Extremely Stable Ag-Based Photonics, Plasmonic, Optical, and Electronic Materials and Devices Designed with Surface Chemistry Engineering for Anti-Tarnish.

Silver (Ag) metal-based structures are promising building blocks for next-generation photonics and electronics owing to their unique characteristics, such as high reflectivity, surface plasmonic resonance effects, high electrical conductivity, and tunable electron transport mechanisms. However, Ag structures exhibit poor sustainability in terms of device performance because harsh chemicals, particularly S2- ions present in the air, can damage their structures, lowering their optical and electrical properties. Here, the surface chemistry of Ag structures with (3-mercaptopropyl)trimethoxysilane (MPTS) ligands at room temperature and under ambient conditions is engineered to prevent deterioration of their optical and electrical properties owing to S2- exposure. Regardless of the dimensions of the Ag structures, the MPTS ligands can be applied to each dimension (0D, 1D, and 3D). Consequently, highly sustainable plasmonic effects (Δλ < 2 nm), Fabry-Perot cavity resonance structures (Δλ < 2 nm), reflectors (ΔRReflectance < 0.5%), flexible electrodes (ΔRelectrical < 0.1 Ω), and strain gauge sensors (ΔGF < 1), even in S2- exposing conditions is achieved. This strategy is believed to significantly contribute to environmental pollution reduction by decreasing the volume of electronic waste.

Defect Engineering of Metal Halide Perovskite Nanocrystals via Spontaneous Diffusion of Ag Nanocrystals.

Perovskite nanocrystals (NCs) have emerged as a promising building block for the fabrication of optic-/optoelectronic-/electronic devices owing to their superior characteristics, such as high absorption coefficient, rapid ion mobilities, and tunable energy levels. However, their low structural stability and poor surface passivation have restricted their application to next-generation devices. Herein, a drug delivery system (DDS)-inspired post-treatment strategy is reported for improving their structural stability by doping of Ag into CsPbBr3 (CPB) perovskite NCs; delivery to damaged sites can promote their structural recovery slowly and uniformly, averting the permanent loss of their intrinsic characteristics. Ag NCs are designed through surface-chemistry tuning and structural engineering to enable their circulation in CPB NC dispersions, followed by their delivery to the CPB NC surface, defect-site recovery, and defect prevention. The perovskite-structure healing process through the DDS-type process (with Ag NCs as the drug) is analyzed by a combination of theoretical calculations (with density functional theory) and experimental analyses. The proposed DDS-inspired healing strategy significantly enhances the optical properties and stability of perovskite NCs, enabling the fabrication of white light-emitting diodes.

Morphology Control of Au-Ni Hybrid Nanoparticles: Exploring Heterostructures and Optical Tuning.

Hybrid nanoparticles (NPs) have attracted considerable attention because of their ability to provide diverse properties by integrating the inherent properties of multiple components; however, synthetic strategies to control their morphology remain unexplored. In this study, a new method was used to control the morphology and optical properties of Au-Ni heterostructure (ANH) NPs. Unique morphological changes were observed by varying the Au/Ni precursor ratio from 2:1 to 1:4, exhibiting a shape transformation from dumbbell-like to quasi-spherical owing to the Ni NP size expansion, whereas the Au NP maintained their size. Moreover, increasing the Ni ratio induced plasmonic band broadening and wavelength redshift, resulting in color changes from red to navy and black. In terms of the structure, the atomic orientation of the crystallite showed that even a large lattice mismatch can result in heterojunctions at the NPs. In addition, the reaction aliquots uncovered heterogeneous nucleation and growth of ANH NPs in the colloidal system, demonstrating Ni reduction on the preformed Au NP owing to the reduction in potential gap. This study provides new insights into controlling the morphology of hybrid NPs using colloidal synthesis and the design of optimized materials for various applications.

Trioctylphosphine-assisted morphology control of ZnO nanoparticles.

This study investigates the morphological change in colloidal ZnO nanoparticles (NPs) synthesized with trioctylphosphine (TOP). The addition of TOP to the synthesis causes an evolution in the shape of ZnO NPs to tadpole-like particles from quasi-spherical particles at 300 °C. The total length of the tadpole-like ZnO NPs can be modified by controlling the molar ratio of TOP to oleylamine (OLAM). The tadpole-like particles are elongated as the concentration of TOP increased but decreased when the addition of TOP is excessive. These tadpole-like ZnO NPs transform to quasi-spherical NPs regardless of the amount of TOP at a reaction time of 3 h at 300 °C. At 200 °C, the effect of TOP on the ZnO NP synthesis differs from that at 300 °C. The ZnO NPs synthesized by controlling the molar ratios of surfactant ligands (TOP:OLAM = 2:100 and 70:100) at 200 °C share similar amorphous structures, while a crystalline ZnO phase is formed when the reaction time is 3 h. X-ray photoelectron spectroscopy analysis shows that TOP influences the oxidation of ZnO and suggests that a combination of OLAM and TOP plays a role in controlling the shape of ZnO NPs. These results provide critical insights to the utilization of TOP for a shape controlling ligand in ZnO NPs and suggest a new route to design oxide NPs.

