Chen Weijie

Publication date: September 2020

Source: Applied Materials Today, Volume 20

Author(s): Sirazul Haque, Miguel Alexandre, Manuel J. Mendes, Hugo Águas, Elvira Fortunato, Rodrigo Martins

A synthetic polyhalide ligand (2‐picolyl)amine triiodide as a molecular glue is used to passivate halide vacancies at grain boundaries directionally and throughout grain bulk of perovskites. The inverted perovskite solar cells after passivation are allowed to be more efficient, and are profoundly stabilized in both ambient air and light‐soaking circumstances.

The fundamental instability of hybrid perovskite solar cells originates from the considerable halide vacancies. Furthermore, the local roles of halide vacancies between grain boundaries and grain bulk generally conflict, thus inhibiting complete passivation. To overcome this obstacle, a rational polyhalide ligand, di‐(2‐picolyl)amine triiodide, is designed as a molecular “glue” to achieve comprehensive passivation. Unlike a monohalide ligand, this ligand has multiple iodide ions and a quasiplanar tridentate chelation capability, contributing to directional passivation along the grain boundaries and overall passivation throughout the grain bulk. Using this molecular glue passivation, the best inverted solar cell yields an efficiency of 20.02%. Moreover, the relative stability of this cell in ambient air (≈40% humidity, 800 h aging) and under light‐soaking conditions (500 h aging) is profoundly enhanced by 33.33% and 22.26%, respectively. Herein, important insights into the design of passivating molecules to achieve low‐defect perovskites toward the development of multifunctional devices are provided.

A highly‐transparent and true‐colored indoor light harvester should possess an absorbance, which is mismatched with the emission spectra of the light sources. Porphyrin‐based donor materials are potential candidates, and such a P2:PC71BM cell achieves a power conversion efficiencies (PCE) exceeding 10%, and an illuminance transparency ≈65%, while preserving the color perception of the light sources.

Abstract

Organic photovoltaic (OPV) cells are promising indoor light energy harvesters because organic materials absorb strongly in the visible range. An indoor photovoltaic (IPV) device is an effective tool for the remote off‐grid wireless charging. However, as the indoor light fluxes are much weaker than the 1‐Sun condition, high‐performance indoor cells should have large areas in order to generate appreciable energies. They would then appear as flat, but expansive and dark objects if deployed indoors. Their presence would then alter the indoor lighting environment and affect visual perceptions. This work addresses the lighting and perception issues of IPV cells in three ways. i) A concept is proposed such that a high‐efficiency, semitransparent indoor OPV cell should possess an absorbance which is mismatched with the emission spectra of the light sources. ii) It is demonstrated that bulk heterojunction (BHJ) OPV solar cells with porphyrin donors can serve as high‐transparency and high‐efficiency indoor light harvesters. iii) Quantitative assessment criteria are presented for the transparency and chromaticity of an indoor semitransparent OPV cell, demonstrating that porphyrin‐based P2:PC₇₁BM semitransparent BHJ cells can achieve a power conversion efficiency (PCE) exceeding 10%, and an illuminance transparency ~65%, while preserving the color perception of the light sources.

This study considers the critical functions of the interfacial layer in overcoming the various degradations processed at the interfaces of organic–inorganic hybrid perovskites photovoltaics (PePVs). The mechanisms can also be categorized according to the cause of the degradation. The stabilizing processes that attenuate the corresponding degrading process are studied with respect to organic or inorganic interfacial materials in PePVs.

Abstract

Organic–inorganic hybrid perovskites have excellent optical and electronic properties; exploitation of these traits has increased the power conversion efficiency of perovskite photovoltaics (PePVs) to 25.2%. However, perovskites are chemically unstable, and this deficit has critically impeded their commercialization. Device degradation occurs at the interfaces of PePVs with multiple degradation mechanisms: decomposition of organic cations in perovskites; generation of inorganic byproducts in perovskites; superoxide or trap sites at the interface of the charge‐transport layer; excess charge carriers in perovskites; interfacial migration between perovskites and electrodes. This review considers the critical functions of the interfacial materials to overcome the various degradation at the interfaces of the PePVs. The working mechanisms stabilizing the interface of PePVs are categorized: passivation from atmosphere; inactivation of defect states; migration‐blocking. Then, the outstanding interfacial layers made of organic materials (defect passivation, physical robustness, and chemical inactivation) and inorganic materials (chemically passivating metal oxide, physically passivating metal oxide, and low‐temperature processed inorganic materials) are reviewed according to the stabilizing mechanisms. In addition, the influences of inorganic interconnecting layers in tandem PePVs are reviewed, with respect of various effects of interfacial buffer materials at the interface with perovskites.

