Efficient Tin-Lead Perovskite Solar Cells with a Ultrawide Usage Windows of Precursor Solution Opened by SnF2.

High quality tin-lead perovskite solar cells (Sn─Pb PSCs) can be fabricated via simple solution processing methods. However, the instability of precursor solutions and their narrow usage windows still pose challenges in manufacturing efficient and reproducible Sn─Pb PSCs, hindering the commercialization of PSCs. Fluorine tin (SnF2 ) is widely used as an antioxidant to improve the crystallinity of perovskite. In this study, another role of SnF2 as a stabilizer is found to restrain the deprotonation of methylammonium iodide (MAI) in the precursor solution, which improves their stability and expands their usage windows. Due to the inhibition of SnF2 on oxidation and deprotonation, stable large-sized colloidal clusters form gradually in perovskite precursor solution during aging, leading to uniform nucleation/crystallization during film growth, significantly reducing the roughness and defect density in the films. Because of the competitive deprotonation and oxidation process of Sn2+ , the benefit of larger cluster maximizes after about ten days storage of precursor solution. The champion efficiency of Sn─Pb PSCs prepared with 10 days aged precursor solution is 22.00%. High performance of devices fabricated with precursor solution stored for even ≈40 days discloses the wide usage windows of precursor solution with SnF2 additive.

Chelating Dual Interface for Efficient and Stable Crystal Growth and Iodine Defect Management in Sn-Pb Perovskite Solar Cells.

Suppressing Sn2+ oxidation and rationally controlling the crystallization process of tin-lead perovskite (Sn-Pb PVK) films by suitable bonding methods have emerged as key approaches to achieving efficient and stable Sn-Pb perovskite solar cells (PSCs). Herein, the chelating coordination is performed at the top and bottom interfaces of Sn-Pb PVK films. The chelation strength is stronger toward Sn2+ than Pb2+ by introducing oligomeric proanthocyanidins (OPC) at the bottom interface. This difference in chelation strength resulted in a spontaneous gradient distribution of Sn/Pb within the perovskite layer during crystallization, particularly enhancing the enrichment of Sn2+ at the bottom interface and facilitating the extraction and separation of photogenerated charge carriers in PSCs. Simultaneously, this top-down distribution of gradually increasing Sn content slowed down the crystallization rate of Sn-Pb PVK films, forming higher-quality films. On the top interface of the PVK, trifluoroacetamidine (TFA) was used to inhibit the generation of iodine vacancies (VI) through chelating with surface-uncoordinated Pb2+/Sn2+, further passivating defects while suppressing the oxidation of Sn2+. Ultimately, the PSCs with simultaneous chelation at both top and bottom interfaces achieved a power conversion efficiency (PCE) of 23.31% and an open-circuit voltage (VOC) exceeding 0.90 V. The stability of unencapsulated target devices in different environments also improved.

An Inverted Perovskite Solar Cell with Good Comprehensive Performance Realized by Reducing the Concentration of Precursors.

Inverted perovskite solar cells (PSCs) exhibit great potential for industrial application thanks to their low complexity and low fabrication temperature. Aiming at commercial applications, it is necessary to comprehensively consider the material consumption and its corresponding electrical performance. Here, a simple strategy has been proposed to obtain inverted PSCs with comprehensive performance, that is, reaching an acceptable electrical performance by reducing the usage of perovskite. More precisely, the inverted PSCs, whose perovskite film is prepared by 1.0 M precursor, yields a power conversion efficiency (PCE) of 15.50%, fulfilling the requirement for real commercial application. In addition, the thickness of the electron transport layer (C60 in this work) in the above inverted PSCs was further optimized by comparing the simulated absorption spectrum, J-V characteristics and impedance with three different thicknesses of C60 layer. More excitingly, the optimized device displays high storage stability which maintains more than 90% of its initial PCE for 28 days. Therefore, our work provides a simple and cost-effective method to reach good comprehensive performance of inverted PSCs for commercial applications.

Boosting Performance of Inverted Perovskite Solar Cells by Diluting Hole Transport Layer.

In our study, by developing the diluted PEDOT:PSS (D-PEDOT:PSS) to replace PEDOT:PSS stock solution as hole transport layer (HTL) materials for fabricating the inverted perovskite solar cells (PSCs), the performance of developed device with ITO/D-PEDOT:PSS/MAPbI3-xClx/C60/BCP/Ag structure is enhanced distinctly. Experimental results reveal that when the dilution ratio is 10:1, the optimal power conversion efficiency (PCE) of the D-PEDOT:PSS device can reach up to 17.85% with an increase of 11.28% compared to the undiluted PEDOT:PSS device. A series of investigations have confirmed that the efficiency improvement is mainly attributed to the two aspects: on one hand, the transmittance and conductivity of D-PEDOT:PSS HTL are improved, and the density of defect states at the interface is reduced after dilution, promoting the separation and transmission of charges, thus the short-circuit current (JSC) is significantly increased; on the other hand, the work function of D-PEDOT:PSS becomes more consistent with perovskite layer, and the voltage loss is reduced, so that the higher open circuit voltage (VOC) is obtained. Our research has indicated that diluting HTL develops a simpler, more efficient and cost-effective method to further improve performance for inverted PSCs.

