Bilateral Chemical Linking at NiOx Buried Interface Enables Efficient and Stable Inverted Perovskite Solar Cells and Modules.

Inverted NiOx-based perovskite solar cells (PSCs) exhibit considerable potential because of their low-temperature processing and outstanding excellent stability, while is challenged by the carriers transfer at buried interface owing to the inherent low carrier mobility and abundant surface defects that directly deteriorates the overall device fill factor. Present work demonstrates a chemical linker with the capability of simultaneously grasping NiOx and perovskite crystals by forming a Ni-S-Pb bridge at buried interface to significantly boost the carriers transfer, based on a rationally selected molecule of 1,3-dimethyl-benzoimidazol-2-thione (NCS). The constructed buried interface not only reduces the pinholes and needle-like residual PbI2 at the buried interface, but also deepens the work function and valence band maximum positions of NiOx, resulting in a smaller VBM offset between NiOx and perovskite film. Consequently, the modulated PSCs achieved a high fill factor up to 86.24%, which is as far as we know the highest value in records of NiOx-based inverted PSCs. The NCS custom-tailored PSCs and minimodules (active area of 18 cm2) exhibited a champion efficiency of 25.05% and 21.16%, respectively. The unencapsulated devices remains over 90% of their initial efficiency at maximum power point under continuous illumination for 1700 hours.

Sulfonate-Assisted Surface Iodide Management for High-Performance Perovskite Solar Cells and Modules.

Owing to the ionic nature of lead halide perovskites, their halide-terminated surface is unstable under light-, thermal-, moisture-, or electric-field-driven stresses, resulting in the formation of unfavorable surface defects. As a result, nonradiative recombination generally occurs on perovskite films and deteriorates the efficiency, stability, and hysteresis performances of perovskite solar cells (PSCs). Here, a surface iodide management strategy was developed through the use of cesium sulfonate to stabilize the perovskite surface. It was found that the pristine surface of common perovskite was terminated with extra iodide, that is, with an I-/Pb2+ ratio larger than 3, explaining the origination of surface-related problems. Through post-treatment of perovskite films by cesium sulfonate, the extra iodide on the surface was facilely removed and the as-exposed Pb2+ cations were chelated with sulfonate anions while maintaining the original 3D perovskite structure. Such iodide replacement and lead chelating coordination on perovskite could reduce the commonly existing surface defects and nonradiative recombination, enabling assembled PSCs with an efficiency of 22.06% in 0.12 cm2 cells and 18.1% in 36 cm2 modules with high stability.

Methylamine-Dimer-Induced Phase Transition toward MAPbI3 Films and High-Efficiency Perovskite Solar Modules.

Perovskite films prepared with CH3NH2 molecules under ambient conditions have led to rapid fabrication of perovskite solar cells (PSCs), but there remains a lack of mechanistic studies and inconsistencies with operability in their production. Here the crystal structure of CH3NH2-CH3NH3PbI3 was analyzed to involve hydrogen bonds (CH3NH2···CH3NH3+) and has guided the facile, reproducible preparation of high-quality perovskite films under ambient conditions. Hydrogen bonds within CH3NH2···CH3NH3+ dimers were found in the CH3NH2-CH3NH3PbI3 intermediates, accompanied by 1D-PbI3- chains (δ-phase). The weakly hydrogen-bonded CH3NH2 molecules were easily released from the CH3NH2-CH3NH3PbI3 intermediates, contributing to rapid, spontaneous phase transition from 1D-PbI3- (δ-phase) to 3D-PbI3- (α-phase). Further introduction of CH3NH3Cl into the CH3NH2-CH3NH3PbI3 intermediates led to interruption of 1D-PbI3- transition into 0D-Pb2I9-xClx5-(0 < x < 6), adjusting the phase transition route toward 3D-PbI3-. On the basis of the above understanding, CH3NH2 solution in ethanol and CH3NH3Cl were used for precursors and a best efficiency of 20.3% in PSCs was achieved. Large-scale modules (12 cm2 aperture area) fabricated by a dip-coating technology exhibited an efficiency up to 16.0% and outstanding stability over 10 000 s under continuous output. The developed preparation method of perovskite precursors and insightful research into the methylamine-dimer-induced phase transition mechanism have enabled the production of high-quality perovskite films with robust operability, showing great potential for large-scale commercialization.

Monoammonium Porphyrin for Blade-Coating Stable Large-Area Perovskite Solar Cells with >18% Efficiency.

