Highly Efficient and Stable Flexible Perovskite Solar Cells with Metal Oxides Nanoparticle Charge Extraction Layers

In this study, the fabrication of highly efficient and durable flexible inverted perovskite solar cells (PSCs) is reported. Presynthesized, solution‐derived NiO_x and ZnO nanoparticles films are employed at room temperature as a hole transport layer (HTL) and electron transport layer (ETL), respectively. The triple cation perovskite films are produced in a single step and for the sake of comparison, ultrasmooth and pinhole‐free absorbing layers are also fabricated using MAPbI₃ perovskite. The triple cation perovskite cells exhibit champion power conversion efficiencies (PCEs) of 18.6% with high stabilized power conversion efficiency of 17.7% on rigid glass/indium tin oxide (ITO) substrates (comparing with 16.6% PCE with 16.1% stabilized output efficiency for the flexible polyethylene naphthalate (PEN)/thin film barrier/ITO substrates). More interestingly, the durability of flexible PSC under simulation of operative condition is proved. Over 85% of the maximum stabilized output efficiency is retained after 1000 h aging employing a thin MAPbI₃ perovskite (over 90% after 500 h with a thick triple cation perovskite). This result is comparable to a similar state of the art rigid PSC and represents a breakthrough in the stability of flexible PSC using ETLs and HTLs compatible with roll to roll production speed, thanks to their room temperature processing.     

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.     

Room-temperature synthesis of ZrSnO_4 nanoparticles for electron transport layer in efficient planar hetrojunction perovskite solar cells

The interface engineering plays a key role in controlled optoelectronic properties of perovskite photovoltaic devices,and thus the electron transport layer(ETL) material with tailored optoelectronic properties remains a challenge for achieving high photovoltaic performance of planar perovskite solar cells(PSCs).Here,the fine and crystalline zirconium stanate(ZrSnO_4) nanoparticles(NPs) was synthesized at low temperature,and its optoelectronic properties are systematically investigated.Benefiting from the favorable electronic structure of ZrSnO_4 NPs for applications in ETL,efficient electron transport and extraction with suppre s sed charge recombination are achieved at the interface of perovskite layer.As a result,the optimized ZrSnO_4 NPs synthesized at room-temperature deliver the optimized power conversion efficiency up to 16.76% with acceptable stability.This work opens up a new class of ternary metal oxide for the use in ETL of the planar PSCs and should pave the way toward designing new interfacial materials for practical optoelectronic devices.     

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.     

Gradient Energy Alignment Engineering for Planar Perovskite Solar Cells with Efficiency Over 23%

An electron-transport layer (ETL) with appropriate energy alignment and enhanced charge transfer is critical for perovskite solar cells (PSCs). However, interfacial energy level mismatch limits the electrical performance of PSCs, particularly the open-circuit voltage (V_OC). Herein, a simple low-temperature-processed In₂O₃/SnO₂ bilayer ETL is developed and used for fabricating a new PSC device. The presence of In₂O₃ results in uniform, compact, and low-trap-density perovskite films. Moreover, the conduction band of In₂O₃ is shallower than that of Sn-doped In₂O₃ (ITO), enhancing the charge transfer from perovskite to ETL, thus minimizing V_OC loss at the perovskite and ETL interface. A planar PSC with a power conversion efficiency of 23.24% (certified efficiency of 22.54%) is obtained. A high V_OC of 1.17 V is achieved with the potential loss at only 0.36 V. In contrast, devices based on single SnO₂ layers achieve 21.42% efficiency with a V_OC of 1.13 V. In addition, the new device maintains 97.5% initial efficiency after 80 d in N₂ without encapsulation and retains 91% of its initial efficiency after 180 h under 1 sun continuous illumination. The results demonstrate and pave the way for the development of efficient photovoltaic devices.     

