Enhanced Charge Transfer in Quasi-2D Perovskite by Formamidinium Cation Gradient Incorporation for Efficient and Stable Solar Cells.

Quasi-2D perovskites have attracted much attention in perovskite photovoltaics due to their excellent stability. However, their photoelectric conversion efficiency (PCE) still lags 3D counterparts, particularly with high short-circuit current (JSC) loss. The quantum confinement effect is pointed out to be the sole reason, which introduces widened bandgap and poor exciton dissociation, and undermines the light capture and charge transport. Here, the gradient incorporation of formamidinium (FA) cations into quasi-2D perovskite is proposed to address this issue. It is observed that FA prefers to incorporate into the larger n value phases near the film surface compared to the smaller n value phases in the bulk, resulting in a narrow bandgap and gradient structure within the film. Through charge dynamic analysis using in situ light-dark Kelvin probe force microscopy and transient absorption spectroscopy, it is demonstrated that incorporating 10% FA significantly facilitates efficient charge transfer between low n-value phases in the bulk and high n-value nearby film surface, leading to reduced charge accumulation. Ultimately, the device based on (AA)2(MA0.9FA0.1)4Pb5I16, where AA represents n-amylamine renowned for its exceptional environmental stability as a bulky organic ligand, achieves an impressive power conversion efficiency (PCE) of 18.58% and demonstrates enhanced illumination and thermal stability.

Passivation of Sodium Benzenesulfonate at the Buried Interface of a High-Performance Wide-Bandgap Perovskite Solar Cell.

The phase segregation of wide-bandgap perovskite is detrimental to a device's performance. We find that Sodium Benzenesulfonate (SBS) can improve the interface passivation of PTAA, thus addressing the poor wettability issue of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine](PTAA). This improvement helps mitigate interface defects caused by poor contact between the perovskite and PTAA, reducing non-radiative recombination. Additionally, enhanced interface contact improves the crystallinity of the perovskite, leading to higher-quality perovskite films. By synergistically controlling the crystallization and trap passivation to reduce the phase segregation, SBS-modified perovskite solar cells (PSCs) achieved a power conversion efficiency (PCE) of 20.27%, with an open-circuit voltage (Voc) of 1.18 V, short-circuit current density (Jsc) of 20.93 mA cm-2, and fill factor (FF) of 82.31%.

A N-Ethylcarbazole-Terminated Spiro-Type Hole-Transporting Material for Efficient and Stable Perovskite Solar Cells.

The development of stable and efficient hole-transporting materials (HTMs) is critical for the commercialization of perovskite solar cells (PSCs). Herein, a novel spiro-type HTM was designed and synthesized where N-ethylcarbazole-terminated groups fully substituted the methoxy group of spiro-OMeTAD, named spiro-carbazole. The developed molecule exhibited a lower highest occupied molecular orbital level, higher hole mobility, and extremely high glass transition temperature (Tg =196 °C) compared with spiro-OMeTAD. PSCs with the developed molecule exhibited a champion power conversion efficiency (PCE) of 22.01 %, which surpassed traditional spiro-OMeTAD (21.12 %). Importantly, the spiro-carbazole-based device had dramatically better thermal, humid, and long-term stability than spiro-OMeTAD.

The Main Progress of Perovskite Solar Cells in 2020-2021.

Perovskite solar cells (PSCs) emerging as a promising photovoltaic technology with high efficiency and low manufacturing cost have attracted the attention from all over the world. Both the efficiency and stability of PSCs have increased steadily in recent years, and the research on reducing lead leakage and developing eco-friendly lead-free perovskites pushes forward the commercialization of PSCs step by step. This review summarizes the main progress of PSCs in 2020 and 2021 from the aspects of efficiency, stability, perovskite-based tandem devices, and lead-free PSCs. Moreover, a brief discussion on the development of PSC modules and its challenges toward practical application is provided.

Tetraphenylethylene-Arylamine Derivatives as Hole Transporting Materials for Perovskite Solar Cells.

A series of hole transporting materials (HTMs) with fused tetraphenylethylene cores (9,9'-bifluorenylidene and dibenzo[g,p]chrysene) as well as different substitution positions of arylamine side arms has been designed and synthesized. A reference HTM with a non-fused tetraphenylethylene core is also prepared for a comparative study. It is noted that fused tetraphenylethylene molecules show a bathochromic spectral shift, electronegative character, and lower reorganization energies than the non-fused ones. Furthermore, the molecules with side arms located on the meta-position on the tetraphenylethylene core in terms of a double bond exhibit a deeper highest occupied molecular orbital level than those of the para-position-based ones whether tetraphenylethylene is fused or not. Moreover, the reorganization energies of fused meta-position-based HTMs are lower than those of para-position-based HTMs. Fused tetraphenylethylene HTMs own a better hole-extraction capability than the non-fused ones. When used in perovskite solar cells, all devices with fused tetraphenylethylene HTMs display better performance than those of the non-fused ones. The HTMs based on dibenzo[g,p]chrysene exhibit better performance than those of bifluorenylidene. Moreover, the devices with HTMs with side arms located on the meta-position on the tetraphenylethylene core display higher power conversion efficiency than those of the para-position-based ones. The results give some new insight and reference to develop ideal HTMs for perovskite solar cells.