Efficient control of crystallization and defects of perovskite films are the key factors toward the performance and stability of perovskite solar cells (PSCs), especially for the preparation of large-area PSCs devices. Herein, we directly embedded surfactant-like monoammonium zinc porphyrin (ZnP) compound into the methylammonium (MA+) lead iodide perovskite film to blade-coat large-area uniform perovskite films as large as 16 cm2. Efficiency as high as 18.3% for blade-coating large-area (1.96 cm2) PSCs with ZnP was unprecedentedly achieved, while the best efficiency of fabricated small-area (0.1 cm2) device was up to 20.5%. The detailed analyses demonstrated the functions of ZnP in crystallization control and defects passivation of perovskite surfaces and grain boundaries. As a consequence, the ZnP-encapsulated devices retained over 90% of its initial efficiency after 1000 h with a humidity of about 45% at 85 °C. This research presents a facile way to achieve the synergistic effect of large-area coating, morphology tailoring, and defect suppression based on the molecular encapsulation strategy for perovskite films, further improving the photovoltaic performance and stability of PSCs.

High-Efficiency, Hysteresis-Less, UV-Stable Perovskite Solar Cells with Cascade ZnO-ZnS Electron Transport Layer.

Perovskite solar cells (PSCs) have reached certified efficiencies of up to 23.7% but suffered from frailness and instability when exposed to ambient atmosphere. Zinc oxide (ZnO), when used as electron transport layer (ETL) on PSCs, gives rise to excellent electronic, optic, and photonic properties, yet the Lewis basic nature of ZnO surface leads to deprotonation of the perovskite layer, resulting in serious degradation of PSCs using ZnO as ETL. Here, we report a simple but effective strategy to convert ZnO surface into ZnS at the ZnO/perovskite interface by sulfidation. The sulfide on ZnO-ZnS surface binds strongly with Pb2+ and creates a novel pathway of electron transport to accelerate electron transfer and reduce interfacial charge recombination, yielding a champion efficiency of 20.7% with improved stability and no appreciable hysteresis. The model devices modified with sulfide maintained 88% of their initial performance for 1000 h under storage condition and 87% for 500 h under UV radiation. ZnS is demonstrated to act as both a cascade ETL and a passivating layer for enhancing the performance of PSCs.

Ether-Soluble Cu53 Nanoclusters as an Effective Precursor of High-Quality CuI Films for Optoelectronic Applications.

An effective strategy is developed to synthesize high-nuclearity Cu clusters, [Cu53 (RCOO)10 (C≡CtBu)20 Cl2 H18 ]+ (Cu53 ), which is the largest CuI /Cu0 cluster reported to date. Cu powder and Ph2 SiH2 are employed as the reducing agents in the synthesis. As revealed by single-crystal diffraction, Cu53 is arranged as a four-concentric-shell Cu3 @Cu10 Cl2 @Cu20 @Cu20 structure, possessing an atomic arrangement of concentric M12 icosahedral and M20 dodecahedral shells which popularly occurs in Au/Ag nanoclusters. Surprisingly, Cu53 can be dissolved in diethyl ether and spin coated to form uniform nanoclusters film on organolead halide perovskite. The cluster film can subsequently be converted into high-quality CuI film via in situ iodination at room temperature. The as-fabricated CuI film is an excellent hole-transport layer for fabricating highly stable CuI-based perovskite solar cells (PSCs) with 14.3 % of efficiency.

Identifying the Molecular Structures of Intermediates for Optimizing the Fabrication of High-Quality Perovskite Films.

