Dual Defect Passivation at the Buried Interface for Printable Mesoscopic Perovskite Solar Cells with Reduced Open-Circuit Voltage Loss.

Numerous defects exist at the buried interface between the perovskite and adjacent electron transport layers in perovskite solar cells, resulting in severe non-radiative recombination and excessive open-circuit voltage (VOC) loss. Herein, a dual defect passivation strategy utilizing guanidine sulfate (GUA2SO4) as an interface modifier is first reported. On the one hand, the SO4 2- preferentially interacts with Pb-related defects, generating water-insoluble lead oxysalts complexes. Additionally, GUA+ diffuses into the perovskite and induces the formation of low-dimensional perovskite. These reactions effectively suppress trap states at the buried interface and perovskite boundaries in printable mesoscopic perovskite solar cells (p-MPSCs), thus increasing the carrier lifetime. Meanwhile, GUA2SO4 optimizes the interface energy band alignment, thus accelerating the charge extraction and transfer at the buried interface. This synergistic effect of trap passivation and interface energy band alignment modulation is strongly demonstrated by an increase in average VOC of 70 mV and the power conversion efficiency improvement from 17.51% to 18.70%. This work provides a novel approach to efficiently improve the performance of p-MPSCs through dual-targeted defect passivation at the buried interface.

Printable Counter Electrode with Metal Nitride as the Conductive Medium for Perovskite Solar Cells.

Perovskite solar cells (PSCs) with a booming high power conversion efficiency (PCE) are on their road toward industrialization. A proper design of the counter electrode (CE) with low cost, high conductivity, chemical stability, and good interface contact with the other functional layer atop the perovskite layer is vital for the overall performance of PSCs. Herein, the application of titanium nitride (TiN) is reported as a conductive medium for the printable CE in hole-conductor-free mesoscopic PSCs. TiN improves the conductivity of the CE and reduces the resistivity from 20 to 10 mΩ∙cm. TiN also improves the wettability of the CE with perovskite and enhances the back interface contact, which promotes charge collection. On the other hand, TiN is chemically stable during processing and undergoes no distinguishable chemical reaction with halide perovskite. Devices with TiN as the conductive media in the CE deliver a champion PCE of 19.01%. This work supplies a considerable choice for the CE design of PSCs toward industrial applications.

Stratified Oxygen Vacancies Enhance the Performance of Mesoporous TiO2 Electron Transport Layer in Printable Perovskite Solar Cells.

The low electrical conductivity and the high surface defect density of the TiO2 electron transport layer (ETL) limit the power conversion efficiency (PCE) of corresponding perovskite solar cells (PSCs). Here, the conductivity and defect modulation of the mesoporous TiO2 (mp-TiO2 ) ETL via oxygen vacancy (OV) management by the reduction and oxidation treatment are reported. Reduction treatment via reducing agent introduces abundant OVs into the TiO2 nanocrystalline particles on the surface and at the subsurface. The following oxidation treatment via hydrogen peroxide removes the surface OVs while remains the subsurface OVs, resulting in stratified OVs. The stratified OVs improve the conductivity of TiO2 ETL by increasing carrier donors and decrease nonradiative centers by reducing surface defects. Such synergy ensures the capability of mp-TiO2 as the well-performed ETL with improved energy level alignment, suppressed interface recombination, enhanced carrier extraction, and transport. As a result, printable hole-conductor-free carbon-based mesoscopic PSCs based on the modulated mp-TiO2 ETL demonstrate a highest reported PCE of 18.96%.

Oxygen Vacancy Management for High-Temperature Mesoporous SnO2 Electron Transport Layers in Printable Perovskite Solar Cells.

The planar SnO2 electron transport layer (ETL) has contributed to the reported power conversion efficiency (PCE) record of perovskite solar cells (PSCs), while the high-temperature mesoporous SnO2 ETL (mp-SnO2 ) brings poor device performance. Herein, we report the application of mp-SnO2 for efficient printable PSCs via oxygen vacancy (OV) management by introducing magnesium (Mg) into the paste. We find that high-temperature annealing suppresses self-doping of SnO2 by reducing OVs. The introduced Mg occupies both the Sn site and interstitial site of SnO2 and promotes the formation of OVs. Lattice Mg tends to induce neutral OVs and interstitial Mg could promote the ionization of neutral OVs for self-doping. The synergy effect on OVs increases the carrier density and upshifts the Fermi level energy of mp-SnO2 , ensuring its capability as the well-performed ETL with trap-less charge transport and suppressed surface recombination for dramatic improved device PCE from 6.62 % to 17.25 %.

van der Waals Mixed Valence Tin Oxides for Perovskite Solar Cells as UV-Stable Electron Transport Materials.