Low‐Temperature In Situ Amino Functionalization of TiO2 Nanoparticles Sharpens Electron Management Achieving over 21% Efficient Planar Perovskite Solar Cells

Titanium oxide (TiO₂) has been commonly used as an electron transport layer (ETL) of regular‐structure perovskite solar cells (PSCs), and so far the reported PSC devices with power conversion efficiencies (PCEs) over 21% are mostly based on mesoporous structures containing an indispensable mesoporous TiO₂ layer. However, a high temperature annealing (over 450 °C) treatment is mandatory, which is incompatible with low‐cost fabrication and flexible devices. Herein, a facile one‐step, low‐temperature, nonhydrolytic approach to in situ synthesizing amino‐functionalized TiO₂ nanoparticles (abbreviated as NH₂‐TiO₂ NPs) is developed by chemical bonding of amino (‐NH₂) groups, via Ti? N bonds, onto the surface of TiO₂ NPs. NH₂‐TiO₂ NPs are then incorporated as an efficient ETL in n‐i‐p planar heterojunction (PHJ) PSCs, affording PCE over 21%. Cs_0.05FA_0.83MA_0.12PbI_2.55Br_0.45 (abbreviated as CsFAMA) PHJ PSC devices based on NH₂‐TiO₂ ETL exhibit the best PCE of 21.33%, which is significantly higher than that of the devices based on the pristine TiO₂ ETL (19.82%) and is close to the record PCE for devices with similar structures and fabrication procedures. Besides, due to the passivation of the surface trap states of perovskite film, the hysteresis of current–voltage response is significantly suppressed, and the ambient stability of devices is improved upon amino functionalization.     

Low-temperature processable Sn-doped ZnO films as electron transporting layers for perovskite solar cells

Charge-transporting processable layers at a low temperature is a challenge for fabricating novel, highly stable and flexible optoelectronic devices. In fact, the crystallization of metal oxide usually needs to be processed under a high-temperature to obtain excellent semiconducting properties. In this work, Sn-doped ZnO (TZO) thin films, as electron transporting layers (ETLs) in perovskite solar cells, were prepared via sol–gel method at a temperature of less than 180 °C. The effects of annealing temperature on the properties of TZO thin films were investigated. It was found that the electrical properties of the TZO films were improved with increasing annealing temperature. In addition, an elemental composition analysis revealed that a temperature of only 140 °C sufficed for converting the precursor gel film into TZO film. The perovskite solar cell, which utilized a low-temperature TZO thin film, yielded a better power conversion efficiency than one with high-temperature ETLs (180 °C). These results imply that discovering low-temperature ETL processing for sol–gel enables good-quality metal oxide ETL, which can also be used in flexible solar cell applications.

     

High‐Performance,Solution‐Processed,and Insulating‐Layer‐Free Light‐Emitting Diodes Based on Colloidal Quantum Dots

Quantum‐dot light‐emitting diodes (QLEDs) may combine superior properties of colloidal quantum dots (QDs) and advantages of solution‐based fabrication techniques to realize high‐performance, large‐area, and low‐cost electroluminescence devices. In the state‐of‐the‐art red QLED, an ultrathin insulating layer inserted between the QD layer and the oxide electron‐transporting layer (ETL) is crucial for both optimizing charge balance and preserving the QDs' emissive properties. However, this key insulating layer demands very accurate and precise control over thicknesses at sub‐10 nm level, causing substantial difficulties for industrial production. Here, it is reported that interfacial exciton quenching and charge balance can be independently controlled and optimized, leading to devices with efficiency and lifetime comparable to those of state‐of‐the‐art devices. Suppressing exciton quenching at the ETL–QD interface, which is identified as being obligatory for high‐performance devices, is achieved by adopting Zn_0.9Mg_0.1O nanocrystals, instead of ZnO nanocrystals, as ETLs. Optimizing charge balance is readily addressed by other device engineering approaches, such as controlling the oxide ETL/cathode interface and adjusting the thickness of the oxide ETL. These findings are extended to fabrication of high‐efficiency green QLEDs without ultrathin insulating layers. The work may rationalize the design and fabrication of high‐performance QLEDs without ultrathin insulating layers, representing a step forward to large‐scale production and commercialization.     

