Influence of Donor Skeleton on Intramolecular Electron Transfer Amount for Efficient Perovskite Solar Cells.

The passivation of the defects derived from rapid-crystallization with electron-donating molecules is always a prerequisite to obtain desirable perovskite films for efficient and stable solar cells, thus, the in-depth understanding on the correlations between molecular structure and passivation capacity is of great importance for screening passivators. Here, we introduce the double-ended amide molecule into perovskite precursor solution to modulate crystallization process and passivate defects. By regulating the intermediate bridging skeletons with alkyl, alkenyl and benzene groups, the results show the passivation strength highly depends on the spin-state electronic structure that serves as an intrinsic descriptor to determine the intramolecular charge distribution by controlling orbital electron transfer from the donor segment to acceptor segment. Upon careful optimization, the benzene-bridged amide molecule demonstrates superior efficacy on improving perovskite film quality. As a physical proof-of-concept, the carbon-based, all-inorganic CsPbI2Br solar cell delivers a significantly increased efficiency of 15.51 % with a remarkably improved stability. Based on the same principle, a champion efficiency of 24.20 % is further obtained on the inverted (Cs0.05MA0.05FA0.9)Pb(I0.93Br0.07)3 solar cell. These findings provide new fundamental insights into the influence of spin-state modulation on effective perovskite solar cells.

Phase Control of Cs-Pb-Br Derivatives to Suppress 0D Cs4 PbBr6 for High-Efficiency and Stable All-Inorganic CsPbBr3 Perovskite Solar Cells.

The precise phase control of Cs-Pb-Br derivatives from 3D CsPbBr3 to 0D Cs4 PbBr6 highly determines the photovoltaic performance of all-inorganic CsPbBr3 perovskite solar cells (PSCs). Herein, the preferred phase conversion from precursor to Cs-Pb-Br derivatives is revealed by theoretically calculating the Gibbs free energies (∆G) of various phase conversion processes, allowing for a simplified multi-step solution-processable spin-coating method to hinder the formation of detrimental 0D Cs4 PbBr6 phase and enhance the photovoltaic performance of a PSC because of its large exciton binding energy, which is regarded as a recombination center. By further accelerating the interfacial charge extraction with a novel 2D transition metal dichalcogenide ReSe2 , the hole-free CsPbBr3 PSC achieves a champion efficiency of 10.67% with an impressive open-circuit voltage of 1.622 V and an excellent long-term stability. This work provides an in-depth understanding on the precise Cs-Pb-Br perovskite phase control and the effect of derivatives on photovoltaic performance of advanced CsPbBr3 PSCs.

Thermal-Triggered Dynamic Disulfide Bond Self-Heals Inorganic Perovskite Solar Cells.

One great challenge for perovskite solar cells (PSCs) lies in their poor operational stability under harsh stimuli by humidity, heat, light, etc. Herein, a thermal-triggered self-healing polyurethane (PU) is tailored to simultaneously improve the efficiency and stability of inorganic CsPbIBr2 PSCs. The dynamic covalent disulfide bonds between adjacent molecule chains in PU at high temperatures self-heal the in-service formed defects within the CsPbIBr2 perovskite film. Finally, the best device free of encapsulation achieves a champion efficiency up to 10.61 % and an excellent long-term stability in an air atmosphere over 80 days and persistent heat attack (85 °C) over 35 days. Moreover, the photovoltaic performances are recovered by a simple heat treatment.

p-Type Charge Transfer Doping of Graphene Oxide with (NiCo)1-y Fey Ox for Air-Stable, All-Inorganic CsPbIBr2 Perovskite Solar Cells.

