In Situ Formation of Iodide Precursor for Perovskite Quantum Dots with Application in Efficient Solar Cells.

Perovskite quantum dots (PQDs) become a kind of competitive material for fabricating high-performance solar cells due to their solution processability and outstanding optoelectronic properties. However, the current synthesis method of PQDs is mostly based on the binary-precursor method, which results in a large deviation of the I/Pb input ratio in the reaction system from the stoichiometric ratio of PQDs. Herein, a ternary-precursor method with an iodide source self-filling ability is reported for the synthesis of the CsPbI3 PQDs with high optoelectronic properties. Systematically experimental characterizations and theoretical calculations are conducted to fundamentally understand the effects of the I/Pb input molar ratio on the crystallographic and optoelectronic properties of PQDs. The results reveal that increasing the I/Pb input molar ratio can obtain ideal cubic structure PQDs with iodine-rich surfaces, which can significantly reduce the surface defects of PQDs and realize high orientation of PQD solids, facilitating charge carrier transport in the PQD solids with diminished nonradiative recombination. Consequently, the PQD solar cells exhibit an impressive efficiency of 15.16%, which is largely improved compared with that of 12.83% for the control solar cell. This work provides a feasible strategy for synthesizing high-quality PQDs for high-performance optoelectronic devices.

Tri-Step Water-Assisted Strategy for Suppressing Cs4PbBr6 Phase in Printable Carbon-Based CsPbBr3 Solar Cells to Achieve High Stability.

Often deemed the "natural nemesis" of perovskites, water molecules have been largely circumvented by the majority of researchers in the field of perovskite solar cells. This has resulted in significant hurdles in investigating the beneficial impacts of water molecules on perovskite crystallization. Herein, it is found that by utilizing ethanol with minimal water content and subjecting all-inorganic perovskite to three distinct annealing temperatures within the same solvent, the residual CsBr can be effectively removed, and the formation of the Cs4PbBr6 phase can be curtailed. By selecting an optimal water content, substantial improvements are observed in the crystalline quality of CsPbBr3, the perovskite/carbon interface, and the mesoporous filling effect. The Urbach energy (Eu) is reduced from 38.96 to 35.59 meV, and the defect density decreased from 4.16 × 1014 to 3.39 × 1014 cm-3. As a result, the power conversion efficiency (PCE) improved from 7.55% in the control group to 9.37%. Under severe environmental conditions with a temperature (T) of 85 °C and a relative humidity (RH) of 40%, tracking tests over 1200 h retained 89.3% of the initial PCE. This research signifies a breakthrough in the fabrication of highly stable and efficient all-inorganic printable mesoscopic perovskite solar cells.

Fabrication of Erbium-Doped Upconversion Nanoparticles and Carbon Quantum Dots for Efficient Perovskite Solar Cells.

Upconversion nanoparticles (UCNPs) and carbon quantum dots (CQDs) have emerged as promising candidates for enhancing both the stability and efficiency of perovskite solar cells (PSCs). Their rising prominence is attributed to their dual capabilities: they effectively passivate the surfaces of perovskite-sensitive materials while simultaneously serving as efficient spectrum converters for sunlight. In this work, we synthesized UCNPs doped with erbium ions as down/upconverting ions for ultraviolet (UV) and near-infrared (NIR) light harvesting. Various percentages of the synthesized UCNPs were integrated into the mesoporous layers of PSCs. The best photovoltaic performance was achieved by a PSC device with 30% UCNPs doped in the mesoporous layer, with PCE = 16.22% and a fill factor (FF) of 74%. In addition, the champion PSCs doped with 30% UCNPs were then passivated with carbon quantum dots at different spin coating speeds to improve their photovoltaic performance. When compared to the pristine PSCs, a fabricated PSC device with 30% UCNPs passivated with CQDs at a spin coating speed of 3000 rpm showed improved power conversion efficiency (PCE), from 16.65% to 18.15%; a higher photocurrent, from 20.44 mA/cm2 to 22.25 mA/cm2; and a superior fill factor (FF) of 76%. Furthermore, the PSCs integrated with UCNPs and CQDs showed better stability than the pristine devices. These findings clear the way for the development of effective PSCs for use in renewable energy applications.