Versatility of Carbon Enables All Carbon Based Perovskite Solar Cells to Achieve High Efficiency and High Stability

Carbon‐based perovskite solar cells (PVSCs) without hole transport materials are promising for their high stability and low cost, but the electron transporting layer (ETL) of TiO₂ is notorious for inflicting hysteresis and instability. In view of its electron accepting ability, C₆₀ is used to replace TiO₂ for the ETL, forming a so‐called all carbon based PVSC. With a device structure of fluorine‐doped tin oxide (FTO)/C₆₀/methylammonium lead iodide (MAPbI₃)/carbon, a power conversion efficiency (PCE) is attained up to 15.38% without hysteresis, much higher than that of the TiO₂ ones (12.06% with obvious hysteresis). The C₆₀ ETL is found to effectively improve electron extraction, suppress charge recombination, and reduce the sub‐bandgap states at the interface with MAPbI₃. Moreover, the all carbon based PVSCs are shown to resist moisture and ion migration, leading to a much higher operational stability under ambient, humid, and light‐soaking conditions. To make it an even more genuine all carbon based PVSC, it is further attempted to use graphene as the transparent conductive electrode, reaping a PCE of 13.93%. The high performance of all carbon based PVSCs stems from the bonding flexibility and electronic versatility of carbon, promising commercial developments on account of their favorable balance of cost, efficiency, and stability.     

SnO2退火温度对钙钛矿太阳能电池性能的影响

电子传输层是钙钛矿太阳能电池的关键部分, 起到阻挡空穴、传输电子和减少电子空穴复合的作用。本研究采用低温溶液法制备SnO₂薄膜作为钙钛矿电池的电子传输层, 研究SnO₂的退火温度对电子传输层微观形貌、物理性能以及钙钛矿太阳能电池性能的影响。结果表明: 当退火温度为60、90、120和240 ℃时, SnO₂薄膜表面存在较多的孔隙; 而退火温度为150、180和210 ℃时, 薄膜表面孔隙较少。在实验温度下, 制备的SnO₂薄膜为四方相, FTO玻璃上涂覆SnO₂薄膜后其透过率要优于空白FTO玻璃的透过率。当SnO₂退火温度为180 ℃时, 薄膜的电子迁移率最高, 钙钛矿电池具有最佳的传输电阻和复合电阻, 所得电池的性能最优, 其光电转换效率为17.28%, 开路电压为1.09 V, 短路电流为20.91 mA/cm², 填充因子为75.91%。     

Perovskite solar cells: recent progress and strategies developed for minimizing interfacial recombination

Organometallic perovskite is a new generation photovoltaic material with exemplary properties such as high absorption co-efficient, optimal bandgap, high defect tolerance factor and long carrier diffusion length. However, suitable electrodes and charge transport materials are required to fulfill photovoltaic processes where interfaces between hole transport material/perovskite and perovskite/electron transport material are affected by phenomena of charge carrier separation, transportation, collection by the interfaces and band alignment. Based on recent available literature and several strategies for minimizing the recombination of charge carriers at the interfaces, this review addresses the properties of hole transport materials, relevant working mechanisms, and the interface engineering of perovskite solar cell (PSC) device architecture, which also provides significant insights to design and development of PSC devices with high efficiency.     

