Crystal structures of three N,N,N′-trisubstituted thioureas for reactivity-controlled nanocrystal synthesis

The synthesis and single-crystal X-ray structures of three N,N,N′-trisubstituted thioureas are reported, namely N,N,N′-tribenzylthiourea, C22H22N2S (1), N-methyl-N,N′-diphenylthiourea, C14H14N2S (2), and N,N-di-n-butyl-N′-phenylthiourea, C15H24N2S (3). The influence of the different substituents on the thioureas is clear from the delocalization of the thiourea C—N and C=S bonds, while the crystal structures show infinite chains of N,N,N′-tribenzylthiourea (1), hydrogen-bonded pairs of N-methyl-N,N′-diphenylthiourea (2) and hexamer ring assemblies of N,N-di-n-butyl-N′-phenylthiourea (3) molecules. The above-mentioned compounds were synthesized via a mild, general procedure, readily accessible precursors and with a high yield, providing straightforward access to a whole library of thioureas.

Defects and impurities in colloidal Ga2O3 nanocrystals: new opportunities for photonics and lighting

Defects, both native and extrinsic, critically determine functional properties of metal oxides. Gallium oxide has recently gained significant attention for its promise in microelectronics, owing to the unique combination of conductivity and high breakdown voltage, and solid-state lighting, owing to the strong photoluminescence in the visible spectral region. These properties are associated with the presence of native defects that can form both donor and acceptor states in Ga2O3. Recently, Ga2O3 nanocrystal synthesis in solution and optical glasses has been developed, allowing for a range of new applications in photonics, lighting, and photocatalysis. This review focuses on the structure and properties of Ga2O3 nanocrystals with a particular emphasis on the electronic structure and interaction of defects in reduced dimensions and their role in the observed photoluminescence properties. In addition to native defects, the effect of selected external impurities, including lanthanide and aliovalent dopants, and alloying on the emission properties of Ga2O3 nanocrystals are also discussed.

Cow-to-cow variation in nanocrystal synthesis: learning from technical-grade oleylamine

Many technical-grade reagents, including oleylamine, are broadly used as ligands in nanocrystal synthesis, allowing for cost-effective, and more environmentally friendly, preparation of materials in useful quantities. Impurities can represent 30% or more of these reagent blends, and have frequently emerged as substantial drivers of nanocrystal morphology, assembly, or other physical properties, making it important to understand their composition. Some functional alkyl reagents are derived from natural sources (e.g. often beef tallow, in the case of oleylamine), introducing alkyl chain structures very different than those that might be expected as side products of synthesis from pure feedstocks. Additionally, impurities can exhibit variations based on biological factors (e.g. species, diet, season). In biology, blends of alkyl chains allow for surprisingly sophisticated function of amphiphiles in the cell membrane, pointing to the possibility of similar control in synthetic materials if reagent composition were either better controlled or better understood. Here, we provide brief context on the breadth of roles technical-grade impurities have played in nanocrystal materials, followed by a perspective on oleylamine impurities, their physical properties, and their potential contributions to nanomaterial function.

Tailored growth of single-crystalline InP tetrapods

Despite the technological importance of colloidal covalent III-V nanocrystals with unique optoelectronic properties, their synthetic process still has challenges originating from the complex energy landscape of the reaction. Here, we present InP tetrapod nanocrystals as a crystalline late intermediate in the synthetic pathway that warrants controlled growth. We isolate tetrapod intermediate species with well-defined surfaces of (110) and ($$\bar{1}\bar{1}\bar{1}$$ 1 ¯ 1 ¯ 1 ¯ ) via the suppression of further growth. An additional precursor supply at low temperature induces $$[\bar{1}\bar{1}\bar{1}]$$ [ 1 ¯ 1 ¯ 1 ¯ ] -specific growth, whereas the [110]-directional growth occurs over the activation barrier of 65.7 kJ/mol at a higher temperature, thus finalizes into the (111)-faceted tetrahedron nanocrystals. We address the use of late intermediates with well-defined facets at the sub-10 nm scale for the tailored growth of covalent III-V nanocrystals and highlight the potential for the directed approach of nanocrystal synthesis.

Nanocrystal Quantum Dot Devices: How the Lead Sulfide (PbS) System Teaches Us the Importance of Surfaces

Semiconducting thin films made from nanocrystals hold potential as composite hybrid materials with new functionalities. With nanocrystal syntheses, composition can be controlled at the sub-nanometer level, and, by tuning size, shape, and surface termination of the nanocrystals as well as their packing, it is possible to select the electronic, phononic, and photonic properties of the resulting thin films. While the ability to tune the properties of a semiconductor from the atomistic- to macro-scale using solution-based techniques presents unique opportunities, it also introduces challenges for process control and reproducibility. In this review, we use the example of well-studied lead sulfide (PbS) nanocrystals and describe the key advances in nanocrystal synthesis and thin-film fabrication that have enabled improvement in performance of photovoltaic devices. While research moves forward with novel nanocrystal materials, it is important to consider what decades of work on PbS nanocrystals has taught us and how we can apply these learnings to realize the full potential of nanocrystal solids as highly flexible materials systems for functional semiconductor thin-film devices. One key lesson is the importance of controlling and manipulating surfaces.