A Modified Sequential Deposition Route for High-Performance Carbon-Based Perovskite Solar Cells under Atmosphere Condition

Carbon-based hole transport material (HTM)-free perovskite solar cells have exhibited a promising commercialization prospect, attributed to their outstanding stability and low manufacturing cost. However, the serious charge recombination at the interface of the carbon counter electrode and titanium dioxide (TiO₂) suppresses the improvement in the carbon-based perovskite solar cells’ performance. Here, we propose a modified sequential deposition process in air, which introduces a mixed solvent to improve the morphology of lead iodide (PbI₂) film. Combined with ethanol treatment, the preferred crystallization orientation of the PbI₂ film is generated. This new deposition strategy can prepare a thick and compact methylammonium lead halide (MAPbI₃) film under high-humidity conditions, which acts as a natural active layer that separates the carbon counter electrode and TiO₂. Meanwhile, the modified sequential deposition method provides a simple way to facilitate the conversion of the ultrathick PbI₂ capping layer to MAPbI₃, as the light absorption layer. By adjusting the thickness of the MAPbI₃ capping layer, we achieved a power conversation efficiency (PCE) of 12.5% for the carbon-based perovskite solar cells.     

A Fast Deposition‐Crystallization Procedure for Highly Efficient Lead Iodide Perovskite Thin‐Film Solar Cells

Thin‐film photovoltaics based on alkylammonium lead iodide perovskite light absorbers have recently emerged as a promising low‐cost solar energy harvesting technology. To date, the perovskite layer in these efficient solar cells has generally been fabricated by either vapor deposition or a two‐step sequential deposition process. We report that flat, uniform thin films of this material can be deposited by a one‐step, solvent‐induced, fast crystallization method involving spin‐coating of a DMF solution of CH₃NH₃PbI₃ followed immediately by exposure to chlorobenzene to induce crystallization. Analysis of the devices and films revealed that the perovskite films consist of large crystalline grains with sizes up to microns. Planar heterojunction solar cells constructed with these solution‐processed thin films yielded an average power conversion efficiency of 13.9±0.7 % and a steady state efficiency of 13 % under standard AM 1.5 conditions.     

Limiting Perovskite Solar Cell Performance by Heterogeneous Carrier Extraction

Although the power conversion efficiency of perovskite solar cells has improved rapidly, a rational path for further improvement remains unclear. The effect of large morphological heterogeneity of polycrystalline perovskite films on their device performance by photoluminescence (PL) microscopy has now been studied. Contrary to the common belief on the deleterious effect of morphological heterogeneity on carrier lifetimes and diffusivities, in neat CH₃NH₃PbI₃(Cl) polycrystalline perovskite films, the local (intra‐grain) carrier diffusivities in different grains are all surprisingly high (1.5 to 3.3 cm² s^?1; comparable to bulk single‐crystals), and the local carrier lifetimes are long (ca. 200 ns) and surprisingly homogenous among grains, and uniform across grain boundary and interior. However, there is a large heterogeneity of carrier extraction efficiency at the perovskite grain–electrode interface. Improving homogeneity at perovskite grain–electrode contacts is thus a promising direction for improving the performance of perovskite thin‐film solar cells.     

Monodisperse Adducts-Induced Homogeneous Nucleation Towards High-Quality Tin-Based Perovskite Film

The classic solvent system can't sufficiently separate one-dimensional edge-sharing SnI₂ crystals in solution, which severely restricts the fabrication of high-quality tin-based perovskite film. Herein, a strong Lewis base (hexamethylphosphoramide, HMPA) has been introduced to coordinate Sn²⁺ to modulate solvation behaviours on perovskite precursor and regulate crystallization kinetics. The large molecular volume of HMPA and stronger bind energy of SnI₂ ⋅ 2HMPA (−0.595 eV vs −0.118 eV for SnI₂ ⋅ 2DMSO) change the solvation structure of SnI₂ from edge-sharing cluster to monodisperse adduct, which contributes to uniform nucleation sites and prolongs crystal growth process. Delightfully, a fully-covered perovskite film is formed on the large-area substrate and tin-based perovskite solar cells processed with HMPA exhibit an excellent efficiency of 13.46 %. This research provides novel insights and directions for the solution preparation of smooth and uniform large-area tin-based perovskite film.     

