JIANG ZHI XUAN

Applied Physics Letters, Volume 117, Issue 6, August 2020.
The development of high-performance lead-free perovskite solar cells (PSCs) is important to address the environmental concern of lead perovskite. In recent years, tin perovskite solar cells (TPSCs) have been developing quickly and emerging as a promising candidate for high-efficiency lead-free PSCs. In this Perspective, we summarize recent work of our group including the use of a low-dimensional structure, film growth kinetic control, and device engineering. In the end, the challenges in TPSCs and potential strategies toward high-efficiency TPSCs are discussed.

Publication date: December 2020

Source: Nano Energy, Volume 78

Author(s): Qing Ma, Zhenrong Jia, Lei Meng, Jinyuan Zhang, Huotian Zhang, Wenchao Huang, Jun Yuan, Feng Gao, Yan Wan, Zhanjun Zhang, Yongfang Li

A fibril network strategy is demonstrated to fabricate high‐efficiency thick‐film organic solar cells (OSCs). The fibril network morphology provides effective hole transport channel and the incorporation of high crystalline nonfullerene acceptor ensures high electron transport in a thick film. As a result, the OSCs show high efficiencies to ≈12% with wide toleration of active layer thickness.

Industrial printing production of organic solar cells (OSCs) requires high power conversion efficiency (PCE) with wide toleration of active layer thickness. Herein, high‐efficiency thick‐film OSCs are demonstrated using a polymer fibril network strategy (FNS), which involves a donor polymer (PT2) that can self‐assemble into fibril nanostructure, and two nonfullerene acceptors with different crystalline properties. The fibril network can form a high‐speed hole transport channel and the addition of IDIC as a third component in active layers can improve the electron transport. As a result, the OSCs show high PCEs of ≈12% with wide toleration of active layer thickness (from 100 to 500 nm). The results indicate that FNS is a promising approach for the fabrication of highly efficient thick‐film PSCs, which can facilitate the commercialization of OSCs.

Electronically active ionenes were realized by integration of naphthalene diimide into a polymer backbone. These conductive polymers have a low degree of crystalline order, show a great processing advantage to remove energy barriers between organic semiconductors and metal electrodes, and afford fullerene‐based, non‐fullerene‐based, as well as ternary organic solar cells with high performance and a maximum efficiency of 16.9 %.

Abstract

Self‐doping ionene polymers were efficiently synthesized by reacting functional naphthalene diimide (NDI) with 1,3‐dibromopropane (NDI‐NI) or trans‐1,4‐dibromo‐2‐butene (NDI‐CI) via quaternization polymerization. These NDI‐based ionene polymers are universal interlayers with random molecular orientation, boosting the efficiencies of fullerene‐based, non‐fullerene‐based, and ternary organic solar cells (OSCs) over a wide range of interlayer thicknesses, with a maximum efficiency of 16.9 %. NDI‐NI showed a higher interfacial dipole (Δ), conductivity, and electron mobility than NDI‐CI, affording solar cells with higher efficiencies. These polymers proved to efficiently lower the work function (WF) of air‐stable metals and optimize the contact between metal electrode and organic semiconductor, highlighting their power to overcome energy barriers of electron injection and extraction processes for efficient organic electronics.

A full defects passivation strategy for superior carrier dynamics is demonstrated, which enables highly efficient perovskite solar cells operating in air.

Abstract

The lattice defects in the bulk and on the surface of the halide perovskite layer serve as trap sites and recombination centers to annihilate photogenerated carriers, determining the performance and stability of perovskite optoelectronic devices. Herein, the previously reported surface defects passivation engineering is extended to a full defects passivation strategy through stereoscopically introducing the cysteamine hydrochloride (CSA‐Cl) in the bulk and on the surface of perovskites. First‐principle density functional theory (DFT) calculations are employed to theoretically verify the multiple defects passivation effect of the CAS‐Cl on the perovskite. The perovskite layer with full defects passivation exhibits superior carrier dynamics as revealed by femtosecond transient absorption due to the reduced defect density determined by a highly sensitive photothermal deflection spectroscopy technique. Consequently, a high efficiency approaching 21% is achieved for the inverted planar perovskite solar cells (PVSCs). More importantly, the CAS‐Cl passivated PVSCs exhibit operation in air, which will be beneficial for the in situ device test for understanding the photophysics involved. This work provides a promising strategy to reduce the defects in both the perovskite bulk and surface for superior optoelectronic properties, facilitating the development of highly efficient and stable PVSCs and other optoelectronic devices.

