monovalent-cation-doping-ch3nh3pbi3-for-efficient-perovskite-solar

Monovalent Cation Doping of CH3NH3PbI3 for Efficient Perovskite Solar Cells

Here, we demonstrate the incorporation of monovalent cation additives into CH3NH3PbI3 perovskite in order to adjust the optical, excitonic, and electrical ...

École Polytechnique Fédérale de Lausanne

We report the use of Y(3+)-substituted TiO2 (0.5%Y-TiO₂) in solid-state mesoscopic solar cells, consisting of CH₃NH₃PbI₃ as the light harvester and spiro-OMeTAD as the hole transport material. A power conversion efficiency of 11.2% under simulated AM 1.5 full sun illumination was measured. A 15% improvement in the short-circuit current density was obtained compared with pure TiO₂, due to the effect of Y(3+) on the dimensions of perovskite nanoparticles formed on the semiconductor surface, showing that the surface modification of the semiconductor is an effective way to improve the light harvesters' morphology and electron transfer properties in the solid-state mesoscopic solar cells.

Yttrium-substituted nanocrystalline TiO₂ photoanodes for perovskite based heterojunction solar cells.

We present a photoanode for dye-sensitized solar cell (DSC) based on ZnO nanoshell deposited by atomic layer deposition at 150 °C on a mesoporous insulating template. An ultrathin layer of ZnO between 3 and 6 nm, which exhibits quantum confinement effect, is found to be sufficient to transport the photogenerated electrons to the external contacts and exhibits near-unity collection efficiency. A 6 nm ZnO nanoshell on a 2.5 μm mesoporous nanoparticle Al2O3 template yields photovoltaic power conversion efficiency (PCE) of 4.2% in liquid DSC. Perovskite absorber (CH3NH3PbI3) based solid state solar cells made with similar ZnO nanostructures lead to a high PCE of 7%.

Quantum-confined ZnO nanoshell photoanodes for mesoscopic solar cells.

A low band gap quinolizino acridine based molecule was designed and synthesized as new hole transporting material for organic-inorganic hybrid lead halide perovskite solar cells. The functionalized quinolizino acridine compound showed an effective hole mobility in the same range of the state-of-the-art spiro-MeOTAD and an appropriate oxidation potential of 5.23 eV vs the vacuum level. The device based on this new hole transporting material achieved high power conversion efficiency of 12.8% under the illumination of 98.8 mW cm(-2), which was better than the well-known spiro-MeOTAD under the same conditions. Moreover, this molecule could work alone without any additives, thus making it to be a promising candidate for solid-state photovoltaic application.

Perovskite solar cells with 12.8% efficiency by using conjugated quinolizino acridine based hole transporting material.

As the photovoltaic performance of a device is strongly influenced by the morphology of perovskite, achieving precise control over the crystal formation of organic-inorganic halide perovskites synthesized in the ambience of chloride ions has garnered much attention. Although the resulting morphology dictates the performance of the device considerably, the understanding of the role of chloride ions has been scant. To unravel this mystery, we investigated three different organic-inorganic halide perovskite materials grown from the chloride-containing precursors under different but optimized conditions. Despite the presence of chloride ions in the reaction mixture, scanning transmission electron microscopy- energy dispersive spectroscopy (STEM-EDS) reveals that the CH3NH3PbI3 perovskites formed are chloride-free. Moreover bright field transmission electron microscopy indicates that chloride ions effect the growth of the CH3NH3PbI3.

Investigation regarding the role of chloride in organic-inorganic halide perovskites obtained from chloride containing precursors.

