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With power conversion efficiencies of perovskite-on-silicon and all-perovskite tandem solar cells increasing at rapid pace, wide bandgap (> 1.7 eV) metal-halide perovskites (MHPs) are becoming a major focus of academic and industrial photovoltaic research. Compared to their lower bandgap (< 1.6 eV) counterparts, these types of perovskites suffer from higher levels of non-radiative losses in both the bulk material and in device configurations, constraining their efficiencies far below their thermodynamic potential. In this work, we investigate the energy losses in methylammonium (MA) free high-Br-content widegap perovskites by using a combination of THz spectroscopy, steady-state and time-resolved photoluminescence, coupled with drift-diffusion simulations. The investigation of this system allows us to study charge-carrier recombination in these materials and devices in the absence of halide segregation due to the photostabilty of formamidinium-cesium based lead halide perovskites. We find that these perovskites are characterised by large non-radiative recombination losses in the bulk material and that the interfaces with transport layers in solar cell devices strongly limit their open-circuit voltage. In particular, we discover that the interface with the hole transport layer performs particularly poorly, in contrast to 1.6 eV bandgap MHPs which are generally limited by the interface with the electron-transport layer. To overcome these losses, we incorporate and investigate the recombination mechanisms present with perovskites treated with the ionic additive 1-butyl-1-methylpipiderinium tetrafluoroborate. We find that this additive not only improves the radiative efficiency of the bulk perovskite, but also reduces the non-radiative recombination at both the hole and electron transport layer interfaces of full photovoltaic devices. In addition to unravelling the beneficial effect of this specific treatment, we further optimise our solar cells by introducing an additional LiF interface treatment at the electron transport layer interface. Together these treatments enable MA-free 1.79 eV bandgap perovskite solar cells with open-circuit voltages of 1.22 V and power conversion efficiencies approaching 17 %, which is among the highest reported for this material system.

Despite the incredible progress made, the highest efficiency perovskite solar cells are still restricted to small areas (

This work investigates halide segregation in methylammonium-free wide bandgap perovskites by photoluminescence quantum yield (PLQY) and advanced electron microscopy techniques. Our study reveals ho...

Perovskites offer exciting opportunities to realize efficient multijunction photovoltaic devices. This requires high-VOC and often Br-rich perovskites, which currently suffer from halide segregatio...

Funder: Equal Opportunities Foundation Hong Kong, Funder: University of Surrey; Id: http://dx.doi.org/10.13039/501100003513, Funder: DCSA3 scholarship, Funder: Royal Society; Id: http://dx.doi.org/10.13039/501100000288, Funder: European Research Council; Id: http://dx.doi.org/10.13039/501100000781, Successful manipulation of halide perovskite surfaces is typically achieved via the interactions between modulators and perovskites. Herein, it is demonstrated that a strong‐interaction surface modulator is beneficial to reduce interfacial recombination losses in inverted (p‐i‐n) perovskite solar cells (IPSCs). Two organic ammonium salts are investigated, consisting of 4‐hydroxyphenethylammonium iodide and 2‐thiopheneethylammonium iodide (2‐TEAI). Without thermal annealing, these two modulators can recover the photoluminescence quantum yield of the neat perovskite film in contact with fullerene electron transport layer (ETL). Compared to the hydroxyl‐functionalized phenethylammonium moiety, the thienylammonium facilitates the formation of a quasi‐2D structure onto the perovskite. Density functional theory and quasi‐Fermi level splitting calculations reveal that the 2‐TEAI has a stronger interaction with the perovskite surface, contributing to more suppressed non‐radiative recombination at the perovskite/ETL interface and improved open‐circuit voltage (VOC) of the fabricated IPSCs. As a result, the VOC increases from 1.11 to 1.20 V (based on a perovskite bandgap of 1.63 eV), yielding a power conversion efficiency (PCE) from ≈20% to 21.9% (stabilized PCE of 21.3%, the highest reported PCEs for IPSCs employing poly[N, N′′‐bis(4‐butylphenyl)‐N, N′′‐bis(phenyl)benzidine] as the hole transport layer, alongside the enhanced operational and shelf‐life stability for unencapsulated devices.