In this Review, the crystal structures and preparation methods of group‐VI elemental 2D materials are introduced, the electronic structures of group‐VI 2D materials are briefly reviewed, and the device applications including transistors, photodetectors, and other emerging applications are emphasized.

Abstract

Due to the ultrathin thickness and dangling‐bond‐free surface, 2D materials have been regarded as promising candidates for future nanoelectronics. In recent years, group‐VI elemental 2D materials have been rediscovered and found superior in electrical properties (e.g., high carrier mobility, high photoconductivity, and thermoelectric response). The outstanding semiconducting properties of group‐VI elemental 2D materials enable device applications including high‐performance field‐effect transistors and optoelectronic devices. The excellent environmental stability also facilitates fundamental studies and practical applications of group‐VI elemental 2D materials. This Review first focuses on the crystal structures of group‐VI elemental 2D materials. Afterward, preparation methods for nanostructures of group‐VI materials are introduced with comprehensive studies. A brief Review of the electronic structures is then presented with an understanding of the electrical properties. This Review also contains the device applications of group‐VI elemental 2D materials, emphasizing transistors, photodetectors, and other appealing applications. Finally, this Review provides an outlook for the development of group‐VI elemental 2D materials, highlighting the challenges and opportunities in fundamental studies and technological applications.

Water is added into the precursor solution to assist crystal growths of quasi‐2D perovskite films featuring ordered phase distribution and favored crystal orientation. A champion efficiency of 18.04% is realized in (BA)₂(MA_0.8FA_0.15Cs_0.05)₄Pb₅I₁₆‐based quasi‐2D perovskite solar cells.

Abstract

Organic–inorganic hybrid quasi‐2D perovskites have shown excellent stability for perovskite solar cells (PSCs), while the poor charge transport in quasi‐2D perovskites significantly undermines their power conversion efficiency (PCE). Here, studies on water‐controlled crystal growth of quasi‐2D perovskites are presented to achieve high‐efficiency solar cells. It is demonstrated that the (BA)₂MA₄Pb₅I₁₆‐based PSCs (n = 5) processed with water‐containing precursors display an increased short‐circuit current density (J _sc) of 19.01 mA cm⁻² and PCE over 15%. The enhanced performance is attributed to synergetic growths of the 3D and 2D phase components aided by the formed hydration (MAI∙H₂O), leading to modulations on the crystal orientation and phase distribution of various n‐value components, which facilitate interphase charge transfer and charge sweepout throughout the device. The water‐assisted crystallization is further applied to triple cation‐based (BA)₂(MA_0.8FA_0.15Cs_0.05)₄Pb₅I₁₆ quasi‐2D perovskites, which generate a remarkable PCE of 18.04%. Despite the presence of water in the precursors, the devices exhibit a satisfactory thermal stability with the PCE degradation <15% under continuous thermal aging at 60 °C for over 500 h.

Three homologous small molecule donors with hydrogen, fluorine, and chlorine substitution afford organic solar cells with efficiencies over 10% in combination with a common acceptor. The chlorinated derivative exhibits a more crystalline nanomorphology with relatively pure domains and provides more than 12% efficiency.

