-PPV) and fullerenes exhibit ηc of about 29 percent of electrons per photon and ηe of about 2.9 percent, efficiencies that are better by more than two orders of magnitude than those that have been achieved with devices made with pure MEH-PPV. The efficient charge separation results from photoinduced electron transfer from the MEH-PPV (as donor) to C60 (as acceptor); the high collection efficiency results from a bicontinuous network of internal donor-acceptor heterojunctions.
9,611 citations
TL;DR: In this article, a Co(II/III)tris(bipyridyl)-based redox electrolyte was used in conjunction with a custom synthesized donor-π-bridge-acceptor zinc porphyrin dye as sensitizer (designated YD2-o-C8).
Abstract: The iodide/triiodide redox shuttle has limited the efficiencies accessible in dye-sensitized solar cells. Here, we report mesoscopic solar cells that incorporate a Co(II/III)tris(bipyridyl)–based redox electrolyte in conjunction with a custom synthesized donor-π-bridge-acceptor zinc porphyrin dye as sensitizer (designated YD2-o-C8). The specific molecular design of YD2-o-C8 greatly retards the rate of interfacial back electron transfer from the conduction band of the nanocrystalline titanium dioxide film to the oxidized cobalt mediator, which enables attainment of strikingly high photovoltages approaching 1 volt. Because the YD2-o-C8 porphyrin harvests sunlight across the visible spectrum, large photocurrents are generated. Cosensitization of YD2-o-C8 with another organic dye further enhances the performance of the device, leading to a measured power conversion efficiency of 12.3% under simulated air mass 1.5 global sunlight.
5,462 citations
Journal Article•
TL;DR: Mesoscopic solar cells that incorporate a Co(II/III)tris(bipyridyl)–based redox electrolyte in conjunction with a custom synthesized donor-π-bridge-acceptor zinc porphyrin dye as sensitizer are reported, enabling attainment of strikingly high photovoltages approaching 1 volt.
Abstract: Simultaneous modification of the dye and redox shuttle boosts the efficiency of a dye-sensitized solar cell. The iodide/triiodide redox shuttle has limited the efficiencies accessible in dye-sensitized solar cells. Here, we report mesoscopic solar cells that incorporate a Co(II/III)tris(bipyridyl)–based redox electrolyte in conjunction with a custom synthesized donor-π-bridge-acceptor zinc porphyrin dye as sensitizer (designated YD2-o-C8). The specific molecular design of YD2-o-C8 greatly retards the rate of interfacial back electron transfer from the conduction band of the nanocrystalline titanium dioxide film to the oxidized cobalt mediator, which enables attainment of strikingly high photovoltages approaching 1 volt. Because the YD2-o-C8 porphyrin harvests sunlight across the visible spectrum, large photocurrents are generated. Cosensitization of YD2-o-C8 with another organic dye further enhances the performance of the device, leading to a measured power conversion efficiency of 12.3% under simulated air mass 1.5 global sunlight.
5,385 citations
"Efficient Hybrid Solar Cells Based ..." refers background in this paper
...Efforts have been made to reduce such losses in the DSC by moving from a multielectron iodide/tri-iodide redox couple to one-electron outer-sphere redox couples, such as a cobalt complexes or a solid-state hole-conductor (1, 4, 12, 13)....
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