Chen Weijie

Publication date: 15 January 2020

Source: Joule, Volume 4, Issue 1

Author(s): Chuang-Yi Liao, Yao Chen, Chun-Chieh Lee, Gang Wang, Nai-Wei Teng, Chia-Hao Lee, Wei-Long Li, Yu-Kuang Chen, Chia-Hua Li, Hsiuan-Lin Ho, Phoebe Huei-Shuan Tan, Binghao Wang, Yu-Chin Huang, Ryan M. Young, Michael R. Wasielewski, Tobin J. Marks, Yi-Ming Chang, Antonio Facchetti

Three perylene diimide tetramers annulated by different chalcogen atoms (O, S, and Se) are synthesized for efficient nonfullerene polymer solar cells. O‐fused PDI‐based device exhibits an outstanding power conversion efficiency of 8.904% with a high fill factor of 0.706, outcompeting its S‐ and Se‐annulated counterparts.

Three perylene diimide (PDI) tetramers annulated by oxygen (O), sulfur (S), and selenium (Se), named as SF‐4PDI‐O, SF‐4PDI‐S, and SF‐4PDI‐Se, are designed, synthesized, and paired with polymeric donor PDBT‐T1 to construct organic solar cells. The heteroatoms' effects on photoelectric properties, chemical geometry, charge transport, active‐layer morphology, and photovoltaic performance are investigated in detail. These PDI acceptors exhibit a similar absorption profile, whereas the highest occupied molecular orbitals and lowest unoccupied molecular orbitals are simultaneously upshifted when heteroatoms are altered from O and S to Se due to the gradually weakening electronegativity. Alongside PDBT‐T1, SF‐4PDI‐O achieves an outstanding power conversion efficiency of 8.904% with a high fill factor of 0.706, outcompeting its S‐annulated and Se‐annulated counterparts. The superiority of the PDBT‐T1:SF‐4PDI‐O system lies in its stronger crystallinity, more balanced hole and electron mobilities, and weaker bimolecular recombination, coupled with more efficient charge transfer and collection. These results shed light on the invention of high‐performance PDI acceptors by oxygen‐decorated methodology.

An effective composite electron transport layer (ETL) is fabricated using carboxylic‐acid‐ and hydroxyl‐rich red‐carbon quantum dots to dope low‐temperature solution‐processed SnO₂. The electron mobility of SnO₂ is dramatically increased by ≈20 times from 9.32 × 10⁻⁴ to 1.73 × 10⁻² cm² V⁻¹ s⁻¹. A planar perovskite solar cell based on this novel SnO₂ ETL demonstrates an outstanding improvement in efficiency up to 22.77%.

Abstract

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.

The morphology control of nonfullerene blends is very important to improve device performance. Here, the high boiling point cosolvent is added to the P3HT:O‐IDTBR blend, which separates the crystallization process of P3HT and O‐IDTBR, and prolongs film forming time. As a result, the crystallinity, lateral and phase separation structure are optimized simultaneously, leading to high performance of 7.18%.

Abstract

The morphology with the interpenetrating network and optimized vertical phase separation plays a key role in determining the charge transport and collection in polymer:nonfullerene small molecular acceptors (SMAs) solar cells. However, the crystallization of polymer and SMAs usually occurs simultaneously during film‐forming, thus interfering with the crystallization process of each other, leading to amorphous film with undesirable lateral and vertical phase separation. The poly(3‐hexylthiophene) (P3HT):O‐IDTBR blend is selected as a model system, and controlling film‐forming kinetics to solve these problems is proposed. Herein, a cosolvent 1,2,4‐triclorobenzene (TCB) with selective solubility and a high boiling point is added to the solution, leading to prior crystallization of P3HT and extended film‐forming duration. As a result, the crystallinity of both components is enhanced significantly. Meanwhile, the prior crystallization of P3HT induces solid–liquid phase separation, hence rationalizing the formation of the nano‐interpenetrating network. Moreover, the surface energy drives O‐IDTBR to enrich near the cathode and P3HT to migrate to the anode. Consequently, a highly crystalline nano‐interpenetrating network with proper vertical phase separation is obtained. The optimal morphology improves charge transport and suppresses bimolecular recombination, boosting the power conversion efficiency from 4.45% to 7.18%, which is the highest performance in P3HT‐based binary nonfullerene solar cells.

