20% Efficient Perovskite Solar Cells with 2D Electron Transporting Layer

Herein, a 2D SnS₂ electron transporting layer is reported via self‐assembly stacking deposition for highly efficient planar perovskite solar cells, achieving over 20% power conversion efficiency under AM 1.5 G 100 mW cm^?2 light illumination. To the best of the authors' knowledge, this represents the highest efficiency that has so far been reported for perovskite solar cells using a 2D electron transporting layer. The large‐scaled 2D multilayer SnS₂ sheet structure triggers a heterogeneous nucleation over the perovskite precursor film. The intermolecular Pb???S interactions between perovskite and SnS₂ could passivate the interfacial trap states, which suppress charge recombination and thus facilitate electron extraction for balanced charge transport at interfaces between electron transporting layer/perovskite and hole transporting layer/perovskite. This work demonstrates that 2D materials have great potential for high‐performance perovskite solar cells.     

Metal Oxide Charge Transport Layers for Efficient and Stable Perovskite Solar Cells

Currently, the efficiency of perovskite solar cells (PSCs) is ≈24%. For the fabrication of such high efficiency PSCs, it is necessary to use both electron and hole transport layers to effectively separate the charges generated by light absorption of the perovskite layer and selectively transfer the separated electrons and holes. In addition to the efficiency, the materials used for transporting charges must be resilient to light, heat, and moisture to ensure long‐term stability of PSCs; furthermore, low‐cost fabrication is required to form a charge transport layer at low temperatures by a solution process. For this purpose, metal oxides are best suited as charge transport materials for PSCs because of their advantages such as low cost, long‐term stability, and high efficiency. In this Review, the metal oxide electron and hole transport materials used in PSCs are reviewed and preparation of these materials is summarized. Finally, the challenges and future research direction for metal oxide‐based charge transport materials are described.     

TiO2/SnOxCly double layer for highly efficient planar perovskite solar cells

Recently, perovskite solar cells have attracted tremendous research interest due to their amazing light to electric power conversion efficiency (PCE). However, most high performance devices usually use mesoporous TiO₂ as the electron transport layer (ETL), which increases cost for practical application. Here, TiO₂/SnO_xCl_y double layer was employed as the ETL for planar perovskite solar cells. Compared with bare TiO₂, perovskite solar cell based on TiO₂/SnO_xCl_y shows drastically improved power conversion efficiency and reduced hysteresis. These improvements are attributed to TiO₂/SnO_xCl_y which could enhance electron extraction and reduce surface trap-state.     

A Band‐Edge Potential Gradient Heterostructure to Enhance Electron Extraction Efficiency of the Electron Transport Layer in High‐Performance Perovskite Solar Cells

As the key component in efficient perovskite solar cells, the electron transport layer (ETL) can selectively collect photogenerated charge carriers produced in perovskite absorbers and prevent the recombination of carriers at interfaces, thus ensuring a high power conversion efficiency. Compared with the conventional single‐ or dual‐layered ETLs, a gradient heterojunction (GHJ) strategy is more attractive to facilitate charge separation because the potential gradient created at an appropriately structured heterojunction can act as a driving force to regulate the electron transport toward a desired direction. Here, a SnO₂/TiO₂ GHJ interlayer configuration inside the ETL is reported to simultaneously achieve effective extraction and efficient transport of photoelectrons. With such an interlayer configuration, the GHJs formed at the perovskite/ETL interface act collectively to extract photogenerated electrons from the perovskite layer, while GHJs formed at the boundaries of the interconnected SnO₂ and TiO₂ networks throughout the entire ETL layer can extract electron from the slow electron mobility TiO₂ network to the high electron mobility SnO₂ network. Devices based on GHJ ETL exhibit a champion power conversion efficiency of 18.08%, which is significantly higher than that obtained from the compact TiO₂ ETL constructed under the comparable conditions.     

