Kang Chen

A semiconducting conjugated polymer, poly(bithiophene imide), is successfully introduced to perovskite grain boundaries along with augmented grain sizes. This results in effective defect passivation and hence reduced recombination losses and increased efficiency, as well as reduced ion migration and improved stability.

Abstract

Grain boundaries in lead halide perovskite films lead to increased recombination losses and decreased device stability under illumination due to defect‐mediated ion migration. The effect of a conjugated polymer additive, poly(bithiophene imide) (PBTI), is investigated in the antisolvent treatment step in the perovskite film deposition by comprehensive characterization of perovskite film properties and the performance of inverted planar perovskite solar cells (PSCs). PBTI is found to be incorporated within grain boundaries, which results in an improvement in perovskite film crystallinity and reduced defects. The successful defect passivation by PBTI yields reduces recombination losses and consequently increases power conversion efficiency (PCE). In addition, it gives rise to improved photoluminescence stability and improved PSC stability under illumination which can be attributed to reduced ion migration. The optimal devices exhibit a PCE of 20.67% compared to 18.89% of control devices without PBTI, while they retain over 70% of the initial efficiency after 600 h under 1 sun illumination compared to 56% for the control devices.

The efficiency and photostability of all‐inorganic mixed‐halide perovskite solar cells (PVSCs) can be simultaneously enhanced by introducing an amino‐functionalized polymer PN4N as a novel cathode interlayer and dopant‐free PDCBT hole‐transporting layer. The favorable interaction between perovskite crystal and PN4N/PDCBT can effectively improve CsPbI₂Br film quality, with power conversion efficiency over 16%.

Abstract

A synergic interface design is demonstrated for photostable inorganic mixed‐halide perovskite solar cells (PVSCs) by applying an amino‐functionalized polymer (PN4N) as cathode interlayer and a dopant‐free hole‐transporting polymer poly[5,5′‐bis(2‐butyloctyl)‐(2,2′‐bithiophene)‐4,4′‐dicarboxylate‐alt‐5,5′‐2,2′‐bithiophene] (PDCBT) as anode interlayer. First, the interfacial dipole formed at the cathode interface reduces the workfunction of SnO₂, while PDCBT with deeper‐lying highest occupied molecular orbital (HOMO) level provides a better energy‐level matching at the anode, leading to a significant enhancement in open‐circuit voltage (V _oc) of the PVSCs. Second, the PN4N layer can also tune the surface wetting property to promote the growth of high‐quality all‐inorganic perovskite films with larger grain size and higher crystallinity. Most importantly, both theoretical and experimental results reveal that PN4N and PDCBT can interact strongly with the perovskite crystal, which effectively passivates the electronic surface trap states and suppresses the photoinduced halide segregation of CsPbI₂Br films. Therefore, the optimized CsPbI₂Br PVSCs exhibit reduced interfacial recombination with efficiency over 16%, which is one of the highest efficiencies reported for all‐inorganic PVSCs. A high photostability with a less than 10% efficiency drop is demonstrated for the CsPbI₂Br PVSCs with dual interfacial modifications under continuous 1 sun equivalent illumination for 400 h.

2D Dion–Jacobson perovskites have better carrier charge transport because of the closer interlayer distance. Solar cells based on Dion–Jacobson perovskites having mixed organic cations and using solvent‐engineering methods and hydriodic acid additive achieve higher efficiencies with high fill factors. Most importantly, the Dion–Jacobson perovskite solar cells exhibit better environmental stability compared with butylammonium‐based perovskites and 3D analogs.

