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.

Chitinophaga silvatica sp. nov., isolated from forest soil, and reclassification of Chitinophaga extrema as a later heterotypic synonym of Chitinophaga solisilvae.

A novel bacterial strain, designated K2CV101002-2T, was isolated from forest soil collected at Dinghushan Biosphere Reserve, Guangdong Province, PR China. Phylogenetic analyses based on 16S rRNA gene sequences showed that it belonged to the genus Chitinophaga and was most closely related to Chitinophaga terrae KP01T (99.0 %), followed by Chitinophaga extrema Mgbs1T (98.3 %) and Chitinophaga solisilvae O9T (98.1 %). The draft genome sequence was 6.8 Mb long with a relative low G+C content of 39.8 mol%. The average nucleotide identity and digital DNA-DNA hybridization values between the novel strain and closely related type strains were 71.4‒76.2 % and 18.4‒19.6 %, respectively. Meanwhile the corresponding values between C. extrema Mgbs1T and C. solisilvae O9T were 98.6 and 88.1 %, respectively. The novel strain contained iso-C15:0, C16:1 ω5c and iso-C17:0 3-OH as the major fatty acids and MK-7 as the predominant respiratory quinone. The polyphasic study clearly supported that strain K2CV101002-2T represents a new species of the genus Chitinophaga, for which the name Chtinophaga silvatica sp. nov. (type strain K2CV101002-2T=GDMCC 1.1288T=JCM 32696T) is proposed. In addition, Chitinophaga extrema Goh et al. 2020 should be taken as a later heterotypic synonym of Chitinophaga solisilvae Ping et al. 2020.

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.

Zn-Cu-In-Se Quantum Dot Solar Cells with a Certified Power Conversion Efficiency of 11.6%.

The enhancement of power conversion efficiency (PCE) and the development of toxic Cd-, Pb-free quantum dots (QDs) are critical for the prosperity of QD-based solar cells. It is known that the properties (such as light harvesting range, band gap alignment, density of trap state defects, etc.) of QD light harvesters play a crucial effect on the photovoltaic performance of QD based solar cells. Herein, high quality ∼4 nm Cd-, Pb-free Zn-Cu-In-Se alloyed QDs with an absorption onset extending to ∼1000 nm were developed as effective light harvesters to construct quantum dot sensitized solar cells (QDSCs). Due to the small particle size, the developed QD sensitizer can be efficiently immobilized on TiO2 film electrode in less than 0.5 h. An average PCE of 11.66% and a certified PCE of 11.61% have been demonstrated in the QDSCs based on these Zn-Cu-In-Se QDs. The remarkably improved photovoltaic performance for Zn-Cu-In-Se QDSCs vs Cu-In-Se QDSCs (11.66% vs 9.54% in PCE) is mainly derived from the higher conduction band edge, which favors the photogenerated electron extraction and results in higher photocurrent, and the alloyed structure of Zn-Cu-In-Se QD light harvester, which benefits the suppression of charge recombination at photoanode/electrolyte interfaces and thus improves the photovoltage.

Boosting the Open Circuit Voltage and Fill Factor of QDSSCs Using Hierarchically Assembled ITO@Cu2S Nanowire Array Counter Electrodes.

The key challenges in enhancing the power conversion efficiency (PCE) of a quantum dot-sensitized solar cell (QDSSC) are efficiently achieving charge separation at the photoanode and improving the charge transfer, which is limited by the interface between the electrolyte and the counter electrode (CE). Here, hierarchically assembled ITO@Cu2S nanowire arrays with conductive single-crystalline ITO cores and Cu2S nanocrystal shells were designed as efficient QDSSCs CEs. These arrays not only provided an efficient three-dimensional charge transport network but also allowed for the effective deposition of more Cu2S nanocrystals as active sites to catalyze the electrolyte reaction. This design considerably reduced the sheet and charge transfer resistance of the CE, thus decreasing the series resistance and increasing the shunt resistance of the QDSSC. As a result, QDSSCs with this CE exhibited an unprecedentedly high Voc of 0.688 V, a fill factor of 58.39%, and a PCE of 6.12%, which is 21.2% higher than that of the conventional brass/Cu2S CE.

Boosting power conversion efficiencies of quantum-dot-sensitized solar cells beyond 8% by recombination control.

At present, quantum-dot-sensitized solar cells (QDSCs) still exhibit moderate power conversion efficiency (with record efficiency of 6-7%), limited primarily by charge recombination. Therefore, suppressing recombination processes is a mandatory requirement to boost the performance of QDSCs. Herein, we demonstrate the ability of a novel sequential inorganic ZnS/SiO2 double layer treatment onto the QD-sensitized photoanode for strongly inhibiting interfacial recombination processes in QDSCs while providing improved cell stability. Theoretical modeling and impedance spectroscopy reveal that the combined ZnS/SiO2 treatment reduces interfacial recombination and increases charge collection efficiency when compared with conventional ZnS treatment alone. In line with those results, subpicosecond THz spectroscopy demonstrates that while QD to TiO2 electron-transfer rates and yields are insensitive to inorganic photoanode overcoating, back recombination at the oxide surface is strongly suppressed by subsequent inorganic treatments. By exploiting this approach, CdSe(x)Te(1-x) QDSCs exhibit a certified record efficiency of 8.21% (8.55% for a champion cell), an improvement of 20% over the previous record high efficiency of 6.8%, together with an additional beneficial effect of improved cell stability.

