ZHANG JIAJIA

Applied Physics Letters, Volume 117, Issue 25, December 2020.
We performed in situ x-ray diffraction (XRD) experiments on an inorganic–organic hybrid perovskite, CH3NH3PbI3 (MAPbI3), during its interaction with moisture to understand the degradation mechanism. Although the degradation of inorganic–organic hybrid perovskite is an important factor hampering their development as solar cell materials, understanding of the degradation process is currently limited. The moisture-induced degradation mechanism was revealed by the temperature dependence of the in situ XRD pattern sequences and first-principles calculations based on the nudged elastic band method. The combination of experimental and computational data suggests that the MAPbI3 crystal spontaneously changes into the MAPbI3 mono-hydrate crystal once water molecules activated with an energy of more than ∼0.6 eV penetrate the (100) outer surface of the MAPbI3 lattice. These findings have important implications for the development of more robust inorganic–organic hybrid perovskites as light absorbing layers in solar cells and other applications.

A novel strategy to neutralize charged point defects in organic‐inorganic hybrid perovskite materials is proposed for highly efficient and stable perovskite solar cells by using a zwitterionic L‐alanine additive, which can be passivated simultaneously with both positively and negatively charged defects because it contains both anion and cation functional groups in one molecule.

Abstract

Ionic defects (e.g., organic cations and halide anions), preferably residing along grain boundaries (GBs) and on perovskite film surfaces, are known to be a major source of the notorious environmental instability of perovskite solar cells (PeSCs). Although passivating ionic defects is desirable, previous approaches using Lewis base or acid molecules as additives suppress only the negatively or positively charged defects, thus leaving oppositely charged defects. In this work, both the cationic and anionic defects inside methyl ammonium lead tri‐iodide (MAPbI₃) are simultaneously passivated by introducing a zwitterionic form of the amino acid, L‐alanine, into the precursor solution as an additive. L‐alanine has both positive (NH₃ ⁺) and negative (COO⁻) functional groups at a specific solvent pH, thereby passivating both the cation and anion defects in MAPbI₃. The addition of L‐alanine increases the grain size of the perovskite crystals and lengthens the charge carrier lifetime (τ > 1 µs), leading to improved power conversion efficiencies (PCEs) of 20.3% (from 18.3% without an additive) for small‐area (4.64 mm²) devices and 15.6% (from 13.5%) for large‐area submodules (9.06 cm²). More importantly, the authors’ approach also significantly enhances the shelf storage and photoirradiation stabilities of PeSCs.

A new class of polymer acceptors (P _As, P(BDT2BOY5‐X)) consisting of benzodithiophene (BDT) and non‐fullerene small molecule‐accepting units is developed, which shows excellent material compatibility with an efficient BDT‐based polymer donor (P _D). The resulting all‐polymer solar cells show excellent photovoltaic efficiency, thermal stability, and mechanical robustness at the same time, benefitting from the high chemical and molecular compatibilities between P _D and P _A.

Abstract

All‐polymer solar cells (all‐PSCs) are a highly attractive class of photovoltaics for wearable and portable electronics due to their excellent morphological and mechanical stabilities. Recently, new types of polymer acceptors (P _As) consisting of non‐fullerene small molecule acceptors (NFSMAs) with strong light absorption have been proposed to enhance the power conversion efficiency (PCE) of all‐PSCs. However, polymerization of NFSMAs often reduces entropy of mixing in PSC blends and prevents the formation of intermixed blend domains required for efficient charge generation and morphological stability. One approach to increase compatibility in these systems is to design P _As that contain the same building blocks as their polymer donor (P _D) counterparts. Here, a series of NFSMA‐based P _As [P(BDT2BOY5‐X), (X = H, F, Cl)] are reported, by copolymerizing NFSMA (Y5‐2BO) with benzodithiophene (BDT), a common donating unit in high‐performance P _Ds such as PBDB‐T. All‐PSC blends composed of PBDB‐T P _D and P(BDT2BOY5‐X) P _A show enhanced molecular compatibility, resulting in excellent morphological and electronic properties. Specifically, PBDB‐T:P(BDT2BOY5‐Cl) all‐PSC has a PCE of 11.12%, which is significantly higher than previous PBDB‐T:Y5‐2BO (7.02%) and PBDB‐T:P(NDI2OD‐T2) (6.00%) PSCs. Additionally, the increased compatibility of these all‐PSCs greatly improves their thermal stability and mechanical robustness. For example, the crack onset strain (COS) and toughness of the PBDB‐T:P(BDT2BOY5‐Cl) blend are 15.9% and 3.24 MJ m^–3, respectively, in comparison to the PBDB‐T:Y5‐2BO blends at 2.21% and 0.32 MJ m^–3.

Bridge‐jointed 2D nanosheets are inserted between the methylammonium‐free perovskite and the dopant‐free hole transport layer (HTL) to form a scalable heterostructure, which preserves p‐type semiconduction of HTL and suppresses nonradiative‐recombination. Further, a perovskite solar module with an area of 35.80 cm² shows a certified efficiency of 15.3% and encapsulated modules retain over 91% of initial efficiency after damp heat test for 1000 h.