A tailored optimization of perovskite solar cells requires a detailed understanding of the processes limiting the device efficiency. Here, we study the role of the hole transport layer (HTL) spiro-MeOTAD and its thickness in a mesoscopic TiO2-based solar cell architecture. We find that a sufficiently thick (200 nm) HTL not only increases the charge carrier collection efficiency but also the light harvesting efficiency. This is due to an enhanced reflection of a smooth HTL/Au-electrode interface. The rough CH3NH3PbI3 perovskite surface requires an HTL thickness of >400 nm to avoid surface recombination and guarantee a high open-circuit voltage. Analyses of the electroluminescence efficiency and the diode ideality factor show that the open-circuit voltage becomes completely limited by trap-assisted recombination in the perovskite for a thick HTL. Thus, spiro-MeOTAD is a very good HTL choice from the device physics' point of view. The fill factor analyzed by the Suns-Voc method is not transport limited, but trap-recombination limited as well. Consequently, a further optimization of the device has to focus on defects in the polycrystalline perovskite film.

Light Harvesting and Charge Recombination in CH3NH3PbI3 Perovskite Solar Cells Studied by Hole Transport Layer Thickness Variation.

We investigate two different types of TiO2 blocking layer (BL) deposition techniques commonly used in solid-state methylammonium lead triiodide perovskite (MaPbI3)-based solar cells. Although these BLs lead to similar photovoltaic device performance, their structure and blocking capability is actually very different. In one case, the "blocking" layer is porous, allowing an intimate contact of the perovskite with the fluorine-doped tin-dioxide (FTO)-covered glass substrate serving as transparent electron collector. This interface between the perovskite and the FTO shows rectifying behavior. Reverse biasing of such a solar cell allows the determination of the valence-band position of the MaPbI3 and the theoretical maximum attainable photovoltage. We show that under reverse bias strong photocurrent amplification is observed, permitting the cell to work as a high-gain photodetector at low voltage. Without BL, the solar-cell performance decreased, but the photocurrent amplification increased. At 1 V reverse bias, the photocurrent amplification is above a factor of 10 for AM 1.5 solar light and over 100 for lower light intensities.

Strong Photocurrent Amplification in Perovskite Solar Cells with a Porous TiO2 Blocking Layer under Reverse Bias.

In the past few years, organic-inorganic halide perovskites have rapidly emerged as promising materials for photovoltaic applications, but simultaneously achieving high performance and long-term stability has proved challenging. Here, we show a one-step solution-processing strategy using phosphonic acid ammonium additives that results in efficient perovskite solar cells with enhanced stability. We modify the surface of methylammonium lead triiodide (CH3NH3PbI3) perovskite by spin-coating its precursor solution in the presence of butylphosphonic acid 4-ammonium chloride. Morphological, structural and elemental analyses show that the phosphonic acid ammonium additive acts as a crosslink between neighbouring grains in the perovskite structure, through strong hydrogen bonding of the -PO(OH)2 and -NH3(+) terminal groups to the perovskite surface. The additives facilitate the incorporation of the perovskite within a mesoporous TiO2 scaffold, as well as the growth of a uniform perovskite layer at the surface, enhancing the material's photovoltaic performance from 8.8 to 16.7% as well as its resistance to moisture.

Improved performance and stability of perovskite solar cells by crystal crosslinking with alkylphosphonic acid ω-ammonium chlorides.

Highly ordered 1D TiO2 nanotube arrays are fabricated and applied as nanocontainers and electron transporting material in CH3 NH3 PbI3 perovskite solar cells. The optimized device shows a power conversion efficiency of 14.8%, and improved stability under an illumination of 100 mW cm(-2). This is the best result based on 1D TiO2 nanostructures so far.

Stable and Efficient Perovskite Solar Cells Based on Titania Nanotube Arrays.

Four center symmetrical star-shaped hole transporting materials (HTMs) comprising planar triazatruxene core and electron-rich methoxy-engineered side arms have been synthesized and successfully employed in (FAPbI3)0.85(MAPbBr3)0.15 perovskite solar cells. These HTMs are obtained from relatively cheap starting materials by adopting facile preparation procedure, without using expensive and complicated purification techniques. Developed compounds have suitable highest occupied molecular orbitals (HOMO) with respect to the valence band level of the perovskite, and time-resolved photoluminescence indicates that hole injection from the valence band of perovskite into the HOMO of triazatruxene-based HTMs is relatively more efficient as compared to that of well-studied spiro-OMeTAD. Remarkable power conversion efficiency over 18% was achieved using 5,10,15-trihexyl-3,8,13-tris(4-methoxyphenyl)-10,15-dihydro-5H-diindolo[3,2-a:3',2'-c]carbazole (KR131) with compositive perovskite absorber. This result demonstrates triazatruxene-based compounds as a new class of HTM for the fabrication of highly efficient perovskite solar cells.

