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Lewis Acid Dopants

In article number 1900340, Zong‐Xiang Xu and co‐workers dope poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) with 0.025 mol% molecular organic Lewis acid bis(entafluorophenyl)zinc [Zn(C₆F₅)₂], which exhibits increased hole mobility, hole extraction ability, and well‐matched energy levels. An enhanced highest power conversion efficiency of 17.49% is achieved for the perovskite solar cell based on Zn(C₆F₅)₂ doped P3HT without destroying its stability.

Cubic zinc metatitanate (ZTO) is identified as an excellent electron transport material with interface engineering treatment of dezincification for high efficient perovskite solar cells (PSCs). By integrating an inorganic hole transport layer and rGO protection, the ZTO electron transport layer‐based PSCs exhibit strong resistance to moisture, heat, and ultraviolet light, demonstrating high efficiency and stability toward practical applications.

Perovskite solar cells (PSCs) have experienced considerable development in the past few years. The stability issue has become a focus of research efforts toward their commercial applications. The development and interface engineering of electron transport materials (ETMs) to build up stable interfaces with perovskites has been emerging as a powerful strategy to enhance PSCs' stability. Herein, cubic zinc metatitanate (ZTO) is identified as an excellent ETM with interface engineering treatment of dezincification for fabricating PSCs with much better overall performances than those fabricated from TiO₂, a popularly used ETM. The high electron mobility of ZTO helps minimize the hysteresis. Together with the use of CuSCN as inorganic hole transport material and further protecting the PSCs with reduced graphene oxide, the ZTO‐based PSCs exhibit remarkable enhancement in stability, retaining 95% of initial power conversion efficiency under AM 1.5 G illumination at 85 °C and 85% relative humidity in air for 1000 h at open circuit.

An effective polar molecule of (2‐aminothiazole‐4‐yl)acetic acid (ATAA) is incorporated onto a ZnO electron transport layer to simultaneously achieve defect passivation and work function modulation by forming permanent interface dipoles. It minimizes the charge recombination loss in perovskite solar cells, and the ZnO–ATAA‐based device ultimately achieves an enhanced efficiency of 19.74% while suppressing the device hysteresis.

The intrinsic characteristics of a ZnO electron transport layer (ETL) lead to severe charge loss in perovskite solar cells (PSCs), such as photogenerated charge accumulation recombination in the perovskite layer due to the low electron extraction capacity, and defect‐induced charge recombination at the interface due to the unfavorable defects, causing efficiency loss and device hysteresis. Here, the polar molecule of (2‐aminothiazole‐4‐yl)acetic acid (ATAA) is self‐assembled onto a ZnO layer with the help of oxygen vacancy defects, combining the advantages of lowering the work function by forming the permanent interface dipole and simultaneously passivating defect states. It effectively strengthens the electron extraction capacity and reduces the density of defect states. Therefore, the resulting PSCs with a ZnO–ATAA ETL yield an enhanced efficiency of 19.74% with evidently reduced device hysteresis.

A novel wide bandgap polymer donor PNDT‐ST and a near infrared nonfullerene acceptor Y6‐T are developed for highly efficient organic solar cells. The high lowest unoccupied molecular orbital energy of Y6‐T and the high crystallinity of PNDT‐ST as well as the compatible PNDT‐ST:PNDT‐ST:Y6‐T ternary blend enable the significantly improved power conversion efficiency of 16.57% with minimal energy loss of 0.521 eV.