PbTiO3 as Electron‐Selective Layer for High‐Efficiency Perovskite Solar Cells: Enhanced Electron Extraction via Tunable Ferroelectric Polarization

PbTiO₃ (PTO) is explored as a versatile and tunable electron‐selective layer (ESL) for perovskite solar cells. To demonstrate effectiveness of PTO for electron–hole separation and charge transfer, perovskite solar cells are designed and fabricated in the laboratory with the PTO as the ESL. The cells achieve a power conversion efficiency (PCE) of ≈12.28% upon preliminary optimization. It is found that the PTO ferroelectric layer can not only increase the PCE, but also tune the photocurrent via tuning PTO's ferroelectric polarization. Moreover, to understand the physical mechanism underlying the carrier transport by the ferroelectric polarization, the electronic structure of PTO/CH₃NH₃PbI₃ heterostructure is computed using the first‐principles methods, for which the triplet state is used to simulate charge transfer in the heterostructure. It is shown that the synergistic effect of type II band alignment and the specific ferroelectric polarization direction provide the effective extraction of electrons from the light absorber, while minimize recombination of photogenerated electron–hole pairs. Overall, the ferroelectric PTO is a promising and tunable ESL for optimizing electron transport in the perovskite solar cells. The design offers a different strategy for altering direction of carrier transport in solar cells.     

Improved power conversion efficiency by insertion of RGO–TiO2 composite layer as optical spacer in polymer bulk heterojunction solar cells

We report that the power conversion efficiency (PCE) can be enhanced in polymer bulk heterojunction solar cells by inserting an interfacial electron transporting layer consisting of pristine TiO₂ or reduced graphene oxide–TiO₂ (RGO–TiO₂) between the active layer and cathode Al electrode. The enhancement in the PCE has been analyzed through the optical absorption, current–voltage characteristics under illumination and estimation of photo-induced charge carrier generation rate. It was found that either TiO₂ or RGO–TiO₂ interfacial layers improve the light harvesting, as well as the charge extraction efficiency, acting as a blocking layer for holes, and also reducing charge recombination. The combined enhancement in light harvesting property and charge collection efficiency improves the PCE of the organic solar cell up to 4.18% and 5.33% for TiO₂ and RGO–TiO₂ interfacial layer, respectively, as compared to a value of 3.26% for the polymer solar cell without interfacial layer.     

Boosting the Efficiency of Perovskite Solar Cells with CsBr‐Modified Mesoporous TiO2 Beads as Electron‐Selective Contact

Rapid extraction of photogenerated charge carriers is essential to achieve high efficiencies with perovskite solar cells (PSCs). Here, a new mesoscopic architecture as electron‐selective contact for PSCs featuring 40 nm sized TiO₂ beads endowed with mesopores of a few nanometer diameters is introduced. The bimodal pore distribution inherent to these films produces a very large contact area of 200 m² g^?1 whose access by the perovskite light absorber is facilitated by the interstitial voids between the particles. Modification of the TiO₂ surface by CsBr further strengthens its interaction with the perovskite. As a result, photogenerated electrons are extracted rapidly producing a very high fill factor of close to 80% a V_OC of 1.14 V and a PCE up to 21% with negligible hysteresis.     

Sulfate‐Assisted Interfacial Engineering for High Yield and Efficiency of Triple Cation Perovskite Solar Cells with Alkali‐Doped TiO2 Electron‐Transporting Layers

Facile electron injection and extraction are two key attributes desired in electron transporting layers to enhance the efficiency of planar perovskite solar cells. Herein it is demonstrated that the incorporation of alkali metal dopants in mesoporous TiO₂ can effectively modulate electronic conductivity and improve the charge extraction process by counterbalancing oxygen vacancies acting as nonradiative recombination centers. Moreover, sulfate bridges (SO₄^2?) grafted on the surface of K‐doped mesoporous titania provide a seamless integration of absorber and electron‐transporting layers that accelerate overall transport kinetics. Potassium doping markedly influences the nucleation of the perovskite layer to produce highly dense films with facetted crystallites. Solar cells made from K:TiO₂ electrodes exhibit power conversion efficiencies up to 21.1% with small hysteresis despite all solution coating processes conducted under ambient air conditions (controlled humidity: 25–35%). The higher device efficiencies are attributed to intrinsically tuned electronic conductivity and chemical modification of grain boundaries enabling uniform coverage of perovskite films with large grain size.     

Enhancing the Optoelectronic Performance of Perovskite Solar Cells via a Textured CH3NH3PbI3 Morphology

Perovskite‐based solar cells are generally assembled as planar structures comprising a flat organoammonium metal halide perovskite layer, or mesoscopic structures employing a mesoporous metal‐oxide scaffold into which the perovskite material is infiltrated. To present, little attention has been directed toward the texturing of the perovskite material itself. Herein, a textured CH₃NH₃PbI₃ morphology formed through a thin mesoporous TiO₂ seeding layer and a gas‐assisted crystallization method is reported. The textured morphology comprises a multitiered nanostructure, which allows for significant improvements in the light harvesting and charge extraction performance of the solar cells. Due to these improvements, average short‐circuit current densities for a batch of 28 devices are in excess of 22 mA cm^?2, and the maximum recorded power conversion efficiency is 16.3%. The performance gains concomitant with this textured CH₃NH₃PbI₃ morphology provide further insights into how control of the perovskite microstructure can be used to enhance the cell performance.     

