In Situ Electrochemical Cobalt Doping in Perovskite-Structured Lanthanum Nickelate Thin Film Toward Energy Conversion Enhancement of Polymer Solar Cells.

This study demonstrates that the electrochemical doping of lanthanum nickelate (LNO) with cobalt ions is a promising strategy for enhancing its physical and electrochemical properties, which are critical for energy storage and conversion devices. LNO emerges as a promising hole transport layer (HTL) in solar cells due to its stability, large band gap, and high transparency. Nevertheless, its low conductivity and improperly aligned band positions are persistent problems. Here, in a pioneering endeavor, Co-doped LNO thin films were synthesized electrochemically and applied as the HTL in polymer solar cells (PSCs). Characterization revealed the impact of Co doping on the electrochemical, structural, morphological, and optical properties of LNO thin films. Depending on the Co doping level, PSCs based on 10 mol % Co-doped LNO outperformed pure LNO, achieving a champion efficiency of 6.11% with enhanced short-circuit current density (12.84 mA cm-2), fill factor (68%), open-circuit voltage (0.70 V), and external quantum efficiency (82.6%). This enhancement resulted from decreased series resistance, refined surface morphology, minimized trap-assisted recombination, enhanced conductivity, increased charge carrier production, favorable energy level alignment, and improved current extraction facilitated by LNC0.10O HTL. Moreover, the unencapsulated PSC-LNC0.10O long-term stability notably improved and retained 86% of its initial PCE after 450 h storage in ambient air, 82% after being continuously heated to 85 °C for 300 h, and 80% after operating at maximum power point for 300 h. These findings offer a straightforward approach to enhancing PSC performance through Co doping of LNO, supported by density functional theory (DFT) calculations that validate the experimental results and confirm the improvement in optical properties and stability of PSCs as an HTL.

Stable Inverted Perovskite Solar Cells with Efficiency over 23.0% via Dual-Layer SnO2 on Perovskite.

Perovskite solar cells (PSCs) have shown great potential for reducing costs and improving power conversion efficiency (PCE). One effective method to achieve the latter is to use an all-inorganic charge transport layer (ICTL). However, traditional methods for crystallizing inorganic layers often result in the formation of a powder instead of a continuous film. To address this issue, we designed a dual-layer inorganic electron transport layer (IETL). This dual-layer structure consists of a layer of SnO2 nanocrystals (SnO2 NCs) deposited via a solution process and a dense SnO2 layer deposited through atomic layer deposition (ALD SnO2) to fill the cracks and gaps between the SnO2 NCs. PSCs having these dual-layer SnO2 ETLs achieved a high efficiency of 23.0%. This efficiency surpasses the recorded performance of ICTLs deposited on the perovskite. Furthermore, the PCE is comparable to that achieved with a C60 ETL. Moreover, the high-density structure of the ALD SnO2 layer inhibits the vertical migration of ions, resulting in improved thermal stability. After continuous heating at 85 °C in 10% humidity for 1000 h, the PCE of the dual-layer SnO2 structure decreased by 18%, whereas that of the C60/BCP structure decreased by 36%. The integration of dual-layer SnO2 into PSCs represents a significant advancement in achieving high-performance, commercially viable inverted monolithic PSCs or tandem solar cells.

Modulation of Charge Transport from Two-Dimensional Perovskites to Industrial Charge Transport Layers by the Organic Spacer-Dependent Exciton-Phonon Interactions.

In the past decade, two-dimensional (2D) perovskite surface treatment has emerged as a promising strategy to improve the performance of three-dimensional (3D) perovskite solar cells (PSCs). However, systematic studies on the impact of organic spacers of 2D perovskites on charge transport in 2D/3D PSCs are still lacking. Here, using 2D perovskite film/C60 heterostructures with different organic spacers [butylamine (BA), phenylethylamine (PEA), and 3-fluorophenethylamine (m-F-PEA)], we systematically investigated the carrier diffusion and interfacial transfer process. Using a 2D perovskite film with a thickness of ∼7 nm, we observed subtle differences in electron transfer time between 2D perovskites and C60 layers, which can be attributed to limited thickness and similar electron coupling strength. However, with the thickness of 2D perovskite increasing, electron transfer efficiency in the (BA)2PbI4/C60 heterostructure exhibits the most rapid decrease due to poor carrier diffusion of (BA)2PbI4 caused by stronger exciton-phonon interactions compared to (PEA)2PbI4 and (m-F-PEA)2PbI4 in thickness-dependent charge transfer research. Meanwhile, the fill factor of 2D/3D PSC treated with BAI exhibits the most rapid decrease compared to PEAI- and m-F-PEAI-treated 2D/3D PSCs with the concentration increase of passivators. This study indicates that it is easier to enhance open-circuit voltages and minimize the decrease of fill factor by increasing the concentration of passivators in 2D/3D PSCs when using passivators with a rigid molecular structure.

