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.     

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.     

High-Efficiency Carbon-based CsPbI2Br Perovskite Solar Cells from Dual Direction Thermal Diffusion Treatment with Cadmium Halides

In recent years, carbon-based CsPbI₂Br perovskite solar cells (PSCs) have attracted more attention due to their low cost and good stability. However, the power conversion efficiency (PCE) of carbon-based CsPbI₂Br PSCs is still no more than 16%, because of the defects in CsPbI₂Br or at the interface with the electron transport layer (ETL), as well as the energy level mismatch, which lead to the loss of energy, thus limiting PCE values. Herein, a series of cadmium halides are introduced, including CdCl₂, CdBr₂ and CdI₂ for dual direction thermal diffusion treatment. Some Cd²⁺ ions thermally diffuse downward to passivate the defects inside or on the surface of SnO₂ ETL. Meanwhile, the energy level structure of SnO₂ ETL is adjusted, which is in favor of the transfer of electron carriers and blocking holes. On the other hand, part of Cd²⁺ and Cl⁻ ions thermally diffuse upward into the CsPbI₂Br lattice to passivate crystal defects. Through dual direction thermal diffusion treatment by CdCl₂, CdI₂ and CdBr₂, the performance of devices has been significantly improved, and their PCE has been increased from 13.01% of the original device to 14.47%, 14.31%, and 13.46%, respectively. According to existing reports, 14.47% is one of the highest PCE of carbon-based CsPbI₂Br PSCs with SnO₂ ETLs.     

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.     

Novel Bilayer SnO2 Electron Transport Layers with Atomic Layer Deposition for High-Performance α-FAPbI3 Perovskite Solar Cells

Perovskite solar cells (PSCs) based on the SnO₂ electron transport layer (ETL) have achieved remarkable photovoltaic efficiency. However, the commercial SnO₂ ETLs show various shortcomings. The SnO₂ precursor is prone to agglomeration, resulting in poor morphology with numerous interface defects. Additionally, the open circuit voltage (V_oc) would be constrained by the energy level mismatch between the SnO₂ and the perovskite. And, few studies designed SnO₂-based ETLs to promote crystal growth of PbI₂, a crucial prerequisite for obtaining high-quality perovskite films via the two-step method. Herein, we proposed a novel bilayer SnO₂ structure that combined the atomic layer deposition (ALD) and sol-gel solution to well address the aforementioned issues. Due to the unique conformal effect of ALD-SnO₂, it can effectively modulate the roughness of FTO substrate, enhance the quality of ETL, and induce the growth of PbI₂ crystal phase to develop the crystallinity of perovskite layer. Furthermore, a created built-in field of the bilayer SnO₂ can help to overcome the electron accumulation at the ETL/perovskite interface, leading to a higher V_oc and fill factor. Consequently, the efficiency of PSCs with ionic liquid solvent increases from 22.09% to 23.86%, maintaining 85% initial efficiency in a 20% humidity N2 environment for 1300 h.     

Significant efficiency enhancement of carbon-based CsPbI2Br perovskite solar cells enabled by optimizing tin oxide electron transport layer

Carbon-based perovskite solar cells (C-PSCs) have been popular for achieving low-cost and stable photovoltaics. To overcome an obstacle of high-temperature annealing process for producing titanium dioxide (TiO₂), CsPbI₂Br C-PSCs based on a device structure of FTO/tin oxide (SnO₂)/CsPbI₂Br/carbon electrode can be fabricated at the low-temperature annealing process of 280 °C for 180 s, where SnO₂ is used as the electron transporting layer (ETL). Experimental results showed that the suitable concentration of SnO₂ ETL could yield smooth surface CsPbI₂Br films with free-pinhole and larger grain-sized crystallization. In combination with prolonging annealing time, a champion power conversion efficiency of 9.68% with a larger open-circuit voltage (V_oc) of 1.14 V was obtained for CsPbI₂Br C-PSC based on SnO₂ ETL. Here, a simple low-temperature fabricating process of SnO₂ ETL can be adapted to flexible substrates for C-PSCs and furtherly reduce the manufacturing cost.