Abstract

Perovskite solar cell (PSC) modules employing a hole transport layer (HTL) without unstable dopants possess high potential for improving operational stability. However, the low efficiencies of the devices greatly limit their commercial applications owing to the lower efficacy of the dopant‐free HTL, introduced by the unintentional n‐doping effect of volatile ions from the halide‐rich perovskite surface. Here, a scalable heterostructure integrated by a methylammonium‐free perovskite film with an iodide‐rich surface, an ultrathin interlayer of bridge‐jointed graphene oxide nanosheets (BJ‐GO), and an HTL without additional ionic dopants is developed. In this heterostructure, the iodide ions are physically immobilized by the compact 2D network, and lead defects are chemically passivated by multiple coordination bonds. Moreover, the BJ‐GO with tunable surface energy enables a highly ordered HTL a considerably improved carrier mobility by an order of magnitude. Finally, the PSC module with an area of 35.80 cm² employing this heterostructure shows a certified efficiency of 15.3%. The encapsulated PSC modules retain over 91% of initial efficiency after the damp heat test at 85 °C and ≈85% relative humidity for 1000 h, while maintaining 90% of the initial value for 1000 h at the maximum power point under continuous 1‐Sun illumination at 60 °C.

Advanced Energy Materials, Volume 10, Issue 48, December 22, 2020.

Nonfullerene acceptors dominate organic solar cell research due to their promising high device efficiencies. However, key challenges for achieving high stability in commercially viable devices still remain. In this review, recent progress and challenges toward stable organic solar cells are discussed correlating molecular design and device engineering to device stability.

Abstract

Organic solar cells (OSCs) based on nonfullerene acceptors (NFAs) have made significant breakthrough in their device performance, now achieving a power conversion efficiency of ≈18% for single junction devices, driven by the rapid development in their molecular design and device engineering in recent years. However, achieving long‐term stability remains a major challenge to overcome for their commercialization, due in large part to the current lack of understanding of their degradation mechanisms as well as the design rules for enhancing their stability. In this review, the recent progress in understanding the degradation mechanisms and enhancing the stability of high performance NFA‐based OSCs is a specific focus. First, an overview of the recent advances in the molecular design and device engineering of several classes of high performance NFA‐based OSCs for various targeted applications is provided, before presenting a critical review of the different degradation mechanisms identified through photochemical‐, photo‐, and morphological degradation pathways. Potential strategies to address these degradation mechanisms for further stability enhancement, from molecular design, interfacial engineering, and morphology control perspectives, are also discussed. Finally, an outlook is given highlighting the remaining key challenges toward achieving the long‐term stability of NFA‐OSCs.

Highly efficient CsPbI_1.5Br_1.5 perovskite solar cells (PSCs) are achieved via introducing fluorescein isothiocyanate (FITC) organic dye as passivator. FITC not only reduces the metal ion related trap states but also improves film crystallinity, resulting in an enhancement of device efficiency from 12.3% to 14.05%. In addition, it is demonstrated that CsPbI_1.5Br_1.5 perovskite shows the optimal halide composition for inorganic PSCs.

Abstract

All‐inorganic perovskite solar cells (PSCs) have recently received growing attention as a promising template to solve the thermal instability of organic–inorganic PSCs. However, the thermodynamic phase instability and relatively low device efficiency pose challenges. Herein, highly efficient and stable CsPbI_1.5Br_1.5 compositional perovskite‐based inorganic PSCs are fabricated using an organic dye, fluorescein isothiocyanate (FITC), as a passivator. The carboxyl and thiocyanate groups of FITC not only minimize the trap states by forming interactions with the under‐coordinated Pb²⁺ ions but also significantly increase the grain size and improve the crystallinity of the perovskite films during annealing. Consequently, perovskite films with superior optoelectronic properties, prolonged carrier lifetime, reduced trap density, and improved stability are obtained. The resulting device yields a champion efficiency of 14.05% with negligible hysteresis, which presents the highest reported efficiency for inorganic CsPbI_1.5Br_1.5 solar cells reported thus far. In addition, FITC can be generally adopted as attractive passivator to improve the performance of CsPbI₂Br‐ and CsPbIBr₂‐based PSCs. Furthermore, with a comprehensive comparison of mixed‐halide inorganic perovskites, it is demonstrated that CsPbI_1.5Br_1.5 compositional perovskite is a promising candidate with the optimal halide composition for high‐performance inorganic PSCs.

Utilizing NP‐SC₆‐TiOPc and NP‐SC₆‐ZnPc as passivating agents on perovskite thin film through an antisolvent, improved performance and stability are achieved for perovskite solar cells. The highest power conversion efficiencies (PCEs) of 19.39% and 18.04% are obtained for NP‐SC₆‐TiOPc and NP‐SC₆‐ZnPc passivated devices, which is higher than that of the control devices without post‐treating the MAPbI₃ films (PCE of 17.67%).