Thickness Optimization of Charge Transport Layers on Perovskite Solar Cells for Aerospace Applications.

In aerospace applications, SiOx deposition on perovskite solar cells makes them more stable. However, the reflectance of the light changes and the current density decreases can lower the efficiency of the solar cell. The thickness of the perovskite material, ETL, and HTL must be re-optimized, and testing the number of cases experimentally takes a long time and costs a lot of money. In this paper, an OPAL2 simulation was used to find the thickness and material of ETL and HTL that reduces the amount of light reflected by the perovskite material in a perovskite solar cell with a silicon oxide film. In our simulations, we used an air/SiO2/AZO/transport layer/perovskite structure to find the ratio of incident light to the current density generated by the perovskite material and the thickness of the transport layer to maximize the current density. The results showed that when 7 nm of ZnS material was used for CH3NH3PbI3-nanocrystalline perovskite material, a high ratio of 95.3% was achieved. In the case of CsFAPbIBr with a band gap of 1.70 eV, a high ratio of 94.89% was shown when ZnS was used.

Interfaces and Interfacial Layers in Inorganic Perovskite Solar Cells.

Owing to their superior thermal stability, metal halide inorganic perovskite materials continue to attract interest for photovoltaics applications. The highest reported power conversion efficiency (PCE) for solar cells based on inorganic perovskites is over 20 %. As this PCE corresponds to 73 % of the theoretical limit, there remains more room for further improving the device PCEs than for improving organic-inorganic hybrid perovskite solar cells (PSCs). The main loss is in the photovoltage, which is limited by interfaces in terms of non-radiative recombination caused by traps and energy-level mismatch. Furthermore, inefficient charge extraction at interfacial contacts reduces the photocurrent and fill factor. This Minireview summarizes the recent developments in the fundamental understanding of how the interfaces and interfacial layers influence the performance of solar cells based on inorganic perovskite absorbers. An outlook for the development of highly efficient and stable inorganic PSCs from the interface point of view is also given.

Inverted Polymer Solar Cells with Annealing-Free Solution-Processable NiO.

Nickel oxide (NiO) offers intrinsic p-type behavior and high thermal and chemical stability, making it promising as a hole transport layer (HTL) material in inverted organic solar cells. However, its use in this application has been rare because of a wettability problem caused by use of water as base solvent and high-temperature annealing requirements. In the present work, an annealing-free solution-processable method for NiO deposition is developed and applied in both conventional and inverted non-fullerene polymer solar cells. To overcome the wettability problem, the typical DI water solvent is replaced with a mixed solvent of DI water and isopropyl alcohol with a small amount of 2-butanol additive. This allows a NiO nanoparticle suspension (s-NiO) to be deposited on a hydrophobic active layer surface. An inverted non-fullerene solar cell based on a blend of p-type polymer PTB7-Th and non-fullerene acceptor IEICO-4F exhibits the high efficiency of 11.23% with an s-NiO HTL, comparable to the efficiency of an inverted solar cell with a MoOx HTL deposited by thermal evaporation. Conventionally structured devices including this s-NiO layer show efficiency comparable to that of a conventional device with a PEDOT:PSS HTL.

Highly Efficient and Super Stable Full-Color Quantum Dots Light-Emitting Diodes with Solution-Processed All-Inorganic Charge Transport Layers.