Publication date: 15 July 2020

Source: Joule, Volume 4, Issue 7

Author(s): Bin Sun, Andrew Johnston, Chao Xu, Mingyang Wei, Ziru Huang, Zhang Jiang, Hua Zhou, Yajun Gao, Yitong Dong, Olivier Ouellette, Xiaopeng Zheng, Jiakai Liu, Min-Jae Choi, Yuan Gao, Se-Woong Baek, Frédéric Laquai, Osman M. Bakr, Dayan Ban, Oleksandr Voznyy, F. Pelayo García de Arquer

The role of energy offset between the optical bandgap and charge transfer (CT) state energies in nonradiative voltage loss ΔV _nr in organic solar cells is discussed. It is found that the ΔV _nr reduces considerably down to 0.185 V, when local excited and CT states are remarkably close in energy.

The voltage loss incurred by nonradiative charge recombination should be reduced to further improve the power conversion efficiency of organic solar cells (OSCs). This work discusses the nonradiative voltage loss in OSCs with systematically controlled energy offset between optical bandgap and charge transfer (CT) states. It is demonstrated that the nonradiative voltage loss is a function of the energy offset; it drops sharply with decreasing energy offset. By measuring the quantum yields of electroluminescence from OSCs and decay kinetics of CT states, it is found that the radiative decay rate of CT states becomes larger when the energy offset is negligible compared with those in conventional OSCs with sufficient energy offset. This behavior is rationalized by hybridization between CT and local excited states, resulting in a considerable enhancement of the oscillator strength of CT states. Based on a trend observed in this study, the precise mechanism by which the energy offset affects the nonradiative voltage loss is discussed.

Three novel donor–π‐bridge–acceptor (D–π–A)‐type small organic molecules are designed and synthesized as dopant‐free hole transport materials for perovskite solar cells. Combination of triazatruxene donor, terthiophene π‐bridge, and dicyanovinylene N‐ethyl rhodanine electron‐accepting unit as CI‐B3 creates well‐ordered edge‐on aggregated π–π stacking. Solar cell performance and long‐term stability are significantly improved.

Three donor–π‐bridge–acceptor (D–π–A)‐type organic small molecules coded CI‐B1, CI‐B2, and CI‐B3 are designed, synthesized, and used as dopant‐free hole transporting materials (HTMs) for perovskite solar cells (PSCs). The strong electron‐donating triazatruxene central core (D), terthiophene conjugated arms (π), and three different strong electron‐accepting units (A) provide high intramolecular charge transfer nature and eliminate the need of dopants during the fabrication of PSCs. HTMs are investigated to understand the effect of terminal functional groups on the PSC performance. Interestingly, due to the change of end‐capping, three different organizations of self‐assembly with π–π stacking are observed in the solid thin films. Dopant‐free CI‐B1, CI‐B2, CI‐B3, and spiro‐OMeTAD with dopants are used with triple cation perovskite composition Cs_0.1(MA_0.15FA_0.85)_0.9Pb(I_0.85Br_0.15)₃ (MA: CH₃NH₃ ⁺, FA: NHCHNH₃ ⁺) in n‐i‐p architecture. The cells prepared with CI‐B3 not only exhibits a comparable power conversion efficiency (PCE) of 17.54% to the state‐of‐art of spiro‐OMeTAD with dopants (18.02%), but also demonstrates improved long‐term stability, maintaining 88% of its original PCE after 1000 h of illumination. The superior photovoltaic performance, synthetic simplicity, dopant‐free nature, high durability, and edge‐on molecular orientation of CI‐B3 show its great promise as a HTM candidate for efficient and stable PSCs.