A NH₄Cl additive is introduced in the preparation of AVA₂FA _{n −1}Sn _n I_{3 n +1} (<n> = 5) perovskite, leading to highly vertically oriented tin‐based reduced‐dimensional perovskite films with enhanced efficiency and stability. Herein, under the effects of NH₄Cl additive, the optimized power conversion efficiency of tin‐based quasi‐2D perovskite solar cells increases from 4.19% to 8.71% with enhanced stability.

Abstract

Tin‐based perovskites have exhibited high potential for efficient photovoltaics application due to their outstanding optoelectrical properties. However, the extremely undesired instabilities significantly hinders their development and further commercialization process. A novel tin‐based reduced‐dimensional (quasi‐2D) perovskites is reported here by using 5‐ammoniumvaleric acid (5‐AVA⁺) as the organic spacer. It is demonstrated that by introducing appropriate amount of ammonium chloride (NH₄Cl) as additive, highly vertically oriented tin‐based quasi‐2D perovskite films are obtained, which is proved through the grazing incidence wide‐angle X‐ray scattering characterization. In particular, this approach is confirmed to be a universal method to deliver highly vertically oriented tin‐based quasi‐2D perovskites with various spacers. The highly ordered vertically oriented perovskite films significantly improve the charge collection efficiency between two electrodes. With the optimized NH₄Cl concentration, the solar cells employing quasi‐2D perovskite, AVA₂FA _{n −1}Sn _n I_{3 n +1} (<n> = 5), as light absorbers deliver a power conversion efficiency up to 8.71%. The work paves the way for further employing highly vertically oriented tin‐based quasi‐2D perovskite films for highly efficient and stable photovoltaics.

An electron‐selective contact that simultaneously enables efficient electron selectivity and suppression of parasitic infrared absorption is achieved by a thick ZnO film capped with LiF _x /Al. Combining such an electron‐selective contact with a MoO _x ‐based stack as hole‐selective contact, a fully dopant‐free heterocontact Si solar cell is demonstrated with a record efficiency of 21.4%.

Abstract

Although charge‐carrier selectivity in conventional crystalline silicon (c‐Si) solar cells is usually realized by doping Si, the presence of dopants imposes inherent performance limitations due to parasitic absorption and carrier recombination. The development of alternative carrier‐selective contacts, using non‐Si electron and hole transport layers, has the potential to overcome such drawbacks and simultaneously reduce the cost and/or simplify the fabrication process of c‐Si solar cells. Nevertheless, devices relying on such non‐Si contacts with power conversion efficiencies (PCEs) that rival their classical counterparts are yet to be demonstrated. In this study, one key element is brought forward toward this demonstration by incorporating low‐pressure chemical vapor deposited ZnO as the electron transport layer in c‐Si solar cells. Placed at the rear of the device, it is found that rather thick (75 nm) ZnO film capped with LiF _x /Al simultaneously enables efficient electron selectivity and suppression of parasitic infrared absorption. Next, these electron‐selective contacts are integrated in c‐Si solar cells with MoO _x ‐based hole‐collecting contacts at the device front to realize full‐area dopant‐free‐contact solar cells. In the proof‐of‐concept device, a PCE as high as 21.4% is demonstrated, which is a record for this novel device class and is at the level of conventional industrial solar cells.

A δ‐CsPbI₃ intermediate phase growth (IPG)‐assisted sequential deposition strategy is developed in this work, which not only achieves controllable Cs⁺ incorporation and enlarged perovskite grains, but also manipulates the crystallization, modulates the bandgap, and improves the stability of the final perovskite film. This CsPbI₃‐IPG is a facile and effective strategy to obtain large‐grain Cs⁺ incorporated perovskite films via sequential deposition.