Phase control of quasi-2D perovskite thin films by adding MAPbI3 in the precursor solution.

Quasi two-dimensional (Q-2D) perovskite cells have attracted much attention due to their excellent stability compared to their 3D counterparts. However, the Q-2D perovskite thin films prepared by the solution method have been confirmed to be a mixture of small-n phases and large-n phases instead of a pure phase, where the amount and distribution of these phases have a great significance on the performance of Q-2D perovskite solar cells. Here, commercialized 3D perovskite powder was simply added to an ACI perovskite precursor solution to get a uniform and closely connected heterostructure in which the large-n phases can work as pathways for charge transfer. The characterization results of the films and devices show that the appropriate amount of MAPbI3 in the precursor solution could distribute the 3D phases homogeneously within the final film to promote the photovoltaic performance of the devices. Consequently, the power conversion efficiency of the Q-2D ACI perovskite solar cell has been increased from 10.4% to 13.82% (with a 32.8% performance improvement).

Dual Function Modification of Cs2CO3 for Efficient Perovskite Solar Cells.

Organic-inorganic hybrid perovskite solar cells (PeSCs) attract much attention in the field of solar cells due to their excellent photovoltaic performance. Many efforts have been devoted to improving their power conversion efficiency (PCE). However, few works focus on simultaneously improving their electrical and optical property. Herein, a simple strategy is proposed to improve the PCE from 19.8% of a reference device to 22.9%, by utilizing cesium carbonate (Cs2CO3) to modify indium tin oxide (ITO) substrate. The insertion of a Cs2CO3-modification layer between ITO substrate and SnO2 electron transport layer simultaneously offers two benefits: improving the electron extraction capability and adjusting the light field distribution in the device. The optical optimization effect of Cs2CO3 revealed in this work has not been reported before. This work provides a new and simple strategy to obtain high performance PeSCs by improving the electrical and optical properties of the devices at the same time.

Simultaneous Passivation of Bulk and Interface Defects with Gradient 2D/3D Heterojunction Engineering for Efficient and Stable Perovskite Solar Cells.

Minimizing bulk and interfacial nonradiative recombination losses is key to further improving the photovoltaic performance of perovskite solar cells (PSC) but very challenging. Herein, we report a gradient dimensionality engineering to simultaneously passivate the bulk and interface defects of perovskite films. The 2D/3D heterojunction is skillfully constructed by the diffusion of an amphiphilic spacer cation from the interface to the bulk. The 2D/3D heterojunction engineering strategy has achieved multiple functions, including defect passivation, hole extraction improvement, and moisture stability enhancement. The introduction of tertiary butyl at the spacer cation should be responsible for increased film and device moisture stability. The device with 2D/3D heterojunction engineering delivers a promising efficiency of 22.54% with a high voltage of 1.186 V and high fill factor of 0.841, which benefits from significantly suppressed bulk and interfacial nonradiative recombination losses. Moreover, the modified devices demonstrate excellent light, thermal, and moisture stability over 1000 h. This work paves the way for the commercial application of perovskite photovoltaics.

InSe:Ge-doped InSe van der Waals heterostructure to enhance photogenerated carrier separation for self-powered photoelectrochemical-type photodetectors.

Two-dimensional (2D) van der Waals (vdW) materials with tunable heterostructures and superior optoelectronic properties have opened a new platform for various applications, e.g., field-effect transistors, ultrasensitive photodetectors and photocatalysts. In this work, an InSe/InSe(Ge) (germanium doped InSe) vdW heterostructure is designed to improve the photoresponse performance of sole InSe in a photoelectrochemical (PEC)-type photodetector. Photoelectrochemical measurements demonstrated that this heterostructure has excellent photoresponse characteristics, including a photocurrent density of 9.8 µA cm-2, a photo-responsivity of 64 µA W-1, and a response time/recovery time of 0.128 s/0.1 s. Moreover, the measurements also revealed the self-powering capability and long-term cycling stability of this heterostructure. The electronic properties of the prepared pure and Ge-doped single crystals unveiled a negative and temperature-independent thermoelectric power and temperature-activated resistivity. The negative character of dominating charge carriers was confirmed by Hall measurements, which corroborated by electrical resistivity revealed a carrier concentration below ∼1015 cm-3 and an electron mobility of ∼500 cm2 V-1 s-1 in Ge-doped crystals. Additionally, the Mott-Schottky model explored the mechanism of charge transfer and enhanced PEC performance. Band bending at the InSe/InSe(Ge)-electrolyte interface benefits the separation and transformation of photogenerated carriers from the heterostructure to electrolyte due to the tunable energy band alignment. These results indicate that the InSe/InSe(Ge) vdW heterostructure is promising for PEC-type photodetectors, which provide a novel way to utilize 2D vdW heterostructures in optoelectronics.