Charge extraction in organic solar cells (OSCs) is commonly believed to be limited by bimolecular recombination of photogenerated charges. However, the fill factor of OSCs is usually almost entirely governed by recombination processes that scale with the first order of the light intensity. This linear loss was often interpreted to be a consequence of geminate or trap-assisted recombination. Numerical simulations show that this linear dependence is a direct consequence of the large amount of excess dark charge near the contact. The first-order losses increase with decreasing mobility of minority carriers, and we discuss the impact of several material and device parameters on this loss mechanism. This work highlights that OSCs are especially vulnerable to injected charges as a result of their poor charge transport properties. This implies that dark charges need to be better accounted for when interpreting electro-optical measurements and charge collection based on simple figures of merit.

Recent advancements in perovskite solar cell performance were achieved by stabilizing the α-phase of FAPbI3 in nip-type architectures. However, these advancements could not be directly translated to pin-type devices. Here, we fabricated a high-quality double cation perovskite (MA0.07FA0.93PbI3) with low bandgap energy (1.54 eV) using a two-step approach on a standard polymer (PTAA). The perovskite films exhibit large grains (∼1 μm), high external photoluminescence quantum yields of 20%, and outstanding Shockley-Read-Hall carrier lifetimes of 18.2 μs without further passivation. The exceptional optoelectronic quality of the neat material was translated into efficient pin-type cells (up to 22.5%) with improved stability under illumination. The low-gap cells stand out by their high fill factor (∼83%) due to reduced charge transport losses and short-circuit currents >24 mA cm-2. Using intensity-dependent quasi-Fermi level splitting measurements, we quantify an implied efficiency of 28.4% in the neat material, which can be realized by minimizing interfacial recombination and optical losses.

Perovskite solar cells deliver high efficiencies, but are often made from high-cost bespoke chemicals, such as the archetypical hole-conductor, 2,2′,7,7′-tetrakis(N,N-di-p-methoxy-phenylamine)-9-9′-spirobifluorene (spiro-OMeTAD). Herein, new charge-transporting carbazole-based enamine molecules are reported. The new hole conductors do not require chemical oxidation to reach high power conversion efficiencies (PCEs) when employed in n-type-intrinsic-p-type perovskite solar cells; thus, reducing the risk of moisture degrading the perovskite layer through the hydrophilicity of oxidizing additives that are typically used with conventional hole conductors. Devices made with these new undoped carbazole-based enamines achieve comparable PCEs to those employing doped spiro-OMeTAD, and greatly enhanced stability under 85 °C thermal aging; maintaining 83% of their peak efficiency after 1000 h, compared with spiro-OMeTAD-based devices that degrade to 26% of the peak PCE within 24 h. Furthermore, the carbazole-based enamines can be synthesized without the use of organometallic catalysts and complicated purification techniques, lowering the material cost by one order of magnitude compared with spiro-OMeTAD. As a result, we calculate that the overall manufacturing costs of future photovoltaic (PV) modules are reduced, making the levelized cost of electricity competitive with silicon PV modules.

Perovskite semiconductors have demonstrated outstanding external luminescence quantum yields, enabling high power conversion efficiencies PCEs . However, the precise conditions to advance to an efficiency regime above monocrystalline silicon cells are not well understood. Herein, a simulation model that describes efficient p i n type perovskite solar cells well and a range of different experiments is established. Then, important device and material parameters are studied and it is found that an efficiency regime of 30 can be unlocked by optimizing the built in voltage across the perovskite layer using either highly doped 1019 amp; 8201;cm amp; 8722;3 transport layers TLs , doped interlayers or ultrathin self assembled monolayers. Importantly, only parameters that have been reported in recent literature are considered, that is, a bulk lifetime of 10 amp; 8201; amp; 956;s, interfacial recombination velocities of 10 amp; 8201;cm amp; 8201;s amp; 8722;1, a perovskite bandgap amp; 119864;gap of 1.5 amp; 8201;eV, and an external quantum efficiency EQE of 95 . A maximum efficiency of 31 is predicted for a bandgap of 1.4 amp; 8201;eV. Finally, it is demonstrated that the relatively high mobile ion density does not represent a significant barrier to reach this efficiency regime. The results of this study suggest continuous PCE improvements until perovskites may become the most efficient single junction solar cell technology in the near future