Stable electron transport materials (ETMs) with fewer surface defects and proper energy level alignments with halide perovskite active layers are required for efficient perovskite solar cells (PSCs) with long-term durability. Here, two-dimensional van der Waals mixed valence tin oxides Sn2O3 and Sn3O4 are controllably synthesized and applied as ETMs for planar PSCs. The synthesized Sn2O3 and Sn3O4 have size of 5-20 nm and disperse well in water as stable colloids for months. Both Sn2O3 and Sn3O4 exhibit typical n-type semiconductor energy band structures, low trap density, and suitable energy level alignments with halide perovskites. Steady-state power conversion efficiencies (PCEs) of 22.36% and 21.83% are obtained for Sn2O3-based and Sn3O4-based planar PSCs. In addition, the half cells without hole transport materials and back electrodes show good UV-stability with average PCE of 99.0% and 95.7% for Sn2O3-based and Sn3O4-based devices remaining after 1000 h of ultraviolet soaking with an intensity of 70 mW cm-2.

Fully printable mesoscopic perovskite solar cells with organic silane self-assembled monolayer.

By the introduction of an organic silane self-assembled monolayer, an interface-engineering approach is demonstrated for hole-conductor-free, fully printable mesoscopic perovskite solar cells based on a carbon counter electrode. The self-assembled silane monolayer is incorporated between the TiO2 and CH3NH3PbI3, resulting in optimized interface band alignments and enhanced charge lifetime. The average power conversion efficiency is improved from 9.6% to 11.7%, with a highest efficiency of 12.7%, for this low-cost perovskite solar cell.

Record-Efficiency Printable Hole-Conductor-Free Mesoscopic Perovskite Solar Cells Enabled by the Multifunctional Schiff Base Derivative.

Tailoring multifunctional additives for performing interfacial modifications, improving crystallization, and passivating defects is instrumental for the fabrication of efficient and stable perovskite solar cells (PSCs). Here, a Schiff base derivative, (chloromethylene) dimethyliminium chloride (CDCl), is introduced as an additive to modify the interface between the mesoporous TiO2 electron transport layer and the MAPbI3 light absorber during the annealing process. CDCl chemically links to TiO2 and MAPbI3 through coordination and hydrogen bonding, respectively, and results in the construction of fast electron extraction channels. CDCl also optimizes the energy-level alignment of the TiO2/MAPbI3 heterojunction and improves the pore-filling and crystallization of MAPbI3 in the mesoscopic scaffold, which inhibits nonradiative recombination and eliminates open-circuit voltage losses. As a result, an impressive power conversion efficiency of 19.74%, which is the best one ever reported, is obtained for printable carbon-based hole-conductor-free PSCs based on MAPbI3.

Electron injection and defect passivation for high-efficiency mesoporous perovskite solar cells.

Printable mesoscopic perovskite solar cells (p-MPSCs) do not require the added hole-transport layer needed in traditional p-n junctions but have also exhibited lower power conversion efficiencies of about 19%. We performed device simulation and carrier dynamics analysis to design a p-MPSC with mesoporous layers of semiconducting titanium dioxide, insulating zirconium dioxide, and conducting carbon infiltrated with perovskite that enabled three-dimensional injection of photoexcited electrons into titanium dioxide for collection at a transparent conductor layer. Holes underwent long-distance diffusion toward the carbon back electrode, and this carrier separation reduced recombination at the back contact. Nonradiative recombination at the bulk titanium dioxide/perovskite interface was reduced by ammonium phosphate modification. The resulting p-MPSCs achieved a power conversion efficiency of 22.2% and maintained 97% of their initial efficiency after 750 hours of maximum power point tracking at 55 ± 5°C.

Depth-Dependent Post-Treatment for Reducing Voltage Loss in Printable Mesoscopic Perovskite Solar Cells.