A CsBr buffer layer is inserted between NiO _x hole transport layer and perovskite layer to relieve the lattice mismatch induced interface stress and induce more ordered crystal growth. The results show that the addition of the CsBr buffer layer optimizes the interface between the perovskite and NiO _x , reduces interface defects and traps, and enhances the hole extraction/transfer.

Abstract

Recent research shows that the interface state in perovskite solar cells is the main factor which affects the stability and performance of the device, and interface engineering including strain engineering is an effective method to solve this issue. In this work, a CsBr buffer layer is inserted between NiO _x hole transport layer and perovskite layer to relieve the lattice mismatch induced interface stress and induce more ordered crystal growth. The experimental and theoretical results show that the addition of the CsBr buffer layer optimizes the interface between the perovskite absorber layer and the NiO _x hole transport layer, reduces interface defects and traps, and enhances the hole extraction/transfer. The experimental results show that the power conversion efficiency of optimal device reaches up to 19.7% which is significantly higher than the efficiency of the device without the CsBr buffer layer. Meanwhile, the device stability is also improved. This work provides a deep understanding of the NiO _x /perovskite interface and provides a new strategy for interface optimization.

n‐Type polymer semiconductors with a broad absorption and ultranarrow bandgap down to 1.28 eV are synthesized. When applied as electron acceptor materials, a power conversion efficiency of over 10% with a photoresponse reaching 950 nm is realized for all‐polymer solar cells.

Abstract

Compared to organic solar cells based on narrow‐bandgap nonfullerene small‐molecule acceptors, the performance of all‐polymer solar cells (all‐PSCs) lags much behind due to the lack of high‐performance n‐type polymers, which should have low‐aligned frontier molecular orbital levels and narrow bandgap with broad and intense absorption extended to the near‐infrared region. Herein, two novel polymer acceptors, DCNBT‐TPC and DCNBT‐TPIC, are synthesized with ultranarrow bandgaps (ultra‐NBG) of 1.38 and 1.28 eV, respectively. When applied in transistors, both polymers show efficient charge transport with a highest electron mobility of 1.72 cm² V⁻¹ s⁻¹ obtained for DCNBT‐TPC. Blended with a polymer donor, PBDTTT‐E‐T, the resultant all‐PSCs based on DCNBT‐TPC and DCNBT‐TPIC achieve remarkable power conversion efficiencies (PCEs) of 9.26% and 10.22% with short‐circuit currents up to 19.44 and 22.52 mA cm⁻², respectively. This is the first example that a PCE of over 10% can be achieved using ultra‐NBG polymer acceptors with a photoresponse reaching 950 nm in all‐PSCs. These results demonstrate that ultra‐NBG polymer acceptors, in line with nonfullerene small‐molecule acceptors, are also available as a highly promising class of electron acceptors for maximizing device performance in all‐PSCs.

Halogenation of D–A (donor–acceptor)‐type materials is an effective method to improve the performance of polymer solar cells (PSCs). In this work, recent developments of PSCs by the chlorination strategy are summarized, including the intrinsic property of chlorine atoms, the progress of chlorinated polymers and small molecules, and the synergetic effect of chlorination with other methods to elevate solar conversions.

Abstract

This work summarizes recent developments in polymer solar cells (PSCs) prepared by a chlorination strategy. The intrinsic property of chlorine atoms, the progress of chlorinated polymers and small molecules, and the synergistic effect of chlorination with other methods to elevate solar conversions are discussed. Halogenation of donor–acceptor (D–A) materials is an effective method to improve the performance of PSCs, which mainly affects the push–pull of electrons between donor and acceptor units due to their strong electron‐withdrawing capabilities. Although chlorine is less electronegative than fluorine, it can form very strong noncovalent interactions, such as Cl···S and Cl···π interactions, because its empty 3d orbits can help to accept the electron pairs or π electrons. This synergistic effect of electronegativity together with the empty 3d orbits of chlorine atoms leads to increased intramolecular and intermolecular interactions and a much stronger capability to down‐shift the molecular energy levels. This work is intended to support a better understanding of the chlorination strategy to modify the material properties, and thus improve the performance of solar devices. Eventually, it will provide the research community with a clearer pathway to choose proper substitution methods according to different situations for high and stable solar energy conversion.