Abstract

Compared to conjugated polymers, small‐molecule organic semiconductors present negligible batch‐to‐batch variations, but presently provide comparatively low power conversion efficiencies (PCEs) in small‐molecular organic solar cells (SM‐OSCs), mainly due to suboptimal nanomorphology. Achieving precise control of the nanomorphology remains challenging. Here, two new small‐molecular donors H13 and H14, created by fluorine and chlorine substitution of the original donor molecule H11, are presented that exhibit a similar or higher degree of crystallinity/aggregation and improved open‐circuit voltage with IDIC‐4F as acceptor. Due to kinetic and thermodynamic reasons, H13‐based blend films possess relatively unfavorable molecular packing and morphology. In contrast, annealed H14‐based blends exhibit favorable characteristics, i.e., the highest degree of aggregation with the smallest paracrystalline π–π distortions and a nanomorphology with relatively pure domains, all of which enable generating and collecting charges more efficiently. As a result, blends with H13 give a similar PCE (10.3%) as those made with H11 (10.4%), while annealed H14‐based SM‐OSCs have a significantly higher PCE (12.1%). Presently this represents the highest efficiency for SM‐OSCs using IDIC‐4F as acceptor. The results demonstrate that precise control of phase separation can be achieved by fine‐tuning the molecular structure and film formation conditions, improving PCE and providing guidance for morphology design.

A fibril network strategy is demonstrated to fabricate high‐efficiency thick‐film organic solar cells (OSCs). The fibril network morphology provides effective hole transport channel and the incorporation of high crystalline nonfullerene acceptor ensures high electron transport in a thick film. As a result, the OSCs show high efficiencies to ≈12% with wide toleration of active layer thickness.

Industrial printing production of organic solar cells (OSCs) requires high power conversion efficiency (PCE) with wide toleration of active layer thickness. Herein, high‐efficiency thick‐film OSCs are demonstrated using a polymer fibril network strategy (FNS), which involves a donor polymer (PT2) that can self‐assemble into fibril nanostructure, and two nonfullerene acceptors with different crystalline properties. The fibril network can form a high‐speed hole transport channel and the addition of IDIC as a third component in active layers can improve the electron transport. As a result, the OSCs show high PCEs of ≈12% with wide toleration of active layer thickness (from 100 to 500 nm). The results indicate that FNS is a promising approach for the fabrication of highly efficient thick‐film PSCs, which can facilitate the commercialization of OSCs.

A novel bifacial passivation strategy which simultaneously suppresses trap states within TiO₂ and perovskite through interaction between functional groups and defects is demonstrated for printable mesoscopic PSCs. The passivation treatment to TiO₂ surface not only reduces the energy barrier between TiO₂ and perovskite for accelerating the charge transfer but also passivates the uncoordinated Pb defects on the perovskite interface.

Surface defects, which mediate nonradiative recombination, are detrimental to both the photovoltaic performance and stability of perovskite solar cells (PSCs). Improving photovoltage and fill factor (FF) in screen‐printed mesoporous PSCs is a major challenge for approaching the power conversion efficiency (PCE) of the planar configured devices. Herein, a novel bifacial passivation strategy which simultaneously suppresses deep trap states within TiO₂ and perovskite through interaction between functional groups and defects is demonstrated for fully printable mesoscopic PSCs. The application of monoethanolamine (MEA) treatment to TiO₂ surface not only reduces the energy barrier between TiO₂ and perovskite for accelerating the charge transfer but also passivates the uncoordinated Pb defects on the perovskite interface. Due to the synergistic effect of charge extraction promotion and trap passivation, the fabricated PSCs deliver a champion PCE of 15.5% with an enhanced V _oc of 0.94 V and FF of 70.4% compared with PSCs without MEA passivation, and the device maintains 97% of its topmost PCE after 240 h under constant simulated solar illumination in air atmosphere. This investigation helps exploit new approaches for defect passivation to further improve both the efficiency and stability of printable mesoscopic PSCs.

A methylammonium chloride (MACl) additive is used to synthesize FA_1–x MA _x PbI₃ films. The best molar fraction of this additive is determined. The MA content in thin films actually used in solar cells is x = 0.06. This amount is thermodynamically the best for the stabilization of this highly efficient perovskite. The perovskite solar cell achieves a stabilized power conversion efficiency as high as 22.06%.

