Colloidal Inorganic Ligand-Capped Nanocrystals: Fundamentals, Status, and Insights into Advanced Functional Nanodevices.

Colloidal nanocrystals (NCs) are intriguing building blocks for assembling various functional thin films and devices. The electronic, optoelectronic, and thermoelectric applications of solution-processed, inorganic ligand (IL)-capped colloidal NCs are especially promising as the performance of related devices can substantially outperform their organic ligand-capped counterparts. This in turn highlights the significance of preparing IL-capped NC dispersions. The replacement of initial bulky and insulating ligands capped on NCs with short and conductive inorganic ones is a critical step in solution-phase ligand exchange for preparing IL-capped NCs. Solution-phase ligand exchange is extremely appealing due to the highly concentrated NC inks with completed ligand exchange and homogeneous ligand coverage on the NC surface. In this review, the state-of-the-art of IL-capped NCs derived from solution-phase inorganic ligand exchange (SPILE) reactions are comprehensively reviewed. First, a general overview of the development and recent advancements of the synthesis of IL-capped colloidal NCs, mechanisms of SPILE, elementary reaction principles, surface chemistry, and advanced characterizations is provided. Second, a series of important factors in the SPILE process are offered, followed by an illustration of how properties of NC dispersions evolve after ILE. Third, surface modifications of perovskite NCs with use of inorganic reagents are overviewed. They are necessary because perovskite NCs cannot withstand polar solvents or undergo SPILE due to their soft ionic nature. Fourth, an overview of the research progresses in utilizing IL-capped NCs for a wide range of applications is presented, including NC synthesis, NC solid and film fabrication techniques, field effect transistors, photodetectors, photovoltaic devices, thermoelectric, and photoelectrocatalytic materials. Finally, the review concludes by outlining the remaining challenges in this field and proposing promising directions to further promote the development of IL-capped NCs in practical application in the future.

20.1 % Certified Efficiency of Planar Hole Transport Layer-Free Carbon-Based Perovskite Solar Cells by Spacer Cation Chain Length Engineering of 2D Perovskites.

The planar triple-layer hole transport layer (HTL)-free carbon-based perovskite solar cells (C-PSCs) have outstanding advantages of low cost and high stability, but are limited by low efficiency. The formation of a 3D/2D heterojunction has been widely proven to enhance device performance. However, the 2D perovskite possesses multiple critical properties associated with 3D perovskite, including defect passivation, energy level, and charge transport properties, all of which can impact device performance. It is challenging to find a powerful means to achieve comprehensive regulation and trade-off of these key properties. Herein, we propose a chain-length engineering of alkylammonium spacer cations to achieve this goal. The results show that the 2D perovskite formed by short-chain alkylammonium cations primarily acts to passivate defects. With the increase in cation chain length, the 2D perovskite achieves a more matched energy level with 3D perovskite, enhancing the built-in electric field and promoting charge separation. However, the further increase in chain length impedes the charge transport due to the insulativity of organic cations. Comprehensively, the 2D perovskite formed by tetradecylammonium cations achieves the optimal balance of defect passivation, interface charge separation, and charge transport. The planar HTL-free C-PSCs exhibit a new record efficiency of 20.40 % (certified 20.1 %).

Improving the Electron Transport Performance of TiO2 Film by Regulating TiCl4 Post-Treatment for High-Efficiency Carbon-Based Perovskite Solar Cells.

Titanium oxide (TiO2 ) has been widely used as an electron transport layer (ETL) in perovskite solar cells (PSCs). Typically, TiCl4 post-treatment is indispensable for modifying the surfaces of TiO2 ETL to improve the electron transport performance. However, it is challenging to produce the preferred anatase phase-dominated TiO2 by the TiCl4 post-treatment due to the higher thermodynamic stability of the rutile phase. In this work, a mild continuous pH control strategy for effectively regulating the hydrolysis process of TiCl4 post-treatment is proposed. As the weak organic base, urea has been demonstrated can maintain a moderate pH decrease during the hydrolysis process of TiCl4 while keeping the hydrolysis process relatively mild due to the ultra-weak alkalinity. The improved pH environment is beneficial for the formation of anatase TiO2 . Consequently, a uniform anatase-dominated TiO2 surface layer is formed on the mesoporous TiO2 , resulting in reduced defect density and superior band energy level. The interfacial charge recombination is effectively suppressed, and the charge extraction efficiency is improved simultaneously in the fabricated solar cells. The efficiency of the fabricated carbon electrode-based PSCs (C-PSCs) is improved from 16.63% to 18.08%, which is the highest for C-PSCs based on wide-bandgap perovskites.