During the past two years, the introduction of DMSO has revolutionized the fabrication of high-quality pervoskite MAPbI3 (MA = CH3NH3) films for solar cell applications. In the developed DMSO process, the formation of (MA)2Pb3I8·2DMSO (shorted as Pb3I8) has well recognized as a critical factor to prepare high-quality pervoskite films and thus accomplish excellent performances in perovskite solar cells. However, Pb3I8 is an I-deficient intermediate and must further react with methylammonium iodide (MAI) to be fully converted into MAPbI3. By capturing and solving the molecular structures of several intermediates involved in the fabrication of perovskite films, we report in this work that the importance of DMSO is NOT due to the formation of Pb3I8. The use of different PbI2-DMSO ratios leads to two different structures of PbI2-DMSO precursors (PbI2·DMSO and PbI2·2DMSO), thus dramatically influencing the quality of fabricated perovskite films. However, such an influence can be minimized when the PbI2-DMSO precursor films are thermally treated to create mesoporous PbI2 films before reacting with MAI. Such a development makes the fabrication of high-quality pervoskite films highly reproducible without the need to precisely control the PbI2:DMSO ratio. Moreover, the formation of ionic compound (MA)4PbI6 is observed when excess MAI is used in the preparation of perovskite film. This I-rich phase heavily induces the hysteresis in PSCs, but is readily removed by isopropanol treatment. On the basis of all these findings, we develop a new effective protocol to fabricate high-performance PSCs. In the new protocol, high-quality perovskite films are prepared by simply treating the mesoporous PbI2 films (made from PbI2-DMSO precursors) with an isopropanol solution of MAI, followed by isopropanol washing. The best efficiency of fabricated MAPbI3 PSCs is up to 19.0%. As compared to the previously reported DMSO method, the devices fabricated by the method reported in this work display narrow efficiency distributions in both forward and reverse scans. And the efficiency difference between forward and reverse scans is much smaller.

Linear and stable photonic radio frequency phase shifter based on a dual-parallel Mach-Zehnder modulator using a two-drive scheme.

We theoretically and experimentally demonstrate a linear and stable photonic RF phase shifter based on a dual-parallel Mach-Zehnder modulator (DPMZM) using a two-drive scheme. To avoid the effect of the residual optical carrier and overcome the lowest frequency limit from the optical filter, a local microwave signal and a signal up-converted from the under-phase-shifted RF signal are applied to the two RF inputs of the DPMZM, respectively. A phase-shifted RF signal is generated by beating the two first-order upper sidebands located in the passband of the optical filter. A continuous and linear phase shift of more than 360° and power variation of less than ±0.15 dB at 1 GHz are achieved by simply tuning the bias voltage of the modulator. A phase tuning bandwidth of more than 17 MHz and phase drift of less than 0.5° within 2000 s are also observed.

Conformal Imidazolium 1D Perovskite Capping Layer Stabilized 3D Perovskite Films for Efficient Solar Modules.

Although the perovskite solar cells have been developed rapidly, the industrialization of perovskite photovoltaics is still facing challenges, especially considering their stability issues. Here, the new type of benzimidazolium salt, N,N'-dialkylbenzimidazolium iodide, is proposed and functionalized to convert the three-dimensional (3D) FACs-perovskite films into one-dimensional (1D) capping layer topped 1D/3D structure either in individual device or module levels. This conformal interface modulation demonstrates that not only can effectively stabilize FACs-based perovskite films by inhibiting the lateral and vertical iodide diffusions in devices or modules, ensuring an excellent operation and environmental stability, but also provides an excellent charge transporting channel through the well-designed 1D crystal structure. Consequently, efficient device performance with power conversion efficiency up to 24.3% is readily achieved. And the large-area perovskite solar modules with high efficiency (19.6% for the active areas of 18 cm2 ) and long-term stability (about 500 h in AM 1.5G illumination or about 1000 h under double-85 conditions) are also successfully verified.

Chemical Insights into Interfacial Effects in Inorganic Nanomaterials.

The interfaces between inorganic functional nanomaterials and their surface modifiers play important roles in determining their chemical and physical properties. In numerous situations, interfaces created by organic ligands or secondary inorganic components on inorganic nanomaterials induce significant effects to promote their performances. However, it still remains challenging to understand those interfacial effects at the molecular level. Herein, strategies via the design of model inorganic nanomaterials with well-defined and detectable interfaces to simplify the investigation of interfacial effects in inorganic nanomaterials are summarized. While atomically precise metal nanoclusters enable "seeing" how organic ligands are coordinated on metal surface to create nanoscale metal-organic interfaces, ultrathin low-dimensional nanomaterials modified with organic ligands make it possible to extract the metal-organic interface structure from the average signal to investigate how steric and electronic effects enhance catalysis. The molecular mechanisms of the interfacial effects in supported metal catalysts are disclosed by designing two unique structures of supported catalysts. The interfacial engineering approach will be further extended to optimize the performance and stability of perovskite solar cells. Finally, a perspective on the development of operando characterization techniques is provided to track the dynamic interfacial structures during catalysis.

Perfection of Perovskite Grain Boundary Passivation by Eu-Porphyrin Complex for Overall-Stable Perovskite Solar Cells.

