Triacylphosphines as a Novel Class of Phosphorus Sources for the Synthesis of Transition Metal Phosphide Nanoparticles.

Transition metal phosphide (TMP) nanoparticles (NPs) are versatile materials for energy conversion/storage applications due to their robustness and many possibilities to tailor NPs' electronic, physical, and chemical properties. One of the hurdles toward their broader implementation is their challenging synthesis exacerbated by the limited choice of phosphorus precursors. On the one hand, the synthesis of TMP NPs can employ various alkyl- or arylphosphines requiring prolonged heating at high temperatures, while on the other hand, highly reactive P(SiMe), white phosphorus, or PH pose additional obstacles associated with their hazardous nature, high cost, and limited availability.

Facile and Scalable Colloidal Synthesis of Transition Metal Dichalcogenide Nanoparticles with High-Performance Hydrogen Production.

Transition metal dichalcogenides (TMDs) have garnered significant attention as efficient electrocatalysts for the hydrogen evolution reaction (HER) due to their high activity, stability, and cost-effectiveness. However, the development of a convenient and economical approach for large-scale HER applications remains a persistent challenge. In this study, we present the successful synthesis of TMD nanoparticles (including MoS, RuS, ReS, MoSe, RuSe, and ReSe) using a general colloidal method at room temperature.

Nonclassical Mechanism of Metal-Enhanced Photoluminescence of Quantum Dots.

Metal-enhanced photoluminescence is able to provide a robust signal even from a single emitter and is promising in applications in biosensors and optoelectronic devices. However, its realization with semiconductor nanocrystals (e.g.

Quantum Dots Facilitate 3D Two-Photon Laser Lithography.

In the past two decades, direct laser writing (DLW) technologies have seen tremendous growth. However, strategies that enhance the printing resolution and the development of printing material with assorted functionalities are still sparser than expected. Herein, a cost-effective method to tackle this bottleneck is presented.

Chemical Transformations of Colloidal Semiconductor Nanocrystals Advance Their Applications.

Recently, colloidal semiconductor nanocrystals (NCs) are finding more and more applications in optoelectronic devices. Their usage, however, is still very far from the great potential already demonstrated in many fields owing to their unique features. While researchers are still struggling to achieve a wider gamut of different semiconductor nanomaterials with more controllable properties, the library of already existing candidates is large enough to harness their potential.

Multicolor Patterning of 2D Semiconductor Nanoplatelets.

Nanocrystal micro/nanoarrays with multiplexed functionalities are of broad interest in the field of nanophotonics, cellular dynamics, and biosensing due to their tunable electrical and optical properties. This work focuses on the multicolor patterning of two-dimensional nanoplatelets (NPLs) two sequential self-assembly and direct electron-beam lithography steps. By using scanning electron microscopy, atomic force microscopy, and fluorescence microscopy, we demonstrate the successful fabrication of fluorescent nanoarrays with a thickness of only two or three monolayers (7-11 nm) and a feature line width of ∼40 nm, which is three to four NPLs wide.

Simultaneous Ligand and Cation Exchange of Colloidal CdSe Nanoplatelets toward PbSe Nanoplatelets for Application in Photodetectors.

Cation exchange emerged as a versatile tool to obtain a variety of nanocrystals not yet available via a direct synthesis. Reduced reaction times and moderate temperatures make the method compatible with anisotropic nanoplatelets (NPLs). However, the subtle thermodynamic and kinetic factors governing the exchange require careful control over the reaction parameters to prevent unwanted restructuring.

Design of cross-linked polyisobutylene matrix for efficient encapsulation of quantum dots.

Photoluminescent quantum dots (QDs) are a prominent example of nanomaterials used in practical applications, especially in light-emitting and light-converting devices. Most of the current applications of QDs require formation of thin films or their incorporation in solid matrices. The choice of an appropriate host material capable of preventing QDs from degradation and developing a process of uniform incorporation of QDs in the matrix have become essential scientific and technological challenges.

Temperature-Dependent Photoluminescent Properties of PbSe Nanoplatelets.

Semiconductor colloidal nanoplatelets (NPLs) are a promising new class of nanostructures that can bring much impact on lightning technologies, light-emitting diodes (LED), and laser fabrication. Indeed, great progress has been made in optimizing the optical properties of the NPLs for the visible spectral range, which has already made the implementation of a number of effective devices on their basis possible. To date, state-of-the-art near-infrared (NIR)-emitting NPLs are significantly inferior to their visible-range counterparts, although it would be fair to say that they received significantly less research attention so far.

General Colloidal Synthesis of Transition-Metal Disulfide Nanomaterials as Electrocatalysts for Hydrogen Evolution Reaction.