1D Choline-PbI3 -Based Heterostructure Boosts Efficiency and Stability of CsPbI3 Perovskite Solar Cells.

Defects in perovskite are key factors in limiting the photovoltaic performance and stability of perovskite solar cells (PSCs). Generally, choline halide (ChX) can effectively passivate defects by binding with charged point defects of perovskite. However, we verified that ChI can react with CsPbI3 to form a novel crystal phase of one-dimensional (1D) ChPbI3 , which constructs 1D/3D heterostructure with 3D CsPbI3 , passivating the defects of CsPbI3 more effectively and then resulting in significantly improved photoluminescence lifetime from 20.2 ns to 49.4 ns. Moreover, the outstanding chemical inertness of 1D ChPbI3 and the repair of undesired δ-CsPbI3 deficiency during its formation process can significantly enhance the stability of CsPbI3 film. Benefiting from 1D/3D heterostructure, CsPbI3 carbon-based PSCs (C-PSCs) delivered a champion efficiency of 18.05 % and a new certified record of 17.8 % in hole transport material (HTM)-free inorganic C-PSCs.

Self-Driven Prenucleation-Induced Perovskite Crystallization Enables Efficient Perovskite Solar Cells.

Perovskite film with high crystal quality is fundamental to achieving high-performance solar cells. A fast nucleation process is crucial to improving the crystallization quality. Here, we propose a self-driven prenucleation strategy to achieve fast nucleation. This is realized through rational solvent design. The key characteristics of different solvents are systematically evaluated. Among them, formamide, with ultra-high dielectric constant, low Gutman donor number, and a high boiling point, is selected as the co-solvent. These unique characteristics render formamide a double-face solvent that is a good solvent for formamidinium iodide (FAI) and CsI while a poor solvent for PbI2 . As a result, formamide induces the self-driven prenucleation of PbI2 -DMSO seeding crystals and accelerates the nucleation, improving the crystalline quality of perovskite film. The efficiency of the hole transport layer-free carbon-based perovskite solar cells is boosted beyond 19 % for the first time.

Improving the Efficiency of Quantum Dot Sensitized Solar Cells beyond 15% via Secondary Deposition.

Low loading is one of the bottlenecks limiting the performance of quantum dot sensitized solar cells (QDSCs). Although previous QD secondary deposition relying on electrostatic interaction can improve QD loading, due to the introduction of new recombination centers, it is not capable of enhancing the photovoltage and fill factor. Herein, without the introduction of new recombination centers, a convenient QD secondary deposition approach is developed by creating new adsorption sites via the formation of a metal oxyhydroxide layer around QD presensitized photoanodes. MgCl2 solution treated Zn-Cu-In-S-Se (ZCISSe) QD sensitized TiO2 film electrodes have been chosen as a model device to investigate this secondary deposition approach. The experimental results demonstrate that additional 38% of the QDs are immobilized on the photoanode as a single layer. Due to the increased QD loading and concomitant enhanced light-harvesting capacity and reduced charge recombination, not only photocurrent but also photovoltage and fill factor have been remarkably enhanced. The average PCE of resulted ZCISSe QDSCs is boosted to 15.31% (Jsc = 26.52 mA cm-2, Voc = 0.802 V, FF = 0.720), from the original 13.54% (Jsc = 24.23 mA cm-2, Voc = 0.789 V, FF = 0.708). Furthermore, a new certified PCE record of 15.20% has been obtained for liquid-junction QDSCs.

Antioxidative Stannous Oxalate Derived Lead-Free Stable CsSnX3 (X=Cl, Br, and I) Perovskite Nanocrystals.