The formation of defects at surfaces and grain boundaries (GBs) during the fabrication of solution-processed perovskite film are thought to be responsible for its instability. Herein, Eu-porphyrin complex (Eu-pyP) is directly doped into methylammonium lead triiodide (MAPbI3) precursor, perfectly fabricating 2D (Eu-pyP)0.5MA n -1Pb n I3 n +1 platelets inlaying the GBs of 3D polycrystalline interstices in this protocol. The device based on Eu-pyP doped perovskite film possesses a champion efficiency of 18.2%. More importantly, the doped perovskite solar cells device shows beyond 85% retention of its pristine efficiency value, whereas the pure MAPbI3 device has a rapid drop in efficiency down to 10% within 100 h under 45% humidity at 85 °C in AM 1.5 G. The above acquired perovskite films reveal an unpredictable thermodynamic self-healing ability. Consequently, the findings provide an avenue for defect passivation to synchronously improve resistibility to moisture, heat, and solar light including UV.

Light-Trapping Engineering for the Enhancements of Broadband and Spectra-Selective Photodetection by Self-Assembled Dielectric Microcavity Arrays.

Light manipulation has drawn great attention in photodetectors towards the specific applications with broadband or spectra-selective enhancement in photo-responsivity or conversion efficiency. In this work, a broadband light regulation was realized in photodetectors with the improved spectra-selective photo-responsivity by the optimally fabricated dielectric microcavity arrays (MCAs) on the top of devices. Both experimental and theoretical results reveal that the light absorption enhancement in the cavities is responsible for the improved sensitivity in the detectors, which originated from the light confinement of the whispering-gallery-mode (WGM) resonances and the subsequent photon coupling into active layer through the leaky modes of resonances. In addition, the absorption enhancements in specific wavelength regions were controllably accomplished by manipulating the resonance properties through varying the effective optical length of the cavities. Consequently, a responsivity enhancement up to 25% within the commonly used optical communication and sensing region (800 to 980 nm) was achieved in the MCA-decorated silicon positive-intrinsic-negative (PIN) devices compared with the control ones. This work well demonstrated that the leaky modes of WGM resonant dielectric cavity arrays can effectively improve the light trapping and thus responsivity in broadband or selective spectra for photodetection and will enable future exploration of their applications in other photoelectric conversion devices.

Efficient, Hysteresis-Free, and Stable Perovskite Solar Cells with ZnO as Electron-Transport Layer: Effect of Surface Passivation.

The power conversion efficiency of perovskite solar cells (PSCs) has ascended from 3.8% to 22.1% in recent years. ZnO has been well-documented as an excellent electron-transport material. However, the poor chemical compatibility between ZnO and organo-metal halide perovskite makes it highly challenging to obtain highly efficient and stable PSCs using ZnO as the electron-transport layer. It is demonstrated in this work that the surface passivation of ZnO by a thin layer of MgO and protonated ethanolamine (EA) readily makes ZnO as a very promising electron-transporting material for creating hysteresis-free, efficient, and stable PSCs. Systematic studies in this work reveal several important roles of the modification: (i) MgO inhibits the interfacial charge recombination, and thus enhances cell performance and stability; (ii) the protonated EA promotes the effective electron transport from perovskite to ZnO, further fully eliminating PSCs hysteresis; (iii) the modification makes ZnO compatible with perovskite, nicely resolving the instability of ZnO/perovskite interface. With all these findings, PSCs with the best efficiency up to 21.1% and no hysteresis are successfully fabricated. PSCs stable in air for more than 300 h are achieved when graphene is used to further encapsulate the cells.

Promoting effect of layered titanium phosphate on the electrochemical and photovoltaic performance of dye-sensitized solar cells.

We reported a composite electrolyte prepared by incorporating layered α-titanium phosphate (α-TiP) into an iodide-based electrolyte using 1-ethyl-3-methylimidazolium tetrafluoroborate(EmimBF4) ionic liquid as solvent. The obtained composite electrolyte exhibited excellent electrochemical and photovoltaic properties compared to pure ionic liquid electrolyte. Both the diffusion coefficient of triiodide (I3-) in the electrolyte and the charge-transfer reaction at the electrode/electrolyte interface were improved markedly. The mechanism for the enhanced electrochemical properties of the composite electrolyte was discussed. The highest conversion efficiency of dye-sensitized solar cell (DSSC) was obtained for the composite electrolyte containing 1wt% α-TiP, with an improvement of 58% in the conversion efficiency than the blank one, which offered a broad prospect for the fabrication of stable DSSCs with a high conversion efficiency.