The precise regulation of interfacial charge distribution highly determines the power conversion efficiency of perovskite solar cells (PSCs). Herein, inorganic (NiCo)1-y Fey Ox nanoparticle decorated graphene oxide (GO) is successfully demonstrated as a hole booster for all-inorganic CsPbIBr2 PSC free of precious metal electrode. Arising from the spontaneous electron transfer induced p-type doping of GO from edged oxygen-containing functional groups to (NiCo)1-y Fey Ox , the best all-inorganic CsPbIBr2 PSC achieves an efficiency of 10.95 % under one standard sun owing to the eliminated paradox between charge extraction and charge localization in GO surface. Furthermore, the champion device exhibits an excellent long-term stability at 10 % relative humidity without encapsulation over 70 days because of the suppressed ions migration.

Interfacial Strain Release from the WS2 /CsPbBr3 van der Waals Heterostructure for 1.7†V Voltage All-Inorganic Perovskite Solar Cells.

Perovskite lattice distortion induced by residual tensile strain from the thermal expansion mismatch between the electron-transporting layer (ETL) and perovskite film causes a sluggish charge extraction and transfer dynamics in all-inorganic CsPbBr3 perovskite solar cells (PSCs) because of their higher crystallization temperatures and thermal expansion coefficients. Herein, the interfacial strain is released by fabricating a WS2 /CsPbBr3 van der Waals heterostructure owing to their matched crystal lattice structure and the atomically smooth dangling bond-free surface to act as a lubricant between ETL and CsPbBr3 perovskite. Arising from the strain-released interface and condensed perovskite lattice, the best device achieves an efficiency of 10.65 % with an ultrahigh open-circuit voltage of 1.70 V and significantly improved stability under persistent light irradiation and humidity (80 %) attack over 120 days.

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.

Hole-Boosted Cu(Cr,M)O2 Nanocrystals for All-Inorganic CsPbBr3 Perovskite Solar Cells.

The all-inorganic CsPbBr3 perovskite solar cell (PSC) is a promising solution to balance the high efficiency and poor stability of state-of-the-art organic-inorganic PSCs. Setting inorganic hole-transporting layers at the perovskite/electrode interface decreases charge carrier recombination without sacrificing superiority in air. Now, M-substituted, p-type inorganic Cu(Cr,M)O2 (M=Ba2+ , Ca2+ , or Ni2+ ) nanocrystals with enhanced hole-transporting characteristics by increasing interstitial oxygen effectively extract holes from perovskite. The all-inorganic CsPbBr3 PSC with a device structure of FTO/c-TiO2 /m-TiO2 /CsPbBr3 /Cu(Cr,M)O2 /carbon achieves an efficiency up to 10.18 % and it increases to 10.79 % by doping Sm3+ ions into perovskite halide, which is much higher than 7.39 % for the hole-free device. The unencapsulated Cu(Cr,Ba)O2 -based PSC presents a remarkable stability in air in either 80 % humidity over 60 days or 80 °C conditions over 40 days or light illumination for 7 days.

Simplified Perovskite Solar Cell with 4.1% Efficiency Employing Inorganic CsPbBr3 as Light Absorber.

Perovskite solar cells with cost-effectiveness, high power conversion efficiency, and improved stability are promising solutions to the energy crisis and environmental pollution. However, a wide-bandgap inorganic-semiconductor electron-transporting layer such as TiO2 can harvest ultraviolet light to photodegrade perovskite halides, and the high cost of a state-of-the-art hole-transporting layer is an economic burden for commercialization. Here, the building of a simplified cesium lead bromide (CsPbBr3 ) perovskite solar cell with fluorine-doped tin oxide (FTO)/CsPbBr3 /carbon architecture by a multistep solution-processed deposition technology is demonstrated, achieving an efficiency as high as 4.1% and improved stability upon interfacial modification by graphene quantum dots and CsPbBrI2 quantum dots. This work provides new opportunities of building next-generation solar cells with significantly simplified processes and reduced production costs.

High-Purity Inorganic Perovskite Films for Solar Cells with 9.72 % Efficiency.

