Close-Space Sublimation as a Scalable Method for Perovskite Solar Cells.

Vacuum techniques for perovskite photovoltaics (PV) are promising for their scalability but are rarely studied with techniques readily adaptable for industry. In this work, we study the use of close-space sublimation (CSS) for making perovskite solar cells, a technique that has seen widespread use in industry, including in PV, and benefits from high material-transfer and low working pressures. A pressed pellet of formamidinium iodide (FAI) can be used multiple times as an organic source, without needing replacement. Using CSS at a rough vacuum (10 mbar), efficient cesium formamidinium lead iodide perovskite based solar cells are obtained reaching a maximum photoconversion efficiency (PCE) of 18.7%. They maintain their performance for >650 h when thermally stressed at 85 °C in a nitrogen environment. To explain the initial rise in PCE upon heating, we used drift-diffusion simulations and identified a reduction in bulk trap density as the primary factor.

Fast Coevaporation of 1 µm Thick Perovskite Solar Cells.

Coevaporation of perovskite films allows for a fine control over the material stoichiometry and thickness but is typically slow, leading to several-hour processes to obtain thick films required for photovoltaic applications. In this work, we demonstrate the coevaporation of perovskite layers using faster deposition rates, obtaining 1 µm thick films in approximately 50 min. We observed distinct structural properties and obtained devices with efficiency exceeding 19%, demonstrating the relevance of this deposition process from a material perspective and also in view of potential industrialization.

Pure Iodide Multication Wide Bandgap Perovskites by Vacuum Deposition.

The CsPbI3 perovskite has a suitable bandgap (≈1.7 eV) for application in tandem solar cells. One challenge for this compound is that the semiconducting perovskite phase is not stable at room temperature, when it tends to form a yellow nonperovskite phase with a bandgap of approximately 2.8 eV. Therefore, many reports have been focused on the stabilization of the CsPbI3 black perovskite phase through the use of additives during solution processing. Vacuum deposited CsPbI3 has been seldom reported, as in this case, the insertion of stabilizing agents is more challenging. In this work, we demonstrate the vacuum processing of CsPbI3 perovskite films at room temperature, obtained by incorporating dimethylammonium iodide by cosublimation with CsI and PbI2. As-prepared films were applied in planar solar cells, leading to an average power conversion efficiency (PCE) exceeding 12%. In order to improve the device performance, we introduced a third A-site cation (methylammonium) in a four-source deposition process. This pure iodide formulation can be used in wide bandgap solar cells with a PCE up to 14.8%.

Perovskite/Perovskite Tandem Solar Cells in the Substrate Configuration with Potential for Bifacial Operation.

Perovskite/perovskite tandem solar cells have recently exceeded the record power conversion efficiency (PCE) of single-junction perovskite solar cells. They are typically built in the superstrate configuration, in which the device is illuminated from the substrate side. This limits the fabrication of the solar cell to transparent substrates, typically glass coated with a transparent conductive oxide (TCO), and adds constraints because the first subcell that is deposited on the substrate must contain the wide-bandgap perovskite. However, devices in the substrate configuration could potentially be fabricated on a large variety of opaque and inexpensive substrates, such as plastic and metal foils. Importantly, in the substrate configuration the narrow-bandgap subcell is deposited first, which allows for more freedom in the device design. In this work, we report perovskite/perovskite tandem solar cells fabricated in the substrate configuration. As the substrate we use TCO-coated glass on which a solution-processed narrow-bandgap perovskite solar cell is deposited. All of the other layers are then processed using vacuum sublimation, starting with the charge recombination layers, then the wide-bandgap perovskite subcell, and finishing with the transparent top TCO electrode. Proof-of-concept tandem solar cells show a maximum PCE of 20%, which is still moderate compared to those of best-in-class devices realized in the superstrate configuration yet higher than those of the corresponding single-junction devices in the substrate configuration. As both the top and bottom electrodes are semitransparent, these devices also have the potential to be used as bifacial tandem solar cells.

Mechanistic Insights into the Role of the Bis(trifluoromethanesulfonyl)imide Ion in Coevaporated p-i-n Perovskite Solar Cells.