Dipolar Chemical Bridge Induced CsPbI3 Perovskite Solar Cells with 21.86 % Efficiency.

CsPbI3 perovskite receives tremendous attention for photovoltaic applications due to its ideal band gap and good thermal stability. However, CsPbI3 perovskite solar cells (PSCs) significantly suffer from photovoltage deficits because of serious interfacial energy losses within the PSCs, which to a large extent affects the photovoltaic performance of PSCs. Herein, a dipolar chemical bridge (DCB) is constructed between the perovskite and TiO2 layers to lower interfacial energy losses and thus improve the charge extraction of PSCs. The results reveal that the DCB could form a beneficial interfacial dipole between the perovskite and TiO2 layers, which could optimize the interfacial energetics of perovskite/TiO2 layers and thus improve the energy level alignment within the PSCs. Meanwhile, the constructed DCB could also simultaneously passivate the surface defects of perovskite and TiO2 layers, greatly lowering interfacial recombination. Consequently, the photovoltage deficit of CsPbI3 PSCs is largely reduced, leading to a record efficiency of 21.86 % being realized. Meanwhile, the operation stability of PSCs is also largely improved due to the high-quality perovskite films with released interfacial tensile strain being obtained after forming the DCB within the PSCs.

Hexylammonium Acetate-Regulated Buried Interface for Efficient and Stable Perovskite Solar Cells.

Due to current issues of energy-level mismatch and low transport efficiency in commonly used electron transport layers (ETLs), such as TiO2 and SnO2, finding a more effective method to passivate the ETL and perovskite interface has become an urgent matter. In this work, we integrated a new material, the ionic liquid (IL) hexylammonium acetate (HAAc), into the SnO2/perovskite interface to improve performance via the improvement of perovskite quality formed by the two-step method. The IL anions fill oxygen vacancy defects in SnO2, while the IL cations interact chemically with Pb2+ within the perovskite structure, reducing defects and optimizing the morphology of the perovskite film such that the energy levels of the ETL and perovskite become better matched. Consequently, the decrease in non-radiative recombination promotes enhanced electron transport efficiency. Utilizing HAAc, we successfully regulated the morphology and defect states of the perovskite layer, resulting in devices surpassing 24% efficiency. This research breakthrough not only introduces a novel material but also propels the utilization of ILs in enhancing the performance of perovskite photovoltaic systems using two-step synthesis.

Providing a Photovoltaic Performance Enhancement Relationship from Binary to Ternary Polymer Solar Cells via Machine Learning.

Ternary polymer solar cells (PSCs) are currently the simplest and most efficient way to further improve the device performance in PSCs. To find high-performance organic photovoltaic materials, the established connection between the material structure and device performance before fabrication is of great significance. Herein, firstly, a database of the photovoltaic performance in 874 experimental PSCs reported in the literature is established, and three different fingerprint expressions of a molecular structure are explored as input features; the results show that long fingerprints of 2D atom pairs can contain more effective information and improve the accuracy of the models. Through supervised learning, five machine learning (ML) models were trained to build a mapping of the photovoltaic performance improvement relationship from binary to ternary PSCs. The GBDT model had the best predictive ability and generalization. Eighteen key structural features from a non-fullerene acceptor and the third components that affect the device's PCE were screened based on this model, including a nitrile group with lone-pair electron, a halogen atom, an oxygen atom, etc. Interestingly, the structural features for the enhanced device's PCE were essentially increased by the Jsc or FF. More importantly, the reliability of the ML model was further verified by preparing the highly efficient PSCs. Taking the PM6:BTP-eC9:PY-IT ternary PSC as an example, the PCE prediction (18.03%) by the model was in good agreement with the experimental results (17.78%), the relative prediction error was 1.41%, and the relative error between all experimental results and predicted results was less than 5%. These results indicate that ML is a useful tool for exploring the photovoltaic performance improvement of PSCs and accelerating the design and application with highly efficient non-fullerene materials.

