Perovskite Layer Research Articles

Overcoming stability challenges in perovskite solar cells: Addressing Li ions movement in Spiro-OMeTAD layer through nano-graphdiyne incorporation

The most used hole transport material in high-performance perovskite solar cells (PSCs) is the lithium compounds-doped 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene (Spiro-OMeTAD). However, PSCs based on the Spiro-OMeTAD suffer from serious instability induced by Li+ migration and aggregation. Herein, nano-graphdiyne (nano-GDY) was incorporated into the Spiro-OMeTAD to retard such free Li+ movement and reduce its impact on device operation stability. We verify that the nano-GDY-modified HTL efficiently enhances carrier transport and promotes favorable energy level alignment compared to that of the control HTL, contributing to improved device performance. Furthermore, the coordination interaction between the nano-GDY and Li+ significantly retrains the Li+ migration into the perovskite and SnO2 layers, and meanwhile, eliminates their aggregation with HTLs under elevated temperature and prolonged light soaking. Consequently, the nano-GDY incorporated PSCs exhibit a champion power-conversion efficiency (PCE) of 24.16 % with negligible hysteresis. Encouragingly, the devices also exhibit robust stability, retaining 97 % and 80 % of peak PCE at maxima power point tracking for 6000 s and continuous illumination for 1080 h, respectively.

In situ Blending For Co-Deposition of Electron Transport and Perovskite Layers Enables Over 24% Efficiency Stable Conventional Solar Cells.

Simplifying the manufacturing processes of multilayered high-performance perovskite solar cells (PSCs) is yet of vital importance for their cost-effective production. Herein, an in situ blending strategy is presented for co-deposition of electron transport layer (ETL) and perovskite absorber by incorporating (3-(7-butyl-1,3,6,8-tetraoxo-3,6,7,8-tetrahydrobenzo- [lmn][3,8]phenanthrolin-2(1H)-yl)propyl)phosphonic acid (NDP) into the perovskite precursor solutions. The phosphonic acid-like anchoring group coupled with its large molecular size drives the migration of NDP toward indium tin oxide (ITO) surface to form a distinct ETL during perovskite film forming. This strategy circumvents the critical wetting issue and simultaneously improves the interfacial charge collection efficiencies. Consequently, n-i-p PSCs based on in situ blended NDP achieve a champion power conversion efficiency (PCE) of 24.01%, which is one of the highest values for PSCs using organic ETLs. This performance is notably higher than that of ETL-free (21.19%) and independently spin-coated (21.42%) counterparts. More encouragingly, the in situ blending strategy dramatically enhances the device stability under harsh conditions by retaining over 90% of initial efficiencies after 250h in 100°C or 65% humidity storage. Moreover, this strategy is universally adaptable to various perovskite compositions, device architectures, and electron transport materials (ETMs), showing great potential for applications in diverse optoelectronic devices.

Pushing magnetic spirals beyond room temperature by reducing the uniaxial pyramidal elongation in layered Cu/Fe perovskites

The impact of a 3d divalent substitution for Cu using M2+ ions not presenting elongated MO5 pyramids has been explored in YBaCuFeO5 as a new strategy to upgrade the magnetic properties of this high-temperature spiral magnet and potential multiferroic. In this work we investigate the incidence of the Cu2+ with Co2+ substitution in YBa(Cu1−xCox)FeO5 compounds in which B-site disorder is kept invariant (disorder nd≈36%). The study validates the reduction of the uniaxial elongation distortion at Cu sites as an efficient alternative way to disorder that enables one to enhance the thermal stability of the spiral order. In addition, the rotation plane of the helix is reoriented by the Cu/Co substitution and nearby the triple point (when TS is maximal) the spiral order adopts an almost complete cycloidal magnetic configuration. These results lay the foundation of a new mechanism to tune the stability of the magnetic spirals in layered perovskites based on reducing the uniaxial elongation associated to the (4+1)-coordination of Cu2+ ions in square CuO5 pyramids. Published by the American Physical Society 2024

The development of a bilayer absorption scenario of CsPbI3/Cs2SnI6 PSCs for enhanced efficiency and stability