The material-efficient monolayers of transition-metal dichalcogenides (TMDs) are a promising class of ultrathin nanomaterials with properties ranging from insulating through semiconducting to metallic, opening a wide variety of their potential applications from catalysis and energy storage to optoelectronics, spintronics, and valleytronics. In particular, TMDs have a great potential as emerging inexpensive alternatives to noble metal-based catalysts in electrochemical hydrogen evolution. Herein, we report a straightforward, low-cost, and general colloidal synthesis of various 2D transition-metal disulfide nanomaterials, such as MoS, WS, NiS, FeS, and VS, in the absence of organic ligands.

High-Performance Ultra-Short Channel Field-Effect Transistor Using Solution-Processable Colloidal Nanocrystals.

We demonstrate high-mobility solution-processed inorganic field-effect transistors (FETs) with ultra-short channel (USC) length using semiconductor CdSe nanocrystals (NCs). Capping of the NCs with hybrid inorganic-organic CdCl-butylamine ligands enables coarsening of the NCs during annealing at a moderate temperature, resulting in the devices having good transport characteristics with electron mobilities in the saturation regime reaching 8 cm V s. Solution-based processing of the NCs and fabrication of thin films involve neither harsh conditions nor the use of hydrazine.

Colloidal PbS nanoplatelets synthesized via cation exchange for electronic applications.

In this work, we present a new synthetic approach to colloidal PbS nanoplatelets (NPLs) utilizing a cation exchange (CE) strategy starting from CuS NPLs synthesized via the hot-injection method. Whereas the thickness of the resulting CuS NPLs was fixed at approx. 5 nm, the lateral size could be tuned by varying the reaction conditions, such as time from 6 to 16 h, the reaction temperature (120 °C, 140 °C), and the amount of copper precursor.

Role of the Crystal Structure in Cation Exchange Reactions Involving Colloidal CuSe Nanocrystals.

Stoichiometric CuSe nanocrystals were synthesized in either cubic or hexagonal (metastable) crystal structures and used as the host material in cation exchange reactions with Pb ions. Even if the final product of the exchange, in both cases, was rock-salt PbSe nanocrystals, we show here that the crystal structure of the starting nanocrystals has a strong influence on the exchange pathway. The exposure of cubic CuSe nanocrystals to Pb cations led to the initial formation of PbSe unselectively on the overall surface of the host nanocrystals, generating CuSe@PbSe core@shell nanoheterostructures.

Hybrid N-Butylamine-Based Ligands for Switching the Colloidal Solubility and Regimentation of Inorganic-Capped Nanocrystals.

We report on a simple and effective technique of tuning the colloidal solubility of inorganic-capped CdSe and CdSe/CdS core/shell nanocrystals (NCs) from highly polar to nonpolar media using n-butylamine molecules. The introduction of the short and volatile organic amine mainly results in a modification of the labile diffusion region of the inorganic-capped NCs, enabling a significant extension of their dispersibility and improving the ability to form long-range assemblies. Moreover, the hybrid n-butylamine/inorganic capping can be thermally decomposed under mild heat treatment, making this approach of surface functionalization well-compatible with a low-temperature, solution-processed device fabrication.

Simultaneous Identification of Spectral Properties and Sizes of Multiple Particles in Solution with Subnanometer Resolution.

We report an unsurpassed solution characterization technique based on analytical ultracentrifugation, which demonstrates exceptional potential for resolving particle sizes in solution with sub-nm resolution. We achieve this improvement in resolution by simultaneously measuring UV/Vis spectra while hydrodynamically separating individual components in the mixture. By equipping an analytical ultracentrifuge with a novel multi-wavelength detector, we are adding a new spectral discovery dimension to traditional hydrodynamic characterization, and amplify the information obtained by orders of magnitude.

3D Assembly of All-Inorganic Colloidal Nanocrystals into Gels and Aerogels.

We report an efficient approach to assemble a variety of electrostatically stabilized all-inorganic semiconductor nanocrystals (NCs) by their linking with appropriate ions into multibranched gel networks. These all-inorganic non-ordered 3D assemblies benefit from strong interparticle coupling, which facilitates charge transport between the NCs with diverse morphologies, compositions, sizes, and functional capping ligands. Moreover, the resulting dry gels (aerogels) are highly porous monolithic structures, which preserve the quantum confinement of their building blocks.

Cyclic voltammetry as a sensitive method for in situ probing of chemical transformations in quantum dots.

