Understanding the rate-dependent J–V hysteresis, slow time component, and aging in CH3NH3PbI3 perovskite solar cells: the role of a compensated electric field
05 Mar 2015-Energy and Environmental Science (The Royal Society of Chemistry)-Vol. 8, Iss: 3, pp 995-1004
TL;DR: In this paper, the rate-dependent hysteresis seen in current-voltage scans of CH3NH3PbI3 perovskite solar cells is related to a slow field-induced process that tends to cancel the electric field in the device at each applied bias voltage.
Abstract: In this work we show that the rate-dependent hysteresis seen in current–voltage scans of CH3NH3PbI3 perovskite solar cells is related to a slow field-induced process that tends to cancel the electric field in the device at each applied bias voltage. It is attributed to the build-up of space charge close to the contacts, independent of illumination and most likely due to ionic displacement, which is enhanced when the device undergoes aging. This process can also lead to a reduction of the open-circuit voltage or the steady-state photocurrent and does not directly correlate with the development of the hysteresis if it is measured at a fixed voltage sweep rate.
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TL;DR: Thin films of near-single-crystalline quality are produced, in which the crystallographic planes of the inorganic perovskite component have a strongly preferential out-of-plane alignment with respect to the contacts in planar solar cells to facilitate efficient charge transport.
Abstract: Three-dimensional organic-inorganic perovskites have emerged as one of the most promising thin-film solar cell materials owing to their remarkable photophysical properties, which have led to power conversion efficiencies exceeding 20 per cent, with the prospect of further improvements towards the Shockley-Queisser limit for a single‐junction solar cell (33.5 per cent). Besides efficiency, another critical factor for photovoltaics and other optoelectronic applications is environmental stability and photostability under operating conditions. In contrast to their three-dimensional counterparts, Ruddlesden-Popper phases--layered two-dimensional perovskite films--have shown promising stability, but poor efficiency at only 4.73 per cent. This relatively poor efficiency is attributed to the inhibition of out-of-plane charge transport by the organic cations, which act like insulating spacing layers between the conducting inorganic slabs. Here we overcome this issue in layered perovskites by producing thin films of near-single-crystalline quality, in which the crystallographic planes of the inorganic perovskite component have a strongly preferential out-of-plane alignment with respect to the contacts in planar solar cells to facilitate efficient charge transport. We report a photovoltaic efficiency of 12.52 per cent with no hysteresis, and the devices exhibit greatly improved stability in comparison to their three-dimensional counterparts when subjected to light, humidity and heat stress tests. Unencapsulated two-dimensional perovskite devices retain over 60 per cent of their efficiency for over 2,250 hours under constant, standard (AM1.5G) illumination, and exhibit greater tolerance to 65 per cent relative humidity than do three-dimensional equivalents. When the devices are encapsulated, the layered devices do not show any degradation under constant AM1.5G illumination or humidity. We anticipate that these results will lead to the growth of single-crystalline, solution-processed, layered, hybrid, perovskite thin films, which are essential for high-performance opto-electronic devices with technologically relevant long-term stability.
2,566 citations
TL;DR: The broad tunability and fabrication methods of these materials, the current understanding of the operation of state-of-the-art solar cells and the properties that have delivered light-emitting diodes and lasers are described.
Abstract: Metal-halide perovskites are crystalline materials originally developed out of scientific curiosity. Unexpectedly, solar cells incorporating these perovskites are rapidly emerging as serious contenders to rival the leading photovoltaic technologies. Power conversion efficiencies have jumped from 3% to over 20% in just four years of academic research. Here, we review the rapid progress in perovskite solar cells, as well as their promising use in light-emitting devices. In particular, we describe the broad tunability and fabrication methods of these materials, the current understanding of the operation of state-of-the-art solar cells and we highlight the properties that have delivered light-emitting diodes and lasers. We discuss key thermal and operational stability challenges facing perovskites, and give an outlook of future research avenues that might bring perovskite technology to commercialization.
2,513 citations
TL;DR: The results of this combined computational and experimental study suggest that hybrid halide perovskites are mixed ionic–electronic conductors, a finding that has major implications for solar cell device architectures.
Abstract: Understanding the mechanism of ionic transport in organic–inorganic halide perovskites is crucial for the design of future solar cells. Here, Eames et al. undertake a combined experimental and computational study to elucidate the ion conducting species and help rationalize the unusual behaviour observed in these perovskite-based devices.
2,050 citations
TL;DR: It is demonstrated that, via controlled anion exchange reactions using a range of different halide precursors, this approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs.
Abstract: We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl– or I– ions and reinsertion of Br– ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles.
1,658 citations
TL;DR: Jiang et al. as mentioned in this paper proposed a low-temperature solution-processed SnO2 nanoparticles as an efficient electron transport layer for perovskite solar cells.
Abstract: Planar structures for halide perovskite solar cells have recently garnered attention, due to their simple and low-temperature device fabrication processing. Unfortunately, planar structures typically show I–V hysteresis and lower stable device efficiency compared with mesoporous structures, especially for TiO2-based n-i-p devices. SnO2, which has a deeper conduction band and higher electron mobility compared with traditional TiO2, could enhance charge transfer from perovskite to electron transport layers, and reduce charge accumulation at the interface. Here we report low-temperature solution-processed SnO2 nanoparticles as an efficient electron transport layer for perovskite solar cells. Our SnO2-based devices are almost free of hysteresis, which we propose is due to the enhancement of electron extraction. By introducing a PbI2 passivation phase in the perovskite layer, we obtain a 19.9 ± 0.6% certified efficiency. The devices can be easily processed under low temperature (150 ∘C), offering an efficient method for the large-scale production of perovskite solar cells. Planar structured perovskite solar cells often show hysteresis and lower efficiency than mesoporous ones. Jiang et al. show that using a SnO2 electron transport layer improves the performance of planar devices, reporting a certified efficiency of 19.9%, and enables a lower processing temperature.
1,500 citations
References
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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
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.
9,158 citations
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
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