Introducing ammonium salt into hole transporting materials for perovskite solar cells.

The developed ammonium salt-containing hole transporting material could passivate perovskite defects and transport holes, and exhibits better performance compared with the non-ammonium salt counterpart.

Dimension-Controlled Growth of Antimony-Based Perovskite-like Halides for Lead-Free and Semitransparent Photovoltaics.

Antimony (Sb) has been identified as a promising candidate for replacing toxic lead (Pb) in perovskite materials because Sb-based perovskite-like halides exhibit not only intrinsic thermodynamic stability but also a unique set of intriguing optoelectronic characteristics. However, Sb-based perovskite-like halides still suffer from poor film morphology and uncontrollable halide constituents, which result from the disorder of the growth process. Herein, we propose a simple strategy to facilitate heterogeneous nucleation and control the dimension transformation by introducing bis(trifluoromethane)sulfonimide lithium (LiTFSI), which produces high-quality two-dimensional MA3Sb2I9-xClx films. As the spacer molecule among Sb-based pyramidal clusters, LiTFSI plays a role in forming a zero-dimensional intermediate phase and retarding crystallization. The slower dimension transformation well stabilizes the band gap of perovskite-like films with a fixed Cl/I ratio (∼7:2) and avoids random "x" values in MA3Sb2I9-xClx films prepared from the conventional method. Based on this method, Sb-based perovskite-like solar cells (PLSCs) achieve the highest recorded power conversion efficiency (PCE) of 3.34% and retain 90% of the initial PCE after being stored under ambient conditions for over 1400 h. More importantly, semitransparent Sb-based PLSCs with PCEs from 2.62 to 3.06% and average visible transparencies from 42 to 23% are successfully obtained, which indicates the great potential of the emerging Pb-free halide semiconductor for broad photovoltaic applications.

Fused tetraphenylethylene-triphenylamine as an efficient hole transporting material in perovskite solar cells.

A fused tetraphenylethylene-based hole transporting material shows higher power conversion efficiency and better stability compared with its non-fused counterpart, and the former molecule even outperforms the conventional spiro-OMeTAD.

MACl-Induced Intermediate Engineering for High-Performance Mixed-Cation Perovskite Solar Cells.

Recently, mixed-cation perovskites have been extensively used for high-performance solar cells. Nevertheless, the mixed-cation perovskite based on formamidinium methylammonium lead tri-iodide (FAxMA1-xPbI3) fabricated through the existing methods often suffers from phase stability and trap density. Herein, we demonstrate a facile intermediate engineering approach to improve the quality of the mixed-cation perovskite based on FAxMA1-xPbI3. Varying concentrations of methylammonium chloride (MACl) are used to treat the FA-MA-PbI3-solvent intermediate. It is noted that MACl has a strong impact on the crystallization kinetics and charge carrier dynamics as well as the defect density of the obtained perovskite. The mixed-cation perovskite treated with 20 mg mL-1 MACl yields a large grain size, highly uniform morphology, and better crystalline stability. Subsequently, the device with an acquired high-quality mixed-cation perovskite shows a high efficiency of 20.40%, which is obviously higher than that obtained from the traditional nontreated method. Moreover, the device prepared through the developed method could retain over 85% of the initial efficiency after 860 h at room temperature.

Enhanced Interfacial Binding and Electron Extraction Using Boron-Doped TiO2 for Highly Efficient Hysteresis-Free Perovskite Solar Cells.

Perovskite solar cells (PSCs) have witnessed astonishing improvement in power conversion efficiency (PCE), more recently, with advances in long-term stability and scalable fabrication. However, the presence of an anomalous hysteresis behavior in the current density-voltage characteristic of these devices remains a key obstacle on the road to commercialization. Herein, sol-gel-processed mesoporous boron-doped TiO2 (B-TiO2) is demonstrated as an improved electron transport layer (ETL) for PSCs for the reduction of hysteresis. The incorporation of boron dopant in TiO2 ETL not only reduces the hysteresis behavior but also improves PCE of the perovskite device. The simultaneous improvements are mainly ascribed to the following two reasons. First, the substitution of under-coordinated titanium atom by boron species effectively passivates oxygen vacancy defects in the TiO2 ETL, leading to increased electron mobility and conductivity, thereby greatly facilitating electron transport. Second, the boron dopant upshifts the conduction band edge of TiO2, resulting in more efficient electron extraction with suppressed charge recombination. Consequently, a methylammonium lead iodide (MAPbI3) photovoltaic device based on B-TiO2 ETL achieves a higher efficiency of 20.51% than the 19.06% of the pure TiO2 ETL based device, and the hysteresis is reduced from 0.13% to 0.01% with the B-TiO2 based device showing negligible hysteresis behavior.