The application of electrochemical methods for the characterization of colloidal quantum dots (QDs) attracts considerable attention as these methods may allow for monitoring of some crucial parameters, such as energetic levels of conduction and valence bands as well as surface traps and ligands under real conditions of colloidal solution. In the present work we extend the applications of cyclic voltammetry (CV) to in situ monitoring of degradation processes of water-soluble CdTe QDs. This degradation occurs under lowering of pH to the values around 5, i.

Probing Absolute Electronic Energy Levels in Hg-Doped CdTe Semiconductor Nanocrystals by Electrochemistry and Density Functional Theory.

The absolute electronic energy levels in Hg-doped CdTe semiconductor nanocrystals (CdHgTe NCs) with varying sizes/volumes and Hg contents are determined by using cyclic voltammetry (CV) measurements and density functional theory (DFT) -based calculations. The electrochemical measurements demonstrate several distinct characteristic features in the form of oxidation and reduction peaks in the voltammograms, where the peak positions are dependent on the volume of CdHgTe NCs as well as on their composition. The estimated absolute electronic energy levels for three different volumes, namely 22, 119 and 187 nm(3) with 2.

Tetrazoles: Unique Capping Ligands and Precursors for Nanostructured Materials.

Capping agents play an important role in the colloidal synthesis of nanomaterials because they control the nucleation and growth of particles, as well as their chemical and colloidal stability. During recent years tetrazole derivatives have proven to be advanced capping ligands for the stabilization of semiconductor and metal nanoparticles. Tetrazole-capped nanoparticles can be prepared by solution-phase or solventless single precursor approaches using metal derivatives of tetrazoles.

Morphology-Dependent Electrochemical Properties of CuS Hierarchical Superstructures.

Hierarchical superstructures formed by self-assembled nanoparticles exhibit interesting electrochemical properties that can potentially be exploited in Li-ion batteries (LIBs) as possible electrode materials. In this work, we tested two different morphologies of CuS superstructures for electrodes, namely, tubular dandelion-like and ball-like assemblies, both of which are composed of similar small covellite nanoparticles. These two CuS morphologies are characterized by their markedly different electrochemical performances, suggesting that their complex structures/morphologies influence the electrochemical properties.

Cu Vacancies Boost Cation Exchange Reactions in Copper Selenide Nanocrystals.

We have investigated cation exchange reactions in copper selenide nanocrystals using two different divalent ions as guest cations (Zn(2+) and Cd(2+)) and comparing the reactivity of close to stoichiometric (that is, Cu2Se) nanocrystals with that of nonstoichiometric (Cu(2-x)Se) nanocrystals, to gain insights into the mechanism of cation exchange at the nanoscale. We have found that the presence of a large density of copper vacancies significantly accelerated the exchange process at room temperature and corroborated vacancy diffusion as one of the main drivers in these reactions. Partially exchanged samples exhibited Janus-like heterostructures made of immiscible domains sharing epitaxial interfaces.

From Binary Cu2S to ternary Cu-In-S and quaternary Cu-In-Zn-S nanocrystals with tunable composition via partial cation exchange.

We present an approach for the synthesis of ternary copper indium sulfide (CIS) and quaternary copper indium zinc sulfide (CIZS) nanocrystals (NCs) by means of partial cation exchange with In(3+) and Zn(2+). The approach consists of a sequential three-step synthesis: first, binary Cu2S NCs were synthesized, followed by the homogeneous incorporation of In(3+) by an in situ partial cation-exchange reaction, leading to CIS NCs. In the last step, a second partial exchange was performed where Zn(2+) partially replaced the Cu(+) and In(3+) cations at the surface, creating a ZnS-rich shell with the preservation of the size and shape.

Absolute photoluminescence quantum yields of IR26 and IR-emissive Cd(1-x)Hg(x)Te and PbS quantum dots--method- and material-inherent challenges.

Bright emitters with photoluminescence in the spectral region of 800-1600 nm are increasingly important as optical reporters for molecular imaging, sensing, and telecommunication and as active components in electrooptical and photovoltaic devices. Their rational design is directly linked to suitable methods for the characterization of their signal-relevant properties, especially their photoluminescence quantum yield (Φ(f)). Aiming at the development of bright semiconductor nanocrystals with emission >1000 nm, we designed a new NIR/IR integrating sphere setup for the wavelength region of 600-1600 nm.

Single-mode lasing from colloidal water-soluble CdSe/CdS quantum dot-in-rods.

Core-shell CdSe/CdS nanocrystals are a very promising material for light emitting applications. Their solution-phase synthesis is based on surface-stabilizing ligands that make them soluble in organic solvents, like toluene or chloroform. However, solubility of these materials in water provides many advantages, such as additional process routes and easier handling.