Utilization of natural pigment extracted from pomegranate fruits as sensitizer in solid-state solar cells

The juice extracted from pomegranate fruits containing cyanin (flavylium) is utilized as the light-harvesting analog in a dye sensitized solid-state photovoltaic cell. Strong chelation of flavylium with TiO₂ changes it to quinonoidal form. A higher incident photon to current conversion efficiency is observed in solid-state TiO₂|pomegranate piment|CuI solar cell compare to that of the cells (TiO₂|dye|CuI type) sensitized with other natural pigments.     

Theoretical Treatment of CH3NH3PbI3 Perovskite Solar Cells

Hybrid halide perovskite solar cells (PSCs) giving over 22 % power conversion efficiencies (PCEs) have attracted considerable attention. Although perovskite plays a significant role in the operation of PSCs, the fundamental theories associated with perovskites have not been resolved in spite of the increase in research. In this Minireview, we assess the current understanding, based on the first‐principles calculations, of structural and electronic properties, defects, ionic diffusion, and shift current for CH₃NH₃PbI₃ perovskite, and the effect of ionic transport on the hysteresis of current–voltage curves in PSCs. The shift current connected to the possible presence of ferroelectricity is also discussed. The current state‐of‐the‐art and some open questions regarding PSCs are also highlighted, and the benefits, challenges, and potentials of perovskite for use in PSCs are stressed.     

All‐Inorganic CsPbX3 Perovskite Solar Cells: Progress and Prospects

Recently, lead halide‐based perovskites have become one of the hottest topics in photovoltaic research because of their excellent optoelectronic properties. Among them, organic‐inorganic hybrid perovskite solar cells (PSCs) have made very rapid progress with their power conversion efficiency (PCE) now at 23.7 %. However, the intrinsically unstable nature of these materials, particularly to moisture and heat, may be a problem for their long‐term stability. Replacing the fragile organic group with more robust inorganic Cs⁺ cations forms the cesium lead halide system (CsPbX₃, X is halide) as all‐inorganic perovskites which are much more thermally stable and often more stable to other factors. From the first report in 2015 to now, the PCE of CsPbX₃‐based PSCs has abruptly increased from 2.9 % to 17.1 % with much enhanced stability. In this Review, we summarize the field up to now, propose solutions in terms of development bottlenecks, and attempt to boost further research in CsPbX₃ PSCs.     

Inorganic Pb‐Free Perovskite Light Absorbers for Efficient Perovskite Solar Cells with Enhanced Performance

Recently, enormous efforts have been made to develop the efficient, lead (Pb) free and stable perovskite solar cells (PSCs). In this regards, various strategies were applied and the optoelectronic properties of various Pb free perovskites such as (CH₃NH₃)₃Sb₂I₉, (CH₃NH₃)₃Bi₂I₉, Cs₃Sb₂I₉, Cs₃Bi₂I₉, CH₃NH₃SnI₃ and CH₃NH₃GeI₃ etc have been investigated. However, the photovoltaic performance of the developed PSCs was still low and presence of organic moieties in common hole‐transport materials (HTMs) shows poor stability against moisture and heat. Herein, we have investigated the optoelectronic properties of all inorganic Pb free perovskites (Cs₃Sb₂I₉=1 and Cs₃Bi₂I₉=2) and employed novel strategies (dissolution‐recrystallization) to prepare the efficient Pb free PSCs. The band gaps of the 1 and 2 were found to be 2.2 eV and 2.0 eV, respectively. The developed PSCs with 1 and 2 exhibited the power conversion efficiency of 0.68% and 1.087%, respectively.     

Antioxidant Grain Passivation for Air‐Stable Tin‐Based Perovskite Solar Cells

Tin‐based perovskites with excellent optoelectronic properties and suitable band gaps are promising candidates for the preparation of efficient lead‐free perovskite solar cells (PSCs). However, it is challenging to prepare highly stable and efficient tin‐based PSCs because Sn²⁺ in perovskites can be easily oxidized to Sn⁴⁺ upon air exposure. Here we report the fabrication of air‐stable FASnI₃ solar cells by introducing hydroxybenzene sulfonic acid or its salt as an antioxidant additive into the perovskite precursor solution along with excess SnCl₂. The interaction between the sulfonate group and the Sn²⁺ ion enables the in situ encapsulation of the perovskite grains with a SnCl₂–additive complex layer, which results in greatly enhanced oxidation stability of the perovskite film. The corresponding PSCs are able to maintain 80 % of the efficiency over 500 h upon air exposure without encapsulation, which is over ten times longer than the best result reported previously. Our results suggest a possible strategy for the future design of efficient and stable tin‐based PSCs.     

