Highly Improved Photocurrent Density and Efficiency of Perovskite Solar Cells via Inclined Fluorine Sputtering Process (Adv. Funct. Mater. 25/2023)

Increase in incident light and surface modification of the charge transport layer are powerful routes to achieve high-performance efficiency of perovskite solar cells (PSCs) by improving the short-circuit current density (J_SC) and charge transport characteristics, respectively. However, few techniques are studied to reduce reflection loss and simultaneously improve the electrical performance of the electron transport layer (ETL). Herein, an inclined fluorine (F) sputtering process to fabricate high-performance PSCs is proposed. The proposed process simultaneously implements the antireflection effect of F coating and the effect of F doping on a TiO₂ ETL, which increases the amount of light transmitted into the PSC due to the extremely low refractive index (≈1.39) and drastically improves the electrical properties of TiO₂. Consequently, the J_SC of the F coating and doping perovskite solar cell (F-PSC) increased from 25.05 to 26.01 mA cm⁻², and the power conversion efficiency increased from 24.17% to 25.30%. The unencapsulated F-PSC exhibits enhanced air stability after 900 h of exposure to ambient environment atmosphere (30% relative humidity, 25 °C under dark condition). The inclined F sputtering process in this study can become a universal method for PSCs from the development stage to commercialization in the future.     

Amorphous F-doped TiOx Caulked SnO2 Electron Transport Layer for Flexible Perovskite Solar Cells with Efficiency Exceeding 22.5%

Flexible perovskite solar cells (f-PSCs) show great promise in portable-power applications (e.g., chargers, drones) and low-cost, scalable productions (e.g., roll-to-roll). However, in conventional n–i–p architecture f-PSCs, the low-temperature processed metal oxide electron transport layers (ETLs) usually suffer from high resistance and severe defects that limit the power conversion efficiency (PCE) improvement of f-PSCs. Besides the enhancement in the mobility of metal oxide and passivation for perovskite/ETL interfacial defects reported in previous literature, herein, the electron transport loss between the metal oxide nanocrystallines within the ETL is studied by introducing an amorphous F-doped TiO_x (F-TiO_x) caulked crystalline SnO₂ composite ETL. The F-TiO_x in this novel composite ETL acts as an interstitial medium between adjacent SnO₂ nanocrystallines, which can provide more electron transport channels, effectively passivate oxygen vacancies, and optimize the energy level arrangement, thus significantly enhancing the electron mobility of ETL and reducing the charge transport losses. The composite ETL-based f-PSCs achieve a high PCE of 22.70% and good operational stability. Furthermore, a moderate roughness of the composite ETL endows f-PSCs with superior mechanical reliability by virtue of a strong coupling at the ETL/perovskite interface, by which the f-PSCs can maintain 82.11% of their initial PCE after 4000 bending cycles.     

Inorganic Electron Transport Materials in Perovskite Solar Cells

In the past decade, the perovskite solar cell (PSC) has attracted tremendous attention thanks to the substantial efforts in improving the power conversion efficiency from 3.8% to 25.5% for single-junction devices and even perovskite-silicon tandems have reached 29.15%. This is a result of improvement in composition, solvent, interface, and dimensionality engineering. Furthermore, the long-term stability of PSCs has also been significantly improved. Such rapid developments have made PSCs a competitive candidate for next-generation photovoltaics. The electron transport layer (ETL) is one of the most important functional layers in PSCs, due to its crucial role in contributing to the overall performance of devices. This review provides an up-to-date summary of the developments in inorganic electron transport materials (ETMs) for PSCs. The three most prevalent inorganic ETMs (TiO₂, SnO_2, and ZnO) are examined with a focus on the effects of synthesis and preparation methods, as well as an introduction to their application in tandem devices. The emerging trends in inorganic ETMs used for PSC research are also reviewed. Finally, strategies to optimize the performance of ETL in PSCs, effects the ETL has on J–V hysteresis phenomenon and long-term stability with an outlook on current challenges and further development are discussed.     