Band Engineering of Perovskite Quantum Dot Solids for High-Performance Solar Cells.

CsPbI3 perovskite quantum dot (PQD) shows high potential for next-generation photovoltaics due to their tunable surface chemistry, good solution-processability and unique photophysical properties. However, the remained long-chain ligand attached to the PQD surface significantly impedes the charge carrier transport within the PQD solids, thereby predominantly influencing the charge extraction of PQD solar cells (PQDSCs). Herein, a ligand-induced energy level modulation is reported for band engineering of PQD solids to improve the charge extraction of PQDSCs. Detailed theoretical calculations and systemic experimental studies are performed to comprehensively understand the photophysical properties of the PQD solids dominated by the surface ligands of PQDs. The results reveal that 4-nitrobenzenethiol and 4-methoxybenzenethiol molecules with different dipole moments can firmly anchor to the PQD surface through the thiol group to modulate the energy levels of PQDs, and a gradient band structure within the PQD solid is subsequently realized. Consequently, the band-engineered PQDSC delivers an efficiency of up to 16.44%, which is one of the highest efficiencies of CsPbI3 PQDSCs. This work provides a feasible avenue for the band engineering of PQD solids by tuning the surface chemistry of PQDs for high-performing solar cells or other optoelectronic devices.

Building a Charge Transfer Bridge between g-C3N4 and Perovskite with Molecular Engineering to Achieve Efficient Perovskite Solar Cells.

Effective defect passivation and efficient charge transfer within polycrystalline perovskite grains and corresponding boundaries are necessary to achieve highly efficient perovskite solar cells (PSCs). Herein, focusing on the boundary location of g-C3N4 during the crystallization modulation on perovskite, molecular engineering of 4-carboxyl-3-fluorophenylboronic acid (BF) on g-C3N4 was designed to obtain a novel additive named BFCN. With the help of the strong bonding ability of BF with both g-C3N4 and perovskite and favorable intramolecular charge transfer within BFCN, not only has the crystal quality of perovskite films been improved due to the effective defects passivation, but the charge transfer has also been greatly accelerated due to the formation of additional charge transfer channels on the grain boundaries. As a result, the champion BFCN-based PSCs achieve the highest photoelectric conversion efficiency (PCE) of 23.71% with good stability.

Spiro-Bifluorene-Cored Dopant-Free Conjugated Polymeric Hole-Transporting Materials Containing Passivation Parts for Inverted Perovskite Solar Cells.

Two spiro-bifluorene-based dopant-free HTMs (X22 and X23) have been synthesized by facilely condensing spiro-bifluorene diamine with 3,4-ethylenedioxythiophene (EDOT)-5,7-dicarbonyl dichloride and 2,3,5,6-tetrafluoro-terephthaloyl dichloride, respectively. In the X22 molecule, lone pairs of electrons on the sulfur (S) and oxygen (O) functional groups interact with the perovskite materials. The hole mobility (µh) of X22 (3.9 × 10-4 cm2 V-1 S1-) is more than twice that of X23 (1.4 × 10-4 cm2 V-1 S1-). The conductivity (σ0) of X22 is 2.73 × 10-4 S cm-1, which is also higher than that of X23 (2.39 × 10-4 S cm-1). The EDOT moiety benefits the contact angle of CH3NH3PbI3 precursor solutions on HTMs as low as 24°. The X22-based device with an indium-doped tin oxide/hole transport material (HTM)/CH3NH3PbI3/phenyl-C61-butyric acid methyl ester (PC61BM)/bathocuproine/Ag structure achieves a power conversion efficiency (PCE) of 19.18%. The PCE of the device based on X23 containing fluorine is 18.70%, and the contact angle between HTM and the perovskite precursor solution is 32°. The X22- and X23-based devices at ambient temperature (≈25 °C) in N2 retain 86% and 79% of the initial PCE after 150 days. The effect of S, O, and F heteroatoms plays an important role in the side chain modification of HTMs, improving defect passivation in HTM/CH3NH3PbI3 interfaces by multiple functional groups.

