SnO2: A Wonderful Electron Transport Layer for Perovskite Solar Cells

The highest power conversion efficiency of perovskite solar cells is beyond 22%. Charge transport layers are found to be critical for device performance and stability. A traditional electron transport layer (ETL), such as TiO₂, is not very efficient for charge extraction at the interface, especially in planar structure. In addition, the devices using TiO₂ suffer from serious degradation under ultraviolet illumination. SnO₂ owns a better band alignment with the perovskite absorption layer and high electron mobility, which is helpful for electron extraction. In this Review, recent progresses in efficient and stable perovskite solar cells using SnO₂ as ETL are summarized.     

Solution‐Phase Epitaxial Growth of Perovskite Films on 2D Material Flakes for High‐Performance Solar Cells

The quality of perovskite films is critical to the performance of perovskite solar cells. However, it is challenging to control the crystallinity and orientation of solution‐processed perovskite films. Here, solution‐phase van der Waals epitaxy growth of MAPbI₃ perovskite films on MoS₂ flakes is reported. Under transmission electron microscopy, in‐plane coupling between the perovskite and the MoS₂ crystal lattices is observed, leading to perovskite films with larger grain size, lower trap density, and preferential growth orientation along (110) normal to the MoS₂ surface. In perovskite solar cells, when perovskite active layers are grown on MoS₂ flakes coated on hole‐transport layers, the power conversion efficiency is substantially enhanced for 15%, relatively, due to the increased crystallinity of the perovskite layer and the improved hole extraction and transfer rate at the interface. This work paves a way for preparing high‐performance perovskite solar cells and other optoelectronic devices by introducing 2D materials as interfacial layers.     

Long Electron–Hole Diffusion Length in High‐Quality Lead‐Free Double Perovskite Films

Developing environmentally friendly perovskites has become important in solving the toxicity issue of lead‐based perovskite solar cells. Here, the first double perovskite (Cs₂AgBiBr₆) solar cells using the planar structure are demonstrated. The prepared Cs₂AgBiBr₆ films are composed of high‐crystal‐quality grains with diameters equal to the film thickness, thus minimizing the grain boundary length and the carrier recombination. These high‐quality double perovskite films show long electron–hole diffusion lengths greater than 100 nm, enabling the fabrication of planar structure double perovskite solar cells. The resulting solar cells based on planar TiO₂ exhibit an average power conversion efficiency over 1%. This work represents an important step forward toward the realization of environmentally friendly solar cells and also has important implications for the applications of double perovskites in other optoelectronic devices.     

Improving the Electron Transport Performance of TiO2 Film by Regulating TiCl4 Post-Treatment for High-Efficiency Carbon-Based Perovskite Solar Cells

Titanium oxide (TiO₂) has been widely used as an electron transport layer (ETL) in perovskite solar cells (PSCs). Typically, TiCl₄ post-treatment is indispensable for modifying the surfaces of TiO₂ ETL to improve the electron transport performance. However, it is challenging to produce the preferred anatase phase-dominated TiO₂ by the TiCl₄ post-treatment due to the higher thermodynamic stability of the rutile phase. In this work, a mild continuous pH control strategy for effectively regulating the hydrolysis process of TiCl₄ post-treatment is proposed. As the weak organic base, urea has been demonstrated can maintain a moderate pH decrease during the hydrolysis process of TiCl₄ while keeping the hydrolysis process relatively mild due to the ultra-weak alkalinity. The improved pH environment is beneficial for the formation of anatase TiO₂. Consequently, a uniform anatase-dominated TiO₂ surface layer is formed on the mesoporous TiO₂, resulting in reduced defect density and superior band energy level. The interfacial charge recombination is effectively suppressed, and the charge extraction efficiency is improved simultaneously in the fabricated solar cells. The efficiency of the fabricated carbon electrode-based PSCs (C-PSCs) is improved from 16.63% to 18.08%, which is the highest for C-PSCs based on wide-bandgap perovskites.     