The incorporation of even small amounts of strontium (Sr) into lead-base hybrid quadruple cation perovskite solar cells results in a systematic increase of the open circuit voltage (V-oc) in pin-type perovskite solar cells. We demonstrate via absolute and transient photoluminescence (PL) experiments how the incorporation of Sr significantly reduces the non-radiative recombination losses in the neat perovskite layer. We show that Sr segregates at the perovskite surface, where it induces important changes of morphology and energetics. Notably, the Sr-enriched surface exhibits a wider band gap and a more n-type character, accompanied with significantly stronger surface band bending. As a result, we observe a significant increase of the quasi-Fermi level splitting in the neat perovskite by reduced surface recombination and more importantly, a strong reduction of losses attributed to non-radiative recombination at the interface to the C-60 electron-transporting layer. The resulting solar cells exhibited a V-oc of 1.18 V, which could be further improved to nearly 1.23 V through addition of a thin polymer interlayer, reducing the non-radiative voltage loss to only 110 meV. Our work shows that simply adding a small amount of Sr to the precursor solutions induces a beneficial surface modification in the perovskite, without requiring any post treatment, resulting in high efficiency solar cells with power conversion efficiency (PCE) up to 20.3%. Our results demonstrate very high V-oc values and efficiencies in Sr-containing quadruple cation perovskite pin-type solar cells and highlight the imperative importance of addressing and minimizing the recombination losses at the interface between perovskite and charge transporting layer.

Charge transport layers (CTLs) are key components of diffusion controlled perovskite solar cells, however, they can induce additional non-radiative recombination pathways which limit the open circuit voltage (V-OC) of the cell. In order to realize the full thermodynamic potential of the perovskite absorber, both the electron and hole transport layer (ETL/HTL) need to be as selective as possible. By measuring the photoluminescence yield of perovskite/CTL heterojunctions, we quantify the non-radiative interfacial recombination currents in pin- and nip-type cells including high efficiency devices (21.4%). Our study comprises a wide range of commonly used CTLs, including various hole-transporting polymers, spiro-OMeTAD, metal oxides and fullerenes. We find that all studied CTLs limit the V-OC by inducing an additional non-radiative recombination current that is in most cases substantially larger than the loss in the neat perovskite and that the least-selective interface sets the upper limit for the V-OC of the device. Importantly, the V-OC equals the internal quasi-Fermi level splitting (QFLS) in the absorber layer only in high efficiency cells, while in poor performing devices, the V-OC is substantially lower than the QFLS. Using ultraviolet photoelectron spectroscopy and differential charging capacitance experiments we show that this is due to an energy level mis-alignment at the p-interface. The findings are corroborated by rigorous device simulations which outline important considerations to maximize the V-OC. This work highlights that the challenge to suppress non-radiative recombination losses in perovskite cells on their way to the radiative limit lies in proper energy level alignment and in suppression of defect recombination at the interfaces.