The introduction of heterojunction structures in perovskite solar cells (PSCs) can lead to substantial enhancements in power conversion efficiency (PCE) and stability. Using the SCAPS-1D software, we have theoretically investigated the performance potential of CsPbI3/Cs2SnI6 heterojunction PSCs. The purpose of incorporating a thin layer of Cs2SnI6 perovskite onto the CsPbI3 layer is to enhance the stability of the device through the formation of a protective barrier that prevents the continuous degradation of CsPbI3. The device's overall efficiency was found to be greatly enhanced by meticulously optimizing the acceptor concentration (NA), defect density (Nt), and absorber thickness of CsPbI3. In addition, the influence of various physical parameters such as the operating temperature, the work function of the metal rear contact, and series and shunt resistance on the photovoltaic performance of the device is comprehensively examined. With the systematic optimization of these parameters, the device exhibited improved performance and attained an outstanding PCE of 20.86 %, an open circuit voltage (VOC) of 1.19 V, a fill factor (FF) of 81.77%, and a current density voltage (JSC) of 21.32 mA/cm2. We think that our work will provide theoretical guidance in the advancement of heterojunction devices with much improved efficiency and stability.

The impact of series ([formula omitted]) and shunt resistances ([formula omitted]) on solar cell parameters to enhance the photovoltaic performance of f-PSCs

Flexible Perovskite Solar Cells (f-PSCs) are made on an ITO-coated PET substrate. SnO2 has been used as a transparent inorganic electron transporting layer (ETL), PEDOT: PSS as an organic hole transporting layer (HTL), and C H3 N H3 Pb I3 as a perovskite absorbing layer. Two configurations of the device structure have been formed, one is normal structure ITO/PET/ SnO2/C H3 N H3 Pb I3/PEDOT: PSS/Ag (n-i-p) and the other is inverted structure ITO/PET/PEDOT: PSS/C H3 N H3 Pb I3/ SnO2/Ag (p-i-n). An antisolvent (i.e. ethyl acetate) has been used to control the surface morphology of the perovskite layers during fabrication of f-PSCs. Applying antisolvent in perovskite improves carrier mobility, transport properties, and higher power conversion efficiency (PCE) achieved. This study focuses on the effects of series (Rs) and shunt resistance (Rsh) of f-PSCs on photovoltaic parameters while controlling the surface morphology of perovskite films applied on both structures. The study examines the behaviour of f-PSCs with and without the use of an antisolvent. For normal structure, PCE is found at 11.34 % for f-PSCs with antisolvent and 7.96 % for f-PSCs without antisolvent. On the other hand, inverted structures show PCE 10.36 % and 7.46 % for f-PSCs with and without antisolvent, respectively. PCE has been calculated for the f-PSCs by bending the samples about 3 0o angle and about 20 % decrease in PCE has been found. The oddity of this work is to estimate the series and shunt resistant for f-PSCs and find the cost-effective control of these parameters by controlling interfacial defects.

Lattice Dynamics of Quasi-2D Perovskites from First Principles.

We present the vibrational properties and phonon dispersion for quasi-2D hybrid organic-inorganic perovskites (BA)2CsPb2I7, (HA)2CsPb2I7, (BA)2(MA)Pb2I7, and (HA)2(MA)Pb2I7 calculated from first principles. Given the highly complex nature of these compounds, we first perform careful benchmarking and convergence testing to identify suitable parameters to describe their structural features and vibrational properties. We find that the inclusion of van der Waals corrections on top of generalized gradient approximation (GGA) exchange-correlation functionals provides the best agreement for the equilibrium structure relative to experimental data. We also investigate the impact of the molecular orientation on the equilibrium structure of these layered perovskite systems. Our results suggest ground state ferroelectric alignment of molecular dipoles in the out-of-plane direction is unlikely and support the assignment of the centrosymmetric space group for the low-temperature phase of (HA)2(MA)Pb2I7. Finally, we compute vibrational properties under the harmonic approximation. We find that stringent energy cut-offs are required to obtain well-converged phonon properties, and once converged, the harmonic approximation can capture key physics for such a large, hybrid inorganic-organic system with vastly different atom types, masses, and interatomic interactions. We discuss the obtained phonon modes and dispersion behavior in the context of known properties for bulk 3D perovskites and ligand molecular crystals. While many vibrational properties are inherited from the parent systems, we also observe unique coupled vibrations that cannot be associated with vibrations of the pure constituent perovskite and ligand subphases. Energy dispersion of the low energy phonon branches primarily occurs in the in-plane direction and within the perovskite subphase and arises from bending and breathing modes of the equatorial Pb-I network within the perovskite octahedral plane. The analysis herein provides the foundation for future investigations on this class of materials, such as exciton-phonon coupling, phase transitions, and general temperature-dependent properties.