In Situ Back‐Contact Passivation Improves Photovoltage and Fill Factor in Perovskite Solar Cells

Organic–inorganic hybrid perovskite solar cells (PSCs) have seen a rapid rise in power conversion efficiencies in recent years; however, they still suffer from interfacial recombination and charge extraction losses at interfaces between the perovskite absorber and the charge–transport layers. Here, in situ back‐contact passivation (BCP) that reduces interfacial and extraction losses between the perovskite absorber and the hole transport layer (HTL) is reported. A thin layer of nondoped semiconducting polymer at the perovskite/HTL interface is introduced and it is shown that the use of the semiconductor polymer permits—in contrast with previously studied insulator‐based passivants—the use of a relatively thick passivating layer. It is shown that a flat‐band alignment between the perovskite and polymer passivation layers achieves a high photovoltage and fill factor: the resultant BCP enables a photovoltage of 1.15 V and a fill factor of 83% in 1.53 eV bandgap PSCs, leading to an efficiency of 21.6% in planar solar cells.     

Broadband Light Absorption and Efficient Charge Separation Using a Light Scattering Layer with Mixed Cavities for High‐Performance Perovskite Photovoltaic Cells with Stability

CH₃NH₃PbI₃ is one of the promising light sensitizers for perovskite photovoltaic cells, but a thick layer is required to enhance light absorption in the long‐wavelength regime ranging from PbI₂ absorption edge (500 nm) to its optical band‐gap edge (780 nm) in visible light. Meanwhile, the thick perovskite layer suppresses visible‐light absorption in the short wavelengths below 500 nm and charge extraction capability of electron–hole pairs produced upon light absorption. Herein, we find that a new light scattering layer with the mixed cavities of sizes in 100 and 200 nm between transparent fluorine‐doped tin oxide and mesoporous titanium dioxide electron transport layer enables full absorption of short‐wavelength photons (λ < 500 nm) to the perovskite along with enhanced absorption of long‐wavelength photons (500 nm < λ < 780 nm). Moreover, the light‐driven electric field is proven to allow efficient charge extraction upon light absorption, thereby leading to the increased photocurrent density as well as the fill factor prompted by the slow recombination rate. Additionally, the photocurrent density of the cell with a light scattering layer of mixed cavities is stabilized due to suppressed charge accumulation. Consequently, this work provides a new route to realize broadband light harvesting of visible light for high‐performance perovskite photovoltaic cells.     

Reducing Hysteresis and Enhancing Performance of Perovskite Solar Cells Using Low‐Temperature Processed Y‐Doped SnO2 Nanosheets as Electron Selective Layers

Despite the rapid increase of efficiency, perovskite solar cells (PSCs) still face some challenges, one of which is the current–voltage hysteresis. Herein, it is reported that yttrium‐doped tin dioxide (Y‐SnO₂) electron selective layer (ESL) synthesized by an in situ hydrothermal growth process at 95 °C can significantly reduce the hysteresis and improve the performance of PSCs. Comparison studies reveal two main effects of Y doping of SnO₂ ESLs: (1) it promotes the formation of well‐aligned and more homogeneous distribution of SnO₂ nanosheet arrays (NSAs), which allows better perovskite infiltration, better contacts of perovskite with SnO₂ nanosheets, and improves electron transfer from perovskite to ESL; (2) it enlarges the band gap and upshifts the band energy levels, resulting in better energy level alignment with perovskite and reduced charge recombination at NSA/perovskite interfaces. As a result, PSCs using Y‐SnO₂ NSA ESLs exhibit much less hysteresis and better performance compared with the cells using pristine SnO₂ NSA ESLs. The champion cell using Y‐SnO₂ NSA ESL achieves a photovoltaic conversion efficiency of 17.29% (16.97%) when measured under reverse (forward) voltage scanning and a steady‐state efficiency of 16.25%. The results suggest that low‐temperature hydrothermal‐synthesized Y‐SnO₂ NSA is a promising ESL for fabricating efficient and hysteresis‐less PSC.     