Alkyl‐Chain‐Regulated Charge Transfer in Fluorescent Inorganic CsPbBr3 Perovskite Solar Cells

Improved charge extraction and wide spectral absorption promote power conversion efficiency of perovskite solar cells (PSCs). The state‐of‐the‐art carbon‐based CsPbBr₃ PSCs have an inferior power output capacity because of the large optical band gap of the perovskite film and the high energy barrier at perovskite/carbon interface. Herein, we use alkyl‐chain regulated quantum dots as hole‐conductors to reduce charge recombination. By precisely controlling alkyl‐chain length of ligands, a balance between the surface dipole induced charge coulomb repulsive force and quantum tunneling distance is achieved to maximize charge extraction. A fluorescent carbon electrode is used as a cathode to harvest the unabsorbed incident light and to emit fluorescent light at 516 nm for re‐absorption by the perovskite film. The optimized PSC free of encapsulation achieves a maximum power conversion efficiency up to 10.85 % with nearly unchanged photovoltaic performances under 80 %RH, 80 °C, or light irradiation in air.     

Directly assembled CdSe quantum dots on TiO2 in aqueous solution by adjusting pH value for quantum dot sensitized solar cells

We report an improved quantum dot sensitized solar cell (QDSSC) by loading mercaptopropionic acid (MPA)-capped CdSe QDs on TiO₂ film in aqueous solution. Under suitable pH value, a power conversion efficiency of 1.19% and an incident photon to current conversion efficiency of 26% for the QDSSC were obtained at AM1.5G irradiation. The improved performance of QDSSC is attributed to the large loading and good coverage of QDs on TiO₂ film with optimal pH value.     

Ambient Air Temperature Assisted Crystallization for Inorganic CsPbI2Br Perovskite Solar Cells

Inorganic cesium lead halide perovskites, as alternative light absorbers for organic–inorganic hybrid perovskite solar cells, have attracted more and more attention due to their superb thermal stability for photovoltaic applications. However, the humid air instability of CsPbI₂Br perovskite solar cells (PSCs) hinders their further development. The optoelectronic properties of CsPbI₂Br films are closely related to the quality of films, so preparing high-quality perovskite films is crucial for fabricating high-performance PSCs. For the first time, we demonstrate that the regulation of ambient temperature of the dry air in the glovebox is able to control the growth of CsPbI₂Br crystals and further optimize the morphology of CsPbI₂Br film. Through controlling the ambient air temperature assisted crystallization, high-quality CsPbI₂Br films are obtained, with advantages such as larger crystalline grains, negligible crystal boundaries, absence of pinholes, lower defect density, and faster carrier mobility. Accordingly, the PSCs based on as-prepared CsPbI₂Br film achieve a power conversion efficiency of 15.5% (the maximum stabilized power output of 15.02%). Moreover, the optimized CsPbI₂Br films show excellent robustness against moisture and oxygen and maintain the photovoltaic dark phase after 3 h aging in an air atmosphere at room temperature and 35% relative humidity (R.H.). In comparison, the pristine films are completely converted to the yellow phase in 1.5 h.     

Improving the performance of polymer solar cells by efficient optimizing the hole transport layer-graphene oxide

Graphene oxide (GO) materials have emerged as a promising alternative for hole transport layer (HTL) in polymer solar cells (PSCs) due to their unique structures and properties. However, insulating properties and eco-contaminative production of GO still need to be solved. Here, we report on the preparation of GO through an improved Hummers method without using NaNO₃, which is an eco-friendly option because it avoids the emissions of NO₂ and N₂O₄ toxic gases. Subsequently, the GO as HTL in PSCs is reduced by simple heat treatment of different temperatures in air, and the performance of devices is obviously improved. The FT-IR and XPS spectra show oxygenated functional groups in GO thin films are gradually removed with the increase of annealing temperature, which restores sp² hybridized graphitic structure, and makes the GO thin films more conducive to the charge transfer. The highest power conversion efficiency of PSCs based on the P3HT: PC₇₁BM system with GO as HTL is 3.39%, which approaches that of PSCs with PEDOT: PSS as HTL (3.41%). Moreover, the devices with annealed GO as HTL have better stability compared to devices with PEDOT: PSS.     