Hybrid lead halide perovskites have reached comparable efficiencies to state-of-the-art silicon solar cell technologies. However, a remaining key challenge toward commercialization is the resolution of the perovskite device instability. In this work, we identify for the first time the mobile nature of bis(trifluoromethanesulfonyl)imide (TFSI-), a typical anion extensively employed in p-type dopants for 2,2'7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'spirofluorene (spiro-OMeTAD). We demonstrate that TFSI- can migrate through the perovskite layer via the grain boundaries and accumulate at the perovskite/electron-transporting layer (ETL) interface. Our findings reveal that the migration of TFSI- enhances the device performance and stability, resulting in highly stable p-i-n cells that retain 90% of their initial performance after 1600 h of continuous testing. Our systematic study, which targeted the effect of the nature of the dopant and its concentration, also shows that TFSI- acts as a dynamic defect-healing agent, which self-passivates the perovskite crystal defects during the migration process and thereby decreases nonradiative recombination pathways.

Molecular Design and Operational Stability: Toward Stable 3D/2D Perovskite Interlayers.

Despite organic/inorganic lead halide perovskite solar cells becoming one of the most promising next-generation photovoltaic materials, instability under heat and light soaking remains unsolved. In this work, a highly hydrophobic cation, perfluorobenzylammonium iodide (5FBzAI), is designed and a 2D perovskite with reinforced intermolecular interactions is engineered, providing improved passivation at the interface that reduces charge recombination and enhances cell stability compared with benchmark 2D systems. Motivated by the strong halogen bond interaction, (5FBzAI)2PbI4 used as a capping layer aligns in in-plane crystal orientation, inducing a reproducible increase of ≈60 mV in the V oc, a twofold improvement compared with its analogous monofluorinated phenylethylammonium iodide (PEAI) recently reported. This endows the system with high power conversion efficiency of 21.65% and extended operational stability after 1100 h of continuous illumination, outlining directions for future work.

An Efficient Approach to Fabricate Air-Stable Perovskite Solar Cells via Addition of a Self-Polymerizing Ionic Liquid.

Despite the excellent photovoltaic properties achieved by perovskite solar cells at the laboratory scale, hybrid perovskites decompose in the presence of air, especially at high temperatures and in humid environments. Consequently, high-efficiency perovskites are usually prepared in dry/inert environments, which are expensive and less convenient for scale-up purposes. Here, a new approach based on the inclusion of an in situ polymerizable ionic liquid, 1,3-bis(4-vinylbenzyl)imidazolium chloride ([bvbim]Cl), is presented, which allows perovskite films to be manufactured under humid environments, additionally leading to a material with improved quality and long-term stability. The approach, which is transferrable to several perovskite formulations, allows efficiencies as high as 17% for MAPbI3 processed in air % relative humidity (RH) ≥30 (from an initial 15%), and 19.92% for FAMAPbI3 fabricated in %RH ≥50 (from an initial 17%), providing one of the best performances to date under similar conditions.

Co-evaporation as an optimal technique towards compact methylammonium bismuth iodide layers.

The most studied perovskite-based solar cells reported up to date contain the toxic lead in its composition. Photovoltaic research and development towards non-toxic, lead-free perovskite solar cells are critical to finding alternatives to reduce human health concerns associated with them. Bismuth-based perovskite variants, especially in the form of methylammonium bismuth iodide (MBI), is a good candidate for the non-toxic light absorber. However, the reported perovskite variant MBI thin films prepared by the solution process so far suffers from poor morphology and surface coverage. In this work, we investigate for the first time the optoelectronic, crystallographic and morphological properties of MBI thin films prepared via thermal co-evaporation of MAI and BiI3. We find by modifying the precursor ratio that the layer with pure MBI composition lead to uniform, compact and homogeneous layers, broadening the options of deposition techniques for lead-free based perovskite solar cells.

Azatruxene-Based, Dumbbell-Shaped, Donor-π-Bridge-Donor Hole-Transporting Materials for Perovskite Solar Cells.

