Pushing the Envelope: Achieving an Open‐Circuit Voltage of 1.18 V for Unalloyed MAPbI3 Perovskite Solar Cells of a Planar Architecture

After an overwhelmingly fast increase during the period from 2009 to 2016, the power conversion efficiency of hybrid perovskite solar cells levels at ≈22% during the past two years. Every small advance to theoretical limits of the photovoltaic metrics will significantly deepen the understanding of internal processes inside the perovskite solar cells. Here, by introducing chloroform as the antisolvent, the one‐step deposition method to fabricate methylammonium lead tri‐iodide (MAPbI₃) perovskite films under ambient air condition is optimized. With MAPbI₃ solar cells of a planar architecture, a record high V_oc of 1.18 V is obtained under simulated AM1.5 sunlight. The achievement helps pure MAPbI₃ to reestablish its potential as a model compound for research in hybrid perovskite solar cells. After systematic comparison on different electron transport layers (SnO₂ and TiO₂) and fluorine doped tin oxide (FTO) substrates of different roughness for photon trapping inside MAPbI₃ solar cells, the remaining 0.14 V V_oc loss is elucidated to be due to the poor luminescent property of the MAPbI₃ films.     

Mitigating Surface Deficiencies of Perovskite Single Crystals Enables Efficient Solar Cells with Enhanced Moisture and Reverse-Bias Stability

Metal halide perovskite single crystals are promising for diverse optoelectronic applications due to their outstanding properties. In comparison to the bulk, the crystal surface suffers from high defect density and is moisture sensitive; however, surface modification strategies of perovskite single crystals are relatively deficient. Herein, solar cells based on methylammonium lead triiodide (MAPbI₃) thin single crystals are selected as a prototype to improve single-crystal perovskite devices by surface modification. The surface trap passivation and protection against moisture of MAPbI₃ thin single crystals are achieved by one bifunctional molecule 3-mercaptopropyl(dimethoxy)methylsilane (MDMS). The sulfur atom of MDMS can coordinate with bare Pb²⁺ of MAPbI₃ single crystals to reduce surface defect density and nonradiative recombination. As a result, the modified devices show a remarkable efficiency of 22.2%, which is the highest value for single-crystal MAPbI₃ solar cells. Moreover, MDMS modification mitigates surface ion migration, leading to enhanced reverse-bias stability. Finally, the cross-link of silane molecules forms a protective layer on the crystal surface, which results in enhanced moisture stability of both materials and devices. This work provides an effective way for surface modification of perovskite single crystals, which is important for improving the performance of single-crystal perovskite solar cells, photodetectors, X-ray detectors, etc.     

High‐Performance Inverted Planar Heterojunction Perovskite Solar Cells Based on Lead Acetate Precursor with Efficiency Exceeding 18%

Organic–inorganic lead halide perovskites are emerging materials for the next‐generation photovoltaics. Lead halides are the most commonly used lead precursors for perovskite active layers. Recently, lead acetate (Pb(Ac)₂) has shown its superiority as the potential replacement for traditional lead halides. Here, we demonstrate a strategy to improve the efficiency for the perovskite solar cell based on lead acetate precursor. We utilized methylammonium bromide as an additive in the Pb(Ac)₂ and methylammonium iodide precursor solution, resulting in uniform, compact and pinhole‐free perovskite films. We observed enhanced charge carrier extraction between the perovskite layer and charge collection layers and delivered a champion power conversion efficiency of 18.3% with a stabilized output efficiency of 17.6% at the maximum power point. The optimized devices also exhibited negligible current density–voltage (J–V) hysteresis under the scanning conditions.     

Overcoming Zinc Oxide Interface Instability with a Methylammonium‐Free Perovskite for High‐Performance Solar Cells

Perovskite solar cells have achieved the highest power conversion efficiencies on metal oxide n‐type layers, including SnO₂ and TiO₂. Despite ZnO having superior optoelectronic properties to these metal oxides, such as improved transmittance, higher conductivity, and closer conduction band alignment to methylammonium (MA)PbI₃, ZnO is largely overlooked due to a chemical instability when in contact with metal halide perovskites, which leads to rapid decomposition of the perovskite. While surface passivation techniques have somewhat mitigated this instability, investigations as to whether all metal halide perovskites exhibit this instability with ZnO are yet to be undertaken. Experimental methods to elucidate the degradation mechanisms at ZnO–MAPbI₃ interfaces are developed. By substituting MA with formamidinium (FA) and cesium (Cs), the stability of the perovskite–ZnO interface is greatly enhanced and it is found that stability compares favorably with SnO₂‐based devices after high‐intensity UV irradiation and 85 °C thermal stressing. For devices comprising FA‐ and Cs‐based metal halide perovskite absorber layers on ZnO, a 21.1% scanned power conversion efficiency and 18% steady‐state power output are achieved. This work demonstrates that ZnO appears to be as feasible an n‐type charge extraction layer as SnO₂, with many foreseeable advantages, provided that MA cations are avoided.     