Lead-free CsSnX3 perovskite NCs are becoming a promising alternative to CsPbX3 (X=Cl, Br, I), but suffer from extremely poor stability. Herein, we highlight the significant effect of SnII precursors used in the synthesis on the stability of the resultant CsSnX3 NCs. A method is proposed for synthesizing CsSnX3 NCs using Cs2 CO3 , SnC2 O4 , and NH4 X as corresponding constituent precursors, wherein the ratio of reactants can be easily adjusted. Stable CsSnX3 NCs can be obtained with the use of antioxidative SnC2 O4 as the SnII precursor. Experimental results show that the improvement of NCs stability is mainly ascribed to the role of oxalate in the SnC2 O4 precursor. Oxalate ion has a strong antioxidative ability and can effectively inhibit the oxidation of SnII during the synthesis. Besides, oxalate as a bidentate capping ligand is shown to be coordinated on the surface of formed NCs. This can not only passivate the uncoordinated Sn on the surface but also prevent the oxidation of the NCs.

Zn-Cu-In-S-Se Quinary "Green" Alloyed Quantum-Dot-Sensitized Solar Cells with a Certified Efficiency of 14.4 .

The photoelectronic properties of quantum dots (QDs) have a critical impact on the performance of quantum-dot-sensitized solar cells (QDSCs). Currently, I-III-VI group QDs have become the mainstream light-harvesting materials in high-performance QDSCs. However, it is still a great challenge to achieve satisfactory efficiency for light-harvesting, charge extraction, and charge collection simultaneously in QDSCs. We design and prepare Zn0.4 Cu0.7 In1.0 Sx Se2-x (ZCISSe) quinary alloyed QDs by cation/anion co-alloying strategy. The critical photoelectronic properties of target QDs, including band gap, conduction band energy level, and density of defect trap states, can be conveniently tailored. Experimental results demonstrate that the ZCISSe quinary alloyed QDs can achieve an ideal balance among light-harvesting, photogenerated electron extraction, and charge-collection efficiencies in QDSCs compared to its single anion or cation quaternary alloyed QD counterparts. Consequently, the quinary alloyed QDs boost the certified efficiency of QDSCs to 14.4 %, which is a new efficiency record for liquid-junction QD solar cells.

Quantum dot-sensitized solar cells.

Quantum dot-sensitized solar cells (QDSCs) have emerged as a promising candidate for next-generation solar cells due to the distinct optoelectronic features of quantum dot (QD) light-harvesting materials, such as high light, thermal, and moisture stability, facilely tunable absorption range, high absorption coefficient, multiple exciton generation possibility, and solution processability as well as their facile fabrication and low-cost availability. In recent years, we have witnessed a dramatic boost in the power conversion efficiency (PCE) of QDSCs from 5% to nearly 13%, which is comparable to other kinds of emerging solar cells. Both the exploration of new QD light-harvesting materials and interface engineering have contributed to this fantastically fast improvement. The outstanding development trend of QDSCs indicates their great potential as a promising candidate for next-generation photovoltaic cells. In this review article, we present a comprehensive overview of the development of QDSCs, including: (1) the fundamental principles, (2) a history of the brief evolution of QDSCs, (3) the key materials in QDSCs, (4) recombination control, and (5) stability issues. Finally, some directions that can further promote the development of QDSCs in the future are proposed to help readers grasp the challenges and opportunities for obtaining high-efficiency QDSCs.

Multistack integration of three-dimensional hyperbranched anatase titania architectures for high-efficiency dye-sensitized solar cells.

An unprecedented attempt was conducted on suitably functionalized integration of three-dimensional hyperbranched titania architectures for efficient multistack photoanode, constructed via layer-by-layer assembly of hyperbranched hierarchical tree-like titania nanowires (underlayer), branched hierarchical rambutan-like titania hollow submicrometer-sized spheres (intermediate layer), and hyperbranched hierarchical urchin-like titania micrometer-sized spheres (top layer). Owing to favorable charge-collection, superior light harvesting efficiency and extended electron lifetime, the multilayered TiO2-based devices showed greater J(sc) and V(oc) than those of a conventional TiO2 nanoparticle (TNP), and an overall power conversion efficiency of 11.01% (J(sc) = 18.53 mA cm(-2); V(oc) = 827 mV and FF = 0.72) was attained, which remarkably outperformed that of a TNP-based reference cell (η = 7.62%) with a similar film thickness. Meanwhile, the facile and operable film-fabricating technique (hydrothermal and drop-casting) provides a promising scheme and great simplicity for high performance/cost ratio photovoltaic device processability in a sustainable way.