Nowadays, complex chemistry and precursor solution compositions are developed to stabilize hybrid perovskite films and boost the efficiency of perovskite solar cells (PSCs). In this context, determining the actual composition of these layers, especially in organic cations, and understanding the chemistry behind is challenging. Herein, the introduction of methylammonium (MA⁺) in formamidinium lead iodide (FAPbI₃) 3D perovskite is considered to stabilize the α‐phase, whose quantity must be minimized to reduce the material hydrophilicity and its possible destabilization by degassing. The key effects of methylammonium chloride (MACl) additive on the growth of FA_1–x MA _x PbI₃ perovskite layers are studied. Liquid nuclear magnetic resonance (NMR) is used to analyze the photovoltaic layers. NMR peaks and their origin are identified. The MA and FA content in films actually used in PSCs is reliably measured and prepared over a large additive molar concentration ratio. x is quantified at 0.06 ± 0.01 for pure films, which corresponds to the best entropic compound stabilization. It results in PSCs with a stabilized power conversion efficiency as high as 22.06%. These PSCs are shown to be highly stable under solar irradiation and high moisture.

Studies on effect of additives of FAX (X = Cl, Br, and I, FA = formamidinium) and ACl (A = MA, Cs, Rb, and NH₄) in FAPbI₃‐based perovskite solar cells reveal that the FACl additive shows best performance over other additives due to passivating the grain boundary effectively without altering bandgap of pristine perovskite.

Herein, the dependence of photovoltaic performance on the additives of FAX (X = Cl, Br, and I, FA = formamidinium) and ACl [A = methylammonium (MA), Cs, Rb, and NH₄] in FAPbI₃‐based perovskite solar cells (PSCs) is reported. Effect of concentration on photovoltaic parameters is first screened for each additive, from which optimal concentration is determined with respect to the pristine without additive. Power conversion efficiency (PCE) is significantly improved from 16.55% to 22.51% after adding 20 mol% FACl in the perovskite precursor solution, whereas moderate increase in PCE to 20.08% and 19.97% is observed for FABr and FAI, respectively, indicating an important role of chloride. MACl and CsCl improved PCE to 20.81% and 20.59%, respectively, which is, however, inferior to FACl. A significantly increased carrier lifetime by treating FACl is responsible for the best performance. Energy dispersive X‐ray spectroscopy shows that chloride in the additive FACl is not incorporated in grain but placed on the grain boundary, which plays an important role in passivating iodide‐deficient grain boundary. The FACl additive has benefits over other additives because it cannot change the bandgap of FAPbI₃.

A large‐grained CsPbBr₃ perovskite film with improved energy‐level alignment and hole mobility is fabricated by compositional engineering of Cl ion doping, which suppresses charge recombination thus affording a champion power conversion efficiency (PCE) as high as 9.73% for carbon‐based all‐inorganic CsPbBr_2.98Cl_0.02 PSC free of encapsulation with excellent operational stability.

Carbon‐based CsPbBr₃ perovskite solar cells (PSCs) without hole‐transporting layers (HTLs) have aroused extensive attention due to their low manufacturing cost and prominent ambient stability. However, the defects of perovskite film and the poor charge extraction within PSCs result in severe charge recombination, which restricts the further enhancement of device efficiency. In view of this critical point, a compositional engineering of CsPbBr₃ perovskite via doping with Cl⁻ ions is presented herein to decrease the trap states and enhance the charge extraction. It is revealed that the doping of Cl⁻ ions not only enlarges the grain size and thereby reduces the trap‐state density, but also optimizes the energy‐level alignment and improves the hole mobility of the perovskite film, leading to an evidently suppressed charge recombination and improved charge extraction and transportation. As a result, a champion power conversion efficiency (PCE) of 9.73% is achieved for carbon‐based HTL‐free CsPbBr_2.98Cl_0.02 PSC, yielding a marked enhancement in comparison with 6.69% efficiency for the control. Meanwhile, the thermal and moisture stabilities of unencapsulated CsPbBr_2.98Cl_0.02 PSC are improved, maintaining 93% and 95% of the initial PCE after expose to air atmosphere with 80% relative humidity (RH) and at 80 °C over 60 days, respectively.