Three novel donor-π-bridge-donor (D-π-D) hole-transporting materials (HTMs) featuring triazatruxene electron-donating units bridged by different 3,4-ethylenedioxythiophene (EDOT) π-conjugated linkers have been synthesized, characterized, and implemented in mesoporous perovskite solar cells (PSCs). The optoelectronic properties of the new dumbbell-shaped derivatives (DTTXs) are highly influenced by the chemical structure of the EDOT-based linker. Red-shifted absorption and emission and a stronger donor ability were observed in passing from DTTX-1 to DTTX-2 due to the extended π-conjugation. DTTX-3 featured an intramolecular charge transfer between the external triazatruxene units and the azomethine-EDOT central scaffold, resulting in a more pronounced redshift. The three new derivatives have been tested in combination with the state-of-the-art triple-cation perovskite [(FAPbI3 )0.87 (MAPbBr3 )0.13 ]0.92 [CsPbI3 ]0.08 in standard mesoporous PSCs. Remarkable power conversion efficiencies of 17.48 % and 18.30 % were measured for DTTX-1 and DTTX-2, respectively, close to that measured for the benchmarking HTM spiro-OMeTAD (18.92 %), under 100 mA cm-2 AM 1.5G solar illumination. PSCs with DTTX-3 reached a PCE value of 12.68 %, which is attributed to the poorer film formation in comparison to DTTX-1 and DTTX-2. These PCE values are in perfect agreement with the conductivity and hole mobility values determined for the new compounds and spiro-OMeTAD. Steady-state photoluminescence further confirmed the potential of DTTX-1 and DTTX-2 for hole-transport applications as an alternative to spiro-OMeTAD.

Benzothiadiazole Aryl-amine Based Materials as Efficient Hole Carriers in Perovskite Solar Cells.

Four hole transport materials (HTMs) based on a benzothiadiazole (BT) central core have been synthesized and successfully employed in triple-cation mixed-halide perovskite solar cells (PSCs), reaching 18.05% solar to energy conversion efficiency. The synthesis of these HTMs follows the push-and-pull approach to modulate the HOMO energy level by combining the BT group as an electron acceptor and diphenyl- and triphenyl-amines as electron donors. Here we show that despite adjusting the HOMO energy level to that of the perovskite is a believed requisite to achieve efficient interfacial hole transfer, additional factors must be taken into account to design novel and efficient HTMs, such as a high hole mobility, solubility in organic solvents, and thermal stability.

Minimization of Carrier Losses for Efficient Perovskite Solar Cells through Structural Modification of Triphenylamine Derivatives.

Three hole transport materials (HTMs) based on a substituted triphenylamine moiety have been synthesized and successfully employed in triple-cation mixed-halide PSCs, reaching efficiencies of 19.4 %. The efficiencies, comparable to those obtained using spiro-OMeTAD, point them out as promising candidates for easily attainable and cost-effective alternatives for PSCs, given their facile synthesis from commercially available materials. Interestingly, although all these HTMs show similar chemical and physical properties, they provide different carrier recombination kinetics. Our results demonstrate that is feasible through the molecular design of the HTM to minimize carrier losses and, thus, increase the solar cell efficiencies.

Doped but Stable: Spirobisacridine Hole Transporting Materials for Hysteresis-Free and Stable Perovskite Solar Cells.

Four spirobisacridine (SBA) hole-transporting materials were synthesized and employed in perovskite solar cells (PSCs). The molecules bear electronically inert alkyl chains of different length and bulkiness, attached to in-plane N atoms of nearly orthogonal spiro-connected acridines. Di-p-methoxyphenylamine (DMPA) substituents tailored to the central SBA-platform define electronic properties of the materials mimicking the structure of the benchmark 2,2',7,7'-tetrakis(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (spiro-MeOTAD), while the alkyl pending groups affect molecular packing in thin films and affect the long-term performance of PSCs. Devices with SBA-based hole transporting layers (HTL) attain efficiencies on par with spiro-MeOTAD. More importantly, solar cells with the new HTMs are hysteresis-free and demonstrate good operational stability, despite being doped as spiro-MeOTAD. The best performing MeSBA-DMPA retained 88% of the initial efficiency after a 1000 h aging test under constant illumination. The results clearly demonstrate that SBA-based compounds are potent candidates for a design of new HTMs for PSCs with improved longevity.