Abstract

Hybrid halide 2D perovskites deserve special attention because they exhibit superior environmental stability compared with their 3D analogs. The closer interlayer distance discovered in 2D Dion–Jacobson (DJ) type of halide perovskites relative to 2D Ruddlesden–Popper (RP) perovskites implies better carrier charge transport and superior performance in solar cells. Here, the structure and properties of 2D DJ perovskites employing 3‐(aminomethyl)piperidinium (3AMP²⁺) as the spacing cation and a mixture of methylammonium (MA⁺) and formamidinium (FA⁺) cations in the perovskite cages are presented. Using single‐crystal X‐ray crystallography, it is found that the mixed‐cation (3AMP)(MA_0.75FA_0.25)₃Pb₄I₁₃ perovskite has a narrower bandgap, less distorted inorganic framework, and larger PbIPb angles than the single‐cation (3AMP)(MA)₃Pb₄I₁₃. Furthermore, the (3AMP)(MA_0.75FA_0.25)₃Pb₄I₁₃ films made by a solvent‐engineering method with a small amount of hydriodic acid have a much better film morphology and crystalline quality and more preferred perpendicular orientation. As a result, the (3AMP)(MA_0.75FA_0.25)₃Pb₄I₁₃‐based solar cells exhibit a champion power conversion efficiency of 12.04% with a high fill factor of 81.04% and a 50% average efficiency improvement compared to the pristine (3AMP)(MA)₃Pb₄I₁₃ cells. Most importantly, the 2D DJ 3AMP‐based perovskite films and devices show better air and light stability than the 2D RP butylammonium‐based perovskites and their 3D analogs.

Polymethyl methacrylate is coated on a perovskite grain boundary, blocking moisture penetration. The distributed C60 clusters create a dipole‐like electric field inside the perovskite layer, which favors exciton dissociation, and improves the conversion efficiency of perovskite solar cells.

Abstract

Lead halide perovskite solar cells (PSCs) have demonstrated great potential for realizing low‐cost and easily fabricated photovoltaics. At this juncture, power conversion efficiency and long‐term stability are two important factors limiting their transition. PSCs exhibit rapid environmental degradation since the perovskite layer is very sensitive to factors such as humidity, temperature, and ultraviolet light. Here, a novel successful approach is demonstrated that simultaneously improves the efficiency and stability of PSCs. This approach relies on incorporation of a dual‐functional polymethyl methacrylate (PMMA)–fullerene complex into the perovskite layer. The fullerene within perovskite layer forms a localized dipole‐like electric field that favors electron–hole separation, resulting in significant improvement in current density and fill factor with conversion efficiency reaching 18.4%. The molecular‐scale coating of hydrophobic PMMA on the perovskite grain boundary effectively blocks moisture penetration into the perovskite, thereby, significantly improving the stability against moisture, heat, and light. The PSCs with PMMA–fullerene complex showed no photovoltaic performance degradation for 250 d and exhibited 60 times higher stability compared to the state‐of‐the‐art devices under continuous 1 sun illumination in ambient air.

3D chiral hybrid organic–inorganic perovskites are both kinetically and thermodynamically stable based on theoretical calculation, and chirality is transferred from chiral cations to the perovskite framework, which is of great interest in the fields of piezoelectricity, pyroelectricity, ferroelectricity, topological quantum engineering, circularly polarized optoelectronics, and spintronics.

Abstract

Hybrid organic–inorganic perovskites (HOIPs), in particular 3D HOIPs, have demonstrated remarkable properties, including ultralong charge‐carrier diffusion lengths, high dielectric constants, low trap densities, tunable absorption and emission wavelengths, strong spin–orbit coupling, and large Rashba splitting. These superior properties have generated intensive research interest in HOIPs for high‐performance optoelectronics and spintronics. Here, 3D hybrid organic–inorganic perovskites that implant chirality through introducing the chiral methylammonium cation are demonstrated. Based on structural optimization, phonon spectra, formation energy, and ab initio molecular dynamics simulations, it is found that the chirality of the chiral cations can be successfully transferred to the framework of 3D HOIPs, and the resulting 3D chiral HOIPs are both kinetically and thermodynamically stable. Combining chirality with the impressive optical, electrical, and spintronic properties of 3D perovskites, 3D chiral perovskites is of great interest in the fields of piezoelectricity, pyroelectricity, ferroelectricity, topological quantum engineering, circularly polarized optoelectronics, and spintronics.

Under some exactly predesigned growth conditions identified by utilizing thousands of chemicals through a potential screening process, some intrinsic defects or defect complexes can spontaneously incorporate into the grain boundary (GB) cores, and effectively eliminate the harmful deep‐levels induced by the low‐energy GBs in lead‐free halide double perovskites (type‐I and type‐II).