Dopant‐Free,Amorphous–Crystalline Heterophase SnO2 Electron Transport Bilayer Enables >20% Efficiency in Triple‐Cation Perovskite Solar Cells

Improving the ohmic contact and interfacial morphology between an electron transport layer (ETL) and perovskite film is the key to boost the efficiency of planar perovskite solar cells (PSCs). In the current work, an amorphous–crystalline heterophase tin oxide bilayer (Bi‐SnO₂) ETL is prepared via a low‐temperature solution process. Compared with the amorphous SnO₂ sol–gel film (SG‐SnO₂) or the crystalline SnO₂ nanoparticle (NP‐SnO₂) counterparts, the heterophase Bi‐SnO₂ ETL exhibits improved surface morphology, considerably fewer oxygen defects, and better energy band alignment with the perovskite without sacrificing the optical transmittance. The best PSC device (active area ≈ 0.09 cm²) based on a Bi‐SnO₂ ETL is hysteresis‐less and achieves an outstanding power conversion efficiency of ≈20.39%, which is one of the highest efficiencies reported for SnO₂‐triple cation perovskite system based on green antisolvent. More fascinatingly, large‐area PSCs (active areas of ≈3.55 cm²) based on the Bi‐SnO₂ ETL also achieves an extraordinarily high efficiency of ≈14.93% with negligible hysteresis. The improved device performance of the Bi‐SnO₂‐based PSC arises predominantly from the improved ohmic contact and suppressed bimolecular recombination at the ETL/perovskite interface. The tailored morphology and energy band structure of the Bi‐SnO₂ has enabled the scalable fabrication of highly efficient, hysteresis‐less PSCs.     

Multifunctional Aminoglycoside Antibiotics Modified SnO2 Enabling High Efficiency and Mechanical Stability Perovskite Solar Cells

SnO₂ as an electron transport layer (ETL) has been widely used in regular planar perovskite solar cells (PSCs) owing to its high optical transmittance, less photocatalytic activity, and low-temperature processing. However, SnO₂-based PSCs still face many challenges which greatly impair their efficiency and stability of PSCs. Herein, a novel and effective multifunctional modification strategy is proposed by incorporating streptomycin sulfate (STRS) molecules with multiple functional groups into SnO₂ ETL. STRS can significantly suppress SnO₂ nanoparticle agglomeration, improve the electronic property of SnO₂, as well as reduce nonradiative recombination. At the same time, interfacial residual tensile stress is released and the interfacial energy level alignment becomes more matched. As a result, the STRS-modified PSCs achieve a higher efficiency of 22.89% compared to 20.61% of the control device and exhibit a hysteresis-free feature. The humidity and thermal stability of PSCs based on STRS-SnO₂ are significantly improved. Furthermore, the efficiency of flexible devices increased from 19.74% to 20.79%, and the devices still maintain >80% of initial PCE after 4500 bending cycles with a bend radius of 5 mm. This study provides a low-cost, facile, and efficient strategy for achieving high efficiency and stability in PSCs.     

Combustion Synthesized Zinc Oxide Electron‐Transport Layers for Efficient and Stable Perovskite Solar Cells

Perovskite solar cells (PSCs) have advanced rapidly with power conversion efficiencies (PCEs) now exceeding 22%. Due to the long diffusion lengths of charge carriers in the photoactive layer, a PSC device architecture comprising an electron‐ transporting layer (ETL) is essential to optimize charge flow and collection for maximum performance. Here, a novel approach is reported to low temperature, solution‐processed ZnO ETLs for PSCs using combustion synthesis. Due to the intrinsic passivation effects, high crystallinity, matched energy levels, ideal surface topography, and good chemical compatibility with the perovskite layer, this combustion‐derived ZnO enables PCEs approaching 17–20% for three types of perovskite materials systems with no need for ETL doping or surface functionalization.     