Engineering of the Electron Transport Layer/Perovskite Interface in Solar Cells Designed on TiO2 Rutile Nanorods

The engineering of the electron transport layer (ETL)/light absorber interface is explored in perovskite solar cells. Single‐crystalline TiO₂ nanorod (NR) arrays are used as ETL and methylammonium lead iodide (MAPI) as light absorber. A dual ETL surface modification is investigated, namely by a TiCl₄ treatment combined with a subsequent PC₆₁BM monolayer deposition, and the effects on the device photovoltaic performance were evaluated with respect to single modifications. Under optimized conditions, for the combined treatment synergistic effects are observed that lead to remarkable enhancements in cell efficiency, from 14.2% to 19.5%, and to suppression of hysteresis. The devices show J_SC, V_OC, and fill factor as high as 23.2 mA cm^?2, 1.1 V, and 77%, respectively. These results are ascribed to a more efficient charge transfer across the ETL/perovskite interface, which originates from the passivation of defects and trap states at the ETL surface. To the best of our knowledge, this is the highest cell performance ever reported for TiO₂ NR‐based solar cells fabricated with conventional MAPI light absorber. Perspective wise, this ETL surface functionalization approach combined with more recently developed and better performing light absorbers, such as mixed cation/anion hybrid perovskite materials, is expected to provide further performance enhancements.     

Thin Films of Dendritic Anatase Titania Nanowires Enable Effective Hole‐Blocking and Efficient Light‐Harvesting for High‐Performance Mesoscopic Perovskite Solar Cells

To achieve high‐performance perovskite solar cells, especially with mesoscopic cell structure, the design of the electron transport layer (ETL) is of paramount importance. Highly branched anatase TiO₂ nanowires (ATNWs) with varied orientation are grown via a facile one‐step hydrothermal process on a transparent conducting oxide substrate. These films show good coverage with optimization obtained by controlling the hydrothermal reaction time. A homogeneous methyl­ammonium lead iodide (CH₃NH₃PbI₃) perovskite thin film is deposited onto these ATNW films forming a bilayer architecture comprising of a CH₃NH₃PbI₃ sensitized ATNW bottom layer and a CH₃NH₃PbI₃ capping layer. The formation, grain size, and uniformity of the perovskite crystals strongly depend on the degree of surface coverage and the thickness of the ATNW film. Solar cells constructed using the optimized ATNW thin films (220 nm in thickness) yield power conversion efficiencies up to 14.2% with a short‐circuit photocurrent density of 20.32 mA cm^?2, an open‐circuit photovoltage of 993 mV, and a fill factor of 0.70. The dendritic ETL and additional perovskite capping layer efficiently capture light and thus exhibit a superior light harvesting efficiency. The ATNW film is an effective hole‐blocking layer and efficient electron transport medium for excellent charge separation and collection within the cells.     

Plasmonic Electrically Functionalized TiO2 for High‐Performance Organic Solar Cells

Optical effects of the plasmonic structures and the materials effects of the metal nanomaterials have recently been individually studied for enhancing performance of organic solar cells (OSCs). Here, the effects of plasmonically induced carrier generation and enhanced carrier extraction of the carrier transport layer (i.e., plasmonic‐electrical effects) in OSCs are investigated. Enhanced charge extraction in TiO₂ as a highly efficient electron transport layer by the incorporation of metal nanoparticles (NPs) is proposed and demonstrated. Efficient device performance is demonstrated by using Au NPs incorporated TiO₂ at a plasmonic wavelength (560–600 nm), which is far longer than the originally necessary UV light. By optimizing the concentration ratio of the Au NPs in the NP‐TiO₂ composite, the performances of OSCs with various polymer active layers are enhanced and efficiency of 8.74% is reached. An integrated optical and electrical model, which takes into account plasmonic‐induced hot carrier tunneling probability and extraction barrier between TiO₂ and the active layer, is introduced. The enhanced charge extraction under plasmonic illumination is attributed to the strong charge injection of plasmonically excited electrons from NPs into TiO₂. The mechanism favors trap filling in TiO₂, which can lower the effective energy barrier and facilitate carrier transport in OSCs.     