All-inorganic perovskite solar cells with high efficiency and improved stability are promising for commercialization. A multistep solution-processing method was developed to fabricate high-purity inorganic CsPbBr3 perovskite films for use in efficient solar cells. By tuning the number of deposition cycles (n) of a CsBr solution, the phase conversion from CsPb2 Br5 (n ≤3), to CsPbBr3 (n=4), and Cs4 PbBr6 (n≥5) was optimized to achieve vertical- and monolayer-aligned grains. Upon interfacial modification with graphene quantum dots, the all-inorganic perovskite solar cell (without a hole-transporting layer) achieved a power conversion efficiency (PCE) as high as 9.72 % under standard solar illumination conditions. Under challenging conditions, such as 90 % relative humidity (RH) at 25 °C or 80 °C at zero humidity, the optimized device retained 87 % PCE over 130 days or 95 % over 40 days, compared to the initial efficiency.

Carbon-Electrode-Tailored All-Inorganic Perovskite Solar Cells To Harvest Solar and Water-Vapor Energy.

Moisture is the worst enemy for state-of-the-art perovskite solar cells (PSCs). However, the flowing water vapor within nanoporous carbonaceous materials can create potentials. Therefore, it is a challenge to integrate water vapor and solar energies into a single PSC device. We demonstrate herein all-inorganic cesium lead bromide (CsPbBr3 ) solar cells tailored with carbon electrodes to simultaneously harvest solar and water-vapor energy. Upon interfacial modification and plasma treatment, the bifunctional PSCs yield a maximum power conversion efficiency up to 9.43 % under one sun irradiation according to photoelectric conversion principle and a power output of 0.158 µW with voltage of 0.35 V and current of 0.45 µA in 80 % relative humidity through the flowing potentials at the carbon/water interface. The initial efficiency is only reduced by 2 % on exposing the inorganic PSC with 80 % humidity over 40 days. The successful realization of physical proof-of-concept multi-energy integrated solar cells provides new opportunities of maximizing overall power output.

Strain engineering improves the photovoltaic performance of carbon-based hole-transport-material free CsPbIBr2 perovskite solar cells.

Alkylamines with different chain lengths including n-butylamine, n-hexylamine, and n-octylamine, are applied to regulate the CsPbIBr2 perovskite film quality by strain engineering. The status of residual strains is controllably modulated, resulting in improved efficiency and stability of carbon-based hole-transport-material free CsPbIBr2 perovskite solar cells.

Healing the Buried Interface by a Plant-Derived Green Passivator for Carbon-Based CsPbIBr2 Perovskite Solar Cells.

Perovskite solar cells (PSCs) have attracted extensive attention in photovoltaic applications owing to their superior efficiency, and the buried interface plays a significant role in determining the efficiency and stability of PSCs. Herein, a plant-derived small molecule, ergothioneine (ET), is adopted to heal the defective buried interface of CsPbIBr2-based PSC to improve power conversion efficiency (PCE). Because of the strong interaction between Lewis base groups (-C═O and -C═S) in ET and uncoordinated Pb2+ in the perovskite film from the theoretical simulations and experimental results, the defect density of the CsPbIBr2 perovskite film is significantly reduced, and therefore, the nonradiative recombination in the corresponding device is simultaneously suppressed. Consequently, the target device achieves a high PCE of 11.13% with an open-circuit voltage (VOC) of 1.325 V for hole-free, carbon-based CsPbIBr2 PSCs and 14.56% with a VOC of 1.308 V for CsPbI2Br PSCs. Furthermore, because of the increased ion migration energy, the detrimental phase segregation in this mixed-halide perovskite is weakened, delivering excellent long-term stability for the unencapsulated device in ambient conditions over 70 days with a 96% retention rate of initial efficiency.

A trifunctional polyethylene oxide buffer layer for stable and efficient all-inorganic CsPbBr3 perovskite solar cells.