High performance and super stable all-inorganic full-color quantum dot light-emitting diodes (QLEDs) are constructed by adopting solution-processed Mg-doped NiOx (Mg-NiOx ) nanoparticles as hole transport layer (HTL) and Al-doped ZnO (AZO) as electron transport layer (ETL). Mg-NiOx nanoparticles possess the advantages of low-temperature solution processability, intrinsic stability, and controllable electronic properties. UV-ozone (UVO) treatment is applied to the Mg-NiOx film to modulate its surface composition. By carefully controlling the UVO treating time, favorable energy levels can be achieved to minimize the energy barrier for hole injection. At the cathode side, Al-doping can reduce the conductivity of ZnO ETL and decrease the interface charge transfer, effectively, thus leading to more balanced charge injection and consequent high luminance and efficiency. The maximum luminance and EQE can reach as high as 38 444 cd m-2 and 5.09% for R-QLEDs, 177 825 cd m-2 and 10.1% for G-QLEDs, and 3103 cd m-2 and 2.19% for B-QLEDs. The luminance values are the highest ever reported for all-inorganic QLEDs. Furthermore, the all-inorganic devices show much better resistance to water and oxygen existing in air. The results show that the ion-doped NiOx and AZO nanoparticles would facilitate the design and development of highly efficient and super stable QLEDs.

Hysteresis-Free Planar Perovskite Solar Cells with a Breakthrough Efficiency of 22% and Superior Operational Stability over 2000 h.

Understanding the transport loss and the ways to improving optoelectronic properties of the charge transporting layers is critical to fabricate highly efficient, long-term stable, and hysteresis-free perovskite solar cells (PSCs). Herein, we report success in suppressing hysteresis and boosting the performance of operationally stable planar solar cells using a ruthenium (Ru) doped tin oxide (SnO2) electron transport layer (ETL) and Zn-TFSI2 doped spiro-OMeTAD hole transport layer (HTL). Apparently, the incorporation of Ru drastically shifts the Fermi level of SnO2 ETL upward, which provides a facile route to tailor the ETL/perovskite band-offset to improve built-in electric fields of devices for improving VOC and electron extraction simultaneously. Meanwhile, rapid injection of the photogenerated electrons from perovskite into ETL with reduced trap density is also observed when Ru doped SnO2 is employed as ETL. On the other hand, the conception of Zn-TFSI2 incorporation into HTL not only further boosts the photovoltaic performance but also prolongs the photostability of the devices. Consequently, a breakthrough efficiency of 22% (average 21.8%) with a JSC of 24.6 mA cm-2, VOC of 1.15 V, and FF of 0.78 has been obtained in planar-type PSCs with a loss in efficiency of only ∼3% at maximum power point tracking over 2000 h.

Beyond Fullerenes: Indacenodithiophene-Based Organic Charge-Transport Layer toward Upscaling of Low-Cost Perovskite Solar Cells.

Phenyl-C61-butyric acid methyl ester (PCBM) is universally used as the electron-transport layer (ETL) in the low-cost inverted planar structure of perovskite solar cells (PeSCs). PCBM brings tremendous challenges in upscaling of PeSCs using industry-relevant methods due to its aggregation behavior, which undermines the power conversion efficiency and stability. Herein, we highlight these, seldom reported, challenges with PCBM. Furthermore, we investigate the potential of nonfullerene indacenodithiophene (IDT)-based molecules by employing a commercially available variant, 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3- d:2',3'- d']- s-indaceno[1,2- b:5,6- b'] dithiophene (ITIC), as a PCBM replacement in ambient-processed PeSCs. Films fabrication by laboratory-based spin-coating and industry-relevant slot-die coating methods are compared. Although similar power-conversion efficiencies are achieved with both types of ETL in a simple device structure fabricated by spin-coating, the nanofibriller morphology of ITIC compared to the aggregated morphology of PCBM films enables improved mechanical integrity and stability of ITIC devices. Upon slot-die coating, the aggregation of PCBM is exacerbated, leading to significantly lower power-conversion efficiency of devices than spin-coated PCBM as well as slot-die-coated ITIC devices. Our results clearly indicate that IDT-based molecules have great potential as an ETL in PeSCs, offering superior properties and upscaling compatibility than PCBM. Thus, we present a short summary of recently emerged nonfullerene IDT-based molecules from the field of organic solar cells and discuss their scope in PeSCs as electron or hole-transport layer.