Perovskite photovoltaic (PV) cells have demonstrated power conversion efficiencies (PCE) that are close to those of monocrystalline silicon cells; however, in contrast to silicon PV, perovskites are not limited by Auger recombination under 1‐sun illumination. Nevertheless, compared to GaAs and monocrystalline silicon PV, perovskite cells have significantly lower fill factors due to a combination of resistive and non‐radiative recombination losses. This necessitates a deeper understanding of the underlying loss mechanisms and in particular the ideality factor of the cell. By measuring the intensity dependence of the external open‐circuit voltage and the internal quasi‐Fermi level splitting (QFLS), the transport resistance‐free efficiency of the complete cell as well as the efficiency potential of any neat perovskite film with or without attached transport layers are quantified. Moreover, intensity‐dependent QFLS measurements on different perovskite compositions allows for disentangling of the impact of the interfaces and the perovskite surface on the non‐radiative fill factor and open‐circuit voltage loss. It is found that potassium‐passivated triple cation perovskite films stand out by their exceptionally high implied PCEs > 28%, which could be achieved with ideal transport layers. Finally, strategies are presented to reduce both the ideality factor and transport losses to push the efficiency to the thermodynamic limit.

Ideally, the charge carrier lifetime in a solar cell is limited by the radiative free carrier recombination in the absorber which is a second order process. Yet, real life cells suffer from severe nonradiative recombination in the bulk of the absorber, at interfaces, or within other functional layers. Here, the dynamics of photogenerated charge carriers are probed directly in pin type mixed halide perovskite solar cells with an efficiency gt;20 , using time resolved optical absorption spectroscopy and optoelectronic techniques. The charge carrier dynamics is found to be in complete device to be fully consistent with a superposition of first , second , and third order recombination processes, with no admixture by a non integer order recombination pathways Under solar illumination, recombination in the studied high efficiency solar cells proceeds predominantly through nonradiative first order recombination with a lifetime of 250 ns, which competes with second order free charge recombination which is mostly if not entirely radiative. Results from the transient experiments are further employed to successfully explain the steady state solar cells properties over a wide range of illumination intensities. It is concluded that improving carrier lifetimes to gt;3 s will take perovskite devices into the radiative regime, where their performance will benefit from photon recycling

International audience; Low-dimensional hybrid perovskites have triggered significant research interest due to their intrinsically tunable optoelectronic properties and technologically relevant material stability. In particular, the role of the organic spacer on the inherent structural and optical features in two-dimensional (2D) perovskites is paramount for material optimization. To obtain a deeper understanding of the relationship between spacers and the corresponding 2D perovskite film properties, we explore the influence of the partial substitution of hydrogen atoms by fluorine in an alkylammonium organic cation, resulting in (Lc)2PbI4 and (Lf)2PbI4 2D perovskites, respectively. Consequently, optical analysis reveals a clear 0.2 eV blue-shift in the excitonic position at room temperature. This result can be mainly attributed to a band gap opening, with negligible effects on the exciton binding energy. According to Density Functional Theory (DFT) calculations, the band gap increases due to a larger distortion of the structure that decreases the atomic overlap of the wavefunctions and correspondingly bandwidth of the valence and conduction bands. In addition, fluorination impacts the structural rigidity of the 2D perovskite, resulting in a stable structure at room temperature and the absence of phase transitions at a low temperature, in contrast to the widely reported polymorphism in some non-fluorinated materials that exhibit such a phase transition. This indicates that a small perturbation in the material structure can strongly influence the overall structural stability and related phase transition of 2D perovskites, making them more robust to any phase change. This work provides key information on how the fluorine content in organic spacer influence the structural distortion of 2D perovskites and their optical properties which possess remarkable importance for future optoelectronic applications, for instance in the field of light-emitting devices or sensors.

Perovskite solar cells are among the most exciting photovoltaic systems as they combine low recombination losses, ease of fabrication, and high spectral tunability. The Achilles heel of this technology is the device stability due to the ionic nature of the perovskite crystal, rendering it highly hygroscopic, and the extensive diffusion of ions especially at increased temperatures. Herein, we demonstrate the application of a simple solution-processed perfluorinated self-assembled monolayer (p-SAM) that not only enhances the solar cell efficiency, but also improves the stability of the perovskite absorber and, in turn, the solar cell under increased temperature or humid conditions. The p-i-n-type perovskite devices employing these SAMs exhibited power conversion efficiencies surpassing 21%. Notably, the best performing devices are stable under standardized maximum power point operation at 85 °C in inert atmosphere (ISOS-L-2) for more than 250 h and exhibit superior humidity resilience, maintaining ∼95% device performance even if stored in humid air in ambient conditions over months (∼3000 h, ISOS-D-1). Our work, therefore, demonstrates a strategy towards efficient and stable perovskite solar cells with easily deposited functional interlayers.