     

Stratified Oxygen Vacancies Enhance the Performance of Mesoporous TiO2 Electron Transport Layer in Printable Perovskite Solar Cells

The low electrical conductivity and the high surface defect density of the TiO₂ electron transport layer (ETL) limit the power conversion efficiency (PCE) of corresponding perovskite solar cells (PSCs). Here, the conductivity and defect modulation of the mesoporous TiO₂ (mp-TiO₂) ETL via oxygen vacancy (OV) management by the reduction and oxidation treatment are reported. Reduction treatment via reducing agent introduces abundant OVs into the TiO₂ nanocrystalline particles on the surface and at the subsurface. The following oxidation treatment via hydrogen peroxide removes the surface OVs while remains the subsurface OVs, resulting in stratified OVs. The stratified OVs improve the conductivity of TiO₂ ETL by increasing carrier donors and decrease nonradiative centers by reducing surface defects. Such synergy ensures the capability of mp-TiO₂ as the well-performed ETL with improved energy level alignment, suppressed interface recombination, enhanced carrier extraction, and transport. As a result, printable hole-conductor-free carbon-based mesoscopic PSCs based on the modulated mp-TiO₂ ETL demonstrate a highest reported PCE of 18.96%.     

Effective Carrier‐Concentration Tuning of SnO2 Quantum Dot Electron‐Selective Layers for High‐Performance Planar Perovskite Solar Cells

The carrier concentration of the electron‐selective layer (ESL) and hole‐selective layer can significantly affect the performance of organic–inorganic lead halide perovskite solar cells (PSCs). Herein, a facile yet effective two‐step method, i.e., room‐temperature colloidal synthesis and low‐temperature removal of additive (thiourea), to control the carrier concentration of SnO₂ quantum dot (QD) ESLs to achieve high‐performance PSCs is developed. By optimizing the electron density of SnO₂ QD ESLs, a champion stabilized power output of 20.32% for the planar PSCs using triple cation perovskite absorber and 19.73% for those using CH₃NH₃PbI₃ absorber is achieved. The superior uniformity of low‐temperature processed SnO₂ QD ESLs also enables the fabrication of ≈19% efficiency PSCs with an aperture area of 1.0 cm² and 16.97% efficiency flexible device. The results demonstrate the promise of carrier‐concentration‐controlled SnO₂ QD ESLs for fabricating stable, efficient, reproducible, large‐scale, and flexible planar PSCs.     

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.

     

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.     

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.     

20.67%-Efficiency Inorganic CsPbI3 Solar Cells Enabled by Zwitterion Ion Interface Treatment

All-inorganic CsPbI₃ perovskite solar cells (PSCs) have been extensively studied due to their high thermal stability and unprecedented rise in power conversion efficiency (PCE). Recently, the champion PCE of CsPbI₃ PSCs has reached up to 21%; however, it is still much lower than that of organic–inorganic hybrid PSCs. Interface modification to passivate surface defects and minimize charge recombination and trapping is important to further improve the efficiency of CsPbI₃ PSCs. Herein, a new zwitterion ion is deposited at the interface between electron transporting layer (ETL) and perovskite layer to passivate the defects therein. The zwitterion ions can not only passivate oxygen vacancy (V_O) and iodine vacancy (V_I) defects, but also improve the band alignment at the ETL-perovskite interface. After the interface treatment, the PCE of CsPbI₃ device reaches up to 20.67%, which is among the highest values of CsPbI₃ PSCs so far. Due to the defect passivation and hydrophobicity improvement, the PCE of optimized device remains 94% of its original value after 800 h storing under ambient condition. These results provide an efficient way to improve the quality of ETL-perovskite interface by zwitterion ions for achieving high performance inorganic CsPbI₃ PSCs.     