Solid-solid phase transformations induced through cation exchange and strain in 2D heterostructured copper sulfide nanocrystals.

We demonstrate dual interface formation in nanocrystals (NCs) through cation exchange, creating epitaxial heterostructures within spherical NCs. The thickness of the inner-disk layer can be tuned to form two-dimensional (2D), single atomic layers (<1 nm). During the cation exchange reaction from copper sulfide to zinc sulfide (ZnS), we observe a solid-solid phase transformation of the copper sulfide phase in heterostructured NCs. As the cation exchange reaction is initiated, Cu ions replaced by Zn ions at the interfaces are accommodated in intrinsic Cu vacancy sites present in the initial roxbyite (Cu1.81S) phase of copper sulfide, inducing a full phase transition to djurleite (Cu1.94S)/low chalcocite (Cu2S), a more thermodynamically stable phase than roxbyite. As the reaction proceeds and reduces the size of the copper sulfide layer, the epitaxial strain at the interfaces between copper sulfide and ZnS increases and is maximized for a copper sulfide disk ∼ 5 nm thick. To minimize this strain energy, a second phase transformation occurs back to the roxbyite phase, which shares a similar sulfur sublattice to wurtzite ZnS. The observation of a solid-solid phase transformation in our unique heterostructured NCs provides a new pathway to control desired phases and an insight into the influence of cation exchange on nanoscale phase transitions in heterostructured materials.

Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals.

Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals is a relatively new field of investigation that promises greater tunability of plasmonic properties compared to metal nanoparticles. A novel process by which the LSPR in semiconductor nanocrystals can be altered is through heterostructure formation arising from solution-based cation exchange. Herein, we describe the development of an analytical model of LSPR in heterostructure copper sulfide-zinc sulfide nanocrystals synthesized via a cation exchange reaction between copper sulfide (Cu(1.81)S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tuned from a sphere to a thin disk separating symmetrically-grown sulfide (ZnS) grains. Drude model electronic conduction and Mie-Gans theory are applied to describe how the LSPR wavelength changes during cation exchange, taking into account the morphology evolution and changes to the local permittivity. The results of the modeling indicate that the presence of the ZnS grains has a significant effect on the out-of-plane LSPR mode. By comparing the results of the model to previous studies on solid-solid phase transformations of copper sulfide in these nanocrystals during cation exchange, we show that the carrier concentration is independent of the copper vacancy concentration dictated by its atomic phase. The evolution of the effective carrier concentration calculated from the model suggests that the out-of-plane resonance mode is dominant. The classical model was compared to a simplified quantum mechanical model which suggested that quantum mechanical effects become significant when the characteristic size is less than ~8 nm. Overall, we find that the analytical models are not accurate for these heterostructured semiconductor nanocrystals, indicating the need for new model development for this emerging field.

Binder-free and carbon-free nanoparticle batteries: a method for nanoparticle electrodes without polymeric binders or carbon black.

In this work, we have developed a new fabrication method for nanoparticle (NP) assemblies for Li-ion battery electrodes that require no additional support or conductive materials such as polymeric binders or carbon black. By eliminating these additives, we are able to improve the battery capacity/weight ratio. The NP film is formed by using electrophoretic deposition (EPD) of colloidally synthesized, monodisperse cobalt NPs that are transformed through the nanoscale Kirkendall effect into hollow Co(3)O(4). EPD forms a network of NPs that are mechanically very robust and electrically connected, enabling them to act as the Li-ion battery anode. The morphology change through cycles indicates stable 5-10 nm NPs form after the first lithiation remained throughout the cycling process. This NP-film battery made without binders and conductive additives shows high gravimetric (>830 mAh/g) and volumetric capacities (>2100 mAh/cm(3)) even after 50 cycles. Because similar films made from drop-casting do not perform well under equal conditions, EPD is seen as the critical step to create good contacts between the particles and electrodes resulting in this significant improvement in battery electrode assembly. This is a promising system for colloidal nanoparticles and a template for investigating the mechanism of lithiation and delithiation of NPs.