Abstract

Cs/FA/MA triple cation perovskite films have been well developed in the antisolvent dripping method, attributable to its outstanding photovoltaic and stability performances. However, a facile and effective strategy is still lacking for fabricating high‐quality large‐grain triple cation perovskite films via sequential deposition method a, which is one of the key technologies for high efficiency perovskite solar cells. To address this issue, a δ‐CsPbI₃ intermediate phase growth (CsPbI₃‐IPG) assisted sequential deposition method is demonstrated for the first time. The approach not only achieves incorporation of controllable cesium into (FAPbI₃)_1–x (MAPbBr₃)_x perovskite, but also enlarges the perovskite grains, manipulates the crystallization, modulates the bandgap, and improves the stability of final perovskite films. The photovoltaic performances of the devices based on these Cs/FA/MA perovskite films with various amounts of the δ‐CsPbI₃ intermediate phase are investigated systematically. Benefiting from moderate cesium incorporation and intermediate phase‐assisted grain growth, the optimized Cs/FA/MA perovskite solar cells exhibit a significantly improved power conversion efficiency and operational stability of unencapsulated devices. This facile strategy provides new insights into the compositional engineering of triple or quadruple cation perovskite materials with enlarged grains and superior stability via a sequential deposition method.

Recent progress in first‐principles simulations of carrier recombination in halide perovskites is reviewed. Misunderstandings relating to the impact of the Rashba effect on radiative recombination are clarified. The origin of exceptionally strong Auger recombination and avenues for improved materials design are discussed. Critical analysis of the recombination mechanisms reveals fruitful directions for improving the performance of halide perovskites.

Abstract

In recent years, there have been remarkable developments in halide perovskites, which are used in highly efficient optoelectronic devices and exhibit intriguing materials physics. Detailed knowledge of carrier recombination mechanisms is essential for understanding their excellent performance and to further increase their efficiency. Obtaining such knowledge is challenging however, and different studies have reached divergent conclusions in some cases. This progress report outlines the critical developments in understanding the carrier recombination mechanisms in halide perovskites from a computational perspective. The primary focus is radiative and Auger recombination, since they have not been systematically assessed and discussed before, and a number of important issues have been actively debated. This comprehensive discussion of the carrier recombination mechanisms is aimed at establishing physically justified insights that can form the basis for better materials and devices design.

Research on compositional engineering can realize power conversion efficiency (PCE) over 25%. Interfacial engineering along with optimal perovskite solar cell device structure is expected to lead to stable and theoretical PCE over 30%.

Abstract

Discovery of the 9.7% efficiency, 500 h stable solid‐state perovskite solar cell (PSC) in 2012 triggered off a wave of perovskite photovoltaics. As a result, a certified power conversion efficiency (PCE) of 25.2% was recorded in 2019. Publications on PSCs have increased exponentially since 2012 and the total number of publications reached over 13 200 as of August 2019. PCE has improved by developing device structures from mesoscopic sensitization to planar p‐i‐n (or n‐i‐p) junction and by changing composition from MAPbI₃ to FAPbI₃‐based mixed cations and/or mixed anion perovskites. Long‐term stability has been significantly improved by interfacial engineering with hydrophobic materials or the 2D/3D concept. Although small area cells exhibit superb efficiency, scale‐up technology is required toward commercialization. In this review, research direction toward large‐area, stable, high efficiency PSCs is emphasized. For large‐area perovskite coating, a precursor solution is equally important as coating methods. Precursor engineering and formulation of the precursor solution are described. For hysteresis‐less, stable, and higher efficiency PSCs, interfacial engineering is one of the best ways as defects can be effectively passivated and thereby nonradiative recombination is efficiently reduced. Methodologies are introduced to minimize interfacial and grain boundary recombination.

A novel design for all‐inorganic perovskite solar cells with a modified electron transporting layer facilitates excellent thermal‐air stability. This study demonstrates a dynamic‐hot air method with Mn²⁺ incorporated CsPbI₂Br perovskite based on low temperature processed MgZnO which enables higher thermal‐air stability.