The printable mesoscopic perovskite solar cells consisting of a double layer of metal oxides covered by a porous carbon film have attracted attention due to their industrialization advantages. However, the tens-of-micrometer thickness of the triple scaffold leads to a challenge for perovskite to crystallize and for the charge carriers to separate and travel to the electrode, which limits the open circuit voltage (VOC ) of such devices. In this work, a depth-dependent post-treatment strategy is demonstrated to synergistically passivate defects and tune interfacial energy band alignment. Two thiophene derivatives, namely 3-chlorothiophene (3-CT) and 3-thiophene ethylenediamine (3-TEA), are selected for the post-treatment. Energy-dispersive X-ray spectroscopy proves that 3-CT is uniformly distributed throughout the triple scaffold and effectively passivates the defects of the bulky perovskite, while 3-TEA reacts rapidly with the loose perovskite in the carbon layer to form 2D perovskite, forming a type II energy band alignment at the perovskite/carbon interface. As a result, the defect-assisted recombination is suppressed and the interfacial energy band is regulated, increasing the VOC to 1012 mV. The PCE of the devices is enhanced from 16.26% to 18.49%. This depth-dependent post-treatment strategy takes advantage of the unique structure and provides a new insight for reducing the voltage loss.

Halide Perovskite Crystallization Processes and Methods in Nanocrystals, Single Crystals, and Thin Films.

Halide perovskite semiconductors with extraordinary optoelectronic properties have been fascinatedly studied. Halide perovskite nanocrystals, single crystals, and thin films have been prepared for various fields, such as light emission, light detection, and light harvesting. High-performance devices rely on high crystal quality determined by the nucleation and crystal growth process. Here, the fundamental understanding of the crystallization process driven by supersaturation of the solution is discussed and the methods for halide perovskite crystals are summarized. Supersaturation determines the proportion and the average Gibbs free energy changes for surface and volume molecular units involved in the spontaneous aggregation, which could be stable in the solution and induce homogeneous nucleation only when the solution exceeds a required minimum critical concentration (Cmin ). Crystal growth and heterogeneous nucleation are thermodynamically easier than homogeneous nucleation due to the existent surfaces. Nanocrystals are mainly prepared via the nucleation-dominated process by rapidly increasing the concentration over Cmin , single crystals are mainly prepared via the growth-dominated process by keeping the concentration between solubility and Cmin , while thin films are mainly prepared by compromising the nucleation and growth processes to ensure compactness and grain sizes. Typical strategies for preparing these three forms of halide perovskites are also reviewed.

Constructing Soft Perovskite-Substrate Interfaces for Dynamic Modulation of Perovskite Film in Inverted Solar Cells with Over 6200 Hours Photostability.

High-performance perovskite solar cells (PSCs) depend heavily on the quality of perovskite films, which is closely related to the lattice distortion, perovskite crystallization, and interfacial defects when being spin-coated and annealed on the substrate surface. Here, a dynamic strategy to modulate the perovskite film formation by using a soft perovskite-substrate interface constructed by employing amphiphilic soft molecules (ASMs) with long alkyl chains and Lewis base groups is proposed. The hydrophobic alkyl chains of ASMs interacted with poly(triarylamine) (PTAA) greatly improve the wettability of PTAA to facilitate the nucleation and growth of perovskite crystals, while the Lewis base groups bound to perovskite lattices significantly passivate the defects in situ. More importantly, this soft perovskite-substrate interface with ASMs between PTAA and perovskite film can dynamically match the lattice distortion with reduced interfacial residual strain upon perovskite crystallization and thermal annealing owing to the soft self-adaptive long-chains, leading to high-quality perovskite films. Thus, the inverted PSCs show a power conversion efficiency approaching 20% with good reproducibility and negligible hysteresis. More impressively, the unencapsulated device exhibits state-of-the-art photostability, retaining 84% of its initial efficiency under continuous simulated 1-sun illumination for more than 6200 h at elevated temperature (≈65 °C).

Development of formamidinium lead iodide-based perovskite solar cells: efficiency and stability.

Perovskite materials have been particularly eye-catching by virtue of their excellent properties such as high light absorption coefficient, long carrier lifetime, low exciton binding energy and ambipolar transmission (perovskites have the characteristics of transporting both electrons and holes). Limited by the wider band gap (1.55 eV), worse thermal stability and more defect states, the first widely used methylammonium lead iodide has been gradually replaced by formamidinium lead iodide (FAPbI3) with a narrower band gap of 1.48 eV and better thermal stability. However, FAPbI3 is stabilized as the yellow non-perovskite active phase at low temperatures, and the required black phase (α-FAPbI3) can only be obtained at high temperatures. In this perspective, we summarize the current efforts to stabilize α-FAPbI3, and propose that pure α-FAPbI3 is an ideal material for single-junction cells, and a triple-layer mesoporous architecture could help to stabilize pure α-FAPbI3. Furthermore, reducing the band gap and using tandem solar cells may ulteriorly approach the Shockley-Queisser limit efficiency. We also make a prospect that the enhancement of industrial applications as well as the lifetime of devices may help achieve commercialization of PSCs in the future.