Nanoscale phase management of the 2D/3D heterostructure toward efficient perovskite solar cells

The stabilization of the formamidinium lead iodide (FAPbI3) structure is pivotal for the development of efficient photovoltaic devices. Employing two-dimensional (2D) layers to passivate the three-dimensional (3D) perovskite is essential for maintaining the α-phase of FAPbI3 and enhancing the power conversion efficiency (PCE) of perovskite solar cells (PSCs). However, the role of bulky ligands in the phase management of 2D perovskites, crucial for the stabilization of FAPbI3, has not yet been elucidated. In this study, we synthesized nanoscale 2D perovskite capping crusts with <n> = 1 and 2 Ruddlesden-Popper (RP) perovskite layers, respectively, which form a type-II 2D/3D heterostructure. This heterostructure stabilizes the α-phase of FAPbI3, and facilitates ultrafast carrier extraction from the 3D perovskite network to transport contact layer. We introduced tri-fluorinated ligands to mitigate defects caused by the halide vacancies and uncoordinated Pb2+ ions, thereby reducing nonradiative carrier recombination and extending carrier lifetime. The films produced were incorporated into PSCs that not only achieved a PCE of 25.39% but also maintained 95% of their initial efficiency after 2000 h of continuous light exposure without encapsulation. These findings underscore the effectiveness of a phase-pure 2D/3D heterostructure-terminated film in inhibiting phase transitions passivating the iodide anion vacancy defects, facilitating the charge carrier extraction, and boosting the performance of optoelectronic devices.

Reducing oxygen vacancies of MoO3 by polyaniline functionalization for stable and efficient inorganic tri-brominated perovskite solar cells

The photovoltaic performance of perovskite solar cells (PSCs) is closely dependent on the efficient carrier extraction and transport at the interface. Here, a polyaniline (PANI) functionalized MoO3 (PANI/MoO3) hole transport material (HTM) is exploited to perfect the interface between the perovskite layer and carbon electrode in all-inorganic CsPbBr3 PSCs. After functionalization with PANI, the p-type behavior and the hole mobility and conductivity of MoO3 are improved by reducing the oxygen vacancies, which boosts the hole extraction and transport, energy level arrangement at the interface of CsPbBr3 perovskite/(PANI/MoO3) HTM. Meanwhile, the PANI/MoO3 with rich C–N and N–H groups introduced by PANI passivates the ions trap states of perovskite films by the C–N⋯Pb2+ (Cs+) Lewis acid-base coordination and the N–H⋯Br− hydrogen bonding, leading to an effective suppression of non-radiative recombination for improved carrier extraction. As a result, the PANI/MoO3 HTMs-based CsPbBr3 PSCs obtain a remarkably increased power conversion efficiency of 10.41 %, in comparison with the efficiency of the original device (6.55 %). In addition, the unencapsulated device with PANI/MoO3 HTMs shows excellent long-term stability with 93.9 % maintenance of the initial efficiency after storing in air with 85 % relative humidity and at 85 °C for 30 days.