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.     

Multifunctional Chemical Linker Imidazoleacetic Acid Hydrochloride for 21% Efficient and Stable Planar Perovskite Solar Cells

Chemical interaction at a heterojunction interface induced by an appropriate chemical linker is of crucial importance for high efficiency, hysteresis‐less, and stable perovskite solar cells (PSCs). Effective interface engineering in PSCs is reported via a multifunctional chemical linker of 4‐imidazoleacetic acid hydrochloride (ImAcHCl) that can provide a chemical bridge between SnO₂ and perovskite through an ester bond with SnO₂ via esterification reaction and an electrostatic interaction with perovskite via imidazolium cation in ImAcHCl and iodide anion in perovskite. In addition, the chloride anion in ImAcHCl plays a role in the improvement of crystallinity of perovskite film crystallinity. The introduction of ImAcHCl onto SnO₂ realigns the positions of the conduction and valence bands upwards, reduces nonradiative recombination, and improves carrier life time. As a consequence, average power conversion efficiency (PCE) is increased from 18.60% ± 0.50% to 20.22% ± 0.34% before and after surface modification, respectively, which mainly results from an enhanced voltage from 1.084 ± 0.012 V to 1.143 ± 0.009 V. The best PCE of 21% is achieved by 0.1 mg mL^?1 ImAcHCl treatment, along with negligible hysteresis. Moreover, an unencapsulated device with ImAcHCl‐modified SnO₂ shows much better thermal and moisture stability than unmodified SnO₂.     

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.     

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.     

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.     

Wearable Large‐Scale Perovskite Solar‐Power Source via Nanocellular Scaffold

Dramatic advances in perovskite solar cells (PSCs) and the blossoming of wearable electronics have triggered tremendous demands for flexible solar‐power sources. However, the fracturing of functional crystalline films and transmittance wastage from flexible substrates are critical challenges to approaching the high‐performance PSCs with flexural endurance. In this work, a nanocellular scaffold is introduced to architect a mechanics buffer layer and optics resonant cavity. The nanocellular scaffold releases mechanical stresses during flexural experiences and significantly improves the crystalline quality of the perovskite films. The nanocellular optics resonant cavity optimizes light harvesting and charge transportation of devices. More importantly, these flexible PSCs, which demonstrate excellent performance and mechanical stability, are practically fabricated in modules as a wearable solar‐power source. A power conversion efficiency of 12.32% for a flexible large‐scale device (polyethylene terephthalate substrate, indium tin oxide‐free, 1.01 cm²) is achieved. This ingenious flexible structure will enable a new approach for development of wearable electronics.     

Superfast Room‐Temperature Activation of SnO2 Thin Films via Atmospheric Plasma Oxidation and their Application in Planar Perovskite Photovoltaics

The power conversion efficiency (PCE) of perovskite solar cells (PSCs) has now exceeded 20%; thus, research focus has shifted to establishing the foundations for commercialization. One of the pivotal themes is to curtail the overall fabrication time, to reduce unit cost, and mass‐produce PSCs. Additionally, energy dissipation during the thermal annealing (TA) stage must be minimized by realizing a genuine low‐temperature (LT) process. Here, tin oxide (SnO₂) thin films (TFs) are formulated at extremely high speed, within 5 min, under an almost room‐temperature environment (<50 °C), using atmospheric Ar/O₂ plasma energy (P‐SnO₂) and are applied as an electron transport layer of a “n–i–p”‐type planar PSC. Compared with a thermally annealed SnO₂ TF (T‐SnO₂), the P‐SnO₂ TF yields a more even surface but also outstanding electrical conductivity with higher electron mobility and a lower number of charge trap sites, consequently achieving a superior PCE of 19.56% in P‐SnO₂‐based PSCs. These findings motivate the use of a plasma strategy to fabricate various metal oxide TFs using the sol–gel route.     

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.