Constructing 3D branched nanowire coated macroporous metal oxide electrodes with homogeneous or heterogeneous compositions for efficient solar cells.

Light-harvesting and charge collection have attracted increasing attention in the domain of photovoltaic cells, and can be facilitated dramatically by appropriate design of a photonic nanostructure. However, the applicability of current light-harvesting photoanode materials with single component and/or morphology (such as, particles, spheres, wires, sheets) is still limited by drawbacks such as insufficient electron-hole separation and/or light-trapping. Herein, we introduce a universal method to prepare hierarchical assembly of macroporous material-nanowire coated homogenous or heterogeneous metal oxide composite electrodes (TiO2 -TiO2 , SnO2 -TiO2 , and Zn2 SnO4 -TiO2 ; homogenous refers to a material in which the nanowire and the macroporous material have the same composition, i.e. both are TiO2 . Heterogeneous refers to a material in which the nanowires and the macroporous material have different compositions). The dye-sensitized solar cell based on a TiO2 -macroporous material-TiO2 -nanowire homogenous composition electrode shows an impressive conversion efficiency of 9.51 %, which is much higher than that of pure macroporous material-based photoelectrodes to date.

Improving the efficiency of quantum dot-sensitized solar cells by increasing the QD loading amount.

In quantum dot-sensitized solar cells (QDSCs), optimized quantum dot (QD) loading mode and high QD loading amount are prerequisites for great device performance. Capping ligand-induced self-assembly (CLIS) mode represents the mainstream QD loading strategy in the fabrication of high-efficiency QDSCs. However, there remain limitations in CLIS that constrain further enhancement of QD loading levels. This review illustrates the development of various QD loading methods in QDSCs, with an emphasis on the outstanding merits and bottlenecks of CLIS. Subsequently, thermodynamic and kinetic factors dominating QD loading behaviors in CLIS are analyzed theoretically. Upon understanding driving forces, resistances, and energy effects in a QD assembly process, various novel strategies for improving the QD loading amount in CLIS are summarized, and the related functional mechanism is established. Finally, the article concludes and outlooks some remaining academic issues to be solved, so that higher QD loading amount and efficiencies of QDSCs can be anticipated in the future.

Limitations and Progresses in Carbon-Based Cesium Lead Halide Perovskite Solar Cells.

Inorganic cesium lead halide perovskites (CsPbIxBr3-x, 0≤x≤3) are promising alternatives with great thermal stability. Additionally, the choice of moisture-resistive and dopant-free carbon as the electrode material can simultaneously solve the problems of stability and cost. Therefore, carbon electrode-based inorganic PSCs (C-IPSCs) represent a promising candidate for commercialization, yet both the efficiencies and stability of related devices demand further progress. This article reviews the recent advancement of C-IPSCs and then unravels the distinctive merits and limitations in this field. Subsequently, our perspective on various modification strategies is analyzed on a methodological level. Finally, this article outlooks the promising research contents and the remaining unresolved issues in this field. We believe that understanding and analyzing the related problems in this field are instructive to stimulate the future development of C-IPSCs.

Eliminating Hole Extraction Barrier in 1D/3D Perovskite Heterojunction for Efficient and Stable Carbon-Based CsPbI3 Solar Cells with a Record Efficiency.

Carbon-based perovskite solar cells (C-PSCs) have the advantages of low-cost and high-stability, but their photovoltaic performance is limited by severe defect-induced recombination and low hole extraction efficiency. One-dimensional (1D) perovskite has been proven to effectively passivate the defects on the perovskite surface, therefore reducing non-radiative recombination loss. However, the unsuitable energy level of most 1D perovskite renders an undesired downward band bending for three-dimensional (3D) perovskite, resulting in a high hole extraction barrier and reduced hole extraction efficiency. Therefore, rational design and selection of 1D perovskites as the modifiers are essential in balancing defect passivation and hole extraction. In this work, based on simulation calculations, thiocholine iodide (TchI) is selected to prepare 1D perovskite with high work function, and then constructs TchPbI3/CsPbI3 1D/3D perovskite heterojunction. Experimental results show that this strategy eliminates the hole extraction barrier at perovskite/carbon interface, which improves the hole extraction efficiency of corresponding devices. Meanwhile, the strong interaction between the thiol group and Pb suppresses defect-induced recombination effectively and improves the stability of CsPbI3. The assembled C-PSCs exhibit a champion efficiency of 19.08% and a certified efficiency of 18.7%. To the best of our knowledge, this is a new efficiency record for inorganic C-PSCs. This article is protected by copyright. All rights reserved.