Red-Carbon-Quantum-Dot-Doped SnO2 Composite with Enhanced Electron Mobility for Efficient and Stable Perovskite Solar Cells

An efficient electron transport layer (ETL) plays a key role in promoting carrier separation and electron extraction in planar perovskite solar cells (PSCs). An effective composite ETL is fabricated using carboxylic-acid- and hydroxyl-rich red-carbon quantum dots (RCQs) to dope low-temperature solution-processed SnO₂, which dramatically increases its electron mobility by ≈20 times from 9.32 × 10⁻⁴ to 1.73 × 10⁻² cm² V⁻¹ s⁻¹. The mobility achieved is one of the highest reported electron mobilities for modified SnO₂. Fabricated planar PSCs based on this novel SnO₂ ETL demonstrate an outstanding improvement in efficiency from 19.15% for PSCs without RCQs up to 22.77% and have enhanced long-term stability against humidity, preserving over 95% of the initial efficiency after 1000 h under 40–60% humidity at 25 °C. These significant achievements are solely attributed to the excellent electron mobility of the novel ETL, which is also proven to help the passivation of traps/defects at the ETL/perovskite interface and to promote the formation of highly crystallized perovskite, with an enhanced phase purity and uniformity over a large area. These results demonstrate that inexpensive RCQs are simple but excellent additives for producing efficient ETLs in stable high-performance PSCs as well as other perovskite-based optoelectronics.     

Developing 1D Sb‐Embedded Carbon Nanorods to Improve Efficiency and Stability of Inverted Planar Perovskite Solar Cells

To overcome the zigzag pathway transport of the electron diffusion process and eliminate the surface trap states of phenyl‐C61‐butyric acid methyl ester (PCBM) nanofilms in inverted perovskite solar cells, novel 1D N‐type doped carbon nanorods (CNRs) are developed by a stibonium (Sb) auxiliary ball milling method and introduced into the PCBM film to prepare the PCBM:Sb‐CNRs hybrid transport layer. In this way, the N‐type doped Sb‐CNRs can extend the built‐in electric field between CH₃NH₃PbI₃ and PCBM to facilitate the separation of electron/hole pairs. The discontinuous band with the built‐in potential in the PCBM/Sb‐CNRs heterojunction can boost interfacial charge redistribution and promote electrons diffusion from PCBM to electrode through 1D Sb‐CNRs network. As a result, the high device efficiency of 19.26% with enhanced air stability and little hysteresis are achieved. This work demonstrates a simple strategy to improve the efficiency and stability of perovskite photovoltaic devices using low‐cost carbon nanomaterials.     

Low‐Temperature Soft‐Cover Deposition of Uniform Large‐Scale Perovskite Films for High‐Performance Solar Cells

Large‐scale high‐quality perovskite thin films are crucial to produce high‐performance perovskite solar cells. However, for perovskite films fabricated by solvent‐rich processes, film uniformity can be prevented by convection during thermal evaporation of the solvent. Here, a scalable low‐temperature soft‐cover deposition (LT‐SCD) method is presented, where the thermal convection‐induced defects in perovskite films are eliminated through a strategy of surface tension relaxation. Compact, homogeneous, and convection‐induced‐defects‐free perovskite films are obtained on an area of 12 cm², which enables a power conversion efficiency (PCE) of 15.5% on a solar cell with an area of 5 cm². This is the highest efficiency at this large cell area. A PCE of 15.3% is also obtained on a flexible perovskite solar cell deposited on the polyethylene terephthalate substrate owing to the advantage of presented low‐temperature processing. Hence, the present LT‐SCD technology provides a new non‐spin‐coating route to the deposition of large‐area uniform perovskite films for both rigid and flexible perovskite devices.     

<Emphasis Type="Italic">In situ</Emphasis> fabrication of 2D SnS<Subscript>2</Subscript> nanosheets as a new electron transport layer for perovskite solar cells

To promote commercialization of perovskite solar cells (PSCs), low-temperature processed electron transport layer (ETL) with high carrier mobility still needs to be further developed. Here, we reported two-dimensional (2D) tin disulfide (SnS₂) nanosheets as ETL in PSCs for the first time. The morphologies of the 2D SnS₂ material can be easy controlled by the in situ synthesized method on the conductive fluorine-doped tin oxide (FTO) substrate. We achieved a champion power conversion efficiency (PCE) of 13.63%, with the short-circuit current density (J_SC) of 23.70 mA/cm², open-circuit voltage (V_OC) of 0.95 V, and fill factor (FF) of 0.61. The high J_SC of PSCs results from effective electron collection of the 2D SnS₂ nanosheets from perovskite layer and fast electron transport to the FTO. The low V_OC and FF are the results of the lower conduction band of 2D SnS₂ (4.23 eV) than that of TiO₂ (4.0 eV). These results demonstrate that 2D material is a promising candidate for ETL in PSCs.