Abstract

Semiconducting molecules have been employed to passivate traps extant in the perovskite film for enhancement of perovskite solar cells (PSCs) efficiency and stability. A molecular design strategy to passivate the defects both on the surface and interior of the CH₃NH₃PbI₃ perovskite layer, using two phthalocyanine (Pc) molecules (NP‐SC₆‐ZnPc and NP‐SC₆‐TiOPc) is demonstrated. The presence of lone electron pairs on S, N, and O atoms of the Pc molecular structures provides the opportunity for Lewis acid–base interactions with under‐coordinated Pb²⁺ sites, leading to efficient defect passivation of the perovskite layer. The tendency of both NP‐SC₆‐ZnPc and NP‐SC₆‐TiOPc to relax on the PbI₂ terminated surface of the perovskite layer is also studied using density functional theory (DFT) calculations. The morphology of the perovskite layer is improved due to employing the Pc passivation strategy, resulting in high‐quality thin films with a dense and compact structure and lower surface roughness. Using NP‐SC₆‐ZnPc and NP‐SC₆‐TiOPc as passivating agents, it is observed considerably enhanced power conversion efficiencies (PCEs), from 17.67% for the PSCs based on the pristine perovskite film to 19.39% for NP‐SC₆‐TiOPc passivated devices. Moreover, PSCs fabricated based on the Pc passivation method present a remarkable stability under conditions of high moisture and temperature levels.

Dual‐isomer alkylammonium cation based 2D surface layer outperforms its single‐cation 2D counterparts in surface passivation quality, resulting in high‐performing (champion efficiency: 23.27%) PSCs, with an impressive open‐circuit voltage of 1.21 V for a perovskite composition with an optical bandgap of ≈1.6 eV.

Abstract

Dimensional engineering of perovskite solar cells has attracted significant research attention recently because of the potential to improve both device performance and stability. Here, a novel 2D passivation scheme for 3D perovskite solar cells is demonstrated using a mixed cation composition of 2D perovskite based on two different isomers of butylammonium iodide. The dual‐cation 2D perovskite outperforms its single cation 2D counterparts in surface passivation quality, resulting in devices with an impressive open‐circuit voltage of 1.21 V for a perovskite composition with an optical bandgap of ≈1.6 eV, and a champion efficiency of 23.27%. Using a combination of surface elemental analysis and valence electron spectra decomposition, it is shown that an in situ interaction between the 2D perovskite precursor and the 3D active layer results in surface intermixing of 3D and 2D perovskite phases, providing an effective combination of defect passivation and enhanced charge transfer, despite the semi‐insulating nature of the 2D perovskite phase. The demonstration of the synergistic interaction of multiple organic spacer cations in a 2D passivation layer offers new opportunities for further enhancement of device performance with mixed dimensional perovskite solar cells.

Metal (titanium or Ti) nanopillar arrays (NaPAs), vertically protruding on a TiO₂ compact layer, function as an electron transporting layer in perovskite solar cells. Ti NaPA has highly hydrophilic surfaces passivated with TiO₂, high electron mobility, and low work function; hence it compensates the loss of light harvesting in perovskite and leads to highly efficient, antiaging photovoltaic performance.

Abstract

Electron transporting layers (ETLs), required to be optically transparent in perovskite solar cells (PSCs) having regular structures, possess a determinant effect on electron extraction and collection. Metal oxides (e.g., TiO₂) have overwhelmingly served as ETLs, but usually have low electron mobility (μ_e < 10⁻² cm² V⁻¹ s⁻¹) not favorable for photovoltaic conversion. Here, metal oxides are replaced with metals (e.g., Ti with μ_e ≈ 294 cm² V⁻¹ s⁻¹) that are sculptured via glancing angle deposition to be a close‐packed nanopillar array (NaPA), which vertically protrudes on a transparent electrode to obtain sufficient optical transmission for light harvesting in perovskite. Ti NaPAs, whose rough surfaces are passivated with 5 nm thick TiO₂ (i.e., Ti NaPAs@TiO₂) to suppress exciton recombination, lead to the champion power conversion efficiency (PCE) of 18.89% that is superior to that of MAPbI₃ PSCs without Ti NaPAs@TiO₂ or containing TiO₂ NaPAs@TiO₂, owing to high surface wettability, high μ_e, and relatively low work function of Ti. Furthermore, Ti NaPAs@TiO₂ effectively prevents the decomposition of MAPbI₃ to achieve long‐term shelf stability whereby 50‐day aging only causes 15% PCE degradation. This work paves the way toward widening the material spectrum, from semiconductors to metals, to generate a diverse range of ETLs for producing efficient optoelectronic devices with long‐term shelf stability.

Two degradation patterns are found for nonfullerene acceptors: small molecules like ITIC undergo a light‐mediated reversible degradation related to oxygen‐doping while polymer acceptors (N2200) are subject to permanent damage. Nevertheless, the chemical compatibility between the electron donor (PBDB‐T) and nonfullerene polymer acceptors results in an unprecedented morphological stability up to 200 °C.