TiO2纳米棒和CdSe纳米棒复合膜与聚3-甲基噻吩杂化太阳能电池研究

采用水热法制备了TiO₂和CdSe两种纳米棒材料, 将两种纳米材料制备成TiO₂/CdSe复合纳米棒膜电极, 并在复合膜上电化学聚合生成聚3-甲基噻吩poly(3-methylthiophene) (PMeT), 研究了其光电化学性能. 实验表明, 当TiO₂与CdSe的物质的量复合比为2∶1, PMeT的聚合时间为40 s, 在电极电势为－0.2 V下ITO/TiO₂/CdSe/PMeT电极光电转换效率(IPCE)达到56%, 对比ITO/TiO₂/CdSe复合膜电极在长波方向的光电转换效率明显提高, 光吸收截止波长发生了明显的红移. 同时以ITO/TiO₂/CdSe/PMeT组装了简易的杂化太阳电池, 初步研究了光电池性能, 光电池总效率为0.08%, V_oc＝0.4 V, j_sc＝0.61 mA/cm², ff＝0.33.     

Recent studies on small molecular and polymeric hole-transporting materials for high-performance perovskite solar cells

A decade of significant research has led to the emergence of photovoltaic solar cells based on perovskites that have achieved an exceptionally high-power conversion efficiency of 26.08%. A key breakthrough in perovskite solar cells (PSCs) occurred when solid hole-transporting materials (HTMs) replaced liquid electrolytes in dye-sensitized solar cells (DSSCs), because HTMs play a crucial role in improving photovoltaic performance as well as cell stability. This review is mainly focused on the HTMs that are responsible for hole transport and extraction in PSCs, which is one of the crucial components for efficient devices. Here, we have reviewed small molecular as well as polymeric HTMs that have been reported in the last two years and discussed their performance based on the analysis of their molecular architectures. Finally, we include a perspective on the molecular engineering of new functional HTMs for highly efficient stable PSCs.     

Nucleation and Crystallization in 2D Ruddlesden-Popper Perovskites using Formamidinium-based Organic Semiconductor Spacers for Efficient Solar Cells

The conjugated organic semiconductor spacers have drawn wide attention in two-dimensional (2D) perovskites and formamidinium (FA) has been widely used as A-site cation in high-performance 3D perovskite solar cells (PSCs). However, the FA-based semiconductor spacers have rarely been investigated in 2D Ruddlesden-Popper (RP) perovskites. Here, we developed two FA-based spacers containing thieno[3,2-b]thiophene (TT) and 2,2′-bithiophene (BT) units, namely TTFA and BTFA, respectively, for 2D RP PSCs. The nucleation and crystallization kinetics of TTFA-Pb and BTFA-Pb from sol-gel to film were investigated using in situ optical microscopy and in situ grazing incidence wide-angle X-ray scattering (GIWAXS) measurements. It is found that the TTFA spacer could reduce the energy barrier of nucleation and induces crystal vertical orientation of 2D perovskite by forming larger clusters in precursor solution, resulting in much improved film quality. Benefiting from the enlarged crystal grains, reduced exciton binding energy, and decreased electron-phonon coupling coefficient, the photovoltaic device based on (TTFA)₂MA_n−1Pb_nI_3n+1 (n=5) achieved a champion efficiency of 19.41 %, which is a record for 2D RP PSCs with FA-based spacers. Our work provides deep understanding of the nucleation and crystallization process of 2D RP perovskite films and highlights the great potential of FA-based semiconductor spacers in highly efficient 2D PSCs.     

染料敏化太阳能电池中的敏化剂

染料敏化太阳能电池（DSSC）是一种新型的太阳能电池。染料敏化剂的性能对DSSC的光电转换效率有重要的影响,要获得高的光电转换效率需要有高效、稳定的染料敏化剂。本文介绍了近年来染料敏化剂的设计合成,并讨论了各种敏化剂的优缺点及发展方向。     

Self‐Assembly of Hybrid Oxidant POM@Cu‐BTC for Enhanced Efficiency and Long‐Term Stability of Perovskite Solar Cells