Formamidinium methylammonium (FAMA)‐perovskite‐Cu:NiO and Al₂O₃/Cu:NiO composites are developed for highly stable and efficient perovskite solar cells. The composites not only improve the perovskite film quality but also suppress charge recombination with substantial reduction of trap density. The composites based devices yielded power conversion efficiency of 20.7% with fill factor of 80.5%. More importantly, unencapsulated cells showed significant enhancement of air‐stability, thermal‐ and photo‐stability with retaining 97% of PCE over 240 days under ambient conditions.

Abstract

To solve critical issues related to device stability and performance of perovskite solar cells (PSCs), FA_0.026MA_0.974PbI_{3− y} Cl _y ‐Cu:NiO (formamidinium methylammonium (FAMA)‐perovskite‐Cu:NiO) and Al₂O₃/Cu:NiO composites are developed and utilized for fabrication of highly stable and efficient PSCs through fully‐ambient‐air processes. The FAMA‐perovskite‐Cu:NiO composite crystals prepared without using any antisolvents not only improve the perovskite film quality with large‐size crystals and less grain boundaries but also tailor optical and electronic properties and suppress charge recombination with reduction of trap density. A champion device based on the composites as light absorber and Al₂O₃/Cu:NiO interfacial layer between electron transport layer and active layer yields power conversion efficiency (PCE) of 20.67% with V _OC of 1.047 V, J _SC of 24.51 mA cm⁻², and fill factor of 80.54%. More importantly, such composite‐based PSCs without encapsulation show significant enhancement in long‐term air‐stability, thermal‐ and photostability with retaining 97% of PCE over 240 d under ambient conditions (25–30 °C, 45–55% humidity).

This review summarizes recent advances in the application of inorganic materials such as copper‐based compounds, with an emphasis on copper iodide and copper thiocyanate, transition metal chalcogenides, carbides, and nitrides as well as hybrid materials including copper compounds as hole and electron transport layers in organic and perovskite solar cells.

Abstract

As organic solar cells (OSCs) and perovskite solar cells (PVSCs) move closer to commercialization, further efforts toward optimizing both cell efficiency and stability are needed. As interfaces strongly affect device performance and degradation processes, interfacial engineering by employing various materials as hole transport layers (HTLs) and electron transport layers (ETLs) has been a very active field of research in OSCs and PVSCs. Among them, inorganic materials exhibit significant advantages in promoting device performance due to their excellent charge transporting properties and intrinsic thermal and chemical robustness. In this review, an extensive overview is provided of inorganic semiconductors such as copper‐based ones with emphasis on copper iodide and copper thiocyanate, transition metal chalcogenides, nitrides and carbides as well as hybrid materials based on these inorganic compounds that have been recently employed as HTLs and ETLs in OSCs and PVSCs. Following a short discussion of the main optoelectronic and physical properties that interfacial materials used as HTLs and ETLs should possess, the functionalities of the aforementioned materials as interfacial, charge transport, layers in OSCs and PVSCs are discussed in depth. It is concluded by providing guidelines for further developments that could significantly extend the implementation of these materials in solar cells.

The surface and bulk defects of perovskite films are simultaneously passivated through the treatment of CsBr/methanol solution, in which the methanol helps CsBr penetrate the depth of the perovskite and reconstruct high‐quality films. This strategy can effectively improve the photovoltaic performance and operational stability of the resultant devices.