Control of Solid‐State Dye‐Sensitized Solar Cell Performance by Block‐Copolymer‐Directed TiO2 Synthesis

Hybrid dye‐sensitized solar cells are typically composed of mesoporous titania (TiO₂), light‐harvesting dyes, and organic molecular hole‐transporters. Correctly matching the electronic properties of the materials is critical to ensure efficient device operation. In this study, TiO₂ is synthesized in a well‐defined morphological confinement that arises from the self‐assembly of a diblock copolymer—poly(isoprene‐b‐ethylene oxide) (PI‐b‐PEO). The crystallization environment, tuned by the inorganic (TiO₂ mass) to organic (polymer) ratio, is shown to be a decisive factor in determining the distribution of sub‐bandgap electronic states and the associated electronic function in solid‐state dye‐sensitized solar cells. Interestingly, the tuning of the sub‐bandgap states does not appear to strongly influence the charge transport and recombination in the devices. However, increasing the depth and breadth of the density of sub‐bandgap states correlates well with an increase in photocurrent generation, suggesting that a high density of these sub‐bandgap states is critical for efficient photo‐induced electron transfer and charge separation.     

Efficient and Stable Perovskite Solar Cells via Dual Functionalization of Dopamine Semiquinone Radical with Improved Trap Passivation Capabilities

Highly efficient planar heterojunction perovskite solar cells (PVSCs) with dopamine (DA) semiquinone radical modified poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) (DA‐PEDOT:PSS) as a hole transporting layer (HTL) were fabricated. A combination of characterization techniques were employed to investigate the effects of DA doping on the electron donating capability of DA‐PEDOT:PSS, perovskite film quality and charge recombination kinetics in the solar cells. Our study shows that DA doping endows the DA‐PEDOT:PSS‐modified PVSCs with a higher radical content and greater perovskite to HTL charge extraction capability. In addition, the DA doping also improves work function of the HTL, increases perovskite film crystallinity, and the amino and hydroxyl groups in DA can interact with the undercoordinated Pb atoms on the perovskite crystal, reducing charge‐recombination rate and increasing charge‐extraction efficiency. Therefore, the DA‐PEDOT:PSS‐modified solar cells outperform those based on PEDOT:PSS, increasing open‐circuit voltage (V _oc) and power conversion efficiency (PCE) to 1.08 V and 18.5%, respectively. Even more importantly, the efficiency of the unencapsulated DA‐PEDOT:PSS‐based PVSCs are well retained with only 20% PCE loss after exposure to air for 250 hours. These in‐depth insights into structure and performance provide clear and novel guidelines for the design of effective HTLs to facilitate the practical application of inverted planar heterojunction PVSCs.     

Influence of compact TiO2 layer on the photovoltaic characteristics of the organometal halide perovskite-based solar cells

A series of perovskite-based solar cells were fabricated wherein a compact layer (CL) of TiO₂ of varying thickness (0–390 nm) was introduced by spray pyrolysis deposition between fluorine-doped tin oxide (FTO) electrode and TiO₂ nanoparticle layer in perovskite-based solar cells. Investigations of the CL thickness-dependent current density–voltage (J–V) characteristics, dark current, and open circuit voltage (V_oc) decays showed a similar trend for thickness dependence. A CL thickness of 90 nm afforded the perovskite-based solar cell with the maximum power conversion efficiency (η, 3.17%). Furthermore, two additional devices, perovskite-based solar cell omitting hole transporting materials layer and cell without the TiO₂ nanoparticles, were designed and fabricated to study the influence of the CL thickness on different electron transport paths in perovskite-based solar cells. Solar cells devoid of TiO₂ nanoparticles, but with perovskite and organic hole-transport materials (HTMs), exhibited sustained improvement in photovoltaic performances with increase in the thickness of CL, which is in contrast to the behavior of classical perovskite-based solar cell and common solid state solar cell which showed optimal photovoltaic performances when the thickness of CL is 90 nm. These observations suggested that TiO₂ nanoparticles play a significant role in electron transport in perovskite-based solar cells.     

