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.

Synergistic effect of alkali metal doping and thiocyanate passivation in CsPbBr3 for HTM-free all-inorganic perovskite solar cells.

All-inorganic CsPbBr3 perovskite solar cells (PSCs) without hole-transport materials (HTMs) have attracted widespread attention because of their significant environmental stability. However, the poor quality of perovskite film and the energetics mismatch between CsPbBr3 and charge-transport layers limit the further improvement of the CsPbBr3 PSC performance. To solve this issue, the synergistic effect of alkali metal doping and thiocyanate passivation in NaSCN and KSCN dopants is utilized to improve the properties of the CsPbBr3 film. The Na+ and K+ with smaller ionic radii are doped at the A-site of CsPbBr3 to cause a lattice contraction, which contributes to the formation of CsPbBr3 film with enhanced grain size and crystallinity. The SCN- exerts the function of passivating the uncoordinated Pb2+ defects of CsPbBr3 film, leading to a reduction of trap state density. The incorporation of NaSCN and KSCN dopants also adjusts the band structure of CsPbBr3 film to improve the interfacial energetics match of the device. As a result, the charge recombination is suppressed, and the charge transfer and extraction are effectively promoted, delivering a highly enhanced power conversion efficiency of 10.38% for the champion KSCN doped CsPbBr3 PSCs without HTMs compared to 6.72% efficiency for the original device. Moreover, the stability of the unencapsulated PSCs under ambient conditions with high humidity (85% RH, 25 °C) is distinctly improved, retaining 91.1% of the initial efficiency after 30 days of aging.

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.

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.

Round-comb Fe2O3@SnO2 heterostructures enable efficient light harvesting and charge extraction for high-performance all-inorganic perovskite solar cells.

The precise design of an electron transport layer (ETL) to improve the light-harvesting and quality of perovskite (PVK) film plays a crucial role in the photovoltaic performance of n-i-p perovskite solar cells (PSCs). In this work, a novel three-dimensional (3D) round-comb Fe2O3@SnO2 heterostructure composites with high conductivity and electron mobility induced by its Type-II band alignment and matched lattice spacing is prepared and employed as an efficient mesoporous ETL for all-inorganic CsPbBr3 PSCs. Arising from the multiple light scattering sites provided by the 3D round-comb structure, the diffuse reflectance of Fe2O3@SnO2 composites is increased to improve the light absorption of the deposited PVK film. Besides, the mesoporous Fe2O3@SnO2 ETL affords not only more active surface for sufficient exposure to the CsPbBr3 precursor solution but also a wettable surface to reduce the barrier for heterogeneous nucleation, which realizes the regulated growth of a high-quality PVK film with less undesired defect. Hence, both the light-harvesting capability, the photoelectrons transport and extraction are improved, and the charge recombination is restrained, delivering an optimized power conversion efficiency (PCE) of 10.23 % with a high short-circuit current density of 7.88 mA cm-2 for the c-TiO2/Fe2O3@SnO2 ETL based all-inorganic CsPbBr3 PSCs. Moreover, under lasting erosion at 25 °C and 85 % RH for 30 days and light-soaking (AM 1.5G) for 480 h in air atmosphere, the unencapsulated-device shows superiorly persistent durability.

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.

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.

Enhanced hole extraction by electron-rich alloys in all-inorganic CsPbBr3 perovskite solar cells.

We present the fabrication of electron-rich Pt3M alloy-tailored carbon electrodes to maximize hole extraction. Through optimizing the doses and alloy species systematically, the best all-inorganic CsPbBr3 perovskite solar cell achieved a power conversion efficiency of 9.08% and showed excellent long-term stability at 80% RH over 20 days.

Achieving Concurrent High Energy Density and Efficiency in All-Polymer Layered Paraelectric/Ferroelectric Composites via Introducing a Moderate Layer.

Dielectric polymer capacitors are extensively applied in advanced electronics by virtue of their extremely high power density. However, it remains a challenge to concurrently realize high energy density and high discharge efficiency. In order to solve this conundrum, we herein design a novel all-polymer trilayer structure, where the paraelectric poly(methyl methacrylate) (PMMA) is used as the top layer to obtain a high discharge efficiency, and ferroelectric P(VDF-HFP) is employed as the bottom layer to obtain a high energy density. Particularly, the PMMA/poly(vinylidene fluoride-hexafluoropropylene) (P(VDF-HFP)) blend composite is used as the middle layer to homogenize the electric field inside the trilayer composites, turning out an obviously boosted breakdown strength and elevated energy density. Consequently, an efficiency as high as 85% and an energy density up to 7.5 J/cm3 along with excellent cycling stability are simultaneously realized at an ultrahigh electric field of 490 kV/mm. These attractive characteristics of the all-polymer trilayer structure suggest that the feasible pathway presented herein is significant to realize concurrently a high energy density and discharge efficiency.