Correction: A comparative study of Ir(iii) complexes with pyrazino[2,3-f][1,10]phenanthroline and pyrazino[2,3-f][4,7]phenanthroline ligands in light-emitting electrochemical cells (LECs).

Correction for 'A comparative study of Ir(iii) complexes with pyrazino[2,3-f][1,10]phenanthroline and pyrazino[2,3-f][4,7]phenanthroline ligands in light-emitting electrochemical cells (LECs)' by Iván González et al., Dalton Trans., 2015, 44, 14771-14781.

Crystal Orientation Drives the Interface Physics at Two/Three-Dimensional Hybrid Perovskites.

Combining halide perovskites with tailored dimensionality into two/three-dimensional (2D/3D) systems has revealed a powerful strategy to boost the performances of perovskite photovoltaics (PVs). Despite recent advances, a clear understanding of the intimate link between interface structure and physics is still missing, leading so far to a blind optimization of the 2D/3D PVs. Here, we reveal the impact of 2D/3D crystal alignment in driving interface charge-recombination dynamics. The 2D crystal growth and orientation are manipulated by specific fluorination of phenethylammonium (PEA), used here as the organic cation backbone of the 2D component. By means of time-resolved optoelectronic analysis from the femto- to microsecond regions, we demonstrate a static function of the 2D layer as an electron barrier and homogeneous surface passivant, together with a dynamic role in retarding back charge recombination. Our results reveal a crucial dependence of such beneficial effects with the 2D layer, leading to an enhanced open-circuit voltage (Voc), mostly attributed to the 2D phase which orients parallel on the 3D layer. Such findings provide a deep understanding and delineate precise guidelines for the smart design of multidimensional perovskite interfaces for advanced PVs and beyond.

Inexpensive Hole-Transporting Materials Derived from Tröger's Base Afford Efficient and Stable Perovskite Solar Cells.

The synthesis of three enamine hole-transporting materials (HTMs) based on Tröger's base scaffold are reported. These compounds are obtained in a three-step facile synthesis from commercially available materials without the need of expensive catalysts, inert conditions or time-consuming purification steps. The best performing material, HTM3, demonstrated 18.62 % PCE in PSCs, rivaling spiro-OMeTAD in efficiency, and showing markedly superior long-term stability in non-encapsulated devices. In dopant-free PSCs, HTM3 outperformed spiro-OMeTAD by a factror of 1.6. The high glass-transition temperature (Tg =176 °C) of HTM3 also suggests promising perspectives in device applications.

Picosecond Capture of Photoexcited Electrons Improves Photovoltaic Conversion in MAPbI3 :C70 -Doped Planar and Mesoporous Solar Cells.

In this work, solar cells based on methylammonium lead iodide (MAPbI3 ) doped in solution with C70 fullerene in a mesoporous as well as planar electron-transporting layer (ETL)-free architecture are realized, showcasing in the latter case a record efficiency of 15.7% and an improved open-circuit voltage (VOC ). Contrary to the bulk heterojunction previously reported, the C70 molecules do not phase segregate and they are rather finely dispersed in the perovskite film, possibly infiltrating at the grain boundaries, while assisting the growth of a highly uniform perovskite layer. By means of time-resolved femtosecond-to-nanosecond optical spectroscopy, with an extended spectral coverage, it is observed that electrons photogenerated in the perovskite are transferred to C70 with a time constant of 20 ps. Despite being captured by C70 , electrons are not deeply trapped and can potentially bounce back into the perovskite, as suggested by the high fill factor and enhanced VOC of the MAPbI3 :C70 solar cells, especially in the case of the ETL-free device configuration.

Metal-Halide Perovskites for Gate Dielectrics in Field-Effect Transistors and Photodetectors Enabled by PMMA Lift-Off Process.