Interfacial Passivation of the p‐Doped Hole‐Transporting Layer Using General Insulating Polymers for High‐Performance Inverted Perovskite Solar Cells

Organic–inorganic lead halide perovskite solar cells (PVSCs), as a competing technology with traditional inorganic solar cells, have now realized a high power conversion efficiency (PCE) of 22.1%. In PVSCs, interfacial carrier recombination is one of the dominant energy‐loss mechanisms, which also results in the simultaneous loss of potential efficiency. In this work, for planar inverted PVSCs, the carrier recombination is dominated by the dopant concentration in the p‐doped hole transport layers (HTLs), since the F4‐TCNQ dopant induces more charge traps and electronic transmission channels, thus leading to a decrease in open‐circuit voltages (V_OC). This issue is efficiently overcome by inserting a thin insulating polymer layer (poly(methyl methacrylate) or polystyrene) as a passivation layer with an appropriate thickness, which allows for increases in the V_OC without significantly sacrificing the fill factor. It is believed that the passivation layer attributes to the passivation of interfacial recombination and the suppression of current leakage at the perovskite/HTL interface. By manipulating this interfacial passivation technique, a high PCE of 20.3% is achieved without hysteresis. Consequently, this versatile interfacial passivation methodology is highly useful for further improving the performance of planar inverted PVSCs.     

Improved performance and reproducibility of perovskite solar cells by jointly tuning the hole transport layer and the perovskite layer deposition

Solution processed organometal trihalide materials spur tremendous attention due to their unprecedented performance in photovoltaic applications. However, submicron thick perovskite films are prone to morphological defects in the form of cracks, pinholes and porosity; the traits originated from their solution phase processing and subsequent crystallization. Moreover, pinholes and cracks in the thin film of spincoated Spiro-OMeTAD hole transport layer reduce the performance reliability by forming micro shorts and weaken the defense against moisture ingress to the perovskite layer. For the large scale processing of perovskite solar cell from the economically prudent solution phase processing, morphological shortcomings of both perovskite and hole transport layers need an urgent address. By selecting non-conventional lead precursor (lead acetate) and implementing anti-solvent treatment during film deposition, we able to form pinhole free and compact perovskite film. Crack free hole conducting layer is obtained by blending Spiro-OMeTAD with a conducting polymer without compromising in the solar cell performance. A detail investigation of the charge transport and charge extraction properties of the developed hole transport layers have been carried out. The developed CH₃NH₃PbI₃ based perovskite solar cells show improved repeatability and performance.     

Reduced Interface‐Mediated Recombination for High Open‐Circuit Voltages in CH3NH3PbI3 Solar Cells

Perovskite solar cells with all‐organic transport layers exhibit efficiencies rivaling their counterparts that employ inorganic transport layers, while avoiding high‐temperature processing. Herein, it is investigated how the choice of the fullerene derivative employed in the electron‐transporting layer of inverted perovskite cells affects the open‐circuit voltage (V_OC). It is shown that nonradiative recombination mediated by the electron‐transporting layer is the limiting factor for the V_OC in the cells. By inserting an ultrathin layer of an insulating polymer between the active CH₃NH₃PbI₃ perovskite and the fullerene, an external radiative efficiency of up to 0.3%, a V_OC as high as 1.16 V, and a power conversion efficiency of 19.4% are realized. The results show that the reduction of nonradiative recombination due to charge‐blocking at the perovskite/organic interface is more important than proper level alignment in the search for ideal selective contacts toward high V_OC and efficiency.     