Dimensionality Control of SnO2 Films for Hysteresis-Free, All-Inorganic CsPbBr3 Perovskite Solar Cells with Efficiency Exceeding 10.

The all-inorganic cesium lead bromide (CsPbBr3) perovskite solar cells (PSCs) have attracted considerable interest because of their outstanding environmental stability and low manufacturing cost. However, the state-of-the-art mesoscopic titanium dioxide (TiO2) electron-transporting layers (ETLs) always present low electron mobility, are destructive to perovskites under ultraviolet light illumination, as well as possess high sintering temperature. Nanostructured tin dioxide (SnO2) is a promising electron-transporting material for high-efficiency PSCs due to matching energy-level alignment with the perovskite layer, improved optical transparency, high electron mobility, excellent photostability, and low-temperature processing. Furthermore, rapid but poorly controlled perovskite crystallization makes it difficult to scale up planar PSCs for industrial applications. To address this issue, we adopt a dimensional SnO2 ETL to change the surface wettability for uniform perovskite coverage over large areas and the growth of large-sized CsPbBr3 grains, resulting in a maximum grain size of 1.65 µm. Moreover, the dimensional SnO2 ETL could increase the interfacial contact area between the CsPbBr3 layer and the ETL and enhance the electronic contact for efficient electron extraction to suppress or to eliminate the notorious hysteresis behavior. As expected, a power conversion efficiency (PCE) of 9.51% with an almost hysteresis-free phenomenon is achieved through dimensionality control of SnO2 films attributed to the remarkably enhanced light harvesting, accelerated electron extraction, diminished defect density, and reduced charge recombination. Upon further interfacial modification with graphene quantum dots (GQDs), the PSC based on the two-dimensional SnO2 ETL achieves a champion PCE of 10.34% due to the improved energy-level alignment at the device interface. Moreover, the best all-inorganic CsPbBr3 PSC free of encapsulation retains 93% of initial efficiency over 10 days at 80% relative humidity. This work provides an effective dimensionality control strategy for optimized charge transportation and enlarged perovskite grain size to make stable and efficient all-inorganic CsPbBr3 PSCs.

Enhanced Efficiency of Air-Stable CsPbBr3 Perovskite Solar Cells by Defect Dual Passivation and Grain Size Enlargement with a Multifunctional Additive.

The perovskite solar cells (PSCs) based on cesium lead bromide (CsPbBr3) with outstanding environmental stability and low preparation cost are regarded as one of the most promising photovoltaic devices for commercial applications. However, the performance of CsPbBr3 PSCs can be badly deteriorated by the intense charge recombination arising from the ionic defects at the grain boundaries of perovskite film. To cope with this issue, we adopt an amino acid of l-lysine with two amino and one carboxyl groups as a chemical additive to incorporate into perovskite film to simultaneously anchor the uncoordinated Pb2+ (Cs+) and halogen ion defects. Further, the grain size of CsPbBr3 perovskite is boosted from 688 to over 1000 nm after l-lysine incorporation as a result of the decreased nucleation rate and the sufficient growth of perovskite, which effectively reduce the grain boundaries for load defects. As expected, the optimized device achieves a best power conversion efficiency of 9.69% attributed to the remarkably reduced charge recombination and enhanced charge extraction arising from the efficient defects dual-passivation and enlarged grain size of perovskite film as well as the improved energy level alignment at the device interface after the introduction of l-lysine, which is elevated by 61.23% in comparison to 6.01% efficiency of the pristine one. Moreover, the unencapsulated device with l-lysine incorporation exhibits remarkable long-term stability in air with 80% RH at 25 °C and 0% RH at 80 °C as well as under continuous illumination conditions. This work provides an effective multifunctional additive for imperfection passivation and grain size enlargement of perovskite to build PSCs with high efficiency and stability.

Grain Enlargement and Defect Passivation with Melamine Additives for High Efficiency and Stable CsPbBr3 Perovskite Solar Cells.

The preparation of high-quality perovskite films with low grain boundaries and defect states is a prerequisite for achieving high-efficiency perovskite solar cells (PSCs) with good environmental stability. An effective additive engineering strategy has been developed for simultaneous defect passivation and crystal growth of CsPbBr3 perovskite films by introducing 1,3,5-triazine-2,4,6-triamine (melamine) into the PbBr2 precursor solution. The resultant melamine-PbBr2 film has a loose, large-grained structure and decreased crystallinity, which has a positive effect on the crystallization process of the perovskite as it retards the crystallization rate as a result of the interaction between melamine and lead ions. Additionally, the passivation by melamine gives a high-quality CsPbBr3 perovskite film with fewer grain boundaries, lower defect densities, and better energy level matching is achieved by multistep liquid-phase spin-coating, which greatly suppresses the nonradiative recombination resulting from the defects and promotes charge extraction at the interface. A champion power conversion efficiency as high as 9.65 % with a promising open-circuit voltage of 1.584 V is achieved for PSCs with an architecture of fluorine-doped tin oxide/c-TiO2 /m-TiO2 /melamine-added CsPbBr3 /carbon-based hole-transporting layer. Furthermore, the unencapsulated melamine-added CsPbBr3 PSC shows superior thermal and humidity stability in ambient air at 85 °C or 85 % relative humidity over 720 h.