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Nanoporous p-type NiOx electrode for p-i-n inverted perovskite solar cell toward air stability

Designing air-stable perovskite solar cells (PSCs) is a recent trend in low-cost photovoltaic technology. Metal oxide-based electron transporting layers (ETLs) and hole transporting layers (HTLs) have attracted tremendous attention in PSCs, because of their excellent air stability, high electron mobility, and optical transparency. Herein, we report a co-precipitation method for the synthesis of p-type nanoporous nickel oxide (np-NiOx) thin films as the HTL for inverted (p-i-n) PSCs. The best-performing p-i-n PSC having np-NiOx HTL, (FAPbI₃)_0.85(MAPbBr₃)_0.15 (herein FAPbI₃ stands for formamidinium lead iodide and MAPbBr₃ stands for methylammonium lead bromide) perovskite and phenyl-C₆₁-butyric acid methyl ester (PCBM)/ZnO ETL exhibited a 19.10% (±1%) power conversion efficiency (PCE) with a current density (J_SC) of 22.76?mA?cm^?2, open circuit voltage (V_OC) of 1.076?V and fill factor (FF) of 0.78 under 1?sun (100?mW?cm^?2). Interestingly, the developed p-i-n PSCs based on p-type NiOx and n-type ZnO could retain >80% efficiency after 160?days, which is much higher than conventional PEDOT:PSS HTL-based PSCs. Our findings provide air-stable perovskite solar cells with high efficiency.     

Recent progress in efficient hybrid lead halide perovskite solar cells

Abstract

The efficiency of perovskite solar cells (PSCs) has been improved from 9.7 to 19.3%, with the highest value of 20.1% achieved in 2014. Such a high photovoltaic performance can be attributed to optically high absorption characteristics and balanced charge transport properties with long diffusion lengths of the hybrid lead halide perovskite materials. In this review, some fundamental details of hybrid lead iodide perovskite materials, various fabrication techniques and device structures are described, aiming for a better understanding of these materials and thus highly efficient PSC devices. In addition, some advantages and open issues are discussed here to outline the prospects and challenges of using perovskites in commercial photovoltaic devices.     

Enhancing Crystallization in Hybrid Perovskite Solar Cells Using Thermally Conductive 2D Boron Nitride Nanosheet Additive

Controlling crystallization and grain growth is crucial for realizing highly efficient hybrid perovskite solar cells (PSCs). In this work, enhanced PSC photovoltaic performance and stability by accelerating perovskite crystallization and grain growth via 2D hexagonal boron nitride (hBN) nanosheet additives incorporated into the active perovskite layer are demonstrated. In situ X-ray scattering and infrared thermal imaging during the perovskite annealing process revealed the highly thermally conductive hBN nanosheets promoted the phase conversion and grain growth in the perovskite layer by facilitating a more rapid and spatially uniform temperature rise within the perovskite film. Complementary structural, physicochemical, and electrical characterizations further showed that the hBN nanosheets formed a physical barrier at the perovskite grain boundaries and the interfaces with charge transport layers, passivating defects, and retarding ion migration. As a result, the power conversion efficiency of the PSC is improved from 17.4% to 19.8%, along with enhanced device stability, retaining ≈90% of the initial efficiency even after 500 h ambient air storage. The results not only highlight 2D hBN as an effective additive for PSCs but also suggest enhanced thermal transport as one of the pathways for improved PSC performance by 2D material additives in general.     

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.     

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.