Self‐Assembly of Perovskite for Fabrication of Semitransparent Perovskite Solar Cells

This work reports on the preparation of semitransparent perovskite solar cells. The cells transparency is achieved through a unique wet deposition technique that creates perovskite grids with various dimensions. The perovskite grid is deposited on a mesoporous TiO₂ layer, followed by hole transport material deposition and evaporation of a semitransparent gold film. Control of the transparency of the solar cells is achieved by changing the perovskite solution concentration and the mesh openings. The semitransparent cells demonstrate 20–70% transparency with a power conversion efficiency of 5% at 20% transparency. This is the first demonstration of the possibility to create a controlled perovskite pattern using a direct mesh‐assisted assembly deposition method for fabrication of a semitransparent perovskite‐based solar cell.     

Low-Temperature Chemical Bath Deposition of Conformal and Compact NiOX for Scalable and Efficient Perovskite Solar Modules

A scalable and low-cost deposition of high-quality charge transport layers and photoactive perovskite layers are the grand challenges for large-area and efficient perovskite solar modules and tandem cells. An inverted structure with an inorganic hole transport layer is expected for long-term stability. Among various hole transport materials, nickel oxide has been investigated for highly efficient and stable perovskite solar cells. However, the reported deposition methods are either difficult for large-scale conformal deposition or require a high vacuum process. Chemical bath deposition is supposed to realize a uniform, conformal, and scalable coating by a solution process. However, the conventional chemical bath deposition requires a high annealing temperature of over 400 °C. In this work, an amino-alcohol ligand-based controllable release and deposition of NiO_X using chemical bath deposition with a low calcining temperature of 270 °C is developed. The uniform and conformal in-situ growth precursive films can be adjusted by tuning the ligand structure. The inverted structured perovskite solar cells and large-area solar modules reached a champion PCE of 22.03% and 19.03%, respectively. This study paves an efficient, low-temperature, and scalable chemical bath deposition route for large-area NiO_X thin films for the scalable fabrication of highly efficient perovskite solar modules.     

Charge transfer enhancement of TiO2/perovskite interface in perovskite solar cells

In the conventional perovskite solar cells (PSCs) structure, TiO₂ is the most commonly used electron transport layer (ETL) as it has good energy-level matching with perovskite layer. However, oxygen vacancy defects will appear when TiO₂ is exposed to ultraviolet light for a long time, which would reduce its carrier extraction ability. Here, we report a simple and effective interface engineering method for TiO₂ ETL to achieve a highly efficient PSCs. An ultra-thin [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) layer is used to modify the mesoporous TiO₂/perovskite layer interface. The PCBM effectively passivates defects on the TiO₂ surface, promotes the extraction of electrons, and improves the quality of the perovskite film. Finally, a high efficiency of 16.4% was achieved for the modified device, much higher than 13.5% of the reference devices. After storing for 12 days in an atmosphere with an air humidity of 30?±?5%, the efficiency of the PSCs maintains more than 60% of its initial level. This strategy is beneficial to enhance the efficiency and working stability of PSCs.

     

Polarized Ferroelectric Polymers for High‐Performance Perovskite Solar Cells

In hybrid organic–inorganic lead halide perovskite solar cells, the energy loss is strongly associated with nonradiative recombination in the perovskite layer and at the cell interfaces. Here, a simple but effective strategy is developed to improve the cell performance of perovskite solar cells via the combination of internal doping by a ferroelectric polymer and external control by an electric field. A group of polarized ferroelectric (PFE) polymers are doped into the methylammonium lead iodide (MAPbI₃) layer and/or inserted between the perovskite and the hole‐transporting layers to enhance the build‐in field (BIF), improve the crystallization of MAPbI₃, and regulate the nonradiative recombination in perovskite solar cells. The PFE polymer‐doped MAPbI₃ shows an orderly arrangement of MA⁺ cations, resulting in a preferred growth orientation of polycrystalline perovskite films with reduced trap states. In addition, the BIF is enhanced by the widened depletion region in the device. As an interfacial dipole layer, the PFE polymer plays a critical role in increasing the BIF. This combined effect leads to a substantial reduction in voltage loss of 0.14 V due to the efficient suppression of nonradiative recombination. Consequently, the resulting perovskite solar cells present a power conversion efficiency of 21.38% with a high open‐circuit voltage of 1.14 V.     