Abstract

Halide double perovskites (HDPs) are promising lead‐free perovskites for various optoelectronic applications. However, the device performances of HDPs are far below the optimized values, which open a critical question regarding the origin of low performance in these HDPs. In this article, using first‐principles calculations, it is found that some types of grain boundaries (GBs) are easy to form in polycrystalline HDPs. Importantly, the existence of low‐energy Σ5(310) GBs can induce harmful deep‐level defect states within the bandgaps of type‐I (e.g., Cs₂AgInCl₆) and type‐II (e.g., Cs₂AgBiCl₆) HDPs, which may dramatically reduce the device performances. Interestingly, it is found that the formation of some intrinsic defects and defect complexes could effectively eliminate these deep‐levels in type‐II and type‐I HDPs, respectively. Under some exactly predesigned growth conditions identified by utilizing thousands of chemicals through a potential screening process, these defects or defect complexes can spontaneously incorporate into the GB cores, meanwhile the harmful deep‐level defects in the bulk can also be effectively eliminated. In addition, the self‐passivated GBs could generate band bending, which may be beneficial for charge separation. The understanding of GB formation as well as the self‐passivation mechanism in HDPs can provide a new viewpoint and guidance for designing polycrystalline perovskites with improved optoelectronic performance.

New‐type 2D/3D perovskites are designed by first introducing two hydrophobic ammonium salt cations with halogen functional groups into 3D perovskite. The 2D/3D perovskite devices exhibit optimal power conversion efficiency as high as 20.08% under 1 sun irradiation and superior stability when exposed to humidity, temperature, and continuous UV irradiation.

Abstract

2D perovskites have attracted extensive attention due to their excellent stability compared with 3D perovskites. However, the intrinsic hydrophilicity of introduced alkylammonium salts effects the humidity stability of 2D/3D perovskites. Devices based on longer chain alkylammonium salts show improvement in hydrophobicity but lower efficiency due to the poorer charge transport among various layers. To solve this issue, two hydrophobic short‐chain alkylammonium salts with halogen functional groups (2‐chloroethylamine, CEA⁺ and 2‐bromoethylamine, BEA⁺) are introduced into (Cs_0.1FA_0.9)Pb(I_0.9Br_0.1)₃ 3D perovskites to form 2D/3D perovskite structure, which achieve high‐quality perovskite films with better crystallization and morphology. The optimal 2D/3D perovskite solar cells (PSCs) with 5% CEA⁺ display a power conversion efficiency (PCE) as high as 20.08% under 1 sun irradiation. Because of the notable hydrophobicity of alkylammonium cations with halogen functional groups and the formed 2D/3D perovskite structure, the optimal PSCs exhibit superior moisture resistance and retain 92% initial PCE after aging at 50 ± 5% relative humidity for 2400 h. This work opens up a new direction for the design of new‐type 2D/3D PSCs with improved performance by employing proper alkylammonium salts with different functional groups.

In article number 1802323, Chih‐Ping Chen and co‐workers demonstrate hydrophilic carbon nanodots efficient additives in perovskite solar cells (PSC). The p‐i‐n PSC device incorporating these additives demonstrated a power conversion efficiency of 20.2% and exhibited excellent air‐stability, maintaining high PCEs (25 °C and a humidity of 40%) for over 500 h.

Charge recombination at grain boundaries is a key factor limiting the performance of low‐bandgap mixed tin–lead halide perovskite solar cells. It is found that bromine incorporation can passivate grain boundaries and lower the dark current density by two to three orders of magnitude. The champion cell shows an open‐circuit voltage deficit of 0.384 V and power conversion efficiency exceeding 19%.

Abstract

The unsatisfactory performance of low‐bandgap mixed tin (Sn)–lead (Pb) halide perovskite subcells has been one of the major obstacles hindering the progress of the power conversion efficiencies (PCEs) of all‐perovskite tandem solar cells. By analyzing dark‐current density and distribution, it is identified that charge recombination at grain boundaries is a key factor limiting the performance of low‐bandgap mixed Sn–Pb halide perovskite subcells. It is further found that bromine (Br) incorporation can effectively passivate grain boundaries and lower the dark current density by two–three orders of magnitude. By optimizing the Br concentration, low‐bandgap (1.272 eV) mixed Sn–Pb halide perovskite solar cells are fabricated with open‐circuit voltage deficits as low as 0.384 V and fill factors as high as 75%. The best‐performing device demonstrates a PCE of >19%. The results suggest an important direction for improving the performance of low‐bandgap mixed Sn–Pb halide perovskite solar cells.