Although SnO2 has been reported to give high efficiencies of over 20% for organic-inorganic perovskite solar cells and has been frequently used in perovskite tandem solar cells, very few contributions have explored its feasibility in inorganic perovskite solar cells (IPSCs). Inorganic perovskites with a wide bandgap tunable from 1.7 to 2.0 eV are promising candidates for top cells in tandem structures; development of IPSCs based on SnO2 will greatly benefit their integration into tandem solar cells. We examined SnO2 in comparison to the prevalent TiO2. We found that although SnO2 had a good energy alignment with the inorganic perovskite and exhibited slower nonradiative recombination, the relatively low conduction band minimum energy offset restricted efficient charge extraction. In contrast, TiO2 that had a large energy offset of ∼400 meV led to a high fill factor of 78.7% and a state-of-the-art efficiency of 14.2% for IPSCs with a bandgap of 1.93 eV.

Efficiency from hole-selective contacts Perovskite/silicon tandem solar cells must stabilize a perovskite material with a wide bandgap and also maintain efficient charge carrier transport. Al-Ashouri et al. stabilized a perovskite with a 1.68–electron volt bandgap with a self-assembled monolayer that acted as an efficient hole-selective contact that minimizes nonradiative carrier recombination. In air without encapsulation, a tandem silicon cell retained 95% of its initial power conversion efficiency of 29% after 300 hours of operation. Science , this issue p. 1300

Optimizing the photoluminescence (PL) yield of a solar cell has long been recognized as a key principle to maximize the power conversion efficiency. While PL measurements are routinely applied to perovskite films and solar cells under open circuit conditions (V-OC), it remains unclear how the emission depends on the applied voltage. Here, we performed PL(V) measurements on perovskite cells with different hole transport layer thicknesses and doping concentrations, resulting in remarkably different fill factors (FFs). The results reveal that PL(V) mirrors the current-voltage (JV) characteristics in the power-generating regime, which highlights an interesting correlation between radiative and nonradiative recombination losses. In particular, high FF devices show a rapid quenching of PL(V) from open-circuit to the maximum power point. We conclude that, while the PL has to be maximized at V-OC at lower biases

The measurement of the ideality factor (nid) is a popular tool to infer the dominant recombination type in perovskite solar cells (PSC). However, the true meaning of its values is often misinterpreted in complex multilayered devices such as PSC. In this work, the effects of bulk and interface recombination on the nid are investigated experimentally and theoretically. By coupling intensity‐dependent quasi‐Fermi level splitting measurements with drift diffusion simulations of complete devices and partial cell stacks, it is shown that interfacial recombination leads to a lower nid compared to Shockley–Read–Hall (SRH) recombination in the bulk. As such, the strongest recombination channel determines the nid of the complete cell. An analytical approach is used to rationalize that nid values between 1 and 2 can originate exclusively from a single recombination process. By expanding the study over a wide range of the interfacial energy offsets and interfacial recombination velocities, it is shown that an ideality factor of nearly 1 is usually indicative of strong first‐order non‐radiative interface recombination and that it correlates with a lower device performance. It is only when interface recombination is largely suppressed and bulk SRH recombination dominates that a small nid is again desirable.