Abstract

The high thermal stability and facile synthesis of CsPbI₂Br all‐inorganic perovskite solar cells (AI‐PSCs) have attracted tremendous attention. As far as electron‐transporting layers (ETLs) are concerned, low temperature processing and reduced interfacial recombination centers through tunable energy levels determine the feasibility of the perovskite devices. Although the TiO₂ is the most popular ETL used in PSCs, its processing temperature and moderate electron mobility hamper the performance and feasibility. Herein, the highly stable, low‐temperature processed MgZnO nanocrystal‐based ETLs for dynamic hot‐air processed Mn²⁺ incorporated CsPbI2Br AI‐PSCs are reported. By holding its regular planar “n–i–p” type device architecture, the MgZnO ETL and poly(3‐hexylthiophene‐2,5‐diyl) hole transporting layer, 15.52% power conversion efficiency (PCE) is demonstrated. The thermal‐stability analysis reveals that the conventional ZnO ETL‐based AI‐PSCs show a serious instability and poor efficiency than the Mg²⁺ modified MgZnO ETLs. The photovoltaic and stability analysis of this improved photovoltaic performance is attributed to the suitable wide‐bandgap, low ETL/perovskite interface recombination, and interface stability by Mg²⁺ doping. Interestingly, the thermal stability analysis of the unencapsulated AI‐PSCs maintains >95% of initial PCE more than 400 h at 85 °C for MgZnO ETL, revealing the suitability against thermal degradation than conventional ZnO ETL.

Tetrafluoroborate (BF₄ ⁻) anion can be successfully incorporated into a mixed‐ion perovskite crystal frame, leading to lattice relaxation and a longer photoluminescence lifetime, higher recombination resistance, and 1–2 orders magnitude lower trap density in prepared perovskite solar cells. These advantages result in an improved power conversion efficiency of 20.16% from 17.55% due to enhanced open‐circuit voltage and fill factor.

Abstract

Composition engineering is a particularly simple and effective approach especially using mixed cations and halide anions to optimize the morphology, crystallinity, and light absorption of perovskite films. However, there are very few reports on the use of anion substitutions to develop uniform and highly crystalline perovskite films with large grain size and reduced defects. Here, the first report of employing tetrafluoroborate (BF₄ ⁻) anion substitutions to improve the properties of (FA = formamidinium, MA = methylammonium (FAPbI₃)_0.83(MAPbBr₃)_0.17) perovskite films is demonstrated. The BF₄ ⁻ can be successfully incorporated into a mixed‐ion perovskite crystal frame, leading to lattice relaxation and a longer photoluminescence lifetime, higher recombination resistance, and 1–2 orders magnitude lower trap density in prepared perovskite films and derived solar cells. These advantages benefit the performance of perovskite solar cells (PVSCs), resulting in an improved power conversion efficiency (PCE) of 20.16% from 17.55% due to enhanced open‐circuit voltage (V _OC) and fill factor. This is the highest PCE for BF₄ ⁻ anion substituted lead halide PVSCs reported to date. This work provides insight for further exploration of anion substitutions in perovskites to enhance the performance of PVSCs and other optoelectronic devices.

Rapid crystallization is demonstrated to be necessary in achieving high‐quality 2DRP perovskite films by comparing dimethylacetamide (DMAC), N,N‐dimethylformamide, and dimethyl sulfoxide solvents. The improved stability and efficiency are observed using DMAC due to the accelerating crystallization rate of 2DRP perovskite crystals.