Anti-Solvent-Free Preparation for Efficient and Photostable Pure-Iodide Wide-Bandgap Perovskite Solar Cells

The perovskite/silicon tandem solar cell (TSC) has attracted tremendous attention due to its potential to breakthrough the theoretical efficiency set for single-junction solar cells. However, the perovskite solar cell (PSC) designed as its top component cell suffers from severe photo-induced halide segregation owing to its mixed-halide strategy for achieving desirable wide-bandgap (1.68 eV). Developing pure-iodide wide-bandgap perovskites is a promising route to fabricate photostable perovskite/silicon TSCs. Here, we report efficient and photostable pure-iodide wide-bandgap PSCs made from an anti-solvent-free (ASF) technique. The ASF process is achieved by mixing two precursor solutions, both of which are capable of depositing corresponding perovskite films without involving anti-solvent. The mixed solution finally forms Cs_0.3DMA_0.2MA_0.5PbI₃ perovskite film with a bandgap of 1.68 eV. Furthermore, methylammonium chloride additive is applied to enhance the crystallinity and reduce the trap density of perovskite films. As a result, the pure-iodide wide-bandgap PSC delivers efficiency as high as 21.30 % with excellent photostability, the highest for this type of solar cells. The ASF method significantly improves the device reproducibility as compared with devices made from other anti-solvent methods. Our findings provide a novel recipe to prepare efficient and photostable wide-bandgap PSCs.     

A Self-Formed Stable PbI2/NiOx Interface with Increased Ni3+ Centers for Perovskite Photovoltaics

Nickel oxide (NiO_x) is a promising hole transport material (HTM) for perovskite photovoltaics owing to its chemical stability and low cost. However, most NiO_x based solar cells deliver relatively weak performance because of its insufficient electrical property and interfacial contact. In this work, a self-formed PbI₂/NiO_x interface was developed to stabilize the Ni³⁺ centers, which was beneficial for electrical transport and band alignment in perovskite solar cells. Combined with ultraviolet ozone treatment ( UVO ) and sequential deposition, the density of Ni³⁺ centers was greatly increased and could be stabilized by the PbI₂ interface. These merits contributed coordinately to the fast hole extraction and low energy loss across the PbI₂/NiO_x interface, yielding power conversion efficiencies (PCEs) of over 19 %.     

Volatile Dual-Solvent Assisted Intermediate Phase Regulation for Anti-Solvent-Free Perovskite Photovoltaics

The unprecedented development of perovskite solar cells (PSCs) makes them one of the most promising candidates for terawatt-scale green energy production with low cost. However, the high boiling point solvents during the solution-processed film deposition cause anisotropic crystal growth and toxic solvent vapor during high-throughput manufacturing. Here, a dual-component green solvent consisting of isopropyl acetate and acetonitrile is proposed to form a volatile perovskite precursor, which can realize the high-quality perovskite thin film deposition by intermediate phase regulation. A room-temperature stable perovskite intermediate phase is constructed with the engagement of isopropyl acetate as co-solvent, which suppresses the exploding nucleation rate in volatile perovskite precursor, providing a fine grain growth rate and wide processing window in scalable film deposition. The corresponding PSCs fabricated by blade coating without anti-solvents or gas quenching achieve power conversion efficiency (PCE) of 16.37 % and 15.29 % for the areas of 14.08 cm² and 37.83 cm², respectively.     

Managing Excess Lead Iodide with Functionalized Oxo-Graphene Nanosheets for Stable Perovskite Solar Cells

Stability issues could prevent lead halide perovskite solar cells (PSCs) from commercialization despite it having a comparable power conversion efficiency (PCE) to silicon solar cells. Overcoming drawbacks affecting their long-term stability is gaining incremental importance. Excess lead iodide (PbI₂) causes perovskite degradation, although it aids in crystal growth and defect passivation. Herein, we synthesized functionalized oxo-graphene nanosheets (Dec-oxoG NSs) to effectively manage the excess PbI₂. Dec-oxoG NSs provide anchoring sites to bind the excess PbI₂ and passivate perovskite grain boundaries, thereby reducing charge recombination loss and significantly boosting the extraction of free electrons. The inclusion of Dec-oxoG NSs leads to a PCE of 23.7 % in inverted (p-i-n) PSCs. The devices retain 93.8 % of their initial efficiency after 1,000 hours of tracking at maximum power points under continuous one-sun illumination and exhibit high stability under thermal and ambient conditions.     