Multi-functional Strategy: Ammonium Citrate-Modified SnO2 ETL for Efficient and Stable Perovskite Solar Cells.

The tin oxide (SnO2) electron transport layer (ETL) plays a crucial role in perovskite solar cells (PSCs). However, the heterogeneous dispersion of commercial SnO2 colloidal precursors is far from optimized, resulting in dissatisfied device performance with SnO2 ETL. Herein, a multifunctional modification material, ammonium citrate (TAC), is used to modify the SnO2 ETL, bringing four benefits: (1) due to the electrostatic interaction between TAC molecules and SnO2 colloidal particles, more uniformly dispersed colloidal particles are obtained; (2) the TAC molecules distributed on the surface of SnO2 provide nucleation sites for the perovskite film growth, promoting the vertical growth of the perovskite crystal; (3) TAC-doped SnO2 shows higher electron conductivity and better film quality than pristine SnO2 while offering better energy-level alignment with the perovskite layer; and (4) TAC has functional groups of C═O and N-H containing lone pair electrons, which can passivate the defects on the surface of SnO2 and perovskite films through chemical bonding and inhibit the device hysteresis. In the end, the device based on TAC-doped ETL achieved an increased power conversion efficiency (PCE) of 21.58 from 19.75% of the reference without such treatment. Meanwhile, the PSCs using the TAC-doped SnO2 as the ETL maintained 88% of their initial PCE after being stored for about 1000 h under dark conditions and controlled RH of 10-25%.

Effect of guanidinium chloride in eliminating O2 - electron extraction barrier on a SnO2 surface to enhance the efficiency of perovskite solar cells.

Owing to their low cost, easy fabrication and excellent chemical stability properties, tin dioxide (SnO2) nanoparticles have been widely employed as an electron transfer material in many high-efficiency perovskite solar cells (PeSCs). However, the adsorbed oxygen species (i.e. O2 -) on the surface of the SnO2 layer, which are induced by the annealing process under ambient environment, have always been overlooked. In general, the adsorption of oxygen creates an energy barrier at the SnO2/perovskite interface, impairing the efficiency of PeSCs. In this work, by using guanidinium (GA) chloride to modify the SnO2 surface, we have successfully improved the power conversion efficiency (PCE) of PeSCs from 15.33% (no GA-modification) to 18.46%, with a maximum fill factor of 80%. The performance enhancement is mainly attributed to the reduced energy barrier at the SnO2/perovskite interface due to the strong coupling between the GA and the adsorbed oxygen, which has been supported by the FTIR and XPS results. The strategy of reducing the charge extraction barrier by GA modification has been demonstrated to be an efficient approach to improve both the PCE and stability.

Nuclei position-control and crystal growth-guidance on frozen substrates for high-performance perovskite solar cells.

Nucleation and crystal growth are key stages for high-quality perovskite films that dominate the performance of perovskite solar cells. However, the position of nuclei in the films and the orientation of the crystal growth have not yet been intendedly controlled during their fabrication. In this study, we developed a method of spin-coating perovskite films on frozen substrates to control the position of the nuclei and the direction of the crystal growth at the same time. In this way, the position of the crystal nuclei and the growth orientation of the perovskite crystals in the perovskite films can be simultaneously controlled. A high-quality perovskite film with grains spanning vertically the entire film thickness has been obtained using this new method. And an efficient inverted planar solar cell (ITO/PEDOT:PSS/CH3NH3PbI3/PC61BM/BCP/Ag) with the highest power conversion efficiency of 17.14% and open-circuit voltage of 1.14 V has been achieved by using this technique.

Resistive switching behaviors and memory logic functions in single MnOx nanorod modulated by moisture.

A device with the lateral structure of Ag|MnOx|Ag was developed using a single MnOx nanorod. The device showed a typical resistor property under dry ambience, while it demonstrated the reversion between resistor and memristor under moisture ambience. Memory logic functions including logic gates and displays were feasible under the dual input of electric and moisture signals.

Evolution map of the memristor: from pure capacitive state to resistive switching state.

Memristors possess great application prospects in terabit nonvolatile storage devices, memory-in-logic algorithmic chips and bio-inspired artificial neural network systems. However, "what is the origin state of the memristor?" has remained an unanswered question for half a century. While many applications rely on the memristor, its origin state is becoming a fundamental issue. Herein, we reveal a new state, the pure capacitance state (PCS), which occurs before the memristor is triggered, and the origin state of the memristor can be verified in the memory cells through controlling the ambience parameters. Discovery of the PCS, a missing earlier stage of the memristor, completes the whole evolution map of the memristor from the very beginning to the final developed state.