Solution‐processed metal oxide nanocrystals present unique properties as efficient carrier transport layers in photovoltaic devices. In this review, solution‐processed metal oxide nanocrystal‐based carrier transport layers in organic solar cells and perovskite solar cells, and their low‐temperature solution‐processed synthesis approaches are summarized.

Abstract

There has been rapid progress in solution‐processed organic solar cells (OSCs) and perovskite solar cells (PVSCs) toward low‐cost and high‐throughput photovoltaic technology. Carrier (electron and hole) transport layers (CTLs) play a critical role in boosting their efficiency and long‐time stability. Solution‐processed metal oxide nanocrystals (SMONCs) as a promising CTL candidate, featuring robust process conditions, low‐cost, tunable optoelectronic properties, and intrinsic stability, offer unique advantages for realizing cost‐effective, high‐performance, large‐area, and mechanically flexible photovoltaic devices. In this review, the recent development of SMONC‐based CTLs in OSCs and PVSCs is summarized. This paper starts with the discussion of synthesis approaches of SMONCs. Then, a broad range of SMONC‐based CTLs, including hole transport layers and electron transport layers, are reviewed, in which an emphasis is placed on the improvement of the efficiency and device stability. Finally, for the better understanding of the challenges and opportunities on SMONC‐based CTLs, several strategies and perspectives are outlined.

F4‐TCNQ is applied to manipulate the morphological, electrical, and photovoltaic properties of nonfullerene solar cells. Adding a trace amount of F4‐TCNQ yields a higher current density and fill factor, in comparison to the reference device. The combined techniques evidence that the addition of F4‐TCNQ increases charge lifetime, charge mobility, and mean‐square composition variation.

Abstract

Fluorinated molecule 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4‐TCNQ) and its derivatives have been used in polymer:fullerene solar cells primarily as a dopant to optimize the electrical properties and device performance. However, the underlying mechanism and generality of how F4‐TCNQ affects device operation and possibly the morphology is poorly understood, particularly for emerging nonfullerene organic solar cells. In this work, the influence of F4‐TCNQ on the blend film morphology and photovoltaic performance of nonfullerene solar cells processed by a single halogen‐free solvent is systematically investigated using a set of morphological and electrical characterizations. In solar cells with a high‐performance polymer:small molecule blend FTAZ:IT‐M, F4‐TCNQ has a negligibly small effect on the molecular packing and surface characteristics, while it clearly affects the electronic properties and mean‐square composition variation of the bulk. In comparison to the control devices with an average power conversion efficiency (PCE) of 11.8%, inclusion of a trace amount of F4‐TCNQ in the active layer has improved device fill factor and current density, which has resulted into a PCE of 12.4%. Further increase in F4‐TCNQ content degrades device performance. This investigation aims at delineating the precise role of F4‐TCNQ in nonfullerene bulk heterojunction films, and thereby establishing a facile approach to fabricate highly optimized nonfullerene solar cells.

The intrinsic instability of metal halide perovskites is one of the main factors that limit the commercialization of perovskite solar cells. This review highlights the recent progress in the composition engineering of metal halide perovskites for improving the stability of perovskite solar cells. The strategy of using mixed‐ion hybrid perovskites, low‐dimensional hybrid perovskites, and all‐inorganic perovskites is discussed in detail.

Abstract

Metal halide perovskite solar cells (PSCs) have emerged as promising candidates for photovoltaic technology with their power conversion efficiencies over 23%. For prototypical organic–inorganic metal halide perovskites, their intrinsic instability poses significant challenges to the commercialization of PSCs. Recently, the scientific community has done tremendous work in composition engineering to develop more robust light‐absorbing layers, including mixed‐ion hybrid perovskites, low‐dimensional hybrid perovskites, and all‐inorganic perovskites. This review provides an overview of the impact of these perovskites on the efficiency and long‐term stability of PSCs.

High‐efficiency (21.06%) and durable 2D–3D vertical aligned perovskite solar cells (PSCs) with phase pure 2D perovskite are demonstrated. The phase pure 2D perovskite minimizes photo‐generated charge‐carrier localization in the low‐dimensional perovskite; the dominant vertical alignment does not affect charge‐carrier extraction. The traditional constraint of trade‐off between efficiency and stability in PSC is overcome.