Role of Moisture and Oxygen in Defect Management and Orderly Oxidation Boosting Carbon-Based CsPbI2 Br Solar Cells to a New Record Efficiency.

Large energy loss (Eloss ) caused by defect-assisted recombination makes the photovoltaic performance of carbon-based perovskite solar cells (C-PSCs) inferior to that of metal-electrode ones. Herein, the influence of environmental factors (moisture and oxygen) on defect management during re-annealing process of CsPbI2 Br crystalline films is systematically studied. Density functional theory and experimental results indicate that moisture in the air can significantly reduce the oxidation kinetics of crystalline films, resulting in orderly oxidation. Concomitantly, the oxidation decomposition products PbO and CsPbIBr2 are enriched at grain boundaries, passivating surface defects efficiently. Simultaneously, energy band coupling between CsPbI2 Br and CsPbIBr2 improves the hole extraction efficiency. The photovoltage of corresponding C-PSCs is increased from 1.05 to 1.32 V, indicating a reduced Eloss derived from orderly oxidation strategy. Correspondingly, the champion cell achieves an efficiency of 15.27%, and a certified efficiency of 14.7%, which is a new record efficiency for CsPbI2 Br C-PSCs.

Vanadium Nitride Quantum Dots/Holey Graphene Matrix Boosting Adsorption and Conversion Reaction Kinetics for High-Performance Lithium-Sulfur Batteries.

Lithium-sulfur batteries (LSBs) have been considered as potential next-generation energy storage systems due to their high specific energy of 2600 Wh kg-1 and 2800 Wh L-1. Nevertheless, the practical application of LSBs still faces several hazards, including the shuttle effect of soluble lithium polysulfides, low electrical conductivities of solid sulfur and lithium sulfides, and large volume expansion during charge/discharge cycles. To address this critical challenge, we innovatively proposed facile synthesis of nanostructured VN quantum dots (VNQD)/holey graphene matrix for stabilizing the sulfur cathode by simultaneously promoting the trapping, anchoring, and catalyzing efficiencies of both LiPSs and Li2S. Benefiting from abundant edge catalytic sites of VNQD, in-plane nanopores of graphene, and high electrical conductivity, the sulfur host not only provides high adsorption capability toward soluble polysulfides, strong binding ability for anchoring solid Li2S, and their rapid conversion kinetics but also contributes abundant sulfur storage sites and efficient transport pathways for lithium ions (Li+) and electrons. Consequently, the sulfur cathode exhibits high initial capacities of 1320 mAh g-1, high rate capability (850 mAh g-1 @ 4 mA cm-2), and high capacity retention of 99.95% per cycle after 500 cycles, providing a feasible solution for the practical utilization of shuttle-free Li-S batteries.

Enhancing Adsorption and Reaction Kinetics of Polysulfides Using CoP-Coated N-Doped Mesoporous Carbon for High-Energy-Density Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have shown great potential in the next-generation energy storage devices due to high theoretical energy density and low cost. To obtain high-performance Li-S batteries, it is important to inhibit the polysulfide shuttle effect and improve the reaction kinetics of polysulfides. Herein, CoP nanoparticles coated by metal-organic framework-derived N-doped mesoporous carbon (CoP@N-C) composites are synthesized and applied in both a cathode for a sulfur host and a modified layer on a separator for high-energy-density Li-S batteries since the CoP component has strong chemical anchoring capability toward soluble polysulfides and high electrochemical activity toward polysulfides transformation. Meanwhile, the porous structure of conductive N-doped mesoporous carbon can not only buffer the volume variation of sulfur during the charge/discharge process but also enhance the charge transport rate in the cathode. The constructed batteries have demonstrated a high specific capacity of 1222 mAh g-1 (8.6 mAh cm-2) with a high sulfur areal loading of ∼7.0 mg cm-2 on cathodes, and a mass loading of 0.35 mg cm-2 for modified layer on separators. Its average capacity decay is only 0.076% per cycle after 100 cycles. This work presents the highly competitive performance of Li-S batteries on the areal capacity and capacity decay.