Abstract

A systematic study is conducted to compare the performances and stability of active layers employing a high performance electron donor (PBDB‐T) combined with state‐of‐the‐art fullerene (PC₇₁BM), nonfullerene (ITIC), and polymer (N2200) electron acceptors. The impact of the chemical nature of the acceptor on the durability of organic solar cells (OSCs) is elucidated by monitoring their photovoltaic performances under light exposure or dark conditions in the presence of oxygen. PC₇₁BM molecules exhibit a higher resistance toward oxidation compared to nonfullerene acceptors. Unencapsulated PBDB‐T:PC₇₁BM OSCs display relatively stable performances at room temperature when stored in air for 3 months. However, when exposed to temperatures above 80 °C, their active materials demix causing notable reductions in the short‐circuit densities. Such detrimental demixing can also be seen for PBDB‐T:ITIC active layers above 120 °C. Although N2200 chains irreversibly degrade when exposed to air, thermally induced demixing does not occur in PBDB‐T:N2200 active layers annealed up to 200 °C. In summary, fullerene OSCs may be the best currently available choice for unencapsulated room temperature applications but if oxidation of the polymer acceptors can be avoided, all polymer active layers should enable the fabrication of highly durable OSCs with lifetimes matching the requirements for OSC commercialization.

By introducing moderate phenylethylammonium iodide and lead acetate in CsPbI₃ perovksite, moiture resistance and charge recombination are optimized. The device achieves a 17% power conversion efficiency, a 1.33 V open‐circuit voltage (V _OC) and the smallest 0.38 V V _OC deficit. Meanwhile, the device maintains 94% of its efficiency after 2000 h storage in ambient environment.

Abstract

Cesium lead iodide (CsPbI₃) perovskite has gained great attention due to its potential thermal stability and appropriate bandgap (≈1.73 eV) for tandem cells. However, the moisture‐induced thermodynamically unstable phase and large open‐circuit voltage (V _OC) deficit and also the low efficiency seriously limit its further development. Herein, long chain phenylethylammonium (PEA) is utilized into CsPbI₃ perovskite to stabilize the orthorhombic black perovskite phase (γ‐CsPbI₃) under ambient condition. Furthermore, the moderate lead acetate (Pb(OAc)₂) is controlled to combine with phenylethylammonium iodide to form the 2D perovskite, which can dramatically suppress the charge recombination in CsPbI₃. Unprecedentedly, the resulted CsPbI₃ solar cells achieve a 17% power conversion efficiency with a record V _OC of 1.33 V, the V _OC deficit is only 0.38 V, which is close to those in organic‐inorganic perovskite solar cells (PSCs). Meanwhile, the PEA modified device maintains 94% of its initial efficiency after exceeding 2000 h of storage in the low‐humidity controlled environment without encapsulation.

Deep understanding of electronic and optical properties of nanostructured electronic materials requires considering randomness of the actual number of nonradiative recombination centers (excitation quenchers) per charge/energy migration volume.

Abstract

Long charge carrier diffusion length and large grain size are commonly believed to be inherent properties of highly luminescent polycrystalline thin‐film semiconductors. However, exactly these two properties make luminescence very susceptible to quenching by just one strongly quenching defect state if present in each grain. Moreover, when the number of quenchers per grain is small (say 1–10), it varies greatly from grain to grain, purely for statistical reasons. These fluctuations, which resemble digital signal switching, can be one of the reasons for large differences between the luminescence brightness of different grains in polycrystalline films. This and other peculiarities of photoluminescence in systems where the number of strong quenchers per grain/crystallite is small is discussed in detail using metal halide perovskites as examples.

A newly conceived n‐type small molecule (Y‐Th2) is incorporated as an efficient additive in perovskite solar cells, achieving simultaneous improvements in device performance and stability. Y‐Th2 effectively passivates defects in perovskite crystals by Lewis acid–base interactions and intermolecular hydrogen bonds, obtaining high‐quality perovskite film. The inverted structure device exhibits a power conversion efficiency of 21.5% with notably enhanced operational stability.

Abstract

Significant efforts have been devoted to modulating the grain size and improving the film quality of perovskite in perovskite solar cells (PSCs). Adding materials to the perovskite is especially promising for high‐performance PSCs, because the additives effectively control the crystal structure. Although the additive engineering approach has substantially boosted the efficiency of PSCs, instability of the perovskite film has remained a primary bottleneck for the commercialization of PSCs. Herein, a newly conceived bithiophene‐based n‐type conjugated small molecule (Y‐Th2) is introduced to PSCs, which simultaneously enhances the performance and stability of the cell. The Y‐Th2 effectively passivates the defect states in perovskite through Lewis acid–base interactions, increasing the grain size and quality of the perovskite absorber. An inverted PSC containing the Y‐Th2 additive achieves a power conversion efficiency of 21.5%, versus 18.3% in the reference device. The operational stability is also considerably enhanced by the improved hydrophobicity and intermolecular hydrogen bonds in the perovskite.