Metal-halide perovskites have emerged as promising materials for optoelectronics applications, such as photovoltaics, light-emitting diodes, and photodetectors due to their excellent photoconversion efficiencies. However, their instability in aqueous solutions and most organic solvents has complicated their micropatterning procedures, which are needed for dense device integration, for example, in displays or cameras. In this work, a lift-off process based on poly(methyl methacrylate) and deep ultraviolet lithography on flexible plastic foils is presented. This technique comprises simultaneous patterning of the metal-halide perovskite with a top electrode, which results in microscale vertical device architectures with high spatial resolution and alignment properties. Hence, thin-film transistors (TFTs) with methyl-ammonium lead iodide (MAPbI3 ) gate dielectrics are demonstrated for the first time. The giant dielectric constant of MAPbI3 (>1000) leads to excellent low-voltage TFT switching capabilities with subthreshold swings ≈80 mV decade-1 over ≈5 orders of drain current magnitude. Furthermore, vertically stacked low-power Au-MAPbI3 -Au photodetectors with close-to-ideal linear response (R2 = 0.9997) are created. The mechanical stability down to a tensile radius of 6 mm is demonstrated for the TFTs and photodetectors, simultaneously realized on the same flexible plastic substrate. These results open the way for flexible low-power integrated (opto-)electronic systems based on metal-halide perovskites.

Benzotrithiophene-Based Hole-Transporting Materials for 18.2 % Perovskite Solar Cells.

New star-shaped benzotrithiophene (BTT)-based hole-transporting materials (HTM) BTT-1, BTT-2 and BTT-3 have been obtained through a facile synthetic route by crosslinking triarylamine-based donor groups with a benzotrithiophene (BTT) core. The BTT HTMs were tested on solution-processed lead trihalide perovskite-based solar cells. Power conversion efficiencies in the range of 16 % to 18.2 % were achieved under AM 1.5 sun with the three derivatives. These values are comparable to those obtained with today's most commonly used HTM spiro-OMeTAD, which point them out as promising candidates to be used as readily available and cost-effective alternatives in perovskite solar cells (PSCs).

Low-voltage, high-brightness and deep-red light-emitting electrochemical cells (LECs) based on new ruthenium(ii) phenanthroimidazole complexes.

Light-Emitting Electrochemical Cells (LECs) with a simple device structure ITO/Ru complex/Ga:In were prepared by using heteroleptic ruthenium(ii) complexes containing 2-(2-hydroxyphenyl)-1-(4-bromophenyl)-1h-imidazo[4,5-f][1,10]phenanthroline (hpbpip) as the π-extended ligand. After ancillary ligand modification, the [Ru(hpbpip)(dmbpy)2](ClO4)2 complex shows a deep red electroluminescence emission (2250 cd m(-2) at 6 V) centered at 685 nm, 65 nm red-shifted compared to the [Ru(bpy)3](ClO4)2 benchmark red-emitter at a very low turn voltage (2.6 V), demonstrating its potential for low-cost deep-red light sources. Moreover, the PL quantum yield of the [Ru(hpbpip)(bpy)2](ClO4)2 complex was revealed to be higher (0.121) than the benchmark standard [Ru(bpy)3](2+) (0.095).

Tuning the Emission of Cationic Iridium (III) Complexes Towards the Red Through Methoxy Substitution of the Cyclometalating Ligand.

The synthesis, characterization and evaluation in solid-state devices of a series of 8 cationic iridium complexes bearing different numbers of methoxy groups on the cyclometallating ligands are reported. The optoelectronic characterization showed a dramatic red shift in the absorption and the emission and a reduction of the electrochemical gap of the complexes when a methoxy group was introduced para to the Ir-C bond. The addition of a second or third methoxy group did not lead to a significant further red shift in these spectra. Emission maxima over the series ranged from 595 to 730 nm. All complexes possessing a motif with a methoxy group at the 3-position of the cyclometalating ligands showed very short emission lifetimes and poor photoluminescence quantum yields whereas complexes having a methoxy group at the 4-position were slightly blue shifted compared to the unsubstituted parent complexes, resulting from the inductively electron withdrawing nature of this directing group on the Ir-C bond. Light-emitting electrochemical cells were fabricated and evaluated. These deep red emitters generally showed poor performance with electroluminescence mirroring photoluminescence. DFT calculations accurately modelled the observed photophysical and electrochemical behavior of the complexes and point to an emission from a mixed charge transfer state.