Interface Engineering of Imidazolium Ionic Liquids toward Efficient and Stable CsPbBr3 Perovskite Solar Cells.

The defect passivation of perovskite films is an efficacious way to further boost the power conversion efficiency (PCE) and long-term stability of perovskite solar cells (PSCs). In this work, ionic liquids (ILs) of 1-butyl-2,3-dimethylimidazolium chloride ([BMMIm]Cl) are used as a modification layer in perovskite films in carbon-based CsPbBr3 PSCs without a hole-transporting material (HTM) for passivating the surface defects. The preliminary results demonstrate that the [BMMIm]Cl modifier passivates the surface defects of the perovskite film and reduces the valence band of perovskite close to the work function of the carbon electrode, which causes a remarkably inhibited nonradiative and radiative charge recombination, improved energy-level matching, and decreased energy loss. After optimization, a champion efficiency of 9.92% with a Voc as high as 1.61 V is achieved for the [BMMIm]Cl tailored carbon-based CsPbBr3 PSC without HTM, which is improved by 61.3% in comparison with 6.15% for the control device. Furthermore, the encapsulation-free PSC presents good long-term stability after storage in an air atmosphere with 70% RH at 20 °C or 0% RH at 80 °C as well as under continuous illumination conditions for 30 days. The significantly improved PCE and stability in high humidity or temperature suggest that the perovskite passivation by ILs is an effective strategy for fabricating high-PCE and stable PSCs.

Enhanced charge extraction with all-carbon electrodes for inorganic CsPbBr3 perovskite solar cells.

Perovskite-structured cesium lead bromide (CsPbBr3) halide provides new opportunities for promoting the commercialization of perovskite solar cells (PSC) due to its high carrier mobility and light absorption coefficient as well as remarkable environmental stability at high humidity and high temperatures. Herein, all-carbon electrodes from multi-walled carbon nanotubes (MWCNT) and carbon black (CB) were prepared for all-inorganic CsPbBr3 PSCs with the configuration of FTO/c-TiO2/m-TiO2/CsPbBr3/carbon. The as-prepared electrodes were free of hole-transporting layers and precious metals. The work function and electrical conductivity of the carbon electrode were tuned by changing the MWCNT/CB ratio to reduce charge recombination at the perovskite/carbon interface. The optimal all-inorganic PSC achieves a maximum power conversion efficiency of 7.62% using the MWCNT (75 wt%)/CB (25 wt%) electrode in comparison with 6.24% for the pure MWCNT-based device. Upon persistent attack by 80% RH in air atmosphere, the solar cell retains 95% of its initial efficiency over 1100 h.

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.

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.

Alloy-Controlled Work Function for Enhanced Charge Extraction in All-Inorganic CsPbBr3 Perovskite Solar Cells.

All-inorganic CsPbX3 (X=I, Br) perovskite solar cells are regarded as cost-effective and stable alternatives for next-generation photovoltaics. However, sluggish charge extraction at CsPbX3 /charge-transporting material interfaces, which arises from large interfacial energy differences, have markedly limited the further enhancement of solar cell performance. In this work, the work function (WF) of the back electrode is tuned by doping alloyed PtNi nanowires in carbon ink to promote hole extraction from CsPbBr3 halides, while an intermediate energy by setting carbon quantum dots (CQDs) at TiO2 /CsPbBr3 interface bridges electron transportation. The preliminary results demonstrate that the matching WFs and intermediate energy level markedly reduce charge recombination. A power conversion efficiency of 7.17 % is achieved for the WF-tuned all-inorganic perovskite solar cell, in comparison with 6.10 % for the pristine device, and this is further increased to 7.86 % by simultaneously modifying with CQDs. The high efficiency and improved stability make WF-controlled all-inorganic perovskite solar cells promising to develop advanced photovoltaic platforms.

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 quantum dot tailored counter electrode for 7.01%-rear efficiency in a bifacial dye-sensitized solar cell.

We present here a carbon quantum dot (CQD) tailored counter electrode (CE) for a bifacial dye-sensitized solar cell (DSSC). Arising from wide spectral absorption, high optical transmission and the electron-enriched surface of the CE, the final bifacial DSSC device yields front and rear efficiencies of 9.08% and 7.01%, respectively.