It is challenging to passivate defects that are buried in the depth of perovskite films; most of the reported passivation methods cannot reach the deep defects. Herein, methanol is adopted as a dual‐functional reagent to not only act as a solvent but also help the dissolved ions penetrate the depth of perovskite films. By treating the as‐prepared perovskite films with CsBr/methanol solution, Br⁻ ions can react with the undercoordinated Pb²⁺, and Cs⁺ ions can fill in the cation vacancies. This strategy enables surface and bulk defects passivation to be achieved simultaneously. The nonradiative recombination of the double‐passivated devices is significantly suppressed and the migration of charged defects is remarkably hindered. As a result, an improved power conversion efficiency of 19.5% and an open‐circuit voltage of 1.183 V is achieved. Moreover, the passivated device can retain ≈80% of the initial efficiency after working for 500 h at maximum power point under 1‐sun illumination, whereas the pristine device reaches 80% of the initial efficiency after only 90 h. This work demonstrates that surface and bulk defects passivation is critical to improve the efficiency and long‐term operational stability of the perovskite solar cells.

Ultrathin 2D titanium‐carbide MXenes (Ti₃C₂T_x quantum dots) and Cu_1.8S nanocrystals are simultaneously introduced to enhance the device performance of perovskite solar cells, achieving a remarkable hysteresis‐free power conversion efficiency of 21.64% with high long‐term air stability and light stability. The findings show that Ti₃C₂ and Cu_1.8S can act as superfast electron and hole tunnel for optoelectronic devices.

Abstract

The performance of perovskite solar cells (PSCs) strongly depends on the electron transport layer (ETL), perovskite absorber, hole transport layer (HTL), and their interfaces. Herein, the first approach to utilize ultrathin 2D titanium‐carbide MXenes (Ti₃C₂T _x quantum dots, TQD) by engineering the perovskite/TiO₂ ETL interface and perovskite absorber and introducing Cu_1.8S nanocrystals to perfect the Spiro‐OMeTAD HTL is represented. A significant hysteresis‐free power conversion efficiency improvement from 18.31% to 21.64% of PSCs is achieved after modifications with the enhanced short‐circuit current density, open‐circuit voltages, and fill factor. Various advanced characterizations, including femtosecond transient absorption spectroscopy, electrochemical impedance spectroscopy, and ultraviolet photoelectron spectroscopy, elucidate that the TQD/Cu_1.8S significantly contribute to the improved crystalline quality of the perovskite film with its large grain size and improved electron/holes extraction efficiencies at perovskite/ETL and perovskite/HTL interfaces. Furthermore, the long‐time ambient and light stability of PSCs are largely boosted through the TQD and/or Cu_1.8S nanocrystals doping, originating from the better crystallization of perovskite, suppressing the film aggregation and crystallization of HTL, and inhibiting the ultraviolet‐induced photocatalysis of the ETL. The findings highlight the TQD and Cu_1.8S can act as a superfast electrons and holes tunnel for the optoelectronic devices.

A secondary bond‐constructed isotropic electron transfer 3D‐network is fabricated based on biomass‐derived demethylated kraft lignin (D_MeKL). Secondary bonds successfully modify the contact of the perylene diiminde/active layer and conjugate‐blocked linkages in D_MeKL, to overcome anisotropy‐aroused electron transfer barriers at the cathode interface. The enhancement of cross/vertical‐sectional electron transfer performance and well‐matched energy levels yields the highest power conversion efficiency reported among biomaterial‐based organic solar cells.

Abstract

Fabricating high‐efficient electron transporting interfacial layers (ETLs) with isotropic features is highly desired for all‐directional electron transfer/collection from an anisotropic active layer, achieving excellent power conversion efficiency (PCEs) on nonfullerene acceptor (NFA) organic solar cells (OSCs). The complicated synthesis and cost‐consumption in exploring versatile materials arouse great interest in the development of binary‐doping interlayers without phase separation and flexible manipulation. Herein, for the first time, a novel cathode interfacial layer based on biomass‐derived demethylated kraft lignin (D_MeKL) is proposed. Features of multiple phenolic‐hydroxyl (PhOH) and uniform‐distributed render D_MeKL to exhibit an excellent bonding capacity with amino terminal substituted perylene diiminde (PDIN), and successfully form a high‐efficient isotropic electron transfer 3D network. Synchronously, secondary bonds completely modify conjugate‐blocked linkages of D_MeKL, significantly enhance the electron transporting performance on cross‐section and vertical‐sections, and repair the contact of PDIN with active layer. The D_MeKL/PDIN‐based 3D‐network exhibits well‐matched work function (WF) (–4.34 eV) with cathode (–4.30 eV) and energy level of electron acceptor (–4.11 eV). D_MeKL/PDIN‐based NFAs‐OSC shows excellent short‐circuit current density (26.61 mA cm^–2) and PCE (16.02%) beyond the classic PDIN‐based NFA‐OSC (25.64 mA cm^–2, 15.41%), which is the highest PCEs among biomaterials interlayers. The results supply a novel method to achieve high‐efficient cathode interlayer for NFAs‐OSCs.