Variations of Infiltration and Electronic Contact in Mesoscopic Perovskite Solar Cells Revealed by High‐Resolution Multi‐Mapping Techniques

A combination of high‐resolution mapping techniques is developed to probe the homogeneity and defects of mesoscopic perovskite solar cells. Three types of cells using a one‐step infiltration process with methylammonium lead iodide (MAPbI₃) or 5‐ammoniumvaleric acid‐MAPbI₃ solutions, or two‐step process with MAPbI₃ solution are investigated. The correlation between photoluminescence, photocurrent, electroluminescence, and Raman maps gives a detailed understanding of the different infiltration mechanisms, electronic contact at interfaces, and effect on local photocurrent for the cells. The one‐step MAPbI₃ cell has very limited infiltration of the perovskite solution which results in poor device performance. High loading of the mesopores of the TiO₂ and ZrO₂ scaffold is observed when using 5‐ammoniumvaleric acid, but some micrometer‐sized non‐infiltrated areas remain due to dense carbon flakes hindering perovskite infiltration. The two‐step cell has a complex morphology with features having either beneficial or detrimental effects on the local photocurrent. The results not only provide key insights to achieving better infiltration and homogeneity of the perovskite film in mesoporous devices but can also aid further work on planar devices to develop efficient extraction layers. Moreover, this multi‐mapping approach allows the correlation of the local photophysical properties of full perovskite devices, which would be challenging to obtain by other techniques.     

Synergistic effect of MACl and DMF towards efficient perovskite solar cells

The performance of perovskite solar cells (PSCs) is extremely dependent on morphology and crystallinity of perovskite film. One of the most effective methods to achieve high performance perovskite solar cells has been to introduce additives that serve as dopants, crystallization or passivation agents. Herein a facile strategy by introducing methylammonium chloride (MACl) and polar solvent N,N-Dimethylformamide (DMF) as co-additives in two-step sequential method is proposed to realize high quality perovskite film. It is demonstrated that DMF facilitates methylammonium iodide (MAI) penetrating easily into PbI₂ layer to form highly crystalized perovskite film with uniform morphology which is essential to achieve high V_OC. While MACl induces MAPbI₃ to crystallize in a pure α-phase and suppress non-photovoltaic phase, which guarantees high FF. Pure α-phase perovskite film with uniform morphology can be achieved by adopting MACl and DMF together and the corresponding solar cell illustrates a power conversion efficiency (PCE) of 19.02% with substantially promoted durability. Moreover, A V_OC as high as 1.181 V is succeeded for MAPbI₃ based solar cell benefiting from the synergistic effect.     

Nitrogen‐Dopant‐Induced Organic–Inorganic Hybrid Perovskite Crystal Growth on Carbon Nanotubes

Interfacial engineering of organic–inorganic halide perovskites in conjunction with different functional materials is anticipated to offer novel heterojunction structures with unique functionalities. Unfortunately, complex material compositions and structures of the organic–inorganic hybrid materials make it difficult to tailor a desirable intermolecular interaction at the interface. Spontaneous and highly specific nucleation of perovskite crystals, that is, methylammonium lead iodide perovskite (CH₃NH₃PbI₃, MAPbI₃) at nitrogen‐doped carbon nanotube (NCNT) surfaces for the self‐assembly of MAPbI₃/NCNT hybrids is reported. It is demonstrated that the lone‐pair electrons of pyridinic nitrogen‐dopant sites at NCNTs mediate specific interactions with the cationic component in the perovskite structure and serve as the nucleation sites via coordinate bonding formation, as supported by X‐ray photoelectron spectroscopy and density functional theory calculation. The potential suitability of MAPbI₃/NCNT hybrids is presented for highly sensitive and selective NO₂ sensing layer. This work suggests a reliable self‐assembly route to the molecular level hybridization of organic–inorganic halide perovskites by employing the substitutional dopant sites at graphene‐based nanomaterials.     