Performance Enhancement of Tri‐Cation and Dual‐Anion Mixed Perovskite Solar Cells by Au@SiO2 Nanoparticles

Tri‐cation and dual‐anion mixed perovskites have been widely utilized in perovskite solar cell (PSC) applications due to their novel properties such as high absorption, high stability, and low cost. To commercialize the PSCs, further improving the device performance without detrimentally changing the device configuration is important at present. Herein, Au@SiO₂ nanoparticles (NPs) are introduced to modify the interface between mesoporous TiO₂ (mp‐TiO₂) and mixed perovskite with increased main photovoltaic parameters of the device, resulting in a ≈29% enhancement of power conversion efficiency (PCE) from 15.8% to 20.3%. The origins of the enhancement have been studied by exploring the optical absorption, optical power distribution, and charge carrier behaviors within the system. The small perturbation transient photovoltage measurement exhibits prolonged charge carrier lifetimes after the Au@SiO₂ NPs incorporation, and time of flight photoconductivity measurement shows that charge carrier mobilities of this system are also enhanced. These characteristics make metallic nanostructures a promising functional material in facile tuning of the charge carriers transport and further boosting the PCE of the PSCs.     

Rubidium Fluoride Modified SnO2 for Planar n-i-p Perovskite Solar Cells

Regulating the electron transport layer (ETL) has been an effective way to promote the power conversion efficiency (PCE) of perovskite solar cells (PSCs) as well as suppress their hysteresis. Herein, the SnO₂ ETL using a cost-effective modification material rubidium fluoride (RbF) is modified in two methods: 1) adding RbF into SnO₂ colloidal dispersion, F and Sn have a strong interaction, confirmed via X-ray photoelectron spectra and density functional theory results, contributing to the improved electron mobility of SnO₂; 2) depositing RbF at the SnO₂/perovskite interface, Rb⁺ cations actively escape into the interstitial sites of the perovskite lattice to inhibit ions migration and reduce non-radiative recombination, which dedicates to the improved open-circuit voltage (V_oc) for the PSCs with suppressed hysteresis. In addition, double-sided passivated PSCs, RbF on the SnO₂ surface, and p-methoxyphenethylammonium iodide on the perovskite surface, produces an outstanding PCE of 23.38% with a V_oc of 1.213 V, corresponding to an extremely small V_oc deficit of 0.347 V.     

Surface‐Modified Metallic Ti3C2Tx MXene as Electron Transport Layer for Planar Heterojunction Perovskite Solar Cells

MXenes are a large and rapidly expanding family of 2D materials that, owing to their unique optoelectronic properties and tunable surface termination, find a wide range of applications including energy storage and energy conversion. In this work, Ti₃C₂T_x MXene nanosheets are applied as a novel type of electron transport layer (ETL) in low‐temperature processed planar‐structured perovskite solar cells (PSCs). Interestingly, simple UV‐ozone treatment of the metallic Ti₃C₂T_x that increases the surface Ti? O bonds without any change in its bulk properties such as high electron mobility improves its suitability as an ETL. Improved electron transfer and suppressed recombination at the ETL/perovskite interface results in augmentation of the power conversion efficiency (PCE) from 5.00% in the case of Ti₃C₂T_x without UV‐ozone treatment to the champion PCE of 17.17%, achieved using the Ti₃C₂T_x film after 30 min of UV‐ozone treatment. As the first report on the use of pure MXene layer as an ETL in PSCs, this work shows the great potential of MXenes to be used in PSCs and displays their promise for applications in photovoltaic technology in general.     

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.     