Graphdiyne: Bridging SnO2 and Perovskite in Planar Solar Cells

The matching of charge transport layer and photoactive layer is critical in solar energy conversion devices, especially for planar perovskite solar cells based on the SnO₂ electron‐transfer layer (ETL) owing to its unmatched photogenerated electron and hole extraction rates. Graphdiyne (GDY) with multi‐roles has been incorporated to maximize the matching between SnO₂ and perovskite regarding electron extraction rate optimization and interface engineering towards both perovskite crystallization process and subsequent photovoltaic service duration. The GDY doped SnO₂ layer has fourfold improved electron mobility due to freshly formed C?O σ bond and more facilitated band alignment. The enhanced hydrophobicity inhibits heterogeneous perovskite nucleation, contributing to a high‐quality film with diminished grain boundaries and lower defect density. Also, the interfacial passivation of Pb?I anti‐site defects has been demonstrated via GDY introduction.     

多功能氨基酸衍生物钝化的高性能钙钛矿太阳能电池

采用含有羧基、氨基和苯基等多官能团的氨基酸衍生物分子(Fmoc-L-异亮氨酸,Fmoc-Ile-OH)钝化钙钛矿薄膜表面缺陷。首先,该氨基酸衍生物可降低钙钛矿薄膜中PbI₂杂质含量,并提高钙钛矿薄膜的颗粒尺寸。其次,氨基酸衍生物的引入可有效改善钙钛矿薄膜的光学特性和钙钛矿/电荷传输层界面载流子输运性能。另外,经钝化处理的钙钛矿太阳能电池表现出更优的器件二极管理想因子、更低的陷阱填充极限电压和更高的载流子复合电阻,这些结果证实了Fmoc-Ile-OH可有效钝化钙钛矿薄膜表面缺陷。最后,通过工艺条件优化,制得了转化效率为21.09%的高效钙钛矿太阳能电池器件,其性能远优于对照组器件的效率(18.00%)。     

Managing Secondary Phase Lead Iodide in Hybrid Perovskites via Surface Reconstruction for High-Performance Perovskite Solar Cells with Robust Environmental Stability

Rationally managing the secondary-phase excess lead iodide (PbI₂) in hybrid perovskite is of significance for pursuing high performance perovskite solar cells (PSCs), while the challenge remains on its conversion to a homogeneous layer that is robust stable against environmental stimuli. We herein demonstrate an effective strategy of surface reconstruction that converts the excess PbI₂ into a gradient lead sulfate-silica bi-layer, which substantially stabilizes the perovskite film and reduces interfacial charge transfer barrier in the PSCs device. The perovskite films with such bi-layer could bear harsh conditions such as soaking in water, light illumination at 70 % relative humidity, and the damp-thermal (85 °C and 30 % humidity) environment. The resulted PSCs deliver a champion efficiency up to 24.09 %, as well as remarkable environmental stability, e.g., retaining 78 % of their initial efficiency after 5500 h of shelf storage, and 82 % after 1000 h of operational stability testing.     

Bulk heterojunction perovskite solar cells incorporated with solution-processed TiOx nanoparticles as the electron acceptors

In the past ten years, perovskite solar cells were rapidly developed, but the intrinsic unbalanced charge carrier diffusion lengths within perovskite materials were not fully addressed by either a planar heterojunction or meso-superstructured perovskite solar cells. In this study, we report bulk heterojunction perovskite solar cells, where perovskite materials CH₃NH₃PbI₃ is blended with solution-processed n-type TiO_x nanoparticles as the photoactive layer. Studies indicate that one-step solution-processed CH₃NH₃PbI₃:TiO_x bulk-heterojunction thin film possesses enhanced and balanced charge carrier mobilities, superior film morphology with enlarged crystal sizes, and suppressed trap-induced charge recombination. Thus, bulk heterojunction perovskite solar cells by CH₃NH₃PbI₃ mixed with 5 wt% of TiO_x, which is processed by one-step method rather than typical two-step method, show a short-circuit current density of 20.93 mA/cm², an open-circuit voltage of 0.90 V, a fill factor of 80% and with a corresponding power conversion efficiency of 14.91%, which is more than 30% enhancement as compared with that of perovskite solar cells with a planar heterojunction device structure. Moreover, bulk heterojunction perovskite solar cells possess enhanced device stability. All these results demonstrate that perovskite solar cells with a bulk heterojunction device structure are one of apparent approaches to boost device performance.     