Modeling and Balancing the Solvent Evaporation of Thermal Annealing Process for Metal Halide Perovskites and Solar Cells.

Triple-mesoscopic perovskite solar cells (PSCs) have attracted intensive attention due to the high stability, simple fabrication process, and low material cost. In this structure, the perovskite layer is hosted by a triple-mesoscopic scaffold of TiO2 /ZrO2 /carbon, and thus the crystal quality is sensitive to the thermal annealing process. Typically, the annealing process is conducted in a petri dish, for which the solvent evaporation of the perovskite precursor is slowed down, but not controllable and designable. To control the solvent evaporation, annealing chambers are first designed with different shape and vapor releasing channels. Then, physical simulations are performed by a finite element method, and it is found out that the chamber with a crowned top and releasing channels on the bottom sides can realize homogeneous distribution of the solvent vapor. To verify the simulation results, chambers are fabricated by 3D printing technique, for which the printing deviation can be as low as 100 µm. By balancing the solvent evaporation and release, the optimal solvent evaporation is achieved of the perovskite precursor in the triple-mesoscopic scaffold. This work offers a method to obtain homogeneous distribution of solvent vapor, and provides a new insight into understanding the influence of solvent evaporation during the thermal annealing process for PSCs.

Interfacial Energy Band Alignment Enables the Reduction of Potential Loss for Hole-Conductor-Free Printable Mesoscopic Perovskite Solar Cells.

Perovskite solar cells (PSCs) have achieved high efficiencies with diversified device architectures. In particular, printable mesoscopic PSC has attracted intensive research attention due to its simple fabrication process and superior stability. However, in the absence of hole conductors, the unfavorable energy band alignment between the perovskite and the carbon electrode usually leads to the reduction of device performance, especially the open-circuit voltage (VOC). Here, a p-type molecule, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), is utilized to post-treat the perovskite/carbon interface, which benefits the charge transfer and suppresses the charge recombination within the device. As a result, the post-treated device delivers a power conversion efficiency of 18.05% with an enhanced VOC of 1044 mV. This work provides a facile method for tuning the interfacial energy band alignment and improving performance of printable mesoscopic PSCs.

Approaching the External Quantum Efficiency Limit in 2D Photovoltaic Devices.

2D transition metal dichalcogenides (TMDs) are promising candidates for realizing ultrathin and high-performance photovoltaic devices. However, the external quantum efficiency (EQE) and power conversion efficiency (PCE) of most 2D photovoltaic devices face great challenges in exceeding 50% and 3%, respectively, due to the low efficiency of photocarrier separation and collection. Here, this study demonstrates photovoltaic devices with defect-free interface and recombination-free channel based on 2D WS2 , showing high EQE of 92% approaching the theoretical limit and high PCE of 5.0%. The high performances are attributed to the van der Waals metal contact without interface defects and Fermi-level pinning, and the fully depleted channel without photocarrier recombination, leading to intrinsic photocarrier separation and collection with high efficiency. Furthermore, this study demonstrates that the strategy can be extended to other TMDs such as MoSe2 and WSe2 with EQE of 92% and 94%, respectively. This work proposes a universal strategy for building high-performance 2D photovoltaic devices. The nearly ideal EQE provides great potential for PCE approaching the Shockley-Queisser limit.

Highly oriented MAPbI3 crystals for efficient hole-conductor-free printable mesoscopic perovskite solar cells.