Abstract

A new wide bandgap polymer donor, PNDT‐ST, based on naphtho[2,3‐b:6,7‐b′]dithiophene (NDT) and 1,3‐bis(thiophen‐2‐yl)‐5,7‐bis(2‐ ethylhexyl)benzo[1,2‐c:4,5‐c′]dithiophene‐4,8‐dione (BDD) is developed for efficient nonfullerene polymer solar cells. To better match the energy levels, a new near infrared small molecule of Y6‐T is also developed. The extended π‐conjugation and less twist of PNDT‐ST provides it with higher crystallinity and stronger aggregation than the PBDT‐ST counterpart. The higher lowest occupied molecular orbital level of Y6‐T than Y6 favors the better energy level match with these polymers, resulting in improved open circuit voltage (V _oc) and power conversion efficiency (PCE). The high crystallinity and strong aggregation of PNDT‐ST also induces large phase separation with poorer morphology, leading to lower fill factor and reduced PCE than PBDT‐ST. To mediate the crystallinity and optimize the morphology, PNDT‐ST and PBDT‐ST are blended together with Y6‐T, forming the ternary blend devices. As expected, the two compatible polymers allow continual optimization of the morphology by varying the blend ratio. The optimized ternary blend devices deliver a champion PCE as high as 16.57% with a very small energy loss (E _loss) of 0.521 eV. Such small E _loss is the best record for polymer solar cells with PCEs over 16% to date.

A simple low‐temperature‐processed In₂O₃/SnO₂ bilayer electron‐transport layer (ETL) is used for fabricating efficient perovskite solar cells (PSCs). The bilayer ETL with appropriate energy alignment is beneficial for charge transfer, thus minimizing open‐circuit voltage (V _OC) loss. An optimized planar PSC with a power conversion efficiency (PCE) of 23.24% is obtained. In contrast, devices based on single SnO₂ only achieve efficiency of 21.42%.

Abstract

An electron‐transport layer (ETL) with appropriate energy alignment and enhanced charge transfer is critical for perovskite solar cells (PSCs). However, interfacial energy level mismatch limits the electrical performance of PSCs, particularly the open‐circuit voltage (V _OC). Herein, a simple low‐temperature‐processed In₂O₃/SnO₂ bilayer ETL is developed and used for fabricating a new PSC device. The presence of In₂O₃ results in uniform, compact, and low‐trap‐density perovskite films. Moreover, the conduction band of In₂O₃ is shallower than that of Sn‐doped In₂O₃ (ITO), enhancing the charge transfer from perovskite to ETL, thus minimizing V _OC loss at the perovskite and ETL interface. A planar PSC with a power conversion efficiency of 23.24% (certified efficiency of 22.54%) is obtained. A high V _OC of 1.17 V is achieved with the potential loss at only 0.36 V. In contrast, devices based on single SnO₂ layers achieve 21.42% efficiency with a V _OC of 1.13 V. In addition, the new device maintains 97.5% initial efficiency after 80 d in N₂ without encapsulation and retains 91% of its initial efficiency after 180 h under 1 sun continuous illumination. The results demonstrate and pave the way for the development of efficient photovoltaic devices.

Gadolinium fluoride (GdF₃) and aminobutanol are introduced for Ostwald ripening in the crystal growth of perovskite to overcome the double dilemma of internal defects and external humidity. A GdF₃‐ and aminobutanol‐treated perovskite solar cell achieves a power conversion efficiency of 21.21% with good stability and small hysteresis, while the pristine device only shows an efficiency of 18.10%.

Abstract

As one kind of promising next‐generation photovoltaic devices, perovskite solar cells (PVSCs) have experienced unprecedented rapid growth in device performance over the past few years. However, the practical applications of PVSCs require much improved device long‐term stability and performance, and internal defects and external humidity sensitivity are two key limitation need to be overcome. Here, gadolinium fluoride (GdF₃) is added into perovskite precursor as a redox shuttle and growth‐assist; meanwhile, aminobutanol vapor is used for Ostwald ripening in the formation of the perovskite layer. Consequently, a high‐quality perovskite film with large grain size and few grain boundaries is obtained, resulting in the reduction of trap state density and carrier recombination. As a result, a power conversion efficiency of 21.21% is achieved with superior stability and negligible hysteresis.