In Situ Dehydration Condensation of Self‐Assembled Molecules Enables Stabilization of CsPbI3 Perovskites for Efficient Photovoltaics

AbstractInorganic perovskites, with Cs+ substituting volatile organic components, show great promise in photovoltaic applications due to their outstanding optoelectronic properties and thermal stability. However, the black‐to‐yellow phase transition of CsPbI3 remains a challenge for realizing high‐performance inorganic perovskite solar cells (IPSCs). Herein, an effective approach is reported via incorporating the self‐assembled molecule Me‐4PACz to synergistically stabilize the [PbI6]4− octahedra and form a hydrophobic layer at interface and grain boundaries. An in situ dehydration condensation reaction of Me‐4PACz is observed during film annealing, which favors the reduction of undesired aggregation of Me‐4PACz in humid air, thus leading to enhanced anchoring interaction and more effective hydrophobic protection of CsPbI3. Therefore, the air‐processed CsPbI3 perovskite films show dramatically improved phase purity and humid stability. This strategy also improves the energy level alignment between perovskite and charge transport layers. As a result, a champion efficiency of 20.21% is realized, representing one of the highest reported values for air‐processed inverted IPSCs. Furthermore, it is demonstrated that by combining Me‐4PACz with the previously reported ethacridine lactate (EAL) additive, the device performance can be further boosted to 21.38%, which is a record efficiency for the inverted IPSCs reported to date.

An analysis comparing the performance of lead and tin halides organic Perovskite Solar Cells and numerical simulation with SCAPS

The scientific community focused on finding environmentally safe alternative metal halides to address the instability and toxicity associated with lead perovskite materials. These alternatives are supposed to replace lead halides without altering the distinctive properties of lead perovskite materials. Additionally, they should contribute to producing longer-lasting and stable perovskite in solar cells. This research presents a practical investigation of using tin- and lead-based composites in perovskite iodide solar cells with Titanium dioxide (TiO2) and Copper oxide (CuO) as electron transport materials (ETM) and hole transport materials (HTM), respectively. The performance parameters of the perovskite solar cells (PSCs) are compared with those of lead-based and lead-free PSCs with the same charge transport layers of ETM and HTM, as well as compare the practical results with the software results of Solar Cell Capacitance Simulation (SCAPS) package. In this study, the performance of PSCs with an absorption layer ((CH3NH3PbI3)t/(CH3NH3SnI3)1-t) was examined. The thickness of the perovskite layer is represented by (t), which can take the values(t = 1, 0.5, or 0) μm. The results of the laboratory study were compared to the performance of PSCs based on numerical analysis of SCAPS modeling. PSCs were prepared with a configuration structure (FTO/compact TiO2/(CH3NH3PbI3)t/(CH3NH3SnI3)1-t/CuO/Cu-electrode). A tetragonal phase was obtained for perovskite materials CH3NH3PbI3 and CH3NH3SnI3 with a direct optical energy gap estimated at (1.55 and 1.35) eV, respectively. The l-V curve of the prepared PSCs was studied, and the performance of the solar cells was examined under a light intensity of 100 mW/cm2. The power conversion efficiency, PCE, of the prepared solar cells, was (PCE = 2.9, 3.11, or 0.5) at (t = 1, 0.5, or 0)μm, respectively. A comparative analysis was also performed between the empirical performance of the manufactured PSCs and the theoretical results acquired by the SCAPS package software.

Facile Doping of 2,2,2-Trifluoroethanol to Single-Walled Carbon Nanotubes Electrodes for Durable Perovskite Solar Cells

Perovskite solar cells with an indium tin oxide (ITO)/SnO2/CH3NH3PbI3/Spiro-OMeTAD/2,2,2-trifluoroethanol (TFE) doped single-walled carbon nanotube (SWCNT) structure were developed by dropping TFE onto SWCNTs, which replaced the metal back electrode, and a conversion efficiency of 14.1% was achieved. Traditionally, acidic doping of the back electrode, SWCNT, has been challenging due to the potential damage it may cause to the perovskite layer. However, TFE has facilitated easy doping of SWCNT as the back electrode. The sheet resistance of the SWCNTs decreased and their ionization potential shifted to deeper levels, resulting in improved hole transport properties with a lower barrier to carrier transport. Furthermore, the Seebeck coefficient (S) increased from 34.5 μV/K to 73.1 μV/K when TFE was dropped instead of EtOH, indicating an enhancement in the behavior of p-type charge carriers. It was observed that hydrophilic substances adhered less to the SWCNT surface, and the formation of PbI2 was suppressed. These effects resulted in higher conversion efficiency and improved solar cell performance. Furthermore, the decrease in conversion efficiency after 260 days was suppressed, showing improved durability. The study suggests that combining SWCNTs and TFEs improves solar cell performance and stability.