An aqueous‐solution‐processed cathode interlayer based on cost‐effective organosilica nanodots (OSiNDs) is demonstrated for organic solar cells (OSCs) with power conversion efficiency over 17% and excellent operational stability. The high photostability of OSiNDs‐based OSCs is attributed to the avoidance of photoinduced shunts and the photocatalytic effect, which are ineluctable shortcomings in inverted OSCs based on ZnO cathode interlayers.

Abstract

The performance and industrial viability of organic photovoltaics are strongly influenced by the functionality and stability of interface layers. Many of the interface materials most commonly used in the lab are limited in their operational stability or their materials cost and are frequently not transferred toward large‐scale production and industrial applications. In this work, an advanced aqueous‐solution‐processed cathode interface layer is demonstrated based on cost‐effective organosilica nanodots (OSiNDs) synthesized via a simple one‐step hydrothermal reaction. Compared to the interface layers optimized for inverted organic solar cells (i‐OSCs), the OSiNDs cathode interlayer shows improved charge carrier extraction and excellent operational stability for various model photoactive systems, achieving a remarkably high power conversion efficiency up to 17.15%. More importantly, the OSiNDs’ interlayer is extremely stable under thermal stress or photoillumination (UV and AM 1.5G) and undergoes no photochemical reaction with the photoactive materials used. As a result, the operational stability of inverted OSCs under continuous 1 sun illumination (AM 1.5G, 100 mW cm⁻²) is significantly improved by replacing the commonly used ZnO interlayer with OSiND‐based interfaces.

Antisolvent engineering is employed to tune the crystal nucleation and grain growth of perovskite for achieving efficient perovskite solar cells. The engineering of perovskites treated with the green antisolvent MABr‐Eth, suppressing defects‐induced nonradiative recombination in perovskite solar cells, is developed. As expected, the device delivers over 21% power conversion efficiency and a better storage and light‐soaking stability.

Abstract

Organic–inorganic hybrid perovskites have attracted considerable attention due to their superior optoelectronic properties. Traditional one‐step solution‐processed perovskites often suffer from defects‐induced nonradiative recombination, which significantly hinders the improvement of device performance. Herein, treatment with green antisolvents for achieving high‐quality perovskite films is reported. Compared to defects‐filled ones, perovskite films by antisolvent treatment using methylamine bromide (MABr) in ethanol (MABr‐Eth) not only enhances the resultant perovskite crystallinity with large grain size, but also passivates the surface defects. In this case, the engineering of MABr‐Eth‐treated perovskites suppressing defects‐induced nonradiative recombination in perovskite solar cells (PSCs) is demonstrated. As a result, the fabricated inverted planar heterojunction device of ITO/PTAA/Cs_0.15FA_0.85PbI₃/PC₆₁BM/Phen‐NADPO/Ag exhibits the best power conversion efficiency of 21.53%. Furthermore, the corresponding PSCs possess a better storage and light‐soaking stability.

High‐performance semitransparent organic solar cells are achieved through combined design efforts on the formulation of near‐infrared ternary blends and optical control over photonic reflectors, which exhibit excellent features of power generation, they being see‐through, and infrared reflection.

Abstract

Clean energy production and saving play vital impacts on the sustainability of the global community. Herein, high‐performance semitransparent organic solar cells (ST‐OSCs) with excellent features of power generation, being see‐through, and infrared reflection of heat dissipation, with promising perspectives for building‐integrated photovoltaics (BIPVs) are reported. To simultaneously improve average visible transmittance (AVT) and power conversion efficiency (PCE), formally in a trade‐off relationship, of ST‐OSCs, new ternary blends with alloy‐like near‐infrared (NIR) acceptors are employed, which are effective to improve device efficiency while maintaining visible absorption unchanged, resulting in PCEs of 16.8% for opaque devices and 13.1% for semitransparent OSCs (AVT of 22.4% and infrared photon radiation rejection (IRR) of 77%). Further, multifunctional ST‐OSCs are realized via introducing simple, yet effective photonic reflectors, together with optical simulation, leading to not only perfect fitting of the visible transmittance peak (555 nm) to the photopic response of the human eye but also an excellent IRR of 90% (780–2500 nm), along with 23% AVT and over 12% PCE. This is thought to be the best‐performing multifunctional ST‐OSC with promising prospects as BIPVs in terms of power generation, heat dissipation, and being see‐through.