Highly crystalline perovskite films with large grains and few grain boundaries are conducive for efficient and stable perovskite solar cells. Current methods for preparing perovskite films are mostly based on a fast crystallization process, with rapid nucleation and insufficient growth. In this study, MAPbI3 perovskite with inhibited nucleation and promoted growth in the TiO2/ZrO2/carbon triple mesoscopic scaffold was crystallized by modulating the precursor and the crystallization process. N-methylformamide showed high solubility for both methylammonium iodide and PbI2 and hampered the formation of large colloids in the MAPbI3 precursor solution. Furthermore, methylammonium chloride was added to reduce large colloids, which are a possible source of nucleation sites. During the crystallization of MAPbI3, the solvent was removed at a slow controlled speed, to avoid rapid nucleation and provide sufficient time for crystal growth. As a result, highly oriented MAPbI3 crystals with suppressed non-radiative recombination and promoted charge transport were obtained in the triple mesoscopic layer with disordered pores. The corresponding hole-conductor-free, printable mesoscopic perovskite solar cells exhibited a highest power conversion efficiency of 18.82%. The device also exhibited promising long-term operational stability of 1000 h under continuous illumination at maximum power point at 55 ± 5 °C and damp-heat stability of 1340 h aging at 85 °C as well as 85% relative humidity.

Investigating the iodide and bromide ion exchange in metal halide perovskite single crystals and thin films.

The anion exchange between MAPbX3 (X = I- or Br-) and MAX salts in a solution environment is investigated. We find that I- can enter MAPbBr3 single crystals (SC) in millimeter scale, while Br- can only penetrate the surface of MAPbI3 SC in a micrometer scale. Due to the lattice variation, the reaction is partially reversible.

Influence of precursor concentration on printable mesoscopic perovskite solar cells.

Over the last decade, the power conversion efficiency of hybrid organic-inorganic perovskite solar cells (PSCs) has increased dramatically from 3.8% to 25.2%. This rapid progress has been possible due to the accurate control of the morphology and crystallinity of solution-processed perovskites, which are significantly affected by the concentration of the precursor used. This study explores the influence of precursor concentrations on the performance of printable hole-conductor-free mesoscopic PSCs via a simple one-step drop-coating method. The results reveal that lower concentrations lead to larger grains with inferior pore filling, while higher concentrations result in smaller grains with improved pore filling. Among concentrations ranging from 0.24-1.20 M1), devices based on a moderate strength of 0.70 M were confirmed to exhibit the best efficiency at 16.32%.

Mesoporous-Carbon-Based Fully-Printable All-Inorganic Monoclinic CsPbBr3 Perovskite Solar Cells with Ultrastability under High Temperature and High Humidity.

The all-inorganic CsPb(IxBr1-x)3 (0 ≤ x ≤ 1) perovskite solar cells (PSCs) are attractive by virtue of their high environmental and thermal stability. Nevertheless, multiple-step deposition and high annealing temperature (>250 °C) and the structural and optoelectronic properties changes upon temperature-dependent phase-transition are potential impediments for highly efficient and stable PSCs. Herein, a space-confined method to fabricate stable lower-order symmetric pure monoclinic CsPbBr3 phase at low temperature (<50 °C) is for the first time reported. It is found that the carbon-based mesoporous fully printable area can inhibit the phase transition to get a pure phase. Therefore, the device exhibits a power conversion efficiency of 7.52% with a low hysteresis index of 0.024. Moreover, the device passed the 1000 h 85 °C thermal test and the 200 cycles thermal cycling test according to IEC-61625 stability tests. These are critical progresses for achieving long-term stability and the stable pure inorganic perovskite phase of high-performance photovoltaics.

In situ transfer of CH3NH3PbI3 single crystals in mesoporous scaffolds for efficient perovskite solar cells.

Printable mesoscopic perovskite solar cells are usually fabricated by drop-casting perovskite precursor solution on a screen-printed mesoporous TiO2/ZrO2/carbon triple-layer followed by thermal annealing. They have attracted much attention due to their simple fabrication process and remarkable stability. However, challenges lie in how to achieve complete pore fillings of perovskites in the meso-pores and to obtain high-quality perovskite crystals. Here, we report an in situ crystal transfer (ICT) process based on gas-solid interaction to deposit perovskite CH3NH3PbI3 absorber in the scaffold. CH3NH3PbI3 single crystals are first transformed into a liquid phase via exposure to methylamine gas flow. After complete infiltration into the nano-structured scaffolds, the liquid phase is converted back to the solid phase with reduction of methylamine gas partial pressure, maintaining the high-quality of CH3NH3PbI3 single crystals. Compared with the conventional drop-casting method, the ICT method effectively leads to interconnected morphology and prolongs the charge-carrier lifetime (from ∼37.52 ns to ∼110.85 ns) of the perovskite absorber in the scaffold. As a result, the devices can deliver a power conversion efficiency of 15.89%, which is attributed to the suppressed charge recombination and correspondingly enhanced open-circuit voltage of 0.98 V.