Abstract

Due to the additional introduction of bulky organic ammonium and the competition between bulky organic ammonium and methyl ammonium in 2D Ruddlesden‐Popper (2DRP) perovskite, the crystallization process becomes complicated. Here, it is demonstrated that the rapid crystallization controlled by processing solvents plays an important role in achieving high‐quality 2DRP perovskite films. It is found that the processing solvents, e.g., dimethylacetamide (DMAC), N,N‐dimethylformamide (DMF), and dimethyl sulfoxide (DMSO), with a different polarity and boiling point, have almost no effect on crystal structure and phase distribution but have a remarkable effect on crystallization kinetics, crystal growth orientation, and crystallinity of 2DRP perovskite. Compared to polar aprotic solvent DMF and DMSO with a high boiling point, DMAC with low polarity and a suitable boiling point has a weak coordination to lead and ammonium salts and is easy to escape during solution processing, which is able to accelerate the crystallization rate of 2DRP perovskite. Benefitting from the rapid crystallization enabled high‐quality 2DRP perovskite films, the best‐performing device with improved stability and a power conversion efficiency of 12.15% is obtained using DMAC solvent. These findings may give guidance for solvent engineering for highly efficient 2DRP perovskite solar cells in the future.

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 an 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.

Here, intermediate‐controlled crystal growth is reported via solvent tuning to prepare highly oriented 2D perovskite films with faster transport, longer carrier lifetime, and lower defect density.

Abstract

Reduced‐dimensional hybrid perovskite semiconductors have recently attracted significant attention due to their promising stability and optoelectronic properties. However, the issue of poor charge transport in 2D perovskites limits its application. Here, studies on intermediate‐controlled crystal growth are reported to improve charge carrier transport in 2D perovskite thin films. It is shown that the coordination strength of solvents with perovskite precursor affects the initial state of intermediate phase formation as well as the subsequent perovskite layer growth. Tuning the solvent composition with a mixture (5:5) of dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) leads to the growth of highly orientated 2D perovskite films with much‐improved optoelectronic properties (faster transport by ≈50x, longer carrier lifetime by ≈4x, and lower defect density by ≈30x) than the film prepared with pure DMF. Consequently, perovskite solar cells based on DMF/DMSO (5:5) show >80% efficiency improvement than the devices based on pure DMF.

Here, urea treatment of hole transport layer (e.g., poly(3,4‐ethylene dioxythiophene):polystyrene sulfonate (PEDOT:PSS)) is reported to effectively tune its morphology, conductivity, and work function for improving the efficiency and stability of inverted CH₃NH₃PbI₃ perovskite solar cells.

Abstract

Interface engineering is critical to the development of highly efficient perovskite solar cells. Here, urea treatment of hole transport layer (e.g., poly(3,4‐ethylene dioxythiophene):polystyrene sulfonate (PEDOT:PSS)) is reported to effectively tune its morphology, conductivity, and work function for improving the efficiency and stability of inverted MAPbI₃ perovskite solar cells (PSCs). This treatment has significantly increased MAPbI₃ photovoltaic performance to 18.8% for the urea treated PEDOT:PSS PSCs from 14.4% for pristine PEDOT:PSS devices. The use of urea controls phase separation between PEDOT and PSS segments, leading to the formation of a unique fiber‐shaped PEDOT:PSS film morphology with well‐organized charge transport pathways for improved conductivity from 0.2 S cm⁻¹ for pristine PEDOT:PSS to 12.75 S cm⁻¹ for 5 wt% urea treated PEDOT:PSS. The urea‐treatment also addresses a general challenge associated with the acidic nature of PEDOT:PSS, leading to a much improved ambient stability of PSCs. In addition, the device hysteresis is significantly minimized by optimizing the urea content in the treatment.

Solution‐cast lead iodide films can exhibit different metastable solvated states in the presence of DMF. Using in situ diagnostics, it is shown that conversion of PbI₂ to MAPbI₃ from its crystalline solvated state can occur spontaneously at room temperature and lead to high‐quality perovskite films with reduced trap state density and a high power conversion efficiency.