Carbon-based all-inorganic perovskite solar cells have attracted growing interest owing to their simple fabrication process, low cost, and high stability in air. On account of the large interfacial energy barriers and polycrystalline features of perovskite films, the carrier interface recombination and inherent defects in the perovskite layer are still great challenges in further increasing the power conversion efficiency and stability of carbon-based PSCs. We present here a trifunctional polyethylene oxide buffer layer at the perovskite/carbon interface to promote the PCE and stability of carbon-based all-inorganic CsPbBr3 PSCs: (i) the PEO layer increases the crystallinity of inorganic CsPbBr3 grains for low defect state density; (ii) the oxygenic groups in PEO chains passivate the defects on the perovskite surface; and (iii) the long hydrophobic alkyl chains improve the stability in moisture. The best encapsulated PSC achieves a PCE of 8.84% and maintains 84.8% of its initial efficiency in air with 80% RH over 30 days.

Self-powered PtNi-polyaniline films for converting rain energy into electricity.

Developing novel rainwater energy harvesting beyond conventional electricity is a promising strategy to address the problems of the energy crisis and environmental pollution. In this current work, a class of self-powered PtNi and optimal PtNi-polyaniline (PANI) films are successfully developed to convert rainwater into electricity for power generation. The maximized current, voltage and power of the self-powered PtNi-PANI films are 4.95 µA per droplet, 69.85 µV per droplet and 416.54 pW per droplet, respectively, which are attributed to the charging/discharging electrical signals between the cations provided by the rainwater and the electrons offered by the films. These results indicate that the optimized signal values are highly dependent on the elevated electron concentration of films, as well as the concentration, radius and charge of ions in rainwater. This work provides fresh insights into rain energy and enriches our knowledge of how to convert renewable energy into electricity generation.

Charge transfer doping of graphene oxide with nickel oxide nanoparticles for stable and efficient carbon-based, all-inorganic CsPbBr3 perovskite solar cells.

All-inorganic CsPbBr3 perovskite solar cells have received growing attention in the photovoltaic field due to their high stability, low cost, and simple preparation processes. However, the high-density defects in perovskite films and the large energy differences at interfaces have been the main challenges for achieving high power conversion efficiency and good stability. In this work, nickel oxide (NiOx) decorated graphene oxide (GO) is used as a hole collector at the perovskite/carbon interface for a carbon-based CsPbBr3 perovskite solar cell. The crystallinity of the CsPbBr3 perovskite layer and the hole extraction ability are markedly enhanced because of the p-type charge transfer doping of GO from oxygenic groups to NiOx. Finally, the all-inorganic CsPbBr3 perovskite solar cell achieves a power conversion efficiency of 8.59%. More importantly, the best solar cell free of encapsulation retains 94.2% of its initial efficiency in an air environment over 21 days.

Liquid buried interface to slide lattice and heal defects in inorganic perovskite solar cells.

The residual tensile strain, which is induced by lattice and thermal expansion coefficient difference between upper perovskite film and underlying charge transporting layer, significantly deteriorates the power conversion efficiency (PCE) and stability of a halide perovskite solar cell (PSC). To overcome this technical bottleneck, herein, we propose a universal liquid buried interface (LBI) by introducing a low melting-point small molecule to replace traditional solid-solid interface. Arising from the movability upon solid-to-liquid phase conversion, LBI plays a role of "lubricant" to effectively free the soft perovskite lattice shrinkage or expansion rather than anchoring onto the substrate, leading to the reduced defects due to the healing of strained lattice. Finally, the inorganic CsPbIBr2 PSC and CsPbI2Br cell achieve the best PCEs of 11.13 % and 14.05 %, respectively, and the photo-stability is improved by 33.3-fold because of the suppressed halide segregation. This work provides new insights on the LBI for making high-efficiency and stable PSC platforms.

Universal Energy Solution for Triboelectric Sensors Toward the 5G Era and Internet of Things.