Advanced Energy Materials, Volume 10, Issue 46, December 8, 2020.

This work is the first to integrate the multimechanism recombination parameters with the density of states (DOS) distribution and effective bandgap in the framework of a semiempirical analytical model of temperature and light intensity dependent V _oc. The proposed approach is expected to be a useful tool for quantifying the full spectrum of recombination‐ and DOS‐related parameters of nonfullerene organic solar cells.

Abstract

The relationship of the temperature–light intensity dependence of open‐circuit voltage V _oc in nonfullerene‐based organic solar cells with their material characteristics and multimechanism recombination parameters is described. The systematic variation of the effective bandgap E _g,eff and the electrode layers allows the observation of different relative contributions of bimolecular, bulk, and surface trap‐assisted recombination mechanisms. The complementary advantages of the analytical model and the established voltage‐impedance spectroscopy technique provide a useful tool to quantify multimechanism recombination parameters, effective density of states N _c, and energetic disorder σ in organic solar cells under operating conditions. The validity of the proposed model to understand the temperature and light intensity dependent of V _oc is shown by applying it to four different donor:nonfullerene acceptor blend systems with conventional or inverted device architectures.

A narrow bandgap polymer acceptor PYF‐T with fluorinated end groups on monomer sub‐units is synthesized, showing stronger and red‐shifted absorption, lower‐lying frontier molecular orbitals, higher electron mobility, enhanced intermolecular packing, and without sacrificing photovoltage compared to its non‐fluorinated counterpart (PY‐T). When employed in all‐polymer solar cells, PYF‐T yields an outstanding efficiency of 14.10%.

Abstract

Fluorination of end groups has been a great success in developing efficient small molecule acceptors. However, this strategy has not been applied to the development of polymer acceptors. Here, a dihalogenated end group modified by fluorine and bromine atoms simultaneously, namely IC‐FBr, is first developed, then employed to construct a new polymer acceptor (named PYF‐T) for all‐polymer solar cells (all‐PSCs). In comparison with its non‐fluorinated counterpart (PY‐T), PYF‐T exhibits stronger and red‐shifted absorption spectra, stronger molecular packing and higher electron mobility. Meanwhile, the fluorination on the end groups down‐shifts the energy levels of PYF‐T, which matches better with the donor polymer PM6, leading to efficient charge transfer and small voltage loss. As a result, an all‐PSC based on PM6:PYF‐T yields a higher power conversion efficiency (PCE) of 14.1% than that of PM6:PY‐T (11.1%), which is among the highest values for all‐PSCs reported to date. This work demonstrates the effectiveness of fluorination of end‐groups in designing high‐performance polymer acceptors, which paves the way toward developing more efficient and stable all‐PSCs.

The power conversion efficiencies (PCEs) of single‐junction organic solar cells have now reached over 18%. Recent progress that has been made in understanding the morphology and the device photophysics of high performing polymer:non‐fullerene acceptor blends and some of the major challenges that must be overcome to attain PCEs of over 20% are highlighted.

Abstract

The power conversion efficiencies (PCEs) of single‐junction organic solar cells (OSC) have now reached over 18%. This rapid recent progress can be attributed to the development of new nonfullerene electron acceptors (NFAs) that are paired with suitable high performing polymer electron donors. Substantial improvements in the PCEs and long‐term stability enabled by NFA OSCs have allowed the development and integration of these systems into many niche and novel applications. Here, the recent progress that has been made in understanding the device photophysics of high performing polymer:NFA blends is highlighted. As the bulk heterojunction morphology is intrinsically linked to the device photophysics, this review focuses on studies that have provided noteworthy morphological insights using advanced techniques such as solid‐state NMR and resonant soft X‐ray scattering. Through this, some of the major challenges that must be overcome to attain PCEs of over 20% in NFA OSCs are addressed.

Conformation effects of Y6‐type acceptors are systematically studied based on asymmetric design strategies. Z‐shape and W‐shape conformations‐based acceptors can help reduce energy loss in devices through significantly suppressed nonradiative energy loss. Benefiting from the high open‐circuit voltage of BP5T‐4F in the devices, ternary organic solar cells based on PM6:BP5T‐4F:CH1007 achieve a 17.2% efficiency.

Abstract

Y6, as a state‐of‐the‐art nonfullerene acceptor (NFA), is extensively optimized by modifying its side chains and terminal groups. However, the conformation effects on molecular properties and photovoltaic performance of Y6 and its derivatives have not yet been systematically studied. Herein, three Y6 analogs, namely, BP4T‐4F, BP5T‐4F, and ABP4T‐4F, are designed and synthesized. Owing to the asymmetric molecular design strategies, three representative molecular conformations for Y6‐type NFAs are obtained through regulating the lateral thiophene orientation of the fused core. It is found that conformation adjustment imposes comprehensive effects on the molecular properties in neat and blend films of these NFAs. As a result, organic solar cells (OSCs) fabricated with PM6:BP4T‐4F, PM6:BP5T‐4F, and PM6:ABP4T‐4F show high power conversion efficiency of 17.1%, 16.7%, and 15.2%, respectively. Interestingly, these NFAs with different conformations also show reduced energy loss (E _loss) in devices via gradually suppressed nonradiative E _loss. Moreover, by employing a selenium‐containing analog, CH1007, as the complementary third component, ternary OSCs based on PM6:BP5T‐4F:CH1007 (1:1.02:0.18) achieve a 17.2% efficiency. This work helps shed light on engineering the molecular conformation of NFAs to achieve high efficiency OSCs with reduced voltage loss.