Two electron donor (D)–electron acceptor (A)‐type polymers PBDTT and PBTTT are developed as hole‐transporting materials for perovskite solar cells (PVSCs). Both polymers endow the PVSCs promising device performance. A power conversion efficiency of 20.28% is achieved from the devices with dopant‐free PBDTT. High device stability can be expected by employing these compact and hydrophobic polymeric hole‐transporting layers.

Abstract

The rich molecular design of electron donor (D)–acceptor (A) polymers offers many valuable clues to obtain high‐efficiency hole‐transporting materials (HTMs) for use in perovskite solar cells (PVSCs). The fused aromatic or heteroaromatic units can increase the conjugation of the polymer backbone to facilitate electron delocalization, which increases the rigidity of adjacent units to prevent rotational disorder and lower the reorganization energy, leading to improved carrier mobility and optimized film morphology. In this work, fused‐ring ladder‐type indacenodithiophene and indacenodithieno[3,2‐b]thiophene are used as D units, benzodithiophene‐4,8‐dione as the A unit, and thienothiophene as a π‐bridge to form the D–A polymers PBDTT and PBTTT, respectively. Both polymers exhibit favorable properties as HTMs including suitable energy levels, high hole mobility, and excellent film quality. Both dopant‐free HTMs endow n‐i‐p PVSCs with promising performance and stability. A maximum power conversion efficiency of 20.28% is achieved for PBDTT‐based devices, which is among the highest values reported to date.

High‐efficiency stable perovskite/gallium arsenide two‐terminal and four‐terminal tandem cells are demonstrated for the first time. For this purpose, high‐performance photostable wide‐bandgap perovskite photovoltaics (PVs) (1.8–1.9 eV) are developed by a solvent‐controlled process. Tandem architectures are shown to be feasible for thin‐film flexible devices with superior bendability, essential to commercialization. This approach is expected to improve the usability of GaAs PV with enhanced efficiency and lower cost.

Abstract

Gallium arsenide (GaAs) photovoltaic (PV) cells have been widely investigated due to their merits such as thin‐film feasibility, flexibility, and high efficiency. To further increase their performance, a wider bandgap PV structure such as indium gallium phosphide (InGaP) has been integrated in two‐terminal (2T) tandem configuration. However, it increases the overall fabrication cost, complicated tunnel‐junction diode connecting subcells are inevitable, and materials are limited by lattice matching. Here, high‐efficiency and stable wide‐bandgap perovskite PVs having comparable bandgap to InGaP (1.8–1.9 eV) are developed, which can be stable low‐cost add‐on layers to further enhance the performance of GaAs PVs as tandem configurations by showing an efficiency improvement from 21.68% to 24.27% (2T configuration) and 25.19% (4T configuration). This approach is also feasible for thin‐film GaAs PV, essential to reduce its fabrication cost for commercialization, with performance increasing from 21.85% to 24.32% and superior flexibility (1000 times bending) in a tandem configuration. Additionally, potential routes to over 30% stable perovskite/GaAs tandems, comparable to InGaP/GaAs with lower cost, are considered. This work can be an initial step to reach the objective of improving the usability of GaAs PV technology with enhanced performance for applications for which lightness and flexibility are crucial, without a significant additional cost increase.

A crosslinkable organic small molecule, thioctic acid (TA), is introduced into perovskite solar cells as a new bifacial passivation agent. This TA can simultaneously be chemically anchored to the surface of TiO₂ and methylammonium lead iodide through coordination effects and then in situ crosslinked to form a robust continuous polymer (Poly(TA)) network after thermal treatment.