Dramatically boosted device performance is observed from perovskite photovoltaics by magnetic field‐aligned CH₃NH₃PbI₃:Fe₃O₄ composite thin films, which possesses superior film morphology, boosted and balanced charge carrier mobility, suppressed trap density and charge carrier recombination, and promoted charge carrier extraction time.

Abstract

Perovskite photovoltaics have drawn great attention in both academic and industrial sectors in the past decade. To date, impressive device performance has been achieved in state‐of‐the‐art device architectures through morphological manipulation and generic interface engineering. In this study, enhanced device performance of perovskite photovoltaics by magnetic field‐aligned CH₃NH₃PbI₃‐mixed Fe₃O₄ magnetic nanoparticles (CH₃NH₃PbI₃:Fe₃O₄) composite thin films is reported. It is found that magnetic field‐aligned CH₃NH₃PbI₃:Fe₃O₄ composite thin films possess superior film morphology, boosted and balanced charge carrier mobility, and suppressed trap density. Moreover, perovskite photovoltaics by magnetic field‐aligned CH₃NH₃PbI₃:Fe₃O₄ composite thin films exhibit suppressed charge carrier recombination and shorter charge carrier extraction time. As a result, perovskite solar cells by magnetic field‐aligned CH₃NH₃PbI₃:Fe₃O₄ composite thin films exhibit 20.23% power conversion efficiency with significantly reduced photocurrent hysteresis. Moreover, perovskite photodetectors by magnetic field‐aligned CH₃NH₃PbI₃:Fe₃O₄ composite thin films exhibit a photoresponsivity of 858 mA W⁻¹, a photodetectivity over 10¹³ Jones (1 Jones = 1 cm Hz^1/2 W⁻¹) and a linear dynamic range over 160 dB at room temperature. All these device performance parameters are significantly better than those by pristine CH₃NH₃PbI₃ thin film. Thus, these studies provide a facile way to boost device performance of perovskite photovoltaics.

A multi‐technique in situ structural and optoelectronic characterization on planar perovskite solar cells reveals perovskite amorphization and phase segregation as the crucial degradation mechanisms due to ion migration on a daily timescale. The degradation has a severe negative impact on the charge collection, which reduces the photocurrent and the power conversion efficiency. The mechanism is partially reversible after rest in the dark.

Abstract

The operation of halide perovskite optoelectronic devices, including solar cells and LEDs, is strongly influenced by the mobility of ions comprising the crystal structure. This peculiarity is particularly true when considering the long‐term stability of devices. A detailed understanding of the ion migration‐driven degradation pathways is critical to design effective stabilization strategies. Nonetheless, despite substantial research in this first decade of perovskite photovoltaics, the long‐term effects of ion migration remain elusive due to the complex chemistry of lead halide perovskites. By linking materials chemistry to device optoelectronics, this study highlights that electrical bias‐induced perovskite amorphization and phase segregation is a crucial degradation mechanism in planar mixed halide perovskite solar cells. Depending on the biasing potential and the injected charge, halide segregation occurs, forming crystalline iodide‐rich domains, which govern light emission and participate in light absorption and photocurrent generation. Additionally, the loss of crystallinity limits charge collection efficiency and eventually degrades the device performance.

A simple, generic, and effective concentration‐induced morphology manipulation approach is demonstrated to prompt the state‐of‐the‐art all‐small‐molecule (ASM) BTR‐Cl:Y6 and BTR:PC₇₁BM organic solar cells (OSCs) to a record level. This approach provides a promising way to delicately control the morphology toward high‐performance ASM OSCs.