Applied Physics Letters, Volume 117, Issue 22, November 2020.
Due to large binding energy and oscillator strength, 2D Ruddlesden–Popper perovskites are promising materials for the realization of room temperature coupled exciton-polaritons. Here, we demonstrate room temperature exciton-polaritons in high-quality exfoliated 2D RPP (BA)2(MA)n−1PbnI3n+1 (n = 3, 4) flakes without the use of external Distributed Bragg Reflectors. By angle-resolved PL spectroscopy, we obtain multi-mode low polariton branches and the Rabi splitting in the range of about 160 meV–180 meV for n = 3 and n = 4 flakes. The realization of room temperature exciton-polaritons in 2D RPPs with a large n value provides a potential platform for polaritonic device applications.

By introducing moderate phenylethylammonium iodide and lead acetate in CsPbI₃ perovksite, moiture resistance and charge recombination are optimized. The device achieves a 17% power conversion efficiency, a 1.33 V open‐circuit voltage (V _OC) and the smallest 0.38 V V _OC deficit. Meanwhile, the device maintains 94% of its efficiency after 2000 h storage in ambient environment.

Abstract

Cesium lead iodide (CsPbI₃) perovskite has gained great attention due to its potential thermal stability and appropriate bandgap (≈1.73 eV) for tandem cells. However, the moisture‐induced thermodynamically unstable phase and large open‐circuit voltage (V _OC) deficit and also the low efficiency seriously limit its further development. Herein, long chain phenylethylammonium (PEA) is utilized into CsPbI₃ perovskite to stabilize the orthorhombic black perovskite phase (γ‐CsPbI₃) under ambient condition. Furthermore, the moderate lead acetate (Pb(OAc)₂) is controlled to combine with phenylethylammonium iodide to form the 2D perovskite, which can dramatically suppress the charge recombination in CsPbI₃. Unprecedentedly, the resulted CsPbI₃ solar cells achieve a 17% power conversion efficiency with a record V _OC of 1.33 V, the V _OC deficit is only 0.38 V, which is close to those in organic‐inorganic perovskite solar cells (PSCs). Meanwhile, the PEA modified device maintains 94% of its initial efficiency after exceeding 2000 h of storage in the low‐humidity controlled environment without encapsulation.

A facile and effective additive strategy is devised by introducing bifunctional guanidine sulfamate (GuaSM) molecules into perovskite (PVK) layer. The synergistic effect of the SM⁻ anions and the Gua⁺ cations are demonstrated, which effectively reduces the trap density and the recombination in PVK, so that the photovoltaic performance and stability of the perovskite solar cells are improved noticeably.

Abstract

High efficiency and good stability are the challenges for perovskite solar cells (PSCs) toward commercialization. However, the intrinsic high defect density and internal nonradiative recombination of perovskite (PVK) limit its development. In this work, a facile additive strategy is devised by introducing bifunctional guanidine sulfamate (GuaSM; CH₆N₃ ⁺, Gua⁺; H₂N−SO₃ ⁻, SM⁻) into PVK. The size of Gua⁺ ion is suitable with Pb(BrI)₂ cavity relatively, so it can participate in the formation of low‐dimensional PVK when mixed with Pb(BrI)₂. The O and N atoms of SM⁻ can coordinate with Pb²⁺. The synergistic effect of the anions and cations effectively reduces the trap density and the recombination in PVK, so that it can improve the efficiency and stability of PSCs. At an optimal concentration of GuaSM (2 mol%), the PSC presents a champion power conversion efficiency of 21.66% and a remarkably improved stability and hysteresis. The results provide a novel strategy for highly efficient and stable PSCs by bifunctional additive.

A new, universal vapor‐phase anion‐exchange strategy is developed to realize the precise phase and bandgap control of large‐scale inorganic perovskites by using gas injection cycle. Ab initio calculations unveil the mechanism accounting for the impact of anion exchange on the structural and electronic properties. Tunable photodetectors with wide‐range response (≈100 nm) and ultrahigh spectral resolution (≈1 nm) are fabricated.

Abstract

Anion exchange offers great flexibility and high precision in phase control, compositional engineering, and optoelectronic property tuning. Different from previous successful anion exchange process in liquid solution, herein, a vapor‐phase anion‐exchange strategy is developed to realize the precise phase and bandgap control of large‐scale inorganic perovskites by using gas injection cycle, producing some perovskites such as CsPbCl₃ which has never been reported in thin film morphology. Ab initio calculations also provide the insightful mechanism to understand the impact of anion exchange on tuning the electronic properties and optimizing the structural stability. Furthermore, because of precise control of specific atomic concentrations, intriguing tunable photoluminescence is observed and photodetectors with tunable photoresponse edge from green to ultraviolet light can be realized accurately with an ultrahigh spectral resolution of 1 nm. Therefore, a new, universal vapor‐phase anion exchange method is offered for inorganic perovskite with fine‐tunable optoelectronic properties.