Abstract

Defects, inevitably produced within bulk and at perovskite‐transport layer interfaces (PTLIs), are detrimental to power conversion efficiency (PCE) and stability of perovskite solar cells (PSCs). It is demonstrated that a crosslinkable organic small molecule thioctic acid (TA), which can simultaneously be chemically anchored to the surface of TiO₂ and methylammonium lead iodide (MAPbI₃) through coordination effects and then in situ crosslinked to form a robust continuous polymer (Poly(TA)) network after thermal treatment, can be introduced into PSCs as a new bifacial passivation agent for greatly passivating the defects. It is also discovered that Poly(TA) can additionally enhance the charge extraction efficiency and the water‐resisting and light‐resisting abilities of perovskite film. These newly discovered features of Poly(TA) make PSCs herein achieve among the best PCE of 20.4% ever reported for MAPbI₃ with negligible hysteresis, along with much enhanced ultraviolet, air, and operational stabilities. Density functional theory calculations reveal that the passivation of MAPbI₃ bulk and PTLIs by Poly(TA) occurs through the interaction of functional groups (COOH, CS) in Poly(TA) with under‐coordinated Pb²⁺ in MAPbI₃ and Ti⁴⁺ in TiO₂, which is supported by X‐ray photoelectron spectroscopy and Fourier transform infrared spectroscopy.

The aprotic butyldimethylsulfonium‐driven MAPbI₃ perovskite shows a much more pronounced effect on the improvement of moisture stability compared to the protic butylammonium (BA)‐based counterpart. The BA having a potential hydrogen donor, which exists on the surface and/or grain boundaries, is vulnerable to H₂O‐induced degradation initiators, resulting in the faster hydration followed by the irreversible degradation of perovskites.

Abstract

Many organic cations in halide perovskites have been studied for their application in perovskite solar cells (PSCs). Most organic cations in PSCs are based on the protic nitrogen cores, which are susceptible to deprotonation. Here, a new candidate of fully alkylated sulfonium cation (butyldimethylsulfonium; BDMS) is designed and successfully assembled into PSCs with the aim of increasing humidity stability. The BDMS‐based perovskites retain the structural and optical features of pristine perovskite, which results in the comparable photovoltaic performance. However, the fully alkylated aprotic nature of BDMS shows a much more pronounced effect on the increase in humidity stability, which emphasizes a generic electronic difference between protic ammonium and aprotic sulfonium cation. The current results would pave a new way to explore cations for the development of promising PSCs.

Two electron donor (D)–electron acceptor (A)‐type polymers PBDTT and PBTTT are developed as hole‐transporting materials for perovskite solar cells (PVSCs). Both polymers endow the PVSCs promising device performance. A power conversion efficiency of 20.28% is achieved from the devices with dopant‐free PBDTT. High device stability can be expected by employing these compact and hydrophobic polymeric hole‐transporting layers.

Abstract

The rich molecular design of electron donor (D)–acceptor (A) polymers offers many valuable clues to obtain high‐efficiency hole‐transporting materials (HTMs) for use in perovskite solar cells (PVSCs). The fused aromatic or heteroaromatic units can increase the conjugation of the polymer backbone to facilitate electron delocalization, which increases the rigidity of adjacent units to prevent rotational disorder and lower the reorganization energy, leading to improved carrier mobility and optimized film morphology. In this work, fused‐ring ladder‐type indacenodithiophene and indacenodithieno[3,2‐b]thiophene are used as D units, benzodithiophene‐4,8‐dione as the A unit, and thienothiophene as a π‐bridge to form the D–A polymers PBDTT and PBTTT, respectively. Both polymers exhibit favorable properties as HTMs including suitable energy levels, high hole mobility, and excellent film quality. Both dopant‐free HTMs endow n‐i‐p PVSCs with promising performance and stability. A maximum power conversion efficiency of 20.28% is achieved for PBDTT‐based devices, which is among the highest values reported to date.

The interplay of crystal structure and photophysics in the mixed cation, mixed halide perovskite (FAPbI₃)_0.85(MAPbBr₃)_0.15 is probed. It is found that changes in crystal structure, quantified by structural parameters such as lattice constant ratios and bond angles, influence optoelectronic properties in the film—the bandgap, Stokes shift, and charge carrier recombination rates all exhibit phase specificity.