Abstract

Morphology is a critical factor to determine the photovoltaic performance of organic solar cells (OSCs). However, delicately fine‐tuning the morphology involving only small molecules is an extremely challenging task. Herein, a simple, generic, and effective concentration‐induced morphology manipulation approach is demonstrated to prompt both the state‐of‐the‐art thin‐film BTR‐Cl:Y6 and thick‐film BTR:PC₇₁BM all‐small‐molecule (ASM) OSCs to a record level. The morphology is delicately controlled by subtly altering the prepared solution concentration but maintaining the identical active layer thickness. The remarkable performance enhancement achieved by this approach mainly results from the enhanced absorption, reduced trap‐assistant recombination, increased crystallinity, and optimized phase‐separated network. These findings demonstrate that a concentration‐induced morphology manipulation strategy can further propel the reported best‐performing ASM OSCs to a brand‐new level, and provide a promising way to delicately control the morphology towards high‐performance ASM OSCs.

A formamidinium derivative, 2‐thiopheneformamidinium (ThFA), is successfully developed and used as a spacer in 2D RP perovskite (ThFA)₂MA _{n −1}Pb _n I_{3 n +1} (nominal n = 3). A precursor organic salts‐assisted crystal growth technique is further developed to prepare high‐quality 2D RP perovskite films, resulting in a high power conversion efficiency of 16.72% with negligible hysteresis and improved stability.

Abstract

Formamidinium (FA)‐based 3D perovskite solar cells (PSCs) have been widely studied and they show reduced bandgap, enhanced stability, and improved efficiency compared to MAPbI₃‐based devices. Nevertheless, the FA‐based spacers have rarely been studied for 2D Ruddlesden–Popper (RP) perovskites, which have drawn wide attention due to their enormous potential for fabricating efficient and stable photovoltaic devices. Here, for the first time, FA‐based derivative, 2‐thiopheneformamidinium (ThFA), is successfully synthesized and employed as an organic spacer for 2D RP PSCs. A precursor organic salts‐assisted crystal growth technique is further developed to prepare high quality 2D (ThFA)₂(MA) _{n −1}Pb _n I_{3 n +1} (nominal n = 3) perovskite films, which shows preferential vertical growth orientations, high charge carrier mobilities, and reduced trap density. As a result, the 2D RP PSCs with an inverted planar p‐i‐n structure exhibit a dramatically improved power conversion efficiency (PCE) from 7.23% to 16.72% with negligible hysteresis, which is among the highest PCE in 2D RP PSCs with low nominal n ‐value of 3. Importantly, the optimized 2D PSCs exhibit a dramatically improved stability with less than 1% degradation after storage in N₂ for 3000 h without encapsulation. These findings provide an effective strategy for developing FA‐based organic spacers toward highly efficient and stable 2D PSCs.

Triplet materials are designed by introducing heavy atoms to enhance spin–orbit coupling or constructing donor and acceptor units with a twisted conformation to reduce ΔE _ST. However, the twisted materials have not been applied in solar cells due to weak absorption and low charge‐transport mobilities. Now two nonplanar acceptors with large π‐conjugated core were constructed that achieved over 15 % efficiency.

Abstract

Triplet acceptors have been developed to construct high‐performance organic solar cells (OSCs) as the long lifetime and diffusion range of triplet excitons may dissociate into free charges instead of net recombination when the energy levels of the lowest triplet state (T₁) are close to those of charge‐transfer states (³CT). The current triplet acceptors were designed by introducing heavy atoms to enhance the intersystem crossing, limiting their applications. Herein, two twisted acceptors without heavy atoms, analogues of Y6, constructed with large π‐conjugated core and D‐A structure, were confirmed to be triplet materials, leading to high‐performance OSCs. The mechanism of triplet excitons were investigated to show that the twisted and D‐A structures result in large spin–orbit coupling (SOC) and small energy gap between the singlet and triplet states, and thus efficient intersystem crossing. Moreover, the energy level of T₁ is close to ³CT, facilitating the split of triplet exciton to free charges.

Nature Energy, Published online: 08 June 2020; doi:10.1038/s41560-020-0624-7