Abstract

Producing high efficiency solar cells without high‐temperature processing or use of additives still remains a challenge with the two‐step process. Here, the solution processing of MAPbI₃ from PbI₂ films in N,N‐dimethylformamide (DMF) is investigated. In‐situ grazing incidence wide‐angle X‐ray scattering (GIWAXS) measurements reveal a sol–gel process involving three PbI₂‐DMF solvate complexes—disordered (P₀) and ordered (P₁, P₂)—prior to PbI₂ formation. When the appropriate solvated state of PbI₂ is exposed to MAI (methylammonium Iodide), it can lead to rapid and complete room temperature conversion into MAPbI₃ with higher quality films and improved solar cell performance. Complementary in‐situ optical reflectance, absorbance, and quartz crystal microbalance with dissipation (QCM‐D) measurements show that dry PbI₂ can take up only one third of the MAI taken up by the solvated‐crystalline P₂ phase of PbI₂, requiring additional annealing and yet still underperforming. The perovskite solar cells fabricated from the ordered P₂ precursor show higher power conversion efficiency (PCE) and reproducibility than devices fabricated from other cases. The average PCE of the solar cells is greatly improved from 13.2(±0.53)% (from annealed PbI₂) to 15.7(±0.35)% (from P₂) reaching up to 16.2%. This work demonstrates the importance of controlling the solvation of PbI₂ as an effective strategy for the growth of high‐quality perovskite films and their application in high efficiency and reproducible solar cells.

The application of formamidinium (FA)‐based perovskite solar cells has largely been hindered by phase transition from the dark cubic phase to yellow orthorhombic phase. Here, a highly efficient and phase stable FA‐based perovskite solar cell is fabricated by using NbF₅ as a novel additive. NbF₅ can improve the quality of perovskite films and effectively suppress the formation of the yellow δ‐phase.

Abstract

The HC(NH₂)₂ ⁺(FA⁺) is a well‐known substitute to CH₃NH₃ ⁺(MA⁺) for its capability to extend light utilization for improved power conversion efficiency for perovskite solar cells; unfortunately, the dark cubic phase (α‐phase) can easily transition to the yellow orthorhombic phase (δ‐phase) at room temperature, an issue that prevents its commercial application. In this report, an inorganic material (NbF₅) is developed to stabilize the desired α‐phase perovskite material by incorporating NbF₅ additive into the perovskite films. It is found that the NbF₅ additive effectively suppresses the formation of the yellow δ‐phase in the perovskite synthesis and aging process, thus enhancing the humidity and light‐soaking stability of the perovskite film. As a result, the perovskite solar cells with the NbF₅ additive exhibit improved air stability by tenfold, retaining nearly 80% of their initial efficiency after aging in air for 50 d. In addition, under full‐sun AM 1.5 G illumination of a xenon lamp without any UV‐reduction, the perovskite solar cells with the NbF₅ additive also show fivefold improved illumination stability than the control devices without NbF₅.

Scalable room‐temperature sputtering deposition of the SnO₂ electron transport layer (ETL) with reduced gap states is demonstrated. Perovskite solar cells using a SnO₂ ETL show an efficiency up to 20.2% and a T₈₀ lifetime of 625 h. Mini‐modules with a 22.8 cm₂ aperture area show efficiencies over 12% and a T₈₀ lifetime of 515 h, which indicates the upscalability of our method.

Abstract

Stability and scalability have become the two main challenges for perovskite solar cells (PSCs) with the research focus in the field advancing toward commercialization. One of the prerequisites to solve these challenges is to develop a cost‐effective, uniform, and high quality electron transport layer that is compatible with stable PSCs. Sputtering deposition is widely employed for large area deposition of high quality thin films in the industry. Here the composition, structure, and electronic properties of room temperature sputtered SnO₂ are systematically studied. Ar and O₂ are used as the sputtering and reactive gas, respectively, and it is found that a highly oxidizing environment is essential for the formation of high quality SnO₂ films. With the optimized structure, SnO₂ films with high quality have been prepared. It is demonstrated that PSCs based on the sputtered SnO₂ electron transport layer show an efficiency up to 20.2% (stabilized power output of 19.8%) and a T₈₀ operational lifetime of 625 h. Furthermore, the uniform and thin sputtered SnO₂ film with high conductivity is promising for large area solar modules, which show efficiencies over 12% with an aperture area of 22.8 cm² fabricated on 5 × 5 cm² substrates (geometry fill factor = 91%), and a T₈₀ operational lifetime of 515 h.