Using fluorinated and crosslinkable fullerene derivatives to improve the stability of perovskite solar cells

Organic-inorganic hybrid perovskite solar cell (PSC) is a third-generation photovoltaic technology[1,2],and the certi-fied power conversion efficiency (PCE) has reached 25.5％(https://www.nrel.gov/pv/cell-efficiency.html),which can rival solar cells based on crystalline-Si and other inorganic semi-conductors.The intrinsic instability of perovskite materials could impede PSC commercialization[3].To date,a variety of strategies such as composition engineering,additive engi-neering,interface engineering and encapsulation technique are employed to improve the long-term stability of PSCs[4-9].In particular,fullerene materials with high electron mobility,high electron affinity,small reorganization energy and ad-justable energy level have been widely utilized as interfacial layers or additives in PSCs for efficiency and stability improve-ment[10].Among them,fluorinated and crosslinkable fullerene derivatives can improve the stability of PSCs effectively.The fluorinated fullerene derivatives could improve the mois-ture stability because of the hydrophobicity of fluorine atom.The crosslinked fullerene derivatives can protect the electron-transport layers (ETLs) against solvent erosion during per-ovskite solution deposition,and the as-formed organic net-works can improve mechanical stability of PSCs.     

Efficient and Stable Mesoscopic Perovskite Solar Cells Using PDTITT as a New Hole Transporting Layer

Stability is the main challenge in the field of organic–inorganic perovskite solar cells (PSCs). Finding low‐cost and stable hole transporting layer (HTL) is an effective strategy to address this issue. Here, a new donor polymer, poly(5,5‐didecyl‐5H‐1,8‐dithia‐as‐indacenone‐alt‐thieno[3,2‐b]thiophene) (PDTITT), is synthesized and employed as an HTL in PSCs, which has a suitable band alignment with respect to the double‐A cation perovskite film. Using PDTITT, the hole extraction in PSCs is greatly improved as compared to commonly used HTLs such as 2,2′,7,7′‐tetrakis[N,N‐di(4‐methoxyphenyl)amino]‐9,9′‐spirobifluorene (spiro‐OMeTAD), addressing the hysteresis issue. After careful optimization, an efficient PSC is achieved based on mesoscopic TiO₂ electron transporting layer with a maximum power conversion efficiency (PCE) of 18.42% based on PDTITT HTL, which is comparable with spiro‐OMeTAD‐based PSC (19.21%). Since spiro‐based PSCs suffer from stability issue, the operational stability in the PSC with PDTITT HTL is studied. It is found that the device with PDTITT retains 88% of its initial PCE value after 200 h under illumination, which is better than the spiro‐based PSC (54%).     

Prolonged lifetime of polymer solar cells with amphiphilic monolayers modified cathodes

The short lifetime and low stability of polymer solar cells (PSCs) devices limit their feasibility for commercial use. Modification of the interfacial electron-transport layers (ETL) has been demonstrated as an effective way to enhance power conversion efficiency (PCE) and device stability. In this work, two types of monolayers consisting of amphiphilic molecules (sodium stearate or sodium oleate - a major constituent of “soap”) are introduced as novel ETLs in polymer: PCBM based PSCs. Significant improvement of PCE was demonstrated and an extended operational lifetime by 5–25 times was achieved. We attributed the improved performance to the interface modification by the amphiphilic molecular layers. The amphiphilic interfacial layers established a better contact between the active layer and the cathode by reducing the roughness and forming a compact dipole at the interface, which facilitates charge generation, charge transport to, and charge collection at the electrodes, thereby enhancing the device efficiency and stability. This versatile interface modification approach has shown to be an immediate and promising means to improve the performance of PSCs.     

Multifunctional Small Molecule as Buried Interface Passivator for Efficient Planar Perovskite Solar Cells

The improvement of power conversion efficiency (PCE) and stability of the perovskite solar cell (PSC) is hindered by carrier recombination originating from the defects at the buried interface of the PSC. It is crucial to suppress the nonradiative recombination and facilitate carrier transfer in PSC via interface engineering. Herein, P-biguanylbenzoic acid hydrochloride (PBGH) is developed to modify the tin oxide (SnO₂)/perovskite interface. The effects of PBGH on carrier transportation, perovskite growth, defect passivation, and PSC performance are systematically investigated. On the one hand, the PBGH can effectively passivate the trap states of Sn dangling bonds and O vacancies on the SnO₂ surface via Lewis acid/base coordination, which is conducive to improving the conductivity of SnO₂ film and accelerating the electron extraction. On the other hand, PBGH modification assists the formation of high-quality perovskite film with low defect density due to its strong interaction with PbI₂. Consequently, the PBGH-modified PSC exhibits a champion power conversion efficiency (PCE) of 24.79%, which is one of the highest PCEs among all the FACsPbI₃-based PSCs reported to date. In addition, the stabilities of perovskite films and devices under high temperature/humidity and light illumination conditions are also systematically studied.     