Inorganic perovskites with cesium (Cs+) as the cation have great potential as photovoltaic materials if their phase purity and stability can be addressed. Herein, a series of inorganic perovskites is studied, and it is found that the power conversion efficiency of solar cells with compositions CsPbI1.8Br1.2, CsPbI2.0Br1.0, and CsPbI2.2Br0.8 exhibits a high dependence on the initial annealing step that is found to significantly affect the crystallization and texture behavior of the final perovskite film. At its optimized annealing temperature, CsPbI1.8Br1.2 exhibits a pure orthorhombic phase and only one crystal orientation of the (110) plane. Consequently, this allows for the best efficiency of up to 14.6% and the longest operational lifetime, T-S80, of approximate to 300 h, averaged of over six solar cells, during the maximum power point tracking measurement under continuous light illumination and nitrogen atmosphere. This work provides essential progress on the enhancement of photovoltaic performance and stability of CsPbI3 - xBrx perovskite solar cells., Zweitver��ffentlichungen der Universit��t Potsdam : Mathematisch-Naturwissenschaftliche Reihe; 1210

Monolithic perovskite silicon tandem solar cells can overcome the theoretical efficiency limit of silicon solar cells. This requires an optimum bandgap, high quantum efficiency, and high stability of the perovskite. Herein, a silicon heterojunction bottom cell is combined with a perovskite top cell, with an optimum bandgap of 1.68 amp; 8201;eV in planar p i n tandem configuration. A methylammonium free FA0.75Cs0.25Pb I0.8Br0.2 3 perovskite with high Cs content is investigated for improved stability. A 10 molarity increase to 1.1 amp; 8201;m of the perovskite precursor solution results in amp; 8776;75 amp; 8201;nm thicker absorber layers and 0.7 amp; 8201;mA amp; 8201;cm amp; 8722;2 higher short circuit current density. With the optimized absorber, tandem devices reach a high fill factor of 80 and up to 25.1 certified efficiency. The unencapsulated tandem device shows an efficiency improvement of 2.3 absolute over 5 amp; 8201;months, showing the robustness of the absorber against degradation. Moreover, a photoluminescence quantum yield analysis reveals that with adapted charge transport materials and surface passivation, along with improved antireflection measures, the high bandgap perovskite absorber has the potential for 30 tandem efficiency in the near future

2D Ruddlesden-Popper perovskite (RPP) solar cells have excellent environmental stability. However, the power conversion efficiency (PCE) of RPP cells remains inferior to 3D perovskite-based cells. Herein, 2D (CH3(CH2)(3)NH3)(2)(CH3NH3)(n-1)PbnI3n+1 perovskite cells with different numbers of [PbI6](4-) sheets (n = 2-4) are analyzed. Photoluminescence quantum yield (PLQY) measurements show that nonradiative open-circuit voltage (V-OC) losses outweigh radiative losses in materials with n > 2. The n = 3 and n = 4 films exhibit a higher PLQY than the standard 3D methylammonium lead iodide perovskite although this is accompanied by increased interfacial recombination at the top perovskite/C-60 interface. This tradeoff results in a similar PLQY in all devices, including the n = 2 system where the perovskite bulk dominates the recombination properties of the cell. In most cases the quasi-Fermi level splitting matches the device V-OC within 20 meV, which indicates minimal recombination losses at the metal contacts. The results show that poor charge transport rather than exciton dissociation is the primary reason for the reduction in fill factor of the RPP devices. Optimized n = 4 RPP solar cells had PCEs of 13% with significant potential for further improvements.

Perovskite solar cells now compete with their inorganic counterparts in terms of power conversion efficiency, not least because of their small open-circuit voltage (V-OC) losses. A key to surpass traditional thin-film solar cells is the fill factor (FF). Therefore, more insights into the physical mechanisms that define the bias dependence of the photocurrent are urgently required. In this work, we studied charge extraction and recombination in efficient triple cation perovskite solar cells with undoped organic electron/hole transport layers (ETL/HTL). Using integral time of flight we identify the transit time through the HTL as the key figure of merit for maximizing the fill factor (FF) and efficiency. Complementarily, intensity dependent photocurrent and V-OC measurements elucidate the role of the HTL on the bias dependence of non-radiative and transport-related loss channels. We show that charge transport losses can be completely avoided under certain conditions, yielding devices with FFs of up to 84%. Optimized cells exhibit power conversion efficiencies of above 20% for 6 mm(2) sized pixels and 18.9% for a device area of 1 cm(2). These are record efficiencies for hybrid perovskite devices with dopant-free transport layers, highlighting the potential of this device technology to avoid charge-transport limitations and to approach the Shockley-Queisser limit.