The controllable oxidation of spiro‐OMeTAD and improving the stability of hole‐transport materials (HTMs) layer are crucial for good performance and stability of perovskite solar cells (PSCs). Herein, we report an efficient hybrid polyoxometalate@metal–organic framework (POM@MOF) material, [Cu₂(BTC)_4/3(H₂O)₂]₆[H₃PMo₁₂O₄₀]₂ or POM@Cu‐BTC, for the oxidation of spiro‐OMeTAD with Li‐TFSI and TBP. When POM@Cu‐BTC is introduced to the HTM layer as a dopant, the PSCs achieve a superior fill factor of 0.80 and enhanced power conversion efficiency 21.44 %, as well as improved long‐term stability in an ambient atmosphere without encapsulation. The enhanced performance is attributed to the oxidation activity of POM anions and solid‐state nanoparticles. Therefore, this research presents a facile way by using hybrid porous materials to accelerate oxidation of spiro‐OMeTAD, further improving the efficiency and stability of PSCs.     

Emerging of Inorganic Hole Transporting Materials For Perovskite Solar Cells

Hole transporting material (HTM) is a significant component to achieve the high performance perovskite solar cells (PSCs). Over the years, inorganic, organic and hybrid (organic‐inorganic) material based HTMs have been developed and investigated successfully. Today, perovskite solar cells achieved the efficiency of 22.1 % with with 2,2’,7,7’‐tetrakis(N,N‐di‐p‐methoxyphenyl‐amine) 9,9‐spirobifluorene (spiro‐OMeTAD) as HTM. Nevertheless, synthesis and cost of organic HTMs is a major challenging issue and therefore alternative materials are required. From the past few years, inorganic HTMs showed large improvement in power conversion efficiency (PCE) and stability. Recently CuO_x reached the PCE of 19.0% with better stability. These developments affirms that inorganic HTMs are better alternativesto the organic HTMs for next generation PSCs. In this report, we mainly focussed on the recent advances of inorganic and hybrid HTMs for PSCs and highlighted the efficiency and stability of PSCs improved by changing metal oxides as HTMs. Consequently, we expect that energy levels of these inorganic HTMs matches very well with the valence band of perovskites and improved efficiency helps in future practical deployment of low cost PSCs.     

Effect of hole-transporting materials on the photovoltaic performance and stability of all-ambient-processed perovskite solar cells

High-efficiency perovskite solar cells(PSCs) reported hitherto have been mostly prepared in a moisture and oxygen-free glove-box atmosphere, which hampers upscaling and real-time performance assessment of this exciting photovoltaic technology. In this work, we have systematically studied the feasibility of allambient-processing of PSCs and evaluated their photovoltaic performance. It has been shown that phasepure crystalline tetragonal MAPbI_3 perovskite films are instantly formed in ambient air at room temperature by a two-step spin coating process, undermining the need for dry atmosphere and post-annealing.All-ambient-processed PSCs with a configuration of FTO/TiO_2/MAPbI_3/Spiro-OMeTAD/Au achieve opencircuit voltage(990 mV) and short-circuit current density(20.31 mA/cm~2) comparable to those of best reported glove-box processed devices. Nevertheless, device power conversion efficiency is still constrained at 5% by the unusually low fill-factor of 0.25. Dark current–voltage characteristics reveal poor conductivity of hole-transporting layer caused by lack of oxidized spiro-OMe TAD species, resulting in high seriesresistance and decreased fill-factor. The study also establishes that the above limitations can be readily overcome by employing an inorganic p-type semiconductor, copper thiocyanate, as ambient-processable hole-transporting layer to yield a fill-factor of 0.54 and a power conversion efficiency of 7.19%. The present findings can have important implications in industrially viable fabrication of large-area PSCs.     

3,4‐Phenylenedioxythiophene (PheDOT) Based Hole‐Transporting Materials for Perovskite Solar Cells

Two new electron‐rich molecules based on 3,4‐phenylenedioxythiophene (PheDOT) were synthesized and successfully adopted as hole‐transporting materials (HTMs) in perovskite solar cells (PSCs). X‐ray diffraction, absorption spectra, photoluminescence spectra, electrochemical properties, thermal stabilities, hole mobilities, conductivities, and photovoltaic parameters of PSCs based on these two HTMs were compared with each other. By introducing methoxy substituents into the main skeleton, the energy levels of PheDOT‐core HTM were tuned to match with the perovskite, and its hole mobility was also improved (1.33×10^?4 cm² V^?1 s^?1, being higher than that of spiro‐OMeTAD, 2.34×10^?5 cm² V^?1 s^?1). The PSC based on MeO‐PheDOT as HTM exhibits a short‐circuit current density (J_sc) of 18.31 mA cm^?2, an open‐circuit potential (V_oc) of 0.914 V, and a fill factor (FF) of 0.636, yielding an encouraging power conversion efficiency (PCE) of 10.64 % under AM 1.5G illumination. These results give some insight into how the molecular structures of HTMs affect their performances and pave the way for developing high‐efficiency and low‐cost HTMs for PSCs.     