Linear increase of electron diffusion length per average domain spacing is achieved by tuning chalcopyrite grain growth, assisted by positioning a K‐layer in the bulk Cu(In,Ga)(S,Se)₂ (CIGS) stack, and this is a key strategy to achieve highly efficient solution‐processed CIGS solar cells.

Abstract

Solution‐processed Cu(In,Ga)(S,Se)₂ (CIGS) has a great potential for the production of large‐area photovoltaic devices at low cost. However, CIGS solar cells processed from solution exhibit relatively lower performance compared to vacuum‐processed devices because of a lack of proper composition distribution, which is mainly instigated by the limited Se uptake during chalcogenization. In this work, a unique potassium treatment method is utilized to improve the selenium uptake judiciously, enhancing grain sizes and forming a wider bandgap minimum region. Careful engineering of the bandgap grading structure also results in an enlarged space charge region, which is favorable for electron–hole separation and efficient charge carrier collection. Besides, this device processing approach has led to a linearly increasing electron diffusion length and carrier lifetime with increasing the grain size of the CIGS film, which is a critical achievement for enhancing photocurrent yield. Overall, 15% of power conversion efficiency is achieved in solar cells processed from environmentally benign solutions. This approach offers critical insights for precise device design and processing rules for solution‐processed CIGS solar cells.

Here, a straightforward polyTPD passivation is introduced to reduce the defect‐mediated recombination by elucidating the imperfections on the surface and grain boundaries of perovskite materials. Suppressed non‐radiative recombination and improved interfacial hole extraction result in perovskite solar cells with stabilized efficiency exceeding 21%. Moreover, ultra‐hydrophobic and thermally robust polyTPD passivated devices retain 94% of the initial efficiency after 800 h under operational conditions.

Abstract

The failure of perovskite solar cells (PSCs) to maintain their maximum efficiency over a prolonged time is due to the deterioration of the light harvesting material under environmental factors such as humidity, heat, and light. Systematically elucidating and eliminating such degradation pathways are critical to imminent commercial use of this technology. Here, a straightforward approach is introduced to reduce the level of defect‐states present at the perovskite and hole transporting layer interface by treating the various perovskite surfaces with poly(N,N′‐bis‐4‐butylphenyl‐N,N′‐bisphenyl)benzidine (polyTPD) molecules. This strategy significantly suppresses the defect‐mediated non‐radiative recombination in the ensuing devices and prevents the penetration of degrading agents into the inner layers by passivating the perovskite surface and grain boundaries. Suppressed non‐radiative recombination and improved interfacial hole extraction result in PSCs with stabilized efficiency exceeding 21% with negligible hysteresis (≈19.1% for control device). Moreover, ultra‐hydrophobic polyTPD passivant considerably alleviates moisture penetration, showing ≈91% retention of initial efficiencies after 300 h storage at high relative humidity of 80%. Similarly, passivated device retains 94% of its initial efficiency after 800 h under operational conditions (maximum power point tracking under continuous illumination at 60 °C). In addition to interfacial passivation function, hole‐selective role of dopant‐free polyTPD is also evaluated and discussed in this study.

The recent progress in potentially low‐cost polythiophene:nonfullerene‐based solar cells is reviewed from the viewpoints of molecular engineering and morphology control. The molecular design strategies of polythiophenes and nonfullerene acceptors are discussed, followed by the recent achievements in understanding and controlling the morphology of polythiophene:nonfullerene blends. Finally, the future challenges are delineated for advancing the commercial applications of polythiophenes in solar cells.

Abstract

With the advances in organic photovoltaics (OPVs), the development of low‐cost and easily accessible polymer donors is of vital importance for OPV commercialization. Polythiophene (PT) and its derivatives stand out as the most promising members of the photovoltaic material family for commercial applications, owing to their low cost and high scalability of synthesis. In recent years, PTs, paired with nonfullerene acceptors, have progressed rapidly in photovoltaic performance. This Review gives an overview of the strategies in designing PTs for nonfullerene OPVs from the perspective of energy level modulation. A survey of the typical classes of nonfullerene acceptors designed for pairing with the benchmark PT, i.e., poly(3‐hexylthiophene) (P3HT) is also presented. Furthermore, recent achievements in understanding and controlling the film morphology for PT:nonfullerene blends are discussed in depth. In addition to the effects of molecular weight and blend ratio on film morphology, the crucial roles of miscibility between PT and nonfullerene and processing solvent in determining film microstructure and morphology are highlighted, followed by a discussion on thermal annealing and ternary active layers. Finally, the remaining questions and the prospects of the low‐cost PT:nonfullerene systems are outlined. It is hoped that this review can guide the optimization of PT:nonfullerene blends and advance their commercial applications.