Solution‐Processed Laminated Perovskite Layers for High‐Performance Solar Cells

Laminated multilayers of perovskite films with different optical and electronic characteristics will easily realize high‐performance optoelectronic devices because it is widely demonstrated that differential distribution of film properties in the vertical direction of devices plays particularly important roles in device performance. However, the existing laminated perovskite films are hardly prepared by a solution process because there is no solvent with sufficient selectivity of solubility for different perovskite materials. Here, it is demonstrated that aniline (AN) has a largely different solubility toward the perovskite MAPbI₃ and the MAPbI₃ blend with an additive of hydrochloride diethylammonium chloride. By using AN as the solvent in the perovskite precursor solution, two laminated perovskite layers with different crystal size and optical and electrical characteristics are achieved. Inverted perovskite solar cells with the laminated films as active layers achieve an averaged power conversion efficiency of 20.65% originating from the high V_OC 1.112 V and fill factor of 80.8%. The devices maintain 98% efficiency after 400 h under 65% RH. This work provides a very simple and feasible method for production of laminated perovskite films to achieve high‐performance perovskite solar cells.     

HPbI3: A New Precursor Compound for Highly Efficient Solution‐Processed Perovskite Solar Cells

Recently, there have been extensive research efforts on developing high performance organolead halide based perovskite solar cells. While most studies focused on optimizing the deposition processes of the perovskite films, the selection of the precursors has been rather limited to the lead halide/methylammonium (or formamidium) halide combination. In this work, we developed a new precursor, HPbI₃, to replace lead halide. The new precursor enables formation of highly uniform formamidium lead iodide (FAPbI₃) films through a one‐step spin‐coating process. Furthermore, the FAPbI₃ perovskite films exhibit a highly crystalline phase with strong (110) preferred orientation and excellent thermal stability. The planar heterojunction solar cells based on these perovskite films exhibit an average efficiency of 15.4% and champion efficiency of 17.5% under AM 1.5 G illumination. By comparing the morphology and formation process of the perovskite films fabricated from the formamidium iodide (FAI)/HPbI₃, FAI/PbI₂, and FAI/PbI₂ with HI additive precursor combinations, it is shown that the superior property of the HPbI₃ based perovskite films may originate from 1) a slow crystallization process involving exchange of H⁺ and FA⁺ ions in the PbI₆ octahedral framework and 2) elimination of water in the precursor solution state.     

Ions Matter: Description of the Anomalous Electronic Behavior in Methylammonium Lead Halide Perovskite Devices

Carrier transport in methylammonium lead iodide (MAPbI₃)‐based hybrid organic–inorganic perovskites (HOIPs) is obscured by vacancy‐mediated ion migration. Thus, the nature of migrating species (cation/anion) and their effect on electronic transport in MAPbI₃ has remained controversial. Temperature‐dependent pulsed voltage–current measurements of MAPbI₃ thin films are performed under dark conditions, designed to decouple ion‐migration/accumulation and electronic transport. Measurement conditions (electric‐field history and scan rate) are shown to affect the electronic transport in MAPbI₃ thin films, through a mechanism involving ion migration and accumulation at the electrode interfaces. The presence of thermally activated processes with distinct activation energies (E_a) of 0.1 ± 0.001 and 0.41 ± 0.02 eV is established, and are assigned to electromigration of iodine vacancies and methylammonium vacancies, respectively. Analysis of activation energies obtained from electronic conduction versus capacitive discharge shows that the electromigration of these ionic species is responsible for the modification of interfacial electronic properties of MAPbI₃, and elaborates previously unaddressed issues of “fast” and “slow” ion migration. The results demonstrate that the intrinsic behavior of MAPbI₃ material is responsible for the hysteresis of the solar cells, but also have implications for other HOIP‐based devices, such as memristors, detectors, and energy storage devices.     