Reducing Agents for Improving the Stability of Sn‐based Perovskite Solar Cells

Organic‐inorganic hybrid perovskite solar cells (PSCs) have aroused tremendous research interest for their high efficiency, low cost and solution processability. However, the involvement of toxic lead in state‐of‐art perovskites hinders their market prospects. As an alternative, Sn‐based perovskites exhibit similar semiconductor characteristics and can potentially achieve comparable photovoltaic performance in comparison with their lead‐based counterparts. The main challenge of developing Sn‐based PCSs lies in the intrinsic poor stability of Sn²⁺, which could be oxidized and converted to Sn⁴⁺. Notably, introduction of SnX₂ (X=Cl, Br, I) additive becomes indispensable in the fabrication process, which highlights the importance of incorporating a reducing agent to improve the device stability. Additionally, efforts are made to utilize other reducing agents with different functions for the further enhancement of device performance. Currently, Sn‐based PSCs could attain a record efficiency over 10% with great stability. In this review, we present the recent progress on reducing agents for improving the stability of Sn‐based PSCs, and we hope to shed light on the challenges and opportunities of this research field.     

Large area,waterproof, air stable and cost effective efficient perovskite solar cells through modified carbon hole extraction layer

The conventional unstable and expensive hole transporting materials (HTM) has been replaced by cost effective modified carbon hole extraction layer. Herein, we demonstrated a new recipe toward air stable and waterproof modified carbon hole extraction layer for efficient perovskite solar cells (PSCs). The commercial available carbon ink modified with methylammonium lead iodide (MAI) has been used as hole extraction layer for ambipolar perovskite solar cells. The fabricated optimized perovskite solar cell having Glass/FTO/mp-TiO₂/MAPbI_3-xCl_x/carbon + MAI/Carbon configuration exhibited η = 13.87% power conversion efficiency (PCE) with open circuit voltage (V_OC) 0.997 V, current density (J_SC) = 21.41 mAcm^?2 and fill factor (FF) 0.65. Furthermore, the air stability were tested at room temperature in open atmosphere. The water proof stability was tested under water flushing. Our results revealed that, although our carbon based devices show lower PCE (η = 13.87%) compared to spiro-MeOTAD HTM (η = 15%), the fabricated PSCs could even retain >90% after water exposure >20 times and ambient air stability more than 160 days. Further the large area device (>1 cm²) device shows 13.04% PCE with Jsc = 21.47 mAcm^?2, V_OC = 0.996 V and FF = 0.61. We have also demonstrated >13% efficiency for large area device (>1.1 cm²), demonstrating that the developed method is simple, cost effective and promising towards large area device fabrication. The developed methodology based on low cost carbon hole extraction layer will be helpful towards waterproof and air stable perovskite solar cells for large-area devices.     

Enhanced Charge Transport by Incorporating Formamidinium and Cesium Cations into Two‐Dimensional Perovskite Solar Cells

Organic‐inorganic hybrid two‐dimensional (2D) perovskites (n≤5) have recently attracted significant attention because of their promising stability and optoelectronic properties. Normally, 2D perovskites contain a monocation [e.g., methylammonium (MA⁺) or formamidinium (FA⁺)]. Reported here for the first time is the fabrication of 2D perovskites (n=5) with mixed cations of MA⁺, FA⁺, and cesium (Cs⁺). The use of these triple cations leads to the formation of a smooth, compact surface morphology with larger grain size and fewer grain boundaries compared to the conventional MA‐based counterpart. The resulting perovskite also exhibits longer carrier lifetime and higher conductivity in triple cation 2D perovskite solar cells (PSCs). The power conversion efficiency (PCE) of 2D PSCs with triple cations was enhanced by more than 80 % (from 7.80 to 14.23 %) compared to PSCs fabricated with a monocation. The PCE is also higher than that of PSCs based on binary cation (MA⁺‐FA⁺ or MA⁺‐Cs⁺) 2D structures.