Simultaneous Power Conversion Efficiency and Stability Enhancement of Cs2AgBiBr6 Lead‐Free Inorganic Perovskite Solar Cell through Adopting a Multifunctional Dye Interlayer

Perovskite solar cells (PSCs) are highly promising next‐generation photovoltaic devices because of the cheap raw materials, ideal band gap of ≈1.5 eV, broad absorption range, and high absorption coefficient. Although lead‐based inorganic‐organic PSC has achieved the highest power conversion efficiency (PCE) of 25.2%, the toxic nature of lead and poor stability strongly limits the commercialization. Lead‐free inorganic PSCs are potential alternatives to toxic and unstable organic‐inorganic PSCs. Particularly, double‐perovskite Cs₂AgBiBr₆‐based PSC has received interests for its all inorganic and lead‐free features. However, the PCE is limited by the inherent and extrinsic defects of Cs₂AgBiBr₆ films. Herein, an effective and facile strategy is reported for improving the PCE and stability by introducing an N719 dye interlayer, which plays multifunctional roles such as broadening the absorption spectrum, suppressing the charge carrier recombination, accelerating the hole extraction, and constructing an appropriate energy level alignment. Consequently, the optimizing cell delivers an outstanding PCE of 2.84%, much improved as compared with other Cs₂AgBiBr₆‐based PSCs reported so far in the literature. Moreover, the N719 interlayer greatly enhances the stability of PSCs under ambient conditions. This work highlights a useful strategy to boost the PCE and stability of lead‐free Cs₂AgBiBr₆‐based PSCs simultaneously, accelerating the commercialization of PSC technology.     

Spidermen Strategy for Stable 24% Efficiency Perovskite Solar Cells

The interface energetics-modification plays an important role in improving the power conversion efficiency (PCE) among the perovskite solar cells (PSCs). Considering the low carrier mobility caused by defects in PSCs, a double-layer modification engineering strategy is adopted to introduce the “spiderman” NOBF₄ (nitrosonium tetrafluoroborate) between tin dioxide (SnO₂ and perovskite layers. NO⁺, as the interfacial bonding layer, can passivate the oxygen vacancy in SnO₂, while BF₄⁻ can optimize the defects in the bulk of perovskite. This conclusion is confirmed by theoretical calculation and transmission electron microscopy (TEM). The synergistic effect of NO⁺ and BF₄⁻ distinctly heightens the carrier extraction efficiency, and the PCE of PSCs is 24.04% with a fill factor (FF) of 82.98% and long-term stability. This study underlines the effectiveness of multifunctional additives in improving interface contact and enhancing PCE of PSCs.     

Tailoring the Interface in FAPbI3 Planar Perovskite Solar Cells by Imidazole-Graphene-Quantum-Dots

Organic–inorganic hybrid perovskites have reached an unprecedented high efficiency in photovoltaic applications, which makes the commercialization of perovskite solar cells (PSCs) possible. In the past several years, particular attention has been paid to the stability of PSC devices, which is a critical issue for becoming a practical photovoltaic technology. In particular, the interface-induced degradation of perovskites should be the dominant factor causing poor stability. Here, imidazole bromide functionalized graphene quantum dots (I-GQDs) are demonstrated to regulate the interface between the electron transport layer (ETL) and formamidinium lead iodide (FAPbI₃) perovskite layer. The incorporation of I-GQDs not only reduces the interface defects for achieving a better energy level alignment between ETL and perovskite, but also improves the film quality of FAPbI₃ perovskite including enlarged grain size, lower trap density, and a longer carrier lifetime. Consequently, the planar FAPbI₃ PSCs with I-GQDs regulation achieve a high efficiency of 22.37% with enhanced long-term stability.     