Triazatruxene-Based Hole Transporting Materials for Highly Efficient Perovskite Solar Cells.

We report on a new metal halide perovskite photovoltaic cell that exhibits both very high solar-to-electric power-conversion efficiency and intense electroluminescence. We produce the perovskite films in a single step from a solution containing a mixture of FAI, PbI2, MABr, and PbBr2 (where FA stands for formamidinium cations and MA stands for methylammonium cations). Using mesoporous TiO2 and Spiro-OMeTAD as electron- and hole-specific contacts, respectively, we fabricate perovskite solar cells that achieve a maximum power-conversion efficiency of 20.8% for a PbI2/FAI molar ratio of 1.05 in the precursor solution. Rietveld analysis of x-ray diffraction data reveals that the excess PbI2 content incorporated into such a film is about 3 weight percent. Time-resolved photoluminescence decay measurements show that the small excess of PbI2 suppresses nonradiative charge carrier recombination. This in turn augments the external electroluminescence quantum efficiency to values of about 0.5%, a record for perovskite photovoltaics approaching that of the best silicon solar cells. Correspondingly, the open-circuit photovoltage reaches 1.18 V under AM 1.5 sunlight.

Efficient luminescent solar cells based on tailored mixed-cation perovskites.

We report on the optimization of the interfacial properties of titania in mesoscopic CH3NH3PbI3 solar cells. Modification of the mesoporous TiO2 film by TiCl4 treatment substantially reduced the surface traps, as is evident from the sharpness of the absorption edge with a significant reduction in Urbach energy (from 320 to 140 meV) determined from photothermal deflection spectroscopy, and led to an order of magnitude enhancement in the bulk electron mobility and corresponding decrease in the transport activation energy (from 170 to 90 meV) within a device. After optimization of the photoanode-perovskite interface using various sizes of TiO2 nanoparticles, the best photovoltaic efficiency of 16.3% was achieved with the mesoporous TiO2 composed of 36 nm sized nanoparticles. The improvement in device performance can be attributed to the enhanced charge collection efficiency that is driven by improved charge transport in the mesoporous TiO2 layer. Also, the decreased recombination at the TiO2-perovskite interface and better perovskite coverage play important roles.

Impact of a Mesoporous Titania-Perovskite Interface on the Performance of Hybrid Organic-Inorganic Perovskite Solar Cells.

We report on both the intrinsic and the extrinsic stability of a formamidinium lead bromide [CH(NH2)2PbBr3 = FAPbBr3] perovskite solar cell that yields a high photovoltage. The fabrication of FAPbBr3 devices, displaying an outstanding photovoltage of 1.53 V and a power conversion efficiency of over 8%, was realized by modifying the mesoporous TiO2-FAPbBr3 interface using lithium treatment. Reasons for improved photovoltaic performance were revealed by a combination of techniques, including photothermal deflection absorption spectroscopy (PDS), transient-photovoltage and charge-extraction analysis, and time-integrated and time-resolved photoluminescence. With lithium-treated TiO2 films, PDS reveals that the TiO2-FAPbBr3 interface exhibits low energetic disorder, and the emission dynamics showed that electron injection from the conduction band of FAPbBr3 into that of mesoporous TiO2 is faster than for the untreated scaffold. Moreover, compared to the device with pristine TiO2, the charge carrier recombination rate within a device based on lithium-treated TiO2 film is 1 order of magnitude lower. Importantly, the operational stability of perovskites solar cells examined at a maximum power point revealed that the FAPbBr3 material is intrinsically (under nitrogen) as well as extrinsically (in ambient conditions) stable, as the unsealed devices retained over 95% of the initial efficiency under continuous full sun illumination for 150 h in nitrogen and dry air and 80% in 60% relative humidity (T = ∼60 °C). The demonstration of high photovoltage, a record for FAPbBr3, together with robust stability renders our work of practical significance.