Recent progress is reviewed in applying self‐assembled monolayers in perovskite solar cells to improve surface morphology, energy band alignment, reduced interfacial charge recombination, and the trap passivation mechanism. The opportunities for molecular design of self‐assembled monolayers in enhancing the power conversion efficiency and stability of perovskite solar cells are discussed.

Abstract

Due to a certified 25.2% high efficiency, low cost, and easy fabrication; perovskite solar cells (PSCs) are the focus of interest among the next‐generation photovoltaic technologies. Long‐term stability is one of the most challenging obstacles to bring technology from the lab to the market. In this review, applications of self‐assembled monolayers (SAMs) to enhance the power conversion efficiency (PCE) and stability of PSCs is discussed. In the first part, the introduction of SAMs, and deposition techniques applied to different PSC architectures are described. In the middle section, current efforts to utilize SAMs to fine‐tune the optoelectronic properties to enhance the PCE and stability are detailed. The improvements in surface morphology, energy band alignment, as well as reduced interfacial charge recombination induced by SAMs, and the trap passivation mechanism allowing optimal PCE and stability are described. A general outlook summarizing the importance of SAMs to the improvement of PSCs performance is also given, alongside a discussion of future opportunities and possible research directions.

Photoinduced degradation can happen in each functional layer in perovskite solar cells, including the active layer, electronic transport layer, hole transport layer and their interfaces. An overview of these degradation categories and the corresponding solutions is proposed in this review, in the hope of encouraging further research and optimization of the devices.

Abstract

Solar cells based on metal halide perovskites have reached a power conversion efficiency as high as 25%. Their booming efficiency, feasible processability, and good compatibility with large‐scale deposition techniques make perovskite solar cells (PSCs) desirable candidates for next‐generation photovoltaic devices. Despite these advantages, the lifespans of solar cells are far below the industry‐needed 25 years. In fact, numerous PSCs throughout the literature show severely hampered stability under illumination. Herein, several photoinduced degradation mechanisms are discussed. With light radiation, the organic–inorgainc perovskites are prone to phase segregation or chemical decomposition; the oxide electron transport layers (ETLs) tend to introduce new defects at the interface; the commonly used small molecules‐based hole transport layers (HTLs) typically suffer from poor photostability and dopant diffusion during device operation. It has been demonstrated the photoinduced degradation can take place in every functional layer, including the active layer, ETL, HTL, and their interfaces. An overview of these degradation categories is provided in this review, in the hope of encouraging further research and optimization of relevant devices.

A series of PM6 polymers with different weight‐average molecular weights and polydispersity index are synthesized, and the effects of PM6 polymerization degree on the efficiency and degradation behaviors of the Y6‐based photovoltaic system are systematically studied.

Abstract

The degree of polymerization can cause significant changes in the blend microstructure and physical mechanism of the active layer of non‐fullerene polymer solar cells, resulting in a huge difference in device performance. However, the diversity of stability issues, including photobleaching stability, storage stability, photostability, thermal stability, and mechanical stability, and more, poses a challenge for the degree of polymerization to comprehensively address the trade‐off between device efficiency and stability and reasonably evaluate the application potential of polymer materials. Herein, a series of PM6 polymers with different weight‐average molecular weights (M _w) and polydispersity index (PDI) are synthesized. The effects of the degree of PM6 polymerization on the efficiency and degradation behaviors of the photovoltaic systems based on Y6 as acceptor are investigated systematically. The findings regarding stability issues, together with the trade‐offs in the efficiency‐stability gap, formulate a complete guideline for the material design and performance evaluation in a way that relies much less on trial‐and‐error efforts.

The present work deconvolutes the electronic processes in organic solar cells under short‐circuit conditions by combining readily available experimental methods (current‐voltage characteristics, external quantum efficiency) with optical simulations. The proposed method allows the quantification of geminate recombination, to determine the mobility‐lifetime product, and to quantify extraction. The applicability of this new approach is demonstrated in three different organic photovoltaic systems.

Abstract

The short‐circuit current (J _sc) of organic solar cells is defined by the interplay of exciton photogeneration in the active layer, geminate and non‐geminate recombination losses and free charge carrier extraction. The method proposed in this work allows the quantification of geminate recombination and the determination of the mobility‐lifetime product (µτ) as a single integrated parameter for charge transport and non‐geminate recombination. Furthermore, the extraction efficiency is quantified based on the obtained µτ product. Only readily available experimental methods (current‐voltage characteristics, external quantum efficiency measurements) are employed, which are coupled with an optical transfer matrix method simulation. The required optical properties of common organic photovoltaic (OPV) materials are provided in this work. The new approach is applied to three OPV systems in inverted or conventional device structures, and the results are juxtaposed against the µτ values obtained by an independent method based on the voltage–capacitance spectroscopy technique. Furthermore, it is demonstrated that the new method can accurately predict the optimal active layer thickness.