A Novel Conductive Mesoporous Layer with a Dynamic Two‐Step Deposition Strategy Boosts Efficiency of Perovskite Solar Cells to 20%

Lead halide perovskite solar cells (PSCs) with the high power conversion efficiency (PCE) typically use mesoporous metal oxide nanoparticles as the scaffold and electron‐transport layers. However, the traditional mesoporous layer suffers from low electron conductivity and severe carrier recombination. Here, antimony‐doped tin oxide nanorod arrays are proposed as novel transparent conductive mesoporous layers in PSCs. Such a mesoporous layer improves the electron transport as well as light utilization. To resolve the common problem of uneven growth of perovskite on rough surface, the dynamic two‐step spin coating strategy is proposed to prepare highly smooth, dense, and crystallized perovskite films with micrometer‐scale grains, largely reducing the carrier recombination ratio. The conductive mesoporous layer and high‐quality perovskite film eventually render the PSC with a remarkable PCE of 20.1% with excellent reproducibility. These findings provide a new avenue to further design high‐efficiency PSCs from the aspect of carrier transport and recombination.     

Bifacial Contact Junction Engineering for High‐Performance Perovskite Solar Cells with Efficiency Exceeding 21%

Ordered 1D metal oxide structure is desirable in thin film solar cells owing to its excellent charge collection capability. However, the electron transfer in 1D electron transporting layer (ETL)‐based devices is still limited to a submicrometer‐long pathway that is vertical to the substrate. Here, an innovative closely packed rutile TiO₂ nanowire (CRTNW) network parallel to the facet of fluorine‐doped tin oxide (FTO) substrate is reported, which can serve as a 1D nanoscale electron transport pathway for efficient perovskite solar cells (PSCs). The PSC constructed using newly prepared CRTNW ETL achieves an impressive power conversion efficiency of 21.10%, which can be attributed to the facilitated electron extraction induced by the favorable junctions formed at FTO/ETL and ETL/perovskite interfaces and also the suppressed charge recombination originating from improved perovskite morphology with large grains, flat surface, and good surface coverage. The bifacial contact junctions engineering also enables large‐area device fabrication. The PSC with 1 cm² aperture yields an efficiency of 19.50% under one sun illumination. This work highlights the significance of controlling the orientation and packing density of the ordered 1D oxide nanostructured thin films for highly efficient optoelectronic devices in a large‐scale manner.     

Nonradiative Recombination in Perovskite Solar Cells: The Role of Interfaces

Perovskite solar cells combine high carrier mobilities with long carrier lifetimes and high radiative efficiencies. Despite this, full devices suffer from significant nonradiative recombination losses, limiting their V_OC to values well below the Shockley–Queisser limit. Here, recent advances in understanding nonradiative recombination in perovskite solar cells from picoseconds to steady state are presented, with an emphasis on the interfaces between the perovskite absorber and the charge transport layers. Quantification of the quasi‐Fermi level splitting in perovskite films with and without attached transport layers allows to identify the origin of nonradiative recombination, and to explain the V_OC of operational devices. These measurements prove that in state‐of‐the‐art solar cells, nonradiative recombination at the interfaces between the perovskite and the transport layers is more important than processes in the bulk or at grain boundaries. Optical pump‐probe techniques give complementary access to the interfacial recombination pathways and provide quantitative information on transfer rates and recombination velocities. Promising optimization strategies are also highlighted, in particular in view of the role of energy level alignment and the importance of surface passivation. Recent record perovskite solar cells with low nonradiative losses are presented where interfacial recombination is effectively overcome—paving the way to the thermodynamic efficiency limit.     