Harnessing synergistic effects in GQD@Pt(II) nanocomposites for enhanced photovoltaic performance: a computational study.

CONTEXT: The development of efficient solar energy conversion technologies is crucial for addressing global energy challenges and reducing reliance on fossil fuels. Platinum(II) complexes are promising materials for photovoltaic applications due to their strong light absorption and long-lived excited states. However, their narrow absorption in the visible spectrum and stability issues limit their performance. Combining platinum(II) complexes with graphene quantum dots (GQDs) can enhance photovoltaic performance by leveraging the complementary light harvesting and charge transfer characteristics of the two components. This study utilizes density functional theory (DFT) calculations to explore their electronic structures, charge transfer dynamics, and photoelectric performance. Specifically, it investigates the effects of incorporating different substituents, either electron-donating or electron-withdrawing, onto the fluorene motif of the Pt(II) complex. The findings reveal that combining GQDs with Pt(II) complexes extends light absorption into the UV range, enabling comprehensive solar utilization. Upon photoexcitation, electrons migrate between the GQD conduction band and the Pt(II) complex, stabilizing charges and enhancing extraction. Substituents significantly influence charge transfer dynamics: electron-withdrawing groups promote transfer to the GQD, while electron-donating groups encourage charge separation and delocalization. Nanocomposites featuring electron-donating substituents achieve the highest energy conversion efficiencies, with GQD@Pt(II)-NPh2 reaching 24.6%. This is attributed to improved light harvesting, efficient charge injection, and reduced recombination. These insights guide the rational design of GQD-Pt(II) nanocomposites, optimizing charge separation and transfer processes for enhanced photovoltaic performance. The computational approach employed here provides a robust tool for developing advanced materials in renewable energy technologies. METHODS: The computational studies reported in this work were performed using the DFT approach, specifically employing the hybrid functional PBE0. The PBE0 functional's accuracy in describing electronic structures and excited-state properties is essential for understanding charge transfer processes, photoabsorption, and emission characteristics in metal-organic complexes. Geometry optimizations and time-dependent DFT (TD-DFT) calculations were carried out to investigate the properties of the nanocomposites. The effects of solvents were replicated using the conductor-like polarizable continuum model (CPCM). The charge transfer length (ΔL) and interfragment charge transfer (ΔQ) were calculated using the Multiwfn software package, and all calculations were performed using the BDF software package.

Effect of Number and Position of Chlorine Atoms on the Photovoltaic Performance of Asymmetric Nonfullerene Acceptors.

It has been well proved that the introduction of halogen can effectively modify the optoelectronic properties of classic symmetric nonfullerene acceptors (NFAs). However, the relevant studies for asymmetric NFAs are limited, especially the effect of halogen substitution number and position on the photovoltaic performance is not clear. In this work, four asymmetric NFAs with A-D-A1-A2 structure are developed by tuning the number and position of chlorine atoms on the 1,1-dicyanomethylene-3-indanone end groups, namely, A303, A304, A305, and A306. The related NFAs show progressively deeper energy levels and red-shifted absorption spectra as the degree of chlorination increases. The PM6:A306-constructed organic solar cells (OSCs) give a champion power conversion efficiency (PCE) of 13.03%. This is mainly ascribed to the most efficient exciton dissociation and collection, suppressed charge recombination, and optimal morphology. Moreover, by alternating the substitution position, the PM6:A305-based device yielded a higher PCE of 12.53% than that of PM6:A304 (12.05%). This work offers fresh insights into establishing excellent asymmetric NFAs for OSCs.