Abstract

Mixed cation perovskites currently achieve very promising efficiency and operational stability when used as the active semiconductor in thin‐film photovoltaic devices. However, an in‐depth understanding of the structural and photophysical properties that drive this enhanced performance is still lacking. Here the prototypical mixed‐cation mixed‐halide perovskite (FAPbI₃)_0.85(MAPbBr₃)_0.15 is explored, and temperature‐dependent X‐ray diffraction measurements that are correlated with steady state and time‐resolved photoluminescence data are presented. The measurements indicate that this material adopts a pseudocubic perovskite α phase at room temperature, with a transition to a pseudotetragonal β phase occurring at ≈260 K. It is found that the temperature dependence of the radiative recombination rates correlates with temperature‐dependent changes in the structural configuration, and observed phase transitions also mark changes in the gradient of the optical bandgap. The work illustrates that temperature‐dependent changes in the perovskite crystal structure alter the charge carrier recombination processes and photoluminescence properties within such hybrid organic–inorganic materials. The findings have significant implications for photovoltaic performance at different operating temperatures, as well as providing new insight on the effect of alloying cations and halides on the phase behavior of hybrid perovskite materials.

Deep neural networks, device simulation, and experiment are coupled to demonstrate a general method for the extraction of material parameters from thin‐film solar cells. Mobilities, trap densities, and recombination constants are extracted from transient and steady state data. The method is applicable to all classes of thin‐film devices, and has considerable advantages over previous approaches.

Abstract

There is currently a worldwide effort to develop materials for solar energy harvesting which are efficient and cost effective, and do not emit significant levels of CO₂ during manufacture. When a researcher fabricates a novel device from a novel material system, it often takes many weeks of experimental effort and data analysis to understand why any given device/material combination produces an efficient or poorly optimized cell. It therefore takes the community tens of years to transform a promising material system to a fully optimized cell ready for production (perovskites are a contemporary example). Herein, developed is a new and rapid approach to understanding device/material performance, which uses a combination of machine learning, device modeling, and experiment. Providing a set of electrical device parameters (charge carrier mobilities, recombination rates, trap densities, etc.) in a matter of seconds thus offers a fast way to directly link fabrication conditions to device/material performance, pointing a way to further and more rapid optimization of light harvesting devices. The method is demonstrated by using it to understand annealing temperature and surfactant choice and in terms of charge carrier dynamics in organic solar cells made from the P3HT:PCBM, PBTZT‐stat‐BDTT‐8:PCBM, and PTB7:PCBM material systems.

Among several solution process photovoltaics, perovskite solar cells are evolving at an impressive pace, emerging as the most promising next‐generation photovoltaic devices. Herein, the recent developments in laser technology applicable to perovskite‐based solar devices, technological and process aspects, and an outlook on future applications are reported.

In the last decade, hybrid organic–inorganic perovskite‐based solar cells (PSCs) have shown an impressive rate of growth in performance, reaching power conversion efficiencies (PCEs) comparable with the ones exhibited by crystalline silicon devices. Recently, perovskite‐based solar modules (PSMs) have been developed, showing a similar pace in the progress of the reported PCE. Nevertheless, scaling up the dimensions of devices is not a trivial process. To this effect, different deposition and manufacturing techniques have to be implemented. Laser apparatuses have been demonstrated to be fundamental in the production of PSMs, due to the extreme precision needed for manufacturing processes. Herein, an overview of the recent progresses in the application of laser systems in the production of perovskite‐based solar devices is provided. In particular, lasers are used in small‐area PSCs to realize pulsed laser deposition procedures for the realization of perovskite layers and novel electrodes. In the field of PSMs, lasers have boosted the exploitation of substrates, minimizing the dimension of interconnection areas between the cells that form a module and providing the necessary accuracy, repeatability, and level of automation needed for the future industrialization of perovskite‐based solar technology.