Monodisperse Dual‐Functional Upconversion Nanoparticles Enabled Near‐Infrared Organolead Halide Perovskite Solar Cells

Extending the spectral absorption of organolead halide perovskite solar cells from visible into near‐infrared (NIR) range renders the minimization of non‐absorption loss of solar photons with improved energy alignment. Herein, we report on, for the first time, a viable strategy of capitalizing on judiciously synthesized monodisperse NaYF₄:Yb/Er upconversion nanoparticles (UCNPs) as the mesoporous electrode for CH₃NH₃PbI₃ perovskite solar cells and more importantly confer perovskite solar cells to be operative under NIR light. Uniform NaYF₄:Yb/Er UCNPs are first crafted by employing rationally designed double hydrophilic star‐like poly(acrylic acid)‐block‐poly(ethylene oxide) (PAA‐b‐PEO) diblock copolymer as nanoreactor, imparting the solubility of UCNPs and the tunability of film porosity during the manufacturing process. The subsequent incorporation of NaYF₄:Yb/Er UCNPs as the mesoporous electrode led to a high efficiency of 17.8 %, which was further increased to 18.1 % upon NIR irradiation. The in situ integration of upconversion materials as functional components of perovskite solar cells offers the expanded flexibility for engineering the device architecture and broadening the solar spectral use.     

First-Principles Study of Aziridinium Lead Iodide Perovskite for Photovoltaics

The long-term stability remains one of the main challenges for the commercialization of the rapidly developing hybrid organic-inorganic perovskite solar cells. Herein, we investigate the electronic and optical properties of the recently reported hybrid halide perovskite (CH₂)₂NH₂PbI₃ (AZPbI₃), which exhibits a much better stability than the popular halide perovskites CH₃NH₃PbI₃ and HC(NH₂)₂PbI₃, by using density functional theory (DFT). We find that AZPbI₃ possesses a band gap of 1.31 eV, ideal for single-junction solar cells, and its optical absorption is comparable with those of the popular CH₃NH₃PbI₃ and HC(NH₂)₂PbI₃ materials in the whole visible-light region. In addition, the conductivity of AZPbI₃ can be tuned from efficient p-type to n-type, depending on the growth conditions. Besides, the charge-carrier mobilities and lifetimes are unlikely hampered by deep transition energy levels, which have higher formation energies in AZPbI₃ according to our calculations. Overall, we suggest that the perovskite AZPbI₃ is an excellent candidate as a stable high-performance photovoltaic absorber material.     

Improved photovoltaic performance from high quality perovskite thin film grown with the assistance of PC<Subscript>71</Subscript>BM

The strategy of sequentially spin-coating a perovskite film from the perovskite precursor and an electron transporting layer of [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM) is developed to simplify the fabrication procedure of perovskite solar cells. X-ray diffraction and scanning electron microscopy indicate that PC₇₁BM film on perovskite layer can retard the evaporation of dimethyl sulfoxide (DMSO) efficiently, thus prolonging the transformation of intermediate phase to perovskite crystals, leading to a high quality perovskite thin film. The solar cells with the structure of indium tin oxides (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/CH₃NH₃PbI₃/PC₇₁BM/bathocuproine (BCP)/Ag made from this simplified method exhibit a higher efficiency (12.68%) than those from the conventional one-step method (9.49%).     

Moisture Stability of Perovskite Solar Cells Processed in Supercritical Carbon Dioxide

Performance degradation under environmental conditions currently limits the practical utility of perovskite-based solar cells. The moisture stability of CH₃NH₃PbI₃ perovskite films and solar cells was measured during exposure to three different levels of relative humidity. The films were crystallized at two different temperatures with and without simultaneous exposure to supercritical carbon dioxide. The film crystallinity, optical absorption, and device photoconversion efficiency was measured over time for three relative humidity levels and both crystallization methods. It was determined that film crystallization in supercritical CO₂ resulted in significant improvement in moisture stability for films processed at 50 °C, but negligible improvement in stability for films processed at 100 °C.     