Nanoimprinted Grating‐Embedded Perovskite Solar Cells with Improved Light Management

Organic–inorganic halide perovskite solar cells are one of the most efficient photovoltaic devices, and their power conversion efficiency (PCE) continues to grow rapidly due to the optimization of device architecture and functional materials. The involved optical design has an important impact on performance by affecting the light harvesting capability. Here, demonstrated is a simple and effective strategy to boost device performance from the perspective of light management. A diffraction grating pattern into the TiO₂ scaffold and antireflection layer is simultaneously introduced to construct a double grating design for perovskite solar cells. The grating pattern obtained using a commercial compact disk as the hard mold can modulate light transport by enhancing the light transmittance and, thus, light absorption in perovskite solar cells. The grating pattern‐induced light trapping can significantly increase the short‐circuit current density and PCE by 4.8% and 7.9%, respectively, on average. The present work develops a feasible method by tailoring the morphology‐related optical property to further improve the performance of perovskite solar cells. The double grating design can also generate structural color and can provide an alternative solution for fabricating colorful solar cells.     

Towards Efficient Integrated Perovskite/Organic Bulk Heterojunction Solar Cells: Interfacial Energetic Requirement to Reduce Charge Carrier Recombination Losses

Integrated perovskite/organic bulk heterojunction (BHJ) solar cells have the potential to enhance the efficiency of perovskite solar cells by a simple one‐step deposition of an organic BHJ blend photoactive layer on top of the perovskite absorber. It is found that inverted structure integrated solar cells show significantly increased short‐circuit current (J_sc) gained from the complementary absorption of the organic BHJ layer compared to the reference perovskite‐only devices. However, this increase in J_sc is not directly reflected as an increase in power conversion efficiency of the devices due to a loss of fill factor. Herein, the origin of this efficiency loss is investigated. It is found that a significant energetic barrier (≈250 meV) exists at the perovskite/organic BHJ interface. This interfacial barrier prevents efficient transport of photogenerated charge carriers (holes) from the BHJ layer to the perovskite layer, leading to charge accumulation at the perovskite/BHJ interface. Such accumulation is found to cause undesirable recombination of charge carriers, lowering surface photovoltage of the photoactive layers and device efficiency via fill factor loss. The results highlight a critical role of the interfacial energetics in such integrated cells and provide useful guidelines for photoactive materials (both perovskite and organic semiconductors) required for high‐performance devices.     

A Universal Strategy to Utilize Polymeric Semiconductors for Perovskite Solar Cells with Enhanced Efficiency and Longevity

In this contribution, a facile and universal method is successfully reported to fabricate perovskite solar cells (PSCs) with enhanced efficiency and stability. Through dissolving functional conjugated polymers in antisolvent chlorobenzene to treat the spinning CH₃NH₃PbI₃ perovskite film, the resultant devices exhibit significantly enhanced efficiency and longevity simultaneously. In‐depth characterizations demonstrate that thin polymer layer well covers the top surface of perovskite film, resulting in certain surface passivation and morphology modification. More importantly, it is shown that through rational chemical modification, namely molecular fluorination, the air stability and photostability of the perovskite solar cells are remarkably enhanced. Considering the vast selection of conjugated polymer materials and easy functional design, promising new results are expected in further enhancement of device performance. It is believed that the findings provide exciting insights into the role of conjugated polymer in improving the current perovskite‐based solar cells.     

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.     

Improving the Extraction of Photogenerated Electrons with SnO2 Nanocolloids for Efficient Planar Perovskite Solar Cells

Great attention to cost‐effective high‐efficiency solar power conversion of trihalide perovskite solar cells (PSCs) has been hovering at high levels in the recent 5 years. Among PSC devices, admittedly, TiO₂ is the most widely used electron transport layer (ETL); however, its low mobility which is even less than that of CH₃NH₃PbI₃ makes it not an ideal material. In principle, SnO₂ with higher electron mobility can be regarded as a positive alternative. Herein, a SnO₂ nanocolloid sol with ≈3 nm in size synthesized at 60 °C was spin‐coated onto the fuorine‐doped tin oxide (FTO) glass as the ETL of planar CH₃NH₃PbI₃ perovskite solar cells. TiCl₄ treatment of SnO₂‐coated FTO is found to improve crystallization and increase the surface coverage of perovskites, which plays a pivotal role in improving the power conversion efficiency (PCE). In this report, a champion efficiency of 14.69% (J_sc = 21.19 mA cm^?2, V_oc = 1023 mV, and FF = 0.678) is obtained with a metal mask at one sun illumination (AM 1.5G, 100 mW cm^?2). Compared to the typical TiO₂, the SnO₂ ETL efficiently facilitates the separation and transportation of photogenerated electrons/holes from the perovskite absorber, which results in a significant enhancement of photocurrent and PCE.