Sequential Deposition of Diluted Aqueous SnO2 Dispersion for Perovskite Solar Cells

The widespread use of tin dioxide (SnO2) thin films as electron transport layer (ETL) of perovskite solar cells (PSCs) has been facilitated by commercial SnO2 nanocolloid dispersion. Nevertheless, challenges such as nanoparticle agglomeration have emerged, impacting film quality and interface properties critical for PSC performance. Herein, the efficacy of sequential, multistep spin‐coating of repeatedly diluted SnO2 aqueous suspension as a simple and effective approach to enhance ETL properties is explored. Through systematic experiments using dynamic light scattering, cyclic voltammetry, optical spectroscopy, and photoconductivity, it is demonstrated that the sequential deposition significantly improves the flatness and coverage of SnO2, leading to improved electron transport and transfer from a perovskite layer. Such a synergetic effect enables to fabricate lead iodide PSC (FAPbI3, FA: formamidinium) with a power conversion efficiency of 22.99% compared to 20.48% for the conventional 1‐step SnO2 layer. The findings underscore the potential of sequential SnO2 deposition as a promising technique for robust SnO2 films of photoelectric conversion devices.

Sub-bandgap Photocurrent Spectra of p-i-n Perovskite Solar Cells with n-Doped Fullerene Electron Transport Layers and Bias Illumination.

In p-i-n perovskite solar cells optical excitation of defect states at the interface between the perovskite and fullerene electron transport layer (ETL) creates a photocurrent responsible for a distinct sub-bandgap external quantum efficiency (EQE). The precise nature of these signals and their impact on cell performance are largely unknown. Here, the effect of n-doping the fullerene on the EQE spectra is studied. The n-doped fullerene is either deposited from solution or by coevaporation. The latter method is used to create undoped-doped fullerene bilayers and investigate the effect of the proximity of the doped region on the EQE spectra. The intensity of the sub-bandgap EQE increases when the ETL is n-doped and also when the device is biased with green light. Using these results, the sub-bandgap EQE signal is attributed to originate from electron trap states in the perovskite with an energy below the conduction band that are filled by excitation with low-energy photons. The trapped electrons give rise to photocurrent when they are collected at a nearby electrode. The enhanced sub-bandgap EQE observed when the ETL is n-doped or bias light is applied, is related to a higher probability to extract trapped electrons under these conditions.

Molecular Orientation Regulation of Hole Transport Semicrystalline-Polymer Enables High-Performance Carbon-Electrode Perovskite Solar Cells.

Carbon-based perovskite solar cells (PSCs) coupled with solution-processed hole transport layers (HTLs) have shown potential owing to their combination of low cost and high performance. However, the commonly used poly(3-hexylthiophene) (P3HT) semicrystalline-polymer HTL dominantly shows edge-on molecular orientation, in which the alkyl side chains directly contact the perovskite layer, resulting in an electronically poor contact at the perovskite/P3HT interface. The study adopts a synergetic strategy comprising of additive and solvent engineering to transfer the edge-on molecular orientation of P3HT HTL into 3D molecular orientation. The target P3HT HTL possesses improved charge transport as well as enhanced moisture-repelling capability. Moreover, energy level alignment between target P3HT HTL and perovskite layer is realized. As a result, the champion devices with small (0.04 cm2) and larger areas (1 cm2) deliver notable efficiencies of 20.55% and 18.32%, respectively, which are among the highest efficiency of carbon-electrode PSCs.

Nanometer Control of Ruddlesden-Popper Interlayers by Thermal Evaporation for Efficient Perovskite Photovoltaics.