Highly Repeatable and Recoverable Phototransistors Based on Multifunctional Channels of Photoactive CdS, Fast Charge Transporting ZnO, and Chemically Durable Al2O3 Layers.

Highly repeatable and recoverable phototransistors were explored using a "multifunctional channels" structure with multistacked chalcogenide and oxide semiconductors. These devices were made of (i) photoactive CdS (with a visible band gap), (ii) fast charge transporting ZnO (with a high field-effect mobility), and (iii) a protection layer of Al2O3 (with high chemical durability). The CdS TFT without the Al2O3 protection layer did not show a transfer curve due to the chemical damage that occurred on the ZnO layer during the chemical bath deposition (CBD) process used for CdS deposition. Alternatively, compared to CdS phototransistors with long recovery time and high hysteresis (ΔVth = 19.5 V), our "multi-functional channels" phototransistors showed an extremely low hysteresis loop (ΔVth = 0.5V) and superior photosensitivity with repeatable high photoresponsivity (52.9 A/W at 400 nm). These improvements are likely caused by the physical isolation of the sensing region and charge transport region by the insertion of the ultrathin Al2O3 layer. This approach successfully addresses some of the existing problems in CdS phototransistors, such as the high gate-interface trap site density and high absorption of molecular oxygen, which originate from the polycrystalline CdS.

High-Performance Silver Window Electrodes for Top-Illuminated Organic Photovoltaics Using an Organo-molybdenum Oxide Bronze Interlayer.

We report an organo-molybdenumn oxide bronze that enables the fabrication of high-performance silver window electrodes for top-illuminated solution processed organic photovoltaics without complicating the process of device fabrication. This hybrid material combines the function of wide-band-gap interlayer for efficient hole extraction with the role of metal electrode seed layer, enabling the fabrication of highly transparent, low-sheet-resistance silver window electrodes. Additionally it is also processed from ethanol, which ensures orthogonality with a large range of solution processed organic semiconductors. The key organic component is the low cost small molecule 3-mercaptopropionic acid, which (i) promotes metal film formation and imparts robustness at low metal thickness, (ii) reduces the contact resistance at the Ag/molybdenumn oxide bronze interface, (iii) and greatly improves the film forming properties. Silver electrodes with a thickness of 8 nm deposited by simple vacuum evaporation onto this hybrid interlayer have a sheet resistance as low as 9.7 Ohms per square and mean transparency ∼80% over the wavelength range 400-900 nm without the aid of an antireflecting layer, which makes them well-matched to the needs of organic photovoltaics and applicable to perovskite photovoltaics. The application of this hybrid material is demonstrated in two types of top-illuminated organic photovoltaic devices.

Low-Temperature TiOx Compact Layer for Planar Heterojunction Perovskite Solar Cells.

Here, we demonstrate an effective low-temperature approach to fabricate a uniform and pinhole-free compact TiO2 layer for enhancing photovoltaic performance of perovskite solar cells. TiCl4 was used to modify TiO2 for efficient charge generation and significantly reduced recombination loss. We found that a TiO2 layer with an appropriate TiCl4 treatment possesses a smooth surface with full coverage of the conductive electrode. Further studies on charge carrier dynamics confirmed that the TiCl4 treatment improves the contact of the TiO2/perovskite interface, facilitating charge extraction and suppressing charge recombination. On the basis of the treatment, we improved the open circuit voltage from 1.01 V of the reference cell to 1.08 V, and achieved a power conversion efficiency of 16.4%.

Design and application of carbon nanomaterials for photoactive and charge transport layers in organic solar cells.

Commercialization of organic solar cell (OSC) has faltered due to their low power conversion efficiency (PCE) compared to inorganic solar cell. Low electrical conductivity, low charge mobility, and short-range light absorption of most organic materials limit the PCE of OSCs. Carbon nanomaterials, especially carbon nanotubes (CNTs) and graphenes, are of great interest for use in OSC applications due to their high electrical conductivity, mobility, and unique optical properties for enhancing the performance of OSCs. In this review, recent progress toward the integration of carbon nanomaterials into OSCs is described. The role of carbon nanomaterials and strategies for their integration into various layers of OSCs, including the photoactive layer and charge transport layer, are discussed. Based on these, we also discuss the prospects of carbon nanomaterials for specific OSC layers to maximize the PCE.