Intrinsic and Extrinsic Stability of Formamidinium Lead Bromide Perovskite Solar Cells Yielding High Photovoltage.

Emission characteristics of metal halide perovskites play a key role in the current widespread investigations into their potential uses in optoelectronics and photonics. However, a fundamental understanding of the molecular origin of the unusual blueshift of the bandgap and dual emission in perovskites is still lacking. In this direction, we investigated the extraordinary photoluminescence behavior of three representatives of this important class of photonic materials, that is, CH3NH3PbI3, CH3NH3PbBr3, and CH(NH2)2PbBr3, which emerged from our thorough studies of the effects of temperature on their bandgap and emission decay dynamics using time-integrated and time-resolved photoluminescence spectroscopy. The low-temperature (<100 K) photoluminescence of CH3NH3PbI3 and CH3NH3PbBr3 reveals two distinct emission peaks, whereas that of CH(NH2)2PbBr3 shows a single emission peak. Furthermore, irrespective of perovskite composition, the bandgap exhibits an unusual blueshift by raising the temperature from 15 to 300 K. Density functional theory and classical molecular dynamics simulations allow for assigning the additional photoluminescence peak to the presence of molecularly disordered orthorhombic domains and also rationalize that the unusual blueshift of the bandgap with increasing temperature is due to the stabilization of the valence band maximum. Our findings provide new insights into the salient emission properties of perovskite materials, which define their performance in solar cells and light-emitting devices.

Article	Year
Yttrium-substituted nanocrystalline TiO₂ photoanodes for perovskite based heterojunction solar cells. Nanoscale\| PubMed ID: 24322660	2014
Quantum-confined ZnO nanoshell photoanodes for mesoscopic solar cells. Nano letters\| PubMed ID: 24524200	2014
Perovskite solar cells with 12.8% efficiency by using conjugated quinolizino acridine based hole transporting material. Journal of the American Chemical Society\| PubMed ID: 24866942	2014
Investigation regarding the role of chloride in organic-inorganic halide perovskites obtained from chloride containing precursors. Nano letters\| PubMed ID: 25392941	2014
Light Harvesting and Charge Recombination in CH3NH3PbI3 Perovskite Solar Cells Studied by Hole Transport Layer Thickness Variation. ACS nano\| PubMed ID: 25769194	2015
Strong Photocurrent Amplification in Perovskite Solar Cells with a Porous TiO2 Blocking Layer under Reverse Bias. The journal of physical chemistry letters\| PubMed ID: 26278772	2014
Improved performance and stability of perovskite solar cells by crystal crosslinking with alkylphosphonic acid ω-ammonium chlorides. Nature chemistry\| PubMed ID: 26291941	2015
Stable and Efficient Perovskite Solar Cells Based on Titania Nanotube Arrays. Small (Weinheim an der Bergstrasse, Germany)\| PubMed ID: 26313216	2015
Triazatruxene-Based Hole Transporting Materials for Highly Efficient Perovskite Solar Cells. Journal of the American Chemical Society\| PubMed ID: 26630459	2015
Efficient luminescent solar cells based on tailored mixed-cation perovskites. Science advances\| PubMed ID: 26767196	2016
Impact of a Mesoporous Titania-Perovskite Interface on the Performance of Hybrid Organic-Inorganic Perovskite Solar Cells. The journal of physical chemistry letters\| PubMed ID: 27472458	2016
Intrinsic and Extrinsic Stability of Formamidinium Lead Bromide Perovskite Solar Cells Yielding High Photovoltage. Nano letters\| PubMed ID: 27776210	2016
Origin of unusual bandgap shift and dual emission in organic-inorganic lead halide perovskites. Science advances\| PubMed ID: 27819049	2016

M. Ibrahim Dar

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