Interface Engineering for All‐Inorganic CsPbI2Br Perovskite Solar Cells with Efficiency over 14%

In this work, a SnO₂/ZnO bilayered electron transporting layer (ETL) aimed to achieve low energy loss and large open‐circuit voltage (V_oc) for high‐efficiency all‐inorganic CsPbI₂Br perovskite solar cells (PVSCs) is introduced. The high‐quality CsPbI₂Br film with regular crystal grains and full coverage can be realized on the SnO₂/ZnO surface. The higher‐lying conduction band minimum of ZnO facilitates desirable cascade energy level alignment between the perovskite and SnO₂/ZnO bilayered ETL with superior electron extraction capability, resulting in a suppressed interfacial trap‐assisted recombination with lower charge recombination rate and greater charge extraction efficiency. The as‐optimized all‐inorganic PVSC delivers a high V_oc of 1.23 V and power conversion efficiency (PCE) of 14.6%, which is one of the best efficiencies reported for the Cs‐based all‐inorganic PVSCs to date. More importantly, decent thermal stability with only 20% PCE loss is demonstrated for the SnO₂/ZnO‐based CsPbI₂Br PVSCs after being heated at 85 °C for 300 h. These findings provide important interface design insights that will be crucial to further improve the efficiency of all‐inorganic PVSCs in the future.     

Strategically Constructed Bilayer Tin (IV) Oxide as Electron Transport Layer Boosts Performance and Reduces Hysteresis in Perovskite Solar Cells

Nanostructured tin (IV) oxide (SnO₂) is emerging as an ideal inorganic electron transport layer in n–i–p perovskite devices, due to superior electronic and low‐temperature processing properties. However, significant differences in current–voltage performance and hysteresis phenomena arise as a result of the chosen fabrication technique. This indicates enormous scope to optimize the electron transport layer (ETL), however, to date the understanding of the origin of these phenomena is lacking. Reported here is a first comparison of two common SnO₂ ETLs with contrasting performance and hysteresis phenomena, with an experimental strategy to combine the beneficial properties in a bilayer ETL architecture. In doing so, this is demonstrated to eliminate room‐temperature hysteresis while simultaneously attaining impressive power conversion efficiency (PCE) greater than 20%. This approach highlights a new way to design custom ETLs using functional thin‐film coatings of nanomaterials with optimized characteristics for stable, efficient, perovskite solar cells.     

Planar perovskite solar cells: eco-friendly synthesized cone-like ZnO nanostructure for efficient interfacial electron transport layer

The process of interfacial engineering in planar perovskite solar cells (PPSCs) plays an important role not only in transferring charges from active perovskite layer but also in enhancing the device performance. Considering this, the present study aims to synthesize an eco-friendly solution processed ZnO nanostructure interfacial electron transport layer (ETL) in PPSCs. The optical, structural, morphological and chemical properties of the prepared ZnO nanostructured material are analysed using ultraviolet–visible spectroscopy (UV–Vis), X-ray diffraction analysis (XRD), field emission-scanning electron microscopy (FE-SEM), energy-dispersive X-ray analysis (EDX), Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) analysis, respectively. Under ambient conditions, the device performance in terms of efficiency, stability and device degradation are investigated for both single layer (c-TiO₂ and cone-like ZnO nanostructure) and bilayer (c-TiO₂/cone-like ZnO nanostructure) ETL. Furthermore, the effective way of constructing cone-like nanostructured ZnO ETL on top of c-TiO₂ surface, found to be improved in faster charge transfer at the ETL/perovskite interfaces and reduced recombination losses. As a result, it exhibits maximum power conversion efficiency (PCE), short-circuit current density, fill factor and open-circuit voltage as 8.02%, 15.33 mA cm^?2, 0.52% and 0.99 V, respectively. Besides, the stability of PPSCs fabricated with bilayer exhibits better air stability of?~?87.40% with retained rate of 250 h from its initial value.