Template-Assisted Formation of High-Quality α-Phase HC(NH2)2PbI3 Perovskite Solar Cells.

Formamidinium (FA) lead halide (α-FAPbI3) perovskites are promising materials for photovoltaic applications because of their excellent light harvesting capability (absorption edge 840 nm) and long carrier diffusion length. However, it is extremely difficult to prepare a pure α-FAPbI3 phase because of its easy transformation into a nondesirable δ-FAPbI3 phase. In the present study, a "perovskite" template (MAPbI3-FAI-PbI2-DMSO) structure is used to avoid and suppress the formation of δ-FAPbI3 phases. The perovskite structure is formed via postdeposition involving the treatment of colloidal MAI-PbI2-DMSO film with FAI before annealing. In situ X-ray diffraction in vacuum shows no detectable δ-FAPbI3 phase during the whole synthesis process when the sample is annealed from 100 to 180 °C. This method is found to reduce defects at grain boundaries and enhance the film quality as determined by means of photoluminescence mapping and Kelvin probe force microscopy. The perovskite solar cells (PSCs) fabricated by this method demonstrate a much-enhanced short-circuit current density ( J sc) of 24.99 mA cm-2 and a power conversion efficiency (PCE) of 21.24%, which is the highest efficiency reported for pure FAPbI3, with great stability under 800 h of thermal ageing and 500 h of light soaking in nitrogen.

Self-assembled naphthalimide derivatives as an efficient and low-cost electron extraction layer for n-i-p perovskite solar cells.

Based on self-assembly, novel electron extraction layers (EELs) composed of naphthalimide (NPI) derivatives are constructed for application in n-i-p perovskite solar cells. Upon molecular energy level modulation, the power conversion efficiencies have been largely improved from 5.4% to 16%. Such low-cost and highly regulable EELs are promising for future commercial applications.

Enhancing the Phase Stability of Inorganic α-CsPbI3 by the Bication-Conjugated Organic Molecule for Efficient Perovskite Solar Cells.

Inorganic CsPbI3 perovskite has demonstrated promising potentials for photovoltaic applications, whereas the black perovskite polymorph (α phase) of CsPbI3 was easily prone to converting into yellow phase (δ phase) under ambient moist environment, which restrained its practical application and further studies severely. In this study, p-phenylenediammonium iodide (PPDI) was employed to posttreat CsPbI3 films for controlling the phase conversion, strengthening moisture resistance, and improving device performance. The multiple roles of PPDI were as follows: (1) avoiding spontaneous octahedral tilting by ionic bonds between NH3+ of PPD2+ and I- of [PbI6]4-; (2) enhancing the hydrophobicity induced by exactly exposed oil-wet (hydrophobic) benzene rings; and (3) passivating surface defects and filling I vacancies. As a result, after the treatment, mutable a-CsPbI3 could maintain its α phase for at least 30 d in dry air (<20% RH). The perovskite solar cells with PPDI treatment exhibited reproductive photovoltaic performance with a champion power conversion efficiency (PCE) of 10.4, and 91% of the initial PCE was retained after storage for 504 h in a dark dry box without any encapsulation.

Vertically Oriented BiI3 Template Featured BiI3/Polymer Heterojunction for High Photocurrent and Long-Term Stable Solar Cells.

Nontoxic and stable materials are one of the necessities for commercialization of solar devices. However, most lead-free absorbers have limited light absorption range as well as poor morphology. In this work, a vertically oriented BiI3 template induced by Li-bis(trifluoromethanesulfonyl)imide dopant is intimately integrated with a light-absorbing polymer to form an organic-inorganic BiI3/polymer heterojunction absorber in solar cells. Compared with the dopant-free BiI3/polymer, the broadened light absorption of the doped BiI3/polymer enhances the external quantum efficiency (EQE) of the device beyond 500 nm as well as extends the EQE edge from 650 to 750 nm, which significantly increases the short-circuit current (Jsc) of the device from 1.3 to 3.7 mA cm-2. The polymer top layer is further optimized to improve charge extraction, which achieved the highest Jsc recorded (7.8 mA cm-2) for BiI3-based solar cells and an efficiency of 1.03%. Moreover, the encapsulated device shows no degradation after storing in ambient conditions for nearly 2 years.

Thermally Stable MAPbI3 Perovskite Solar Cells with Efficiency of 19.19% and Area over 1 cm2 achieved by Additive Engineering.