Unintended phosphorus doping of nickel nanoparticles during synthesis with TOP: a discovery through structural analysis.

We report the discovery of unintentional phosphorus (P) doping when tri-n-octylphosphine (TOP) ligands are used in Ni nanoparticle synthesis, which is the most common method for monodisperse Ni nanoparticle synthesis. The nanoparticles appear pure face-centered cubic (fcc) Ni in X-ray diffraction despite the surprisingly high level (5 atomic %) of P. We find that the P doping follows a direct relationship with increased reaction time and temperature and that the P doping can be estimated with the degree of lattice expansion shown from a peak shift in the XRD spectrum. Through EXAFS modeling and density-functional (DFT) calculations of defect formation energies we find that the P atoms are preferentially located on the fcc lattice as substitutional dopants with oxidation state of zero. Magnetic and catalytic properties are shown to be greatly affected by this doping; DFT calculations show magnetization losses in the Ni system, as well as in Fe and Co systems. These findings are likely relevant for other metal syntheses that employ phosphine ligands.

How Do Colloidal Nanoparticles Move in a Solution under an Electric Field?: In Situ Light Scattering Analysis.

Understanding the dynamics of colloidal nanoparticles (NPs) in a solution is the key to assembling them into solids through a solution process such as electrophoretic deposition. In this study, newly developed in situ analysis with light scattering is used to examine NP dynamics induced by a non-uniform electric field. We reveal that the symmetric directions of moving NP aggregates are due to dielectrophoresis between the cylindrical electrodes, while the actual NP deposition is based on the charge of NPs (electrophoresis). Over time, the symmetry of the dynamics becomes less evident, inducing feeble deposition as the less-ordered dynamics become stronger. Eventually, two separate deposition mechanisms emerge as the deposition rate decreases with the change in the NP dynamics. Furthermore, we identify the vortex-like NP motion between the electrodes. These in situ analyses provide insights into the electrophoretic deposition mechanism and NP behavior in a solution under an electric field for fine film construction.

Design of Eu(TTA)3phen-incorporated SiO2-coated transition metal oxide nanoparticles for efficient luminescence and magnetic performance.

The development of multifunctional nanoparticles (NPs) combining individual properties, such as magnetic, luminescence, and optical properties, has attracted significant research interest. In this study, europium (Eu)-incorporating iron oxide nanoparticles (IONPs) with Eu(TTA)3phen (ET-SIOPs) were successfully designed and shown to have luminescence and magnetic properties. The proposed synthetic method has three steps: (1) IONP synthesis, (2) SiO2 layer coating (1st coating), and (3) Eu-SiO2 layer coating (2nd coating). The morphology of the ET-SIOPs was well preserved after the 2nd coating was conducted. According to the photoluminescence (PL) spectra in the range of 500 to 700 nm, the Eu-incorporating SIOPs with Eu(TTA)3phen (ET-SIOPs) exhibited the highest emission intensity compared to the Eu-incorporating SIOPs synthesized with other Eu precursors. Furthermore, the ET-SIOPs exhibited long-term luminescence stability of 6 months. In addition, this method of double-layer coating can be applied to other materials synthesized with different compositions and shapes, such as MnO and SiO2 NPs. The findings of this study will not only provide new insights for the synthesis of luminescent-magnetic NPs with long-term luminescence stability and paramagnetic properties, but can also be applied for the design of various multifunctional NPs.

Controlled synthesis of uniform cobalt phosphide hyperbranched nanocrystals using tri-n-octylphosphine oxide as a phosphorus source.

A new method to produce hyperbranched Co(2)P nanocrystals that are uniform in size, shape, and symmetry was developed. In this reaction tri-n-octylphosphine oxide (TOPO) was used as both a solvent and a phosphorus source. The reaction exhibits a novel monomer-saturation-dependent tunability between Co metal nanoparticle (NP) and Co(2)P NP products. The morphology of Co(2)P can be controlled from sheaflike structures to hexagonal symmetric structures by varying the concentration of the surfactant. This unique product differs significantly from other reported hyperbranched nanocrystals in that the highly anisotropic shapes can be stabilized as the majority shape (>84%). This is the first known use of TOPO as a reagent as well as a coordinating background solvent in NP synthesis.

Contact Enhancement in Nanoparticle Assemblies through Electrophoretic Deposition.