Solution-processed Ruddlesden-Popper (RP) interlayers in lead halide perovskite solar cells (PSCs) present processing challenges due to fast film formation and uncontrolled growth of phases and layer thickness at interfaces. In this work, an alternative, solvent-free, thermal co-evaporation process is developed to deposit RP interlayers. The method provides precise control on interlayer thickness and enables understanding its role on charge-carrier extraction. Studying RP film growth reveals the development of heterointerfaces when deposited on three-dimensional (3D) perovskite layers. This allows a large thickness window with an optimum between 20 nm and 40 nm to improve the optoelectronic properties of the underlying 3D perovskite. Solar cells using evaporated interlayers achieve power conversion efficiency of 21.6%, compared to 19.6% for untreated devices, driven by improvements in the open-circuit voltage and fill factor. This work sheds light on the importance of phase and thickness control of passivation layers, which ultimately determine the solar cell performance in state-of-the-art PSCs.

Ag Intercalation in Layered Cs3Bi2Br9 Perovskite for Enhanced Light Emission with Bound Interlayer Excitons.

Cesium bismuth bromide (CBB) has garnered considerable attention as a vacancy-ordered layered perovskite with notable optoelectronic applications. However, its use as a light source has been limited due to its weak photoluminescence (PL). Here, we demonstrate metal intercalation as a novel approach to engineer the room-temperature PL of CBB using experimental and computational methods. Ag, when introduced into CBB, occupies vacant sites in the spacer region, forming octahedral coordination with surrounding Br anions. First-principles density functional theory calculations reveal that intercalated Ag represents the most energetically stable Ag species compared to other potential forms, such as Ag substituting Bi. The intercalated Ag forms a strong polaronic trap state close to the conduction band minimum and quickly captures photoexcited electrons with holes remaining in CBB layers, leading to the formation of a bound interlayer exciton, or BIE. The radiative recombination of this BIE exhibits bright room-temperature PL at 600 nm and a decay time of 38.6 ns, 35 times greater than that of free excitons, originating from the spatial separation of photocarriers by half a unit cell separation distance. The BIE as a new form of interlayer exciton is expected to inspire new research directions for vacancy-ordered perovskites.

Doping PCBM with fullerene phosphinate derivatives enhances the interface energy alignment and synergistic passivation capability

Phenyl-C61-butyric acid methyl ester (PCBM) serves as a common electron transport layer (ETL) in inverted p-i-n structure perovskite solar cells (IPSCs), yet energy barriers and insufficient passivation at the PCBM-perovskite interface hinder device effectiveness and durability. In this study, we present a series of novel Fullerene Phenylacid Ester Derivatives (FPEDs: FPP, FTPP, FDPP) incorporated into PCBM. Our investigations illustrate that FPEDs effectively act to passivate the perovskite surface by forming robust interactions with uncoordinated Pb2+ ions via the phosphine oxide groups present in their molecular structures, thereby enhancing the stability of the devices. Moreover, these additives elevate the energy level of the lowest unoccupied molecular orbital (LUMO) of ETL, diminish the electron injection barrier, and enhance the efficiency of interlayer electron transport. Incorporating FPEDs enhances ETL coverage on the perovskite layer, reducing leakage current significantly. Notably, Devices with PCBM/FTPP achieved a peak PCE of 23.62% and showed superior stability, maintaining 96.8% of the initial PCE after 500 h, while control devices retained merely 80.7% over the same period.

Silicon‐Inspired Analysis of Interfacial Recombination in Perovskite Photovoltaics