ZnSxSe1-x Alloy Passivation Layer for High-Efficiency Quantum-Dot-Sensitized Solar Cells.

Interface modification is an important means for improving the performance of almost all optoelectronic devices. In quantum-dot-sensitized solar cells (QDSCs), effective surface modification of photoanode also has a critical impact on photovoltaic performance. At present, ZnS and ZnSe wide band gap semiconductors are the mainstream materials used for photoanode/electrolyte interface passivation in QDSCs. However, the problem with these two materials is that the passivation effect and the lattice match with TiO2/QD are difficult to be balanced. Although ZnS can form a larger energetic barrier due to the higher conduction band edge, its lattice mismatch with TiO2 and QD (such as CdSe and CuInSe2) is large, leading to the formation of additional defect states. On the contrary, ZnSe has a small lattice mismatch with TiO2 and QD but a relatively lower conduction band edge. Herein, we propose a strategy to employ ZnSxSe1-x alloy materials as a passivation layer for the first time to solve the drawbacks of single-component passivation layers. The ZnSxSe1-x alloy passivation layer was deposited on the Zn-Cu-In-Se (ZCISe) QD-sensitized TiO2 film electrode via successive ionic layer adsorption and reaction (SILAR) method. A stable polyselenosulfide/sulfide mixed anions were served as anion precursor for the formation of ZnSxSe1-x alloy passivation layer. Experimental results revealed that the alloy passivation layer is more favorable for the suppression of charge recombination at the photoanode/electrolyte interface. In addition, the ZnSxSe1-x alloy passivation layer can significantly improve the photogenerated electron extraction efficiency compared to the current classical ZnS passivation layer as confirmed by the transient absorption (TA) measurement. Consequently, the average efficiency of QDSCs was improved from 12.17 to 13.08% with the replacement of traditional ZnS passivation layer by ZnSSe-10 under AM 1.5G one full sun illumination.

MOF-Derived Co,N Codoped Carbon/Ti Mesh Counter Electrode for High-Efficiency Quantum Dot Sensitized Solar Cells.

Carbon supported on titanium mesh electrodes has been recognized as the best performing counter electrodes (CEs) in quantum dot sensitized solar cells (QDSCs). Herein, layered double hydroxides (LDHs) are applied as a scaffold template for the growth of cobalt-zeolite-imidazole framework (ZIF-67) crystals, and micrometer-sized Co,N codoped porous carbon materials (Co,N-C) are obtained through a carbonization process. The as-prepared Co,N-C exhibits favorable features for electrocatalytic reduction of polysulfide, including a high surface area of 491.36 m2/g, highly effective active sites, and a hierarchical micro/mesoporous structure. Due to the large particle size, the obtained Co,N-C can couple with a Ti mesh substrate for the fabrication of high-performance Co,N-C/Ti CEs for QDSCs. As a result, the corresponding QDSCs exhibit an average efficiency of 13.55% (Jsc = 25.93 mA/cm2, Voc = 0.778 V, FF = 0.672), which is a 10.5% enhancement compared to the previous best result from the N-doped mesoporous carbon counterpart.

Enhancing Loading Amount and Performance of Quantum-Dot-Sensitized Solar Cells Based on Direct Adsorption of Quantum Dots from Bicomponent Solvents.

Intrinsically weak interaction between oil-soluble quantum dots (QDs) and TiO2 in a direct adsorption process limits QD loading and the performance of QD-sensitized solar cells (QDSCs). Herein, the underlying chemistry and mechanisms governing QD adsorption on TiO2 were studied to improve QD loading and cell performance. Experimental results indicate that solvent polarity plays the crucial role in determining QD loading. Compared with single-component solvents, substantially greater QD loading can be realized at the critical point (CP) of bicomponent solvents, where QDs become metastable and start to precipitate. Through this strategy, average efficiency of 12.24% was obtained for ZCISe QDSCs, which is comparable to those based on the capping ligand induced self-assembly route. This report demonstrates the great potential of bicomponent solvents at the CP for high QD loading and excellent cell performance and presents a platform for assembling functional composites with the use of different nanocrystals and substrates.