A strong interparticle connection needs to be realized to harvest unique nanoscale features of colloidal nanoparticles (NPs) in film structures. Constructing a strong contact and adhesion of NPs on a substrate is an essential process for improved NP film properties, and therefore, its key factors should be determined by understanding the NP deposition mechanism. Herein, we investigated the critical factors leading to the robust and strong adherence of the film structure and revealed that the NP deposition mechanism involved the role of surfactant ligands during electrophoretic deposition (EPD). The high amount of surfactant ligand treatment results in a high deposition rate of NPs in the early stage; however, the ligand treatment does not influence the deposition rate in the later stage. Furthermore, the deposition mechanism is found to involve three steps during EPD: island formation, lateral growth, and layer-by-layer deposition. Rapid NP deposition kinetics controlled by ligand treatments demonstrate the strong contact and adhesion of NP film structures; they are characterized by the fast charge transfer, low resistivity, and rigid NP layers of the Cu2-x S NP-based devices. Finally, the controlled role of surfactant ligands in EPD enables design of high-performance nanostructured NP film devices with contact enhancement.

Sensitive and specific capture of polystyrene and polypropylene microplastics using engineered peptide biosensors.

Owing to increased environmental pollution, active research regarding microplastics circulating in the ocean has attracted significant interest in recent times. Microplastics accumulate in the bodies of living organisms and adversely affect them. In this study, a new method for the rapid detection of microplastics using peptides was proposed. Among the various types of plastics distributed in the ocean, polystyrene and polypropylene were selected. The binding affinity of the hydrophobic peptides suitable for each type of plastic was evaluated. The binding affinities of peptides were confirmed in unoxidized plastics and plasma-oxidized plastics in deionised or 3.5% saline water. Also, the detection of microplastics in small animals' intestine extracts were possible with the reported peptide biosensors. We expect plastic-binding peptides to be used in sensors to increase the detection efficiency of microplastics and potentially help separate microplastics from seawater.

Acid-Base Reaction-Assisted Quantum Dot Patterning via Ligand Engineering and Photolithography.

The integration of quantum dots (QDs) into device arrays for high-resolution display and imaging sensor systems remains a significant challenge in research and industry because of issues associated with the QD patterning process. It is difficult for conventional patterning processes such as stamping, inkjet printing, and photolithography to employ QDs and fabricate high-resolution patterns without degrading the properties of QDs. Here, we introduce a novel strategy for the QD patterning process by treating QDs with a bifunctional ligand for acid-base reaction-assisted photolithography. Bifunctional ligands, such as MPA (mercaptopropionic acid) or TGA (thioglycolic acid), have a carboxyl group on one side that allows the QDs to be etched along with the photoresist (PR) by the base developer, while on the opposite side the ligands have a thiol group that passivates the QD surface. Passivating MPA ligands on QDs facilitates patterning of QD films and makes them compatible with harsh photolithography processes. We successfully achieved the patterning of QDs down to 5 µm. We also fabricated high-resolution patterned QD light-emitting diodes (LEDs) and QD photodetector arrays. Our patterning process provides precise control for the fabrication of highly integrated QD-based optoelectronic devices.

Electrophoretic Deposition of Aged and Charge Controlled Colloidal Copper Sulfide Nanoparticles.

Colloidal nanoparticles (NPs) have been recently spotlighted as building blocks for various nanostructured devices. Their collective properties have been exhibited by arranging them on a substrate to form assembled NPs. In particular, electrophoretic deposition (EPD) is an emerging fabrication method for such nanostructured films. To maximize the benefits of this method, further studies are required to fully elucidate the key parameters that influence the NP deposition. Herein, two key parameters are examined, namely: (i) the aging of colloidal NPs and (ii) the charge formation by surface ligands. The aging of Cu2-xS NPs changes the charge states, thus leading to different NP deposition behaviors. The SEM images of NP films, dynamic light scattering, and zeta potential results demonstrated that the charge control and restoration of interparticle interactions for aged NPs were achieved via simple ligand engineering. The charge control of colloidal NPs was found to be more dominant than the influence of aging, which can alter the surface charges of the NPs. The present results thus reveal that the charge formation on the colloidal NPs, which depends on the surface ligands, is an important controllable parameter in EPD.

Facile Sulfurization under Ambient Condition with Na2S to Fabricate Nanostructured Copper Sulfide.