Today s perovskite solar cells PSCs are limited mainly by their open amp; 8208;circuit voltage VOC due to nonradiative recombination. Therefore, a comprehensive understanding of the relevant recombination pathways is needed. Here, intensity amp; 8208;dependent measurements of the quasi amp; 8208;Fermi level splitting QFLS and of the VOC on the very same devices, including pin amp; 8208;type PSCs with efficiencies above 20 , are performed. It is found that the QFLS in the perovskite lies significantly below its radiative limit for all intensities but also that the VOC is generally lower than the QFLS, violating one main assumption of the Shockley amp; 8208;Queisser theory. This has far amp; 8208;reaching implications for the applicability of some well amp; 8208;established techniques, which use the VOC as a measure of the carrier densities in the absorber. By performing drift amp; 8208;diffusion simulations, the intensity dependence of the QFLS, the QFLS amp; 8208;VOC offset and the ideality factor are consistently explained by trap amp; 8208;assisted recombination and energetic misalignment at the interfaces. Additionally, it is found that the saturation of the VOC at high intensities is caused by insufficient contact selectivity while heating effects are of minor importance. It is concluded that the analysis of the VOC does not provide reliable conclusions of the recombination pathways and that the knowledge of the QFLS amp; 8208;VOC relation is of great importance

Approaches to boost the efficiency and stability of perovskite solar cells often address one singular problem in a specific device configuration. In this work, we utilize a poly(ionic liquid) (PIL) to introduce a multi-functional interlayer to improve the device efficiency and stability for different perovskite compositions and architectures. The presence of the PIL at the perovskite surface reduces the non-radiative losses down to 60 meV already in the neat material, indicating effective surface trap passivation, thereby pushing the external photoluminescence quantum yield up to 7%. In devices, the PIL treatment induces a bi-functionality of the surface where insulating areas act as a blocking layer reducing interfacial charge recombination and increasing the VOC, whereas, at the same time, the passivated neighbouring regions provide more efficient charge extraction, increasing the FF. As a result, these solar cells exhibit outstanding VOC and FF values of 1.17 V and 83% respectively, with the best devices reaching conversion efficiencies up to 21.4%. The PIL-treated devices additionally show enhanced stability during maximum power point tracking (>700 h) and unchanged efficiencies after 10 months of shelf storage. By applying the PIL to small and wide bandgap perovskites, and to nip cells, we corroborate the generality of this methodology to improve the efficiency in various cell architectures and perovskite compositions. This journal is

Engineering two-dimensional (2D) / three-dimensional (3D) perovskites has emerged as an attractive route to efficient and durable perovskite solar cells. Beyond improving the surface stability of the 3D layer and acting as a trap passivation agent, the exact function of 2D/3D device interface remains vague. Here, we provide evidence that 2D/3D perovskite interface that forms a p-n junction is capable to reduce the electron density at the hole-transporting layer interface and ultimately suppress interfacial recombination. By a novel ultraviolet photoelectron spectroscopy (UPS) depth-profiling technique, we show that engineering of the 2D organic cations, in this case by simply varying the halide counter ions in thiophene methylammonium-salts, modifies the 2D/3D perovskite energy alignment. These measurements enable the true identification of the energetic across the 2D/3D interface, so far unclear. When integrated in solar cells, due to the electron blocking nature of the 2D layer, the optimized 2D/3D structures suppress the interfacial recombination losses, leading to open-circuit voltage (VOC) which approaches the potential internal Quasi-Fermi Level Splitting (QFLS) voltage of the perovskite absorber. The devices exhibit an improved fill factor (FF) driven by the enhanced hole extraction efficiency and reduced electron density at the 2D/3D interface. We thus identify the essential parameters and energetic alignment scenario required for 2D/3D perovskite systems in order to surpass the current limitations of hybrid perovskite solar cell performances.