High-efficiency "green" quantum dot solar cells.

Semiconductor quantum dots (QDs) are extremely interesting materials for the development of photovoltaic devices, but currently the present the drawback is that the most efficient devices have been prepared with toxic heavy metals of Cd or Pb. Solar cells based on "green" QDs--totally free of Cd or Pb--present a modest efficiency of 2.52%. Herein we achieve effective surface passivation of the ternary CuInS2 (CIS) QDs that provides high photovoltaic quality core/shell CIS/ZnS (CIS-Z) QDs, leading to the development of high-efficiency green QD solar cells that surpass the performance of those based on the toxic cadmium and lead chalcogenides QDs. Using wide absorption range QDs, CIS-Z-based quantum dot sensitized solar cell (QDSC) configuration with high QD loading and with the benefit of the recombination reduction with type-I core/shell structure, we boost the power conversion efficiency of Cd- and Pb-free QDSC to a record of 7.04% (with certified efficiency of 6.66%) under AM 1.5G one sun irradiation. This efficiency is the best performance to date for QDSCs and also demonstrates that it is possible to obtain comparable or even better photovoltaic performance from green CIS QDs to the toxic cadmium and lead chalcogenides QDs.

Visual detection of biological thiols based on lightening quantum dot-TiO2 composites.

The quenched fluorescence of quantum dots (QDs) attached to TiO2 nanoparticles was selectively switched on by biothiols through ligand replacement, which makes it feasible for facilely sensing biothiols based on the fluorescence turn on mechanism. The present sensor exhibited excellent selectivity and high sensitivity. Furthermore, a novel fluorescent indicating paper was constructed by immobilizing the probe on filter paper to visually detect biothiols in which only a UV lamp was used.

Adenosine capped QDs based fluorescent sensor for detection of dopamine with high selectivity and sensitivity.

Facile detection of dopamine (DA) in biological samples for diagnostics remains a challenge. This paper reported an effective fluorescent sensor based on adenosine capped CdSe/ZnS quantum dots (A-QDs) for highly sensitive detection of DA in human urine samples. In this assay, adenosine serves as a capping ligand or stabilizer for QDs to render high-quality QDs dispersed in water, and as a receptor for DA to attach DA onto the surface of A-QDs. DA molecules can bind to A-QDs via non-covalent bonding, leading to the fluorescence quenching of A-QDs due to electron transfer. The A-QDs based fluorescence probe showed a limit of detection (LOD) of ca. 29.3 nM for DA detection. This facile method exhibited high selectivity and anti-interference in the presence of amino acid, ascorbic acid (AA), uric acid (UA) and glucide with 100-fold higher concentration in PBS solution. Furthermore, it was also successfully used in the detection of DA in the human urine samples with quantitative recoveries (94.80-103.40%).

Nanostructure and charge transfer in Bi2S3-TiO2 heterostructures.

Interfacial nanostructures in Bi2S3-TiO2 nanorod-nanoparticle heterostructures with a change of coupling mode have been engineered. The samples were characterized by x-ray diffraction, scanning electron microscopy, transmission electron microscopy, and ultraviolet-visual light absorption spectroscopy. By means of in situ growth of TiO2 nanoparticles on the surfaces of Bi2S3 nanorods in one pot, heterostructures with high-quality interfaces were obtained in which the {105} facet of anatase TiO2 selectively coupled with the {010} facet of orthorhombic Bi2S3 nanorods without any crystal defects, showing the epitaxial relationship of Bi2S3 {011} // TiO2 {101}. By means of a two-step method, TiO2 nanoparticles also could be grown on the {310} facet of the pre-prepared Bi2S3 nanorods to form heterostructures but with interfacial defects. Charge transfer in the interface-different heterostructures was evaluated by photodegradation of methyl orange under visible-light irradiation. The defect-free interfaces favored electron-hole separation and transfer, resulting in improved photocatalytic activity. The current structural characterization and interface engineering should be expanded to other heterostructures when studying the relationship between synthesis, interfacial structure, and photocatalytic or photovoltaic applications.

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.

A Novel Recombinant Human Filaggrin Segment (rhFLA-10) Alleviated a Skin Lesion of Atopic Dermatitis.

Atopic dermatitis (AD), a prevalent chronic inflammatory skin disorder, is marked by impaired skin barrier function and persistent pruritus. It significantly deteriorates patients' quality of life, making it one of the most burdensome non-lethal skin disorders. Filaggrin plays a crucial role in the pathophysiology of barrier disruption in AD, interacting with inflammatory mediators. It is an integral part of the extracellular matrix architecture, serving to protect the skin barrier and attenuate the inflammatory cascade. In this study, we engineered a novel recombinant human filaggrin (rhFLA-10) expression vector, which was subsequently synthesized and purified. In vitro and ex vivo efficacy experiments were conducted for AD. rhFLA-10, at low concentrations (5 to 20 µg/mL), was non-toxic to HACaT cells, significantly inhibited the degranulation of P815 mast cells, and was readily absorbed by cells, thereby exerting a soothing therapeutic effect. Furthermore, rhFLA-10 demonstrated anti-inflammatory properties (p < 0.05). In vivo, efficacy experiments further substantiated that rhFLA-10 could effectively ameliorate AD in mice and facilitate the repair of damaged skin (p < 0.001). These findings underscore the considerable potential of rhFLA-10 in the treatment of AD.