Here a method to grow wafer‐size thin halide perovskite multiple crystals on aqueous solution surface is reported. The efficiency of lateral‐structure solar cells based on the single‐crystalline perovskite wafer reaches 5.9%.

Abstract

Solar‐grade single or multiple crystalline wafers are needed in large quantities in the solar cell industry, and are generally formed by a top‐down process from crystal ingots, which causes a significant waste of materials and energy during slicing, polishing, and other processing. Here, a bottom‐up technique that allows the growth of wafer‐size hybrid perovskite multiple crystals directly from aqueous solution is reported. Single‐crystalline hybrid perovskite wafers with centimeter size are grown at the top surface of a perovskite precursor solution. As well as saving raw materials, this method provides unprecedented advantages such as easily tunable thickness and rapid growth of the crystals. These crystalline wafers show high crystallinity, broader light absorption, and a long carrier recombination lifetime, comparable with those of bulk single crystals. Lateral‐structure perovskite solar cells made of these crystals demonstrate a record power conversion efficiency of 5.9%.

The morphology control of nonfullerene blends is very important to improve device performance. Here, the high boiling point cosolvent is added to the P3HT:O‐IDTBR blend, which separates the crystallization process of P3HT and O‐IDTBR, and prolongs film forming time. As a result, the crystallinity, lateral and phase separation structure are optimized simultaneously, leading to high performance of 7.18%.

Abstract

The morphology with the interpenetrating network and optimized vertical phase separation plays a key role in determining the charge transport and collection in polymer:nonfullerene small molecular acceptors (SMAs) solar cells. However, the crystallization of polymer and SMAs usually occurs simultaneously during film‐forming, thus interfering with the crystallization process of each other, leading to amorphous film with undesirable lateral and vertical phase separation. The poly(3‐hexylthiophene) (P3HT):O‐IDTBR blend is selected as a model system, and controlling film‐forming kinetics to solve these problems is proposed. Herein, a cosolvent 1,2,4‐triclorobenzene (TCB) with selective solubility and a high boiling point is added to the solution, leading to prior crystallization of P3HT and extended film‐forming duration. As a result, the crystallinity of both components is enhanced significantly. Meanwhile, the prior crystallization of P3HT induces solid–liquid phase separation, hence rationalizing the formation of the nano‐interpenetrating network. Moreover, the surface energy drives O‐IDTBR to enrich near the cathode and P3HT to migrate to the anode. Consequently, a highly crystalline nano‐interpenetrating network with proper vertical phase separation is obtained. The optimal morphology improves charge transport and suppresses bimolecular recombination, boosting the power conversion efficiency from 4.45% to 7.18%, which is the highest performance in P3HT‐based binary nonfullerene solar cells.

A novel, photoprotective effect based on an ultrafast, long‐range energy transfer from a fullerene acceptor to a stable small molecule donor significantly enhances the stability of organic photovoltaic devices. Transient absorption spectroscopy studies reveal that this occurs via an ultrafast quenching of the acceptor excited state, which would otherwise lead to rapid degradation of the material.

Abstract

Despite many advances toward improving the stability of organic photovoltaic devices, environmental degradation under ambient conditions remains a challenging obstacle for future application. Particularly conventional systems employing fullerene derivatives are prone to oxidize under illumination, limiting their applicability. Here, the environmental stability of the small molecule donor DRCN5T together with the fullerene acceptor PC₇₀BM is reported. It is found that this system exhibits exceptional device stability, mainly due to almost constant short‐circuit current. By employing ultrafast femtosecond transient absorption spectroscopy, this remarkable stability is attributed to two separate mechanisms: 1) DRCN5T exhibits high intrinsic resistance toward external factors, showing no signs of deterioration. 2) The highly sensitive PC₇₀BM is stabilized against degradation by the presence of DRCN5T through ultrafast, long‐range energy transfer to the donor, rapidly quenching the fullerene excited states which are otherwise precursors for chemical oxidation. It is proposed that this photoprotective mechanism be utilized to improve the device stability of other systems, including nonfullerene acceptors and ternary blends.