An Environmentally Stable and Lead‐Free Chalcogenide Perovskite

Organic–inorganic halide perovskites are intrinsically unstable when exposed to moisture and/or light. Additionally, the presence of lead in many perovskites raises toxicity concerns. Herein, a thin film of barium zirconium sulfide (BaZrS₃), a lead‐free chalcogenide perovskite, is reported. Photoluminescence and X‐ray diffraction measurements show that BaZrS₃ is far more stable than methylammonium lead iodide (MAPbI₃) in moist environments. Moisture‐ and light‐induced degradations in BaZrS₃ and MAPbI₃ are compared by using simulations and calculations based on density functional theory. The simulations reveal drastically slower degradation in BaZrS₃ due to two factors—weak interaction with water and very low rates of ion migration. BaZrS₃ photodetecting devices with photoresponsivity of ≈46.5 mA W^?1 are also reported. The devices retain ≈60% of their initial photoresponse after 4 weeks under ambient conditions. Similar MAPbI₃ devices degrade rapidly and show a ≈95% decrease in photoresponsivity in just 4 days. The findings establish the superior stability of BaZrS₃ and strengthen the case for its use in optoelectronics. New possibilities for thermoelectric energy conversion using these materials are also demonstrated.     

Impact of the Solvation State of Lead Iodide on Its Two‐Step Conversion to MAPbI3: An In Situ Investigation

Producing high efficiency solar cells without high‐temperature processing or use of additives still remains a challenge with the two‐step process. Here, the solution processing of MAPbI₃ from PbI₂ films in N,N‐dimethylformamide (DMF) is investigated. In‐situ grazing incidence wide‐angle X‐ray scattering (GIWAXS) measurements reveal a sol–gel process involving three PbI₂‐DMF solvate complexes—disordered (P₀) and ordered (P₁, P₂)—prior to PbI₂ formation. When the appropriate solvated state of PbI₂ is exposed to MAI (methylammonium Iodide), it can lead to rapid and complete room temperature conversion into MAPbI₃ with higher quality films and improved solar cell performance. Complementary in‐situ optical reflectance, absorbance, and quartz crystal microbalance with dissipation (QCM‐D) measurements show that dry PbI₂ can take up only one third of the MAI taken up by the solvated‐crystalline P₂ phase of PbI₂, requiring additional annealing and yet still underperforming. The perovskite solar cells fabricated from the ordered P₂ precursor show higher power conversion efficiency (PCE) and reproducibility than devices fabricated from other cases. The average PCE of the solar cells is greatly improved from 13.2(±0.53)% (from annealed PbI₂) to 15.7(±0.35)% (from P₂) reaching up to 16.2%. This work demonstrates the importance of controlling the solvation of PbI₂ as an effective strategy for the growth of high‐quality perovskite films and their application in high efficiency and reproducible solar cells.     

In Situ Photosynthesis of an MAPbI3/CoP Hybrid Heterojunction for Efficient Photocatalytic Hydrogen Evolution

Halide perovskite like methylammonium lead iodide perovskite (MAPbI₃) with its prominent optoelectronic properties has triggered substantial concerns in photocatalytic H₂ evolution. In this work, to attain preferable photocatalytic performance, a MAPbI₃/cobalt phosphide (CoP) hybrid heterojunction is constructed by a facile in situ photosynthesis approach. Systematic investigations reveal that the CoP nanoparticle can work as co‐catalyst to not only extract photogenerated electrons effectively from MAPbI₃ to improve the photoinduced charge separation, but also facilitate the interfacial catalytic reaction. As a result, the as‐achieved MAPbI₃/CoP hybrid displays a superior H₂ evolution rate of 785.9 µmol h^?1 g^?1 in hydroiodic acid solution within 3 h, which is ≈8.0 times higher than that of pristine MAPbI₃. Furthermore, the H₂ evolution rate of MAPbI₃/CoP hybrid can reach 2087.5 µmol h^?1 g^?1 when the photocatalytic reaction time reaches 27 h. This study employs a facile in situ photosynthesis strategy to deposit the metal phosphide co‐catalyst on halide perovskite nanocrystals to conduct photocatalytic H₂ evolution reaction, which may stimulate the intensive investigation of perovskite/co‐catalyst hybrid systems for future photocatalytic applications.     