Abstract

Three‐dimensional (3D) metal‐halide perovskite solar cells (PSCs) have demonstrated exceptional high efficiency. However, instability of the 3D perovskite is the main challenge for industrialization. Incorporation of some long organic cations into perovskite crystal to terminate the lattice, and function as moisture and oxygen passivation layer and ion migration blocking layer, is proven to be an effective method to enhance the perovskite stability. Unfortunately, this method typically sacrifices charge‐carrier extraction efficiency of the perovskites. Even in 2D–3D vertically aligned heterostructures, a spread of bandgaps in the 2D due to varying degrees of quantum confinement also results in charge‐carrier localization and carrier mobility reduction. A trade‐off between the power conversion efficiency and stability is made. Here, by introducing 2D C₆H₁₈N₂O₂PbI₄ (EDBEPbI₄) microcrystals into the precursor solution, the grain boundaries of the deposited 3D perovskite film are vertically passivated with phase pure 2D perovskite. The phases pure (inorganic layer number n = 1) 2D perovskite can minimize photogenerated charge‐carrier localization in the low‐dimensional perovskite. The dominant vertical alignment does not affect charge‐carrier extraction. Therefore, high‐efficiency (21.06%) and ultrastable (retain 90% of the initial efficiency after 3000 h in air) planar PSCs are demonstrated with these 2D–3D mixtures.

A graded bilayered inorganic hole‐transporting layer (including compact NiO _x and mesoporous CuGaO₂) is developed for inverted perovskite solar cells. The resulting devices demonstrate both high efficiency, with the champion one giving a stabilized efficiency of ≈20% and superior thermal stability with >80% of the initial efficiency being retained subject to 1000 hours' thermal aging at 85 °C.

Abstract

The unstable feature of the widely employed organic hole‐transporting materials (HTMs) (e.g., spiro‐MeOTAD) significantly limits the practical application of perovskite solar cells (PSCs). Therefore, it is desirable to design new structured PSCs with stable HTMs presenting excellent carrier extraction and transfer properties. This work demonstrates a new inverted PSC configuration. The new PSC has a graded band alignment and bilayered inorganic HTMs (i.e., compact NiO_x and mesoporous CuGaO₂). In comparison with planar‐structured PSCs, the mesoporous CuGaO₂ can effectively extract holes from perovskite due to the increased contact area of the perovskite/HTM. The graded energy alignment constructed in the ultrathin compact NiO_x, mesoporous CuGaO₂, and perovskite can facilitate carrier transfer and depress charge recombination. As a result, the champion device based on the newly designed mesoscopic PSCs yields a stabilized efficiency of ≈20%, which is considered one of the best results for inverted PSCs with inorganic HTMs. Additionally, the unencapsulated PSC device retains more than 80% of its original efficiency when subjected to thermal aging at 85 °C for 1000 h in a nitrogen atmosphere, thus demonstrating superior thermal stability of the device. This study may pave a new avenue to rational design of highly efficient and stable PSCs.

A nearly formamidinium (FA) lead–tin (Pb–Sn) mixed perovskite FAPb_0.75Sn_0.25I₃ is exploited to fabricate a low‐bandgap perovskite solar cell. By combination with a NiO _x hole transport layer, a power conversion efficiency of 17.25% is obtained. This low‐bandgap perovskite solar cell maintains about 91% of its original efficiency at 80 °C for 20 h, which demonstrates good thermal stability.

Abstract

Low bandgap lead–tin (Pb–Sn) mixed perovskite solar cells have achieved high power conversion efficiency in excess of 17%. However, methylammonium (MA) cation is usually contained, and the thermal stability of MA is always a great concern. In this work, according to composition engineering, a nearly formamidinium (FA) based low‐bandgap Pb–Sn mixed perovskite FAPb_0.75Sn_0.25I₃ is being tried to explore as the absorber layer. Combined with interface engineering by replacing poly(3,4‐ethylenedioxythiophene)‐polystyrenesulfonic acid (PEDOT:PSS), layer with NiO _x as hole transport layer, a power conversion efficiency of 17.25% is obtained. This low‐bandgap perovskite solar cell maintains about 91% of its original efficiency at 80 °C for 20 h, and 92% of its initial performance after 46 days storage at the room temperature. The good thermal stability of nearly FA based low‐bandgap perovskite could be good for delivering efficient and stable perovskite‐perovskite tandem solar cells.