AbstractPerovskite solar cells have reached an impressive certified efficiency of 26.1%, with a considerable fraction of the remaining losses attributed to carrier recombination at perovskite interfaces. This work demonstrates how time‐resolved photoluminescence spectroscopy (TRPL) can be utilized to locate and quantify remaining recombination losses in perovskite solar cells, analogous to methods established to improve silicon solar cell passivation and contact layers. It is shown how TRPL analysis can be extended to determine the bulk and surface lifetimes, surface recombination velocity, the recombination parameter, J0, and the implied open‐circuit voltage (iVoc) of any perovskite device configuration. This framework is used to compare 18 carrier‐selective and passivating contacts commonly used or emerging for perovskite photovoltaics. Furthermore, the iVoc values calculated from the TRPL‐based framework are directly compared to those calculated from photoluminescence quantum yields and the measured solar cell Voc. This simple technique serves as a practical guide for screening and selecting multifunctional, passivating perovskite contact layers. As with silicon solar cells, most of the material and interface analysis can be done without fabricating full devices or measuring efficiency. These purely optical measurements are even preferable when studying bulk and interfacial passivation approaches, since they remove complicating effects from poor carrier extraction.

Porphyrin-Based Hole-Transporting Materials for Perovskite Solar Cells: Boosting Performance with Smart Synthesis.

Perovskite solar cells (PSCs) are becoming a promising and revolutionary advancement within the photovoltaic field globally. Continuous improvement in efficiency, straightforward processing methods, and use of lightweight and cost-effective materials represent superior features, among other notable aspects. Still, long-term stability and durability are issues to address to facilitate widespread commercial adoption and practical application prospects. Research has focused on overcoming these challenges, and charge transport materials play a critical role in determining charge dynamics, photovoltaic performance, and device stability. Conventional hole-transporting materials (HTMs), spiro-OMeTAD and PTAA, contribute to remarkable power conversion efficiencies owing to high thin-film quality and matched energy alignment. However, they often show a high material cost, low carrier mobility, and poor stability, which greatly limit their practical applications. Now, this review outlines recent advances in synthetic approaches to porphyrin-based HTMs to tune the charge dynamics by optimizing their molecular structures and properties. The main structural features comprise porphyrins of A4-type, trans A2B2-type, and photosynthetic pigment analogues. Strategies include well-established routes to provide the required macrocycles, such as condensation of pyrrole or dipyrromethanes with suitable aldehydes, metalation of the porphyrin inner core, and postfunctionalization of peripheral positions. These functionalizations involve conventional procedures (e.g., halogenation, esterification, transesterification, nucleophilic oxidation, reduction, and nucleophilic substitution) as well as metal-catalyzed ones such as Suzuki-Miyaura, Sonogashira, Buchwald-Hartwig, and Ullmann cross-coupling reactions. As HTMs can also protect the perovskite layer from the external environment, porphyrin structures play a pivotal role in chemical, mechanical, and environmental stability, with their high hydrophobicity ability as the most significant parameter. The impact of porphyrins on the hole hopping of other HTMs while acting as an additive or an interlayer, passivating defects, and improving charge transport is also highlighted to provide real insights into ways to develop efficient and stable porphyrin-based materials for PSCs. This perspective aims to guide the scientific community in the design of new porphyrin molecules to place PSCs as an outperformer in photovoltaic technologies.

Optimized preparation of La3Mn2O7 with superior lattice oxygen mobility and adsorbed oxygen utilization for catalytic removal of toluene

The R-P type layered perovskite La3Mn2O7 (LLM) is considered a more promising toluene oxidation catalyst than perovskite LaMnO3 (LMO) due to the versatile environment it provides for oxygen atoms, yet the challenge of realizing an optimal synthesis route remains. Herein, we revealed how calcination temperature influenced the structure–activity relationship and the mechanism by which the layered structure enhanced oxygen species reactivity. LLM700 possesses optimal toluene adsorption performance, oxygen species activation capability and low-temperature reducibility, thus exhibiting the highest catalytic activity (T90 = 283 °C) among single layered perovskite catalysts. The large interlayer gaps in the layered structure, combined with the weaker Mn-O bond strength near the layered structure, facilitate the easy removal of oxygen atoms, creating oxygen vacancies that act as pathways for oxygen ions to migrate within the lattice. Together, these factors enable the layered structure to enhance the mobility of lattice oxygen and the utilization of adsorbed oxygen, making LLM an ideal model for catalyzing the oxidation of toluene. Furthermore, the possible reaction pathway for the oxidation of toluene on LLM700 was inferred using GC–MS. This work paves the way for the catalytic applications of layered perovskites.