Water‐Soluble Triazolium Ionic‐Liquid‐Induced Surface Self‐Assembly to Enhance the Stability and Efficiency of Perovskite Solar Cells

Despite being a promising candidate for next‐generation photovoltaics, perovskite solar cells (PSCs) exhibit limited stability that hinders their practical application. In order to improve the humidity stability of PSCs, herein, a series of ionic liquids (ILs) “1‐alkyl‐4‐amino‐1,2,4‐triazolium” (termed as RATZ; R represents alkyl chain, and ATZ represents 4‐amino‐1,2,4‐triazolium) as cations are designed and used as additives in methylammonium lead iodide (MAPbI₃) perovskite precursor solution, obtaining triazolium ILs‐modified PSCs for the first time (termed as MA/RATZ PSCs). As opposed to from traditional methods that seek to improve the stability of PSCs by functionalizing perovskite film with hydrophobic molecules, humidity‐stable perovskite films are prepared by exploiting the self‐assembled monolayer (SAM) formation of water‐soluble triazolium ILs on a hydrophilic perovskite surface. The mechanism is validated by experimental and theoretical calculation. This strategy means that the MA/RATZ devices exhibit good humidity stability, maintaining around 80% initial efficiency for 3500 h under 40 ± 5% relative humidity. Meanwhile, the MA/RATZ PSCs exhibit enhanced thermal stability and photostability. Tuning the molecule structure of the ILs additives achieves a maximum power conversion efficiency (PCE) of 20.03%. This work demonstrates the potential of using triazolium ILs as additives and SAM and molecular design to achieve high performance PSCs.     

In situ recycle of PbI2 as a step towards sustainable perovskite solar cells

The development of organometal halide perovskite solar cells has grown rapidly and the highest efficiency of the devices has recently surpassed 22%. Because these solar cells contain toxic lead, a sustainable strategy is required to prevent environmental pollution and avoid healthy hazard caused by possible lead outflow. Here, in situ recycling PbI₂ from thermal decomposition CH₃NH₃PbI₃ perovskite films for efficient perovskite solar cells was developed. The thermal behavior of CH₃NH₃PbI₃ perovskite and its individual components were examined by thermogravimetric analysis. By optimizing the process of thermal decomposition CH₃NH₃PbI₃ film, the complete conversion from CH₃NH₃PbI₃ to pure PbI₂ layer with a mesoporous scaffold was achieved. The mesoporous structure readily promotes the conversion efficiency of perovskite and consequently results in high‐performance device. A perovskite crystal growth mechanism on the mesoporous PbI₂ structure was proposed. These results suggest that in situ recycled PbI₂ scaffolds can be a new route in manipulating the morphology of the perovskite active layer, providing new possibilities for high performance. Meanwhile, the risk of lead outflow can be released, and the saving‐energy fabrication of efficient solar cells can be realized.     

Efficient 4,4′,4″‐tris(3‐methylphenylphenylamino)triphenylamine (m‐MTDATA) Hole Transport Layer in Perovskite Solar Cells Enabled by Using the Nonstoichiometric Precursors

To overcome the drawbacks of the acidic and hygroscopic nature of the poly(3,4‐ethylenedio‐xythiophene):poly(styrenesulfonate) hole transport layer (HTL), the p‐type polymeric hole transport materials have attracted great attention and have been applied into perovskite solar cells. Here, a starburst amine molecule 4,4′,4″‐tris(3‐methylphenylphenylamino)triphenylamine (m‐MTDATA) without any additive is demonstrated as an effective hole transport material in perovskite solar cells. Meanwhile, considering the different surface affinity of precursor's composition on m‐MTDATA, the influence of the molar ratios between lead iodine (PbI₂) and methylammonium iodide in precursor solution on the perovskite characteristics and device performance is investigated in‐depth. Ultimately, an enhanced efficiency of 17.73% and a high fill factor of 79.6% are achieved, which attribute to the strong passivation effect of traps and small resistance loss from appropriate unreacted PbI₂ left in the perovskite layer. This work not only provides a remarkable HTL, but also reveals that the adjustment of precursor ratio is necessary for the one‐step solution approach, because the affinities of precursor's composition may be different with the underlying transport layers.     