The launching of 5G technology provides excellent opportunity for the prosperous development of Internet of Things (IoT) devices and intelligent wireless sensor nodes. However, deploying of tremendous wireless sensor nodes network presents a great challenge to sustainable power supply and self-powered active sensing. Triboelectric nanogenerator (TENG) has shown great capability for powering wireless sensors and work as self-powered sensors since its discovery in 2012. Nevertheless, its inherent property of large internal impedance and pulsed "high-voltage and low-current" output characteristic seriously limit its direct application as stable power supply. Herein, a generic triboelectric sensor module (TSM) is developed toward managing the high output of TENG into signals that can be directly utilized by commercial electronics. Finally, an IoT-based smart switching system is realized by integrating the TSM with a typical vertical contact-separation mode TENG and microcontroller, which is able to monitor the real-time appliance status and location information. Such design of a universal energy solution for triboelectric sensors is applicable for managing and normalizing the wide output range generated from various working modes of TENGs and suitable for facile integration with IoT platform, representing a significant step toward scaling up TENG applications in future smart sensing.

Electronic metal-support interaction constructed for preparing sinter-resistant nano-platinum catalyst with redox property.

Generally, support materials with particular structural properties could effectively anchor metal nanoparticles and provide lower activation barriers in heterogeneous catalysis. To tailor the structure of stable iron oxide, NiFe2O4 of inverse spinel structure was obtained by combining nickel with iron element under an alkaline environment and high-temperature calcination. The p-type conductivity of NiFe2O4 provides the possibility of constructing electronic interfacial interaction with Pt nanoparticles by electron transfer. The constructed metal-support interaction could effectively stabilize Pt nanoparticles and be further enhanced during long-term harsh calcination (700 °C for 48 h) even under an O2 atmosphere. Meanwhile, the abundant structural defects of NiFe2O4 are beneficial for constructing low-temperature redox centers with the aid of Pt nanoparticles. Pt/NiFe2O4 exhibited not only excellent activity in room-temperature oxidation (CO and HCHO) and reduction reactions (chemo-selective hydrogenation of nitroarenes), but also high stability even after storage for more than 6 months. A self-adjusting mechanism triggered by structural defects is disclosed by in situ characterization and systematic reaction results. This work demonstrates an alternative concept to construct sinter-resistant and highly-effective nano-platinum catalysts robust for oxidation and reduction reactions.

In situ formation of inorganic healing overlayer for interface-stabilized all-inorganic CsPbIBr2 perovskite solar cells.

A perovskite layer functionalized to be an outermost screen can strongly affect the capacity of the underlying device to avoid becoming decomposed under external stimuli, and subsequently affect the photovoltaic performance as well. Herein, we report an interface-stabilization strategy for an all-inorganic CsPbIBr2 film involving forming in situ an inorganic ZrO2 layer to solidify the soft perovskite lattice. As a result of defect passivation and self-encapsulation, the best device achieved an enhanced efficiency of up to 10.12%, which was much higher than the 7.47% efficiency for the reference device tested, with prolonged stability under conditions of persistent light irradiation and exposure to air.

Universal Dynamic Liquid Interface for Healing Perovskite Solar Cells.

Healing charge-selective contact interfaces in perovskite solar cells (PSCs) highly determines the power conversion efficiency (PCE) and stability. However, the state-of-the-art strategies are often static by one-off formation of a functional interlayer, which delivers fixed interfacial properties during the subsequent operation. As a result, defects formed in-service will gradually deteriorate the photovoltaic performances. Herein, a dynamic healing interface (DHI) is presented by incorporating a low-melting-point small molecule onto perovskite film surface for highly efficient and stable PSCs. Arising from the reduced non-radiative recombination, the DHI boosts the PCE to 12.05% for an all-inorganic CsPbIBr2 solar cell and 14.14% for a CsPbI2 Br cell, as well as 23.37% for an FA0.92 MA0.08 PbI3 (FA = formamidinium, MA = methylammonium) cell. The solid-to-liquid phase conversion of DHI at elevated temperature causes a longitudinal infiltration into the bulk perovskite film to maximize the charge extraction, passivate defects at grain boundaries, and suppress ion migration. Furthermore, the stability is remarkably enhanced under air, heat, and persistent light-irradiation conditions, paving a universal strategy for advanced perovskite-based optoelectronics.