Water is added into the precursor solution to assist crystal growths of quasi‐2D perovskite films featuring ordered phase distribution and favored crystal orientation. A champion efficiency of 18.04% is realized in (BA)₂(MA_0.8FA_0.15Cs_0.05)₄Pb₅I₁₆‐based quasi‐2D perovskite solar cells.

Abstract

Organic–inorganic hybrid quasi‐2D perovskites have shown excellent stability for perovskite solar cells (PSCs), while the poor charge transport in quasi‐2D perovskites significantly undermines their power conversion efficiency (PCE). Here, studies on water‐controlled crystal growth of quasi‐2D perovskites are presented to achieve high‐efficiency solar cells. It is demonstrated that the (BA)₂MA₄Pb₅I₁₆‐based PSCs (n = 5) processed with water‐containing precursors display an increased short‐circuit current density (J _sc) of 19.01 mA cm⁻² and PCE over 15%. The enhanced performance is attributed to synergetic growths of the 3D and 2D phase components aided by the formed hydration (MAI∙H₂O), leading to modulations on the crystal orientation and phase distribution of various n‐value components, which facilitate interphase charge transfer and charge sweepout throughout the device. The water‐assisted crystallization is further applied to triple cation‐based (BA)₂(MA_0.8FA_0.15Cs_0.05)₄Pb₅I₁₆ quasi‐2D perovskites, which generate a remarkable PCE of 18.04%. Despite the presence of water in the precursors, the devices exhibit a satisfactory thermal stability with the PCE degradation <15% under continuous thermal aging at 60 °C for over 500 h.

The M13 bacteriophage functions as an effective perovskite growth template and a passivator in perovskite solar cells. This is owing to its filamentous and uniform dimension, as well as the amino acids on its surface. These effects enhance when the M13 viruses are denatured at high temperature. The efficiency increases from 17.8% to 20.1% upon addition of the denatured viruses.

Abstract

The M13 bacteriophage, a nature‐inspired environmentally friendly biomaterial, is used as a perovskite crystal growth template and a grain boundary passivator in perovskite solar cells. The amino groups and carboxyl groups of amino acids on the M13 bacteriophage surface function as Lewis bases, interacting with the perovskite materials. The M13 bacteriophage‐added perovskite films show a larger grain size and reduced trap‐sites compared with the reference perovskite films. In addition, the existence of the M13 bacteriophage induces light scattering effect, which enhances the light absorption particularly in the long‐wavelength region around 825 nm. Both the passivation effect of the M13 bacteriophage coordinating to the perovskite defect sites and the light scattering effect intensify when the M13 virus‐added perovskite precursor solution is heated at 90 °C prior to the film formation. Heating the solution denatures the M13 bacteriophage by breaking their inter‐ and intra‐molecular bondings. The denatured M13 bacteriophage‐added perovskite solar cells exhibit an efficiency of 20.1% while the reference devices give an efficiency of 17.8%. The great improvement in efficiency comes from all of the three photovoltaic parameters, namely short‐circuit current, open‐circuit voltage, and fill factor, which correspond to the perovskite grain size, trap‐site passivation, and charge transport, respectively.

Publication date: October 2020

Source: Solar Energy Materials and Solar Cells, Volume 216

Author(s): Jianxing Xia, Junsheng Luo, Hua Yang, Zhongquan Wan, Haseeb Ashraf Malik, Yu Shi, Xiaojun Yao, Chunyang Jia