Investigating the Superoxide Formation and Stability in Mesoporous Carbon Perovskite Solar Cells with an Aminovaleric Acid Additive

Perovskite solar cells have attracted a great deal of attention thanks to their high efficiency, ease of manufacturing, and potential low cost. However, the stability of these devices is considered their main drawback and needs to be addressed. Mesoporous carbon perovskite solar cells (m‐CPSC), consisting of three mesoporous layers (TiO₂/ZrO₂/C) infiltrated with CH₃NH₃PbI₃ (MAPI) perovskite, have presented excellent lifetimes of more than 10 000 h when the additive NH₂(CH₂)₄CO₂HI (5‐ aminovaleric acid iodide; 5‐AVAI) is used to modify the perovskite structure. Yet, the role of 5‐AVAI in enhancing the stability has yet to be determined. Here, superoxide‐mediated degradation of MAPI m‐CPSC with and without the 5‐AVAI additive is studied using the fluorescence probe dihydroethidium for superoxide detection. In situ X‐ray diffractometry shows that aminovaleric acid methylammonium lead iodide (AVA‐MAPI) perovskite infiltrated in mesoporous layers presents higher stability in an ambient environment under illumination, evidenced by a slower decrease of the MAPI/PbI₂ peak ratio. Superoxide yield measurements demonstrate that AVA‐MAPI generates more superoxide than regular MAPI when deposited on glass but generates significantly less when infiltrated in mesoporous layers. It is believed that superoxide formation in m‐CPSC is dependent on a combination of competitive factors including oxygen diffusion, sample morphology, grain size, and defect concentration.     

Unveiling a Key Intermediate in Solvent Vapor Postannealing to Enlarge Crystalline Domains of Organometal Halide Perovskite Films

Hybrid organic/inorganic perovskite solar cells (PSCs) have shown great potential in meeting the future challenges in energy and environment. Solvent‐vapor‐assisted posttreatment strategies are developed to improve the perovskite film quality for achieving higher efficiency. However, the intrinsic working mechanisms of these strategies have not been well understood yet. This study identifies an MA₂Pb₃I₈(DMSO)₂ intermediate phase formed during the annealing process of methylammonium lead triiodide in dimethyl sulfoxide (DMSO) atmosphere and located the reaction sites at perovskite grain boundaries by observing and rationalizing the growth of nanorods of the intermediate. This enables us to propose and validate an intermediate‐assisted grain‐coarsening model, which highlights the activation energy reduction for grain boundary migration. Leveraging this mechanism, this study uses MABr/DMSO mixed vapor to further enhance grain boundary migration kinetics and successfully obtain even larger grains, leading to an impressive improvement in power conversion efficiency (17.64%) relative to the pristine PSCs (15.13%). The revelation of grain boundary migration‐assisted grain growth provides a guide for the future development of polycrystalline perovskite thin‐film solar cells.     

Precursor Solution Annealing Forms Cubic‐Phase Perovskite and Improves Humidity Resistance of Solar Cells

Solar cells with light‐absorbing layers comprising organometal halide perovskites have recently exceeded 22% efficiency. Despite high power‐conversion efficiencies, the stability of these devices, particularly when exposed to humidity and oxygen, remains poor. In the current study, a pathway to increase the stability of methylammonium lead iodide (CH₃NH₃PbI₃) based solar cells towards humidity is demonstrated, while maintaining the simplicity and solution‐processability of the active layers. Thermal annealing of the precursor solution prior to deposition induces the formation of cubic‐phase perovskite films in the solid state at room temperature. The experiments demonstrate that this improved ambient stability is correlated with the presence of the cubic phase at device operating temperatures, with the cubic phase resisting the formation of perovskite monohydrate—a pathway of degradation in conventionally processed perovskite thin films—on exposure to humidity.     

Interface engineering in efficient vacuum deposited perovskite solar cells

We studied the effect of the charge transport layers in p-i-n perovskite solar cells using vacuum deposited methylammonium lead iodide thin-film absorbers. While solution-processed perovskite films are frequently deposited directly on PEDOT:PSS leading to good solar cell performances, in some cases even to very good V_oc values, we show that in devices employing vacuum deposited MAPbI₃ perovskites, the removal of the polyTPD electron blocker substantially reduces the photovoltaic behavior. This is indicative of rather different charge transport properties in the vacuum deposited MAPbI₃ perovskites compared to those prepared from solution. On the other hand, we investigated the use of ionic interlayers as a possible alternative to low work function electrodes, whose reactivity towards air and moisture compromises the device stability. Two different electron extraction materials were evaluated as interlayers between the fullerene electron transport layer and a silver electrode, in particular a perylenediimide derivative and a conjugated polyelectrolyte. By studying the photovoltaic response and the electroluminescence properties of planar diodes using the ionic films and comparing them with devices employing barium, we found that such ionic interlayers can successfully replace the use of reactive electrodes, since they facilitate the electron extraction while reducing the non-radiative recombination at the electron transport interface.