Efficient and Ambient‐Air‐Stable Solar Cell with Highly Oriented 2D@3D Perovskites

3D organic–inorganic lead halide perovskites have shown great potential in efficient photovoltaic devices. However, the low stability of the 3D perovskite layer and random arrangement of the perovskite crystals hinder its commercialization road. Herein, a highly oriented 2D@3D ((AVA)₂PbI₄@MAPbI₃) perovskite structure combining the advantages of both 2D and 3D perovskite is fabricated through an in situ route. The highest power conversion efficiency (PCE) of 18.0% is observed from a 2D@3D perovskite solar cell (PSC), and it also shows significantly enhanced device stability under both inert (90% of initial PCE for 32 d) and ambient conditions (72% of initial PCE for 20 d) without encapsulation. The high efficiency of 18.0% and nearly twofold improvement of device stability in ambient compared with pure 3D PSCs confirm that such 2D@3D perovskite structure is an effective strategy for high performance and increasing stability and thus will enable the timely commercialization of PSCs.     

TBP precursor agent passivated ZnO electron transport layer for highly efficient polymer solar cells

Defects passivation in electron transport layer (ETL) is a key issue to optimize the performance of polymer solar cells (PSCs). In this work, a novel strategy is developed to form defects passivated ZnO ETL by introducing 4-tert-butylpyridine (TBP) agent into precursor. While the power conversion efficiency (PCE) of the inverted PSCs based poly{4,8-bis [(2-ethylhexyl)oxy]benzo [1,2-b:4,5-b']dithiophene-2,6-diyl-alt-3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno [3,4-b]thiophene-4,6-diyl}:[6,6]-phenyl C71-butyric acid methyl ester (PTB7:PC₇₁BM) with the pure ZnO ETL is 8.02%, that of the device with modified ZnO ETL is dramatically improved to 10.26%, with TBP accounting for ~28% efficiency improvement. Our study demonstrates that the precursor agent significantly affect the surface morphology and size of ZnO in ETL. Furthermore, it proves that the ZnO ETL with TBP (T-ZnO) is beneficial to polish interfacial contact between ETL and active layer and depress exciton quenching loss, resulting in enhanced exciton dissociation, efficient carrier collection and reduced charge recombination, thus improving the device performance. To verify the universality of T-ZnO ETL, the champion photovoltaic performance with a PCE of 11.74% (10% improvement) is obtained in the PBDB-T-2F:IT-4F based nonfullerene PSCs using T-ZnO as ETL. Our work developed a new, universal and facile strategy for designing highly efficient PSCs based on fullerene and nonfullerene blend systems.     

Enhanced Performance of Planar Perovskite Solar Cells Induced by Van Der Waals Epitaxial Growth of Mixed Perovskite Films on WS2 Flakes

Organic–inorganic metal halide perovskite solar cells (PSCs) have attracted much research interest owing to their high power conversion efficiency (PCE), solution processability, and the great potential for commercialization. However, the device performance is closely related to the quality of the perovskite film and the interface properties, which cannot be easily controlled by solution processes. Here, 2D WS₂ flakes with defect‐free surfaces are introduced as a template for van der Waals epitaxial growth of mixed perovskite films by solution process for the first time. The mixed perovskite films demonstrate a preferable growth along (001) direction on WS₂ surfaces. In addition, the WS₂/perovskite heterojunction forms a cascade energy alignment for efficient charge extraction and reduced interfacial recombination. The inverted PSCs with WS₂ interlayers show high PCEs up to 21.1%, which is among the highest efficiency of inverted planar PSCs. This work demonstrates that high‐mobility 2D materials can find important applications in PSCs as well as other perovskite‐based optoelectronic devices.