Solution-processed perovskite (PSC) solar cells have achieved extremely high power conversion efficiencies (PCEs) over 20%, but practical application of this photovoltaic technology requires further advancements on both long-term stability and large-area device demonstration. Here, an additive-engineering strategy is developed to realize a facile and convenient fabrication method of large-area uniform perovskite films composed of large crystal size and low density of defects. The high crystalline quality of the perovskite is found to simultaneously enhance the PCE and the durability of PSCs. By using the simple and widely used methylammonium lead iodide (MAPbI3 ), a certified PCE of 19.19% is achieved for devices with an aperture area of 1.025 cm2 , and the high-performing devices can sustain over 80% of the initial PCE after 500 h of thermal aging at 85 °C, which are among the best results of MAPbI3 -based PSCs so far.

Cost-Performance Analysis of Perovskite Solar Modules.

Perovskite solar cells (PSCs) are promising candidates for the next generation of solar cells because they are easy to fabricate and have high power conversion efficiencies. However, there has been no detailed analysis of the cost of PSC modules. We selected two representative examples of PSCs and performed a cost analysis of their productions: one was a moderate-efficiency module produced from cheap materials, and the other was a high-efficiency module produced from expensive materials. The costs of both modules were found to be lower than those of other photovoltaic technologies. We used the calculated module costs to estimate the levelized cost of electricity (LCOE) of PSCs. The LCOE was calculated to be 3.5-4.9 US cents/kWh with an efficiency and lifetime of greater than 12% and 15 years respectively, below the cost of traditional energy sources.

Enhanced Stability of Perovskite Solar Cells through Corrosion-Free Pyridine Derivatives in Hole-Transporting Materials.

The molecular structure of pyridine derivatives is critical to perovskite solar cell performance, especially stability. Most of the pyridine additives easily form complexes with perovskite. A new pyridine additive with a long alkyl chain substituted at its o-position does not corrode perovskite. The stability of devices containing this additive is the highest among the investigated cells.

Precisely Controlled Synthesis of High Quality Kesterite Cu2ZnSnS4 Thin Film via Co-Electrodeposited CuZnSn Alloy Film.

In this work, a facile co-electrodeposition method was used to fabricate CuZnSn alloy films where the content of copper, zinc and tin could be precisely controlled through manipulating the mass transfer process in the electrochemical deposition. By finely tuning the concentration of the cations of Cu2+, Zn2+ and Sn2+ in the electrochemical bath solution, uniform CuZnSn film with desired composition of copper poor and zinc rich was made. Sulphurisation of the CuZnSn alloy film led to the formation of compact and large grains Cu2ZnSnS4 thin film absorber with an optimum composition of Cu/(Zn+Sn) ≈ 0.8, Zn/Sn ≈ 1.2. Both SEM morphology and EDS mapping results confirmed the uniformity of the CuZnSn and Cu2ZnSnS4 films and the homogeneous distribution of Cu, Zn, Sn and S elements in the bulk films. The XRD and Raman measurements indicated that the synthesized Cu2ZnSnS4 film was kesterite phase without impurities detected. Photoelectrochemical tests were carried out to evaluate the CZTS film's photocurrent response under illumination of green light.

The Light Attracting Effect of Pyridine Derivatives Based Quasi-Solid Electrolyte in Dye-Sensitized Solar Cell.

The pyridine derivatives are added into acetonitrile based electrolyte to establish framework, then form the quasi solid electrolyte. The ion diffusion of cetylpyridinium chloride and cetylpyridinium bromide based electrolytes is enhanced comparing with the ion diffusion of reference acetonitrile electrolyte. The ordered structure of cetylpyridinuium chloride quasi solid electrolyte has been observed by SEM images. Light scattering effect of cetylpyridinuium chloride quasi solid electrolyte is evidenced by the larger resulted by transmitted and scattered spectra. The light harvesting efficiency of device based on C16Cl is much higher than acetonitrile based device. The cell efficiency of C16Cl and C16Br based device are 5.72% and 6.02%, which are 41% and 48% higher than acetonitrile liquid electrolyte based device. The C16l based device produces low cell efficiency 2.06%, which is 49% decrease compare to the blank device due to the limitation of iodide-triodide transportation in the iodide framework.

Efficient panchromatic inorganic-organic heterojunction solar cells with consecutive charge transport tunnels in hole transport material.

A simple solution-processing method was employed to fabricate panchromatic mp-TiO2/CH3NH3PbI3/P3HT-MWNT/Au solar cells. MWNTs in a P3HT-MWNT composite acted as efficient nanostructured charge transport tunnels and induce crystallization of P3HT, hence significantly enhancing the conductivity of the composite. The fill factor of the hybrid solar cells was greatly enhanced by 26.7%.