A Purified,Solvent‐Intercalated Precursor Complex for Wide‐Process‐Window Fabrication of Efficient Perovskite Solar Cells and Modules

A high‐purity methylammonium lead iodide complex with intercalated dimethylformamide (DMF) molecules, CH₃NH₃PbI₃?DMF, is introduced as an effective precursor material for fabricating high‐quality solution‐processed perovskite layers. Spin‐coated films of the solvent‐intercalated complex dissolved in pure dimethyl sulfoxide (DMSO) yielded thick, dense perovskite layers after thermal annealing. The low volatility of the pure DMSO solvent extended the allowable time for low‐speed spin programs and considerably relaxed the precision needed for the antisolvent addition step. An optimized, reliable fabrication method was devised to take advantage of this extended process window and resulted in highly consistent performance of perovskite solar cell devices, with up to 19.8 % power‐conversion efficiency (PCE). The optimized method was also used to fabricate a 22.0 cm², eight‐cell module with 14.2 % PCE (active area) and 8.64 V output (1.08 V/cell).     

A Purified,Solvent‐Intercalated Precursor Complex for Wide‐Process‐Window Fabrication of Efficient Perovskite Solar Cells and Modules

A high‐purity methylammonium lead iodide complex with intercalated dimethylformamide (DMF) molecules, CH₃NH₃PbI₃?DMF, is introduced as an effective precursor material for fabricating high‐quality solution‐processed perovskite layers. Spin‐coated films of the solvent‐intercalated complex dissolved in pure dimethyl sulfoxide (DMSO) yielded thick, dense perovskite layers after thermal annealing. The low volatility of the pure DMSO solvent extended the allowable time for low‐speed spin programs and considerably relaxed the precision needed for the antisolvent addition step. An optimized, reliable fabrication method was devised to take advantage of this extended process window and resulted in highly consistent performance of perovskite solar cell devices, with up to 19.8 % power‐conversion efficiency (PCE). The optimized method was also used to fabricate a 22.0 cm², eight‐cell module with 14.2 % PCE (active area) and 8.64 V output (1.08 V/cell).     

Ion‐Exchange‐Induced 2D–3D Conversion of HMA1−xFAxPbI3Cl Perovskite into a High‐Quality MA1−xFAxPbI3 Perovskite

High‐quality phase‐pure MA_1?xFA_xPbI₃ planar films (MA=methylammonium, FA=formamidinium) with extended absorption and enhanced thermal stability are difficult to deposit by regular simple solution chemistry approaches owing to crystallization competition between the easy‐to‐crystallize but unwanted δ‐FAPbI₃/MAPbI₃ and FA_xMA_1?xPbI₃ requiring rigid crystallization conditions. Here A 2D–3D conversion to transform compact 2D mixed composition HMA_1?xFA_xPbI₃Cl perovskite precursor films into 3D MA_1?xFA_xPbI₃ (x=0.1–0.9) perovskites is presented. The designed Cl/I and H/FA(MA) ion exchange reaction induced fast transformation of compact 2D perovskite film, helping to form the phase‐pure and high quality MA_1?xFA_xPbI₃ without δ‐FAPbI₃ and MAPbI₃ impurity. In all, we successfully developed a facile one‐step method to fabricate high quality phase‐pure MA_1?xFA_xPbI₃ (x=0.1–0.9) perovskite films by 2D–3D conversion of HMA_1?xFA_xPbI₃Cl perovskite. This 2D–3D conversion is a promising strategy for lead halide perovskite fabrication.     

Pseudohalide‐Induced Moisture Tolerance in Perovskite CH3NH3Pb(SCN)2I Thin Films

Two pseudohalide thiocyanate ions (SCN^?) have been used to replace two iodides in CH₃NH₃PbI₃, and the resulting perovskite material was used as the active material in solar cells. In accelerated stability tests, the CH₃NH₃Pb(SCN)₂I perovskite films were shown to be superior to the conventional CH₃NH₃PbI₃ films as no significant degradation was observed after the film had been exposed to air with a relative humidity of 95 % for over four hours, whereas CH₃NH₃PbI₃ films degraded in less than 1.5 hours. Solar cells based on CH₃NH₃Pb(SCN)₂I thin films exhibited an efficiency of 8.3 %, which is comparable to that of CH₃NH₃PbI₃ based cells fabricated in the same way.