The sulfurization reaction was investigated as a promising fabrication method for preparing metal sulfide nanomaterials. Traditional sulfurization processes generally require high vacuum systems, high reaction temperatures, and toxic chemicals, utilizing complicated procedures with poor composition and morphology controllability. Herein, a facile method is reported for synthesizing nanostructured copper sulfide using a sulfurization reaction with Na2S at room temperature under non-vacuum conditions. Moreover, we demonstrate that the morphology, composition, and optical properties of nanostructured copper sulfides could be controlled by the Na2S solution concentration and the reaction time. Nanostructured copper sulfides were synthesized in nanospheres, nanoplates, and nanoplate-based complex morphologies with various oxidation states. Furthermore, by comparing the optical properties of nanostructured copper sulfides with different oxidation states, we determined that reflectivity in the near infrared (NIR) region decreases with increasing oxidation states. These results reveal that the Na2S solution concentration and reaction time are key factors for designing nanostructured copper sulfides, providing new insights for synthesis methods of metal sulfide nanomaterials.

Nanoparticle transformation from ZnO to ZnS through anion exchange with di-tert-butyl disulphide.

The chemical transformation from zinc oxide (ZnO) to zinc sulphide (ZnS), using di-tert-butyl disulphide (TBDS) as a highly reactive sulphur precursor, is demonstrated herein. Through anion exchange, we investigate the phase and morphological changes associated with the nanoparticle (NP) transformation of ZnO to ZnS using TBDS. The Zn-O-S alloy was not formed through the anion exchange reaction, only the ZnO and ZnS phases were detected. The NPs were transformed from a solid sphere to a hollow structure, induced by the nanoscale Kirkendall effect. Even with the dramatic shape and phase changes occurring in the NPs, the Zn oxidation state remained as 2+ throughout the 2 h anion exchange reaction. In addition, trioctylphosphine (TOP), a soft base ligand, increased the anion exchange reaction rate, facilitating the reaction with TBDS. Furthermore, anion exchange with elemental sulphur required a longer reaction time (3 h) than that with TBDS (2 h). Consequently, this study offers not only insights into phase and morphological transformations by anion exchange, but also the advantages of utilizing TBDS as a sulphur precursor.

Labeling and tracking cells with gold nanoparticles.

Gold nanoparticles (AuNPs) have garnered much attention as contrast agents for computerized tomography (CT) because of their facile synthesis and surface functionalization, in addition to their significant X-ray attenuation and minimal cytotoxicity. Cell labeling using AuNPs and tracking of the labeled cells using CT has become a time-efficient and cost-effective method. Actively targeted AuNPs can enhance CT contrast and sensitivity, and further reduce the radiation dosage needed during CT imaging. In this review, we summarize the state-of-the-art use of AuNPs in CT for cell tracking, including the precautionary steps necessary for their use and the difficulty in translating the process into clinical use.

Ion exchange: an advanced synthetic method for complex nanoparticles.

There have been tremendous efforts to develop new synthetic methods for creating novel nanoparticles (NPs) with enhanced and desired properties. Among the many synthetic approaches, NP synthesis through ion exchange is a versatile and powerful technique providing a new pathway to design complex structures as well as metastable NPs, which are not accessible by conventional syntheses. Herein, we introduce kinetic and thermodynamic factors controlling the ion exchange reactions in NPs to fully understand the fundamental mechanisms of the reactions. Additionally, many representative examples are summarized to find related advanced techniques and unique NPs constructed by ion exchange reactions. Cation exchange reactions mainly occur in chalcogenide compounds, while anion exchange reactions are mainly involved in halogen (e.g. perovskite) and metal-chalcogenide compounds. It is expected that NP syntheses through ion exchange reactions can be utilized to create new devices with the required properties by virtue of their versatility and ability to tune fine structures.

Colloidal-annealing of ZnO nanoparticles to passivate traps and improve charge extraction in colloidal quantum dot solar cells.

The popularity of colloidal quantum dot (CQD) solar cells has increased owing to their tunable bandgap, multiple exciton generation, and low-cost solution processes. ZnO nanoparticle (NP) layers are generally employed as electron transport layers in CQD solar cells to efficiently extract the electrons. However, trap sites and the unfavorable band structure of the as-synthesized ZnO NPs have hindered their potential performance. Herein, we introduce a facile method of ZnO NP annealing in the colloidal state. Electrical, structural, and optical analyses demonstrated that the colloidal-annealing of ZnO NPs effectively passivated the defects and simultaneously shifted their band diagram; therefore, colloidal-annealing is a more favorable method as compared to conventional film-annealing. These CQD solar cells based on colloidal-annealed ZnO NPs exhibited efficient charge extraction, reduced recombination and achieved an enhanced power conversion efficiency (PCE) of 9.29%, whereas the CQD solar cells based on ZnO NPs without annealing had a PCE of 8.05%. Moreover, the CQD solar cells using colloidal-annealed ZnO NPs exhibited an improved air stability with 98% retention after 120 days, as compared to that of CQD solar cells using non-annealed ZnO NPs with 84% retention.