Synthesis and theoretical study of a mixed-ligand indium(III) complex for fabrication of ß-In2S3 thin films via chemical vapor deposition.

Two new heteroleptic indium aminothiolate compounds [InClSC2H4N(Me)SC2H4]3[1] and [InSC2H4N(Me)SC2H4(C8H5F3NO)] [2] were synthesized by in situ salt metathesis reaction involving indium trichloride, aminothiol, and N,O-ß-heteroarylalkenol ligands. The complexes were subsequently purified and thoroughly characterized by nuclear magnetic resonance (NMR) analysis, elemental studies, mass spectroscopy, and X-ray diffraction single crystal analysis that showed a trigonal bipyramidal coordination of In(III) in both complexes. Thermogravimetric analysis of [1] revealed a multistep decomposition pathway and the formation of In2S3 at 350 °C, which differed from the pattern of [2] due to the lower thermal stability of [1]. Compound [2] exhibited a three-step decomposition process, resulting in the formation of In2S3 at 300 °C. The Chemical Vapor Deposition (CVD) experiment involving compound [2] was conducted on the FTO substrate, resulting in the production of singular-phase In2S3 deposits. A comprehensive characterization of these deposits, including crystal structure analysis via X-ray diffraction (XRD), and surface topography examination through scanning electron microscopy (SEM) has been completed. The presence of In-S units was also supported by the Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and energy dispersive spectroscopy (EDS) of the as-deposited films. Moreover, the electronic structure and thermal properties of compound [2] were investigated through DFT calculations. Electron density localization analysis revealed that the highest occupied molecular orbital (HOMO) exhibited dense concentration at the aminothiolate moiety of the complex, while the lowest unoccupied molecular orbital (LUMO) predominantly resided at the N,O-ß-heteroarylalkenolate ligand. Furthermore, our computational investigation has validated the formation of indium sulfide by elucidating an intermediate state, effectively identified through EI-MS analysis, as one of the plausible pathways for obtaining In2S3. This intermediate state comprises the aminothiolate ligand (LNS) coordinated with indium metal.

Direct Synthesis of Two-Dimensional SnSe and SnSe2 through Molecular Scale Preorganization.

Two-dimensional tin monoselenide (SnSe) and tin diselenide (SnSe2) materials were efficiently produced by the thermolysis of molecular compounds based on a new class of seleno-ligands. Main group metal chalcogenides are of fundamental interest due to their layered structures, thickness-dependent modulation in electronic structure, and small effective mass, which make them attractive candidates for optoelectronic applications. We demonstrate here the synthesis of stable tin selenide precursors by in situ reductive bond cleavage in the dimeric diselenide ligand (SeC2H4N(Me)C2H4Se)2 in the presence of SnCl4. New molecular precursors [SnIV(SeC2H4N(Me)C2H4Se)2], [SnIVCl2(SeC2H4N(Me)C2H4Se)], and [SnIV(SC2H4N(Me)C2H4S)(SeC2H4N(Me)C2H4Se)] were thoroughly characterized by multinuclear magnetic resonance studies and single-crystal X-ray diffraction analysis that revealed the Sn(IV) center to be octahedrally coordinated by two tridentate dianionic chelating ligands or trigonally pyramidally coordinated by one chelating ligand and two chlorido ligands. Preorganization of metal-selenium bonds in both compounds offered direct and reproducible synthetic access to two-dimensional tin chalcogenides (SnSe and SnSe2) via simple adjustment of the pyrolysis temperature. Additionally, SnSe2 and SnSxSe2-x particles could be successfully synthesized by microwave-assisted decomposition of the molecular precursors, which was unambiguously corroborated by both experimental and computational analyses that explained the formation of a selenium rich SnSxSe2-x phase from a single molecular precursor containing both Sn-Se and Sn-S bonds.

Single source precursor route to nanometric tin chalcogenides.

Low-temperature solution phase synthesis of nanomaterials using designed molecular precursors enjoys tremendous advantages over traditional high-temperature solid-state synthesis. These include atomic-level control over stoichiometry, homogeneous elemental dispersion and uniformly distributed nanoparticles. For exploiting these advantages, however, rationally designed molecular complexes having certain properties are usually required. We report here the synthesis and complete characterization of new molecular precursors containing direct Sn-E bonds (E = S or Se), which undergo facile decomposition under different conditions (solid/solution phase, thermal/microwave heating, single/mixed solvents, varying temperatures, etc.) to afford phase-pure or mixed-phase tin chalcogenide nanoflakes with defined ratios.

Vapor Phase Synthesis of SnS Facilitated by Ligand-Driven "Launch Vehicle" Effect in Tin Precursors.

Extraordinary low-temperature vapor-phase synthesis of SnS thin films from single molecular precursors is attractive over conventional high-temperature solid-state methods. Molecular-level processing of functional materials is accompanied by several intrinsic advantages such as precise control over stoichiometry, phase selective synthesis, and uniform substrate coverage. We report here on the synthesis of a new heteroleptic molecular precursor containing (i) a thiolate ligand forming a direct Sn-S bond, and (ii) a chelating O^N^N-donor ligand introducing a "launch vehicle"-effect into the synthesized compound, thus remarkably increasing its volatility. The newly synthesized tin compound [Sn(SBut)(tfb-dmeda)] 1 was characterized by single-crystal X-ray diffraction analysis that verified the desired Sn:S ratio in the molecule, which was demonstrated in the direct conversion of the molecular complex into SnS thin films. The multi-nuclei (1H, 13C, 19F, and 119Sn) and variable-temperature 1D and 2D NMR studies indicate retention of the overall solid-state structure of 1 in the solution and suggest the presence of a dynamic conformational equilibrium. The fragmentation behavior of 1 was analyzed by mass spectrometry and compared with those of homoleptic tin tertiary butyl thiolates [Sn(SBut)2] and [Sn(SBut)4]. The precursor 1 was then used to deposit SnS thin films on different substrates (FTO, Mo-coated soda-lime glass) by CVD and film growth rates at different temperatures (300-450 °C) and times (15-60 min), film thickness, crystalline quality, and surface morphology were investigated.

Influence of the choice of precursors on the synthesis of two-dimensional transition metal dichalcogenides.

The interest in transition metal dichalcogenides (TMDCs; MEy/2; M = transition metal; E = chalcogenide, y = valence of the metal) has grown exponentially across various science and engineering disciplines due to their unique structural chemistry manifested in a two-dimensional lattice that results in extraordinary electronic and transport properties desired for applications in sensors, energy storage and optoelectronic devices. Since the properties of TMDCs can be tailored by changing the stacking sequence of 2D monolayers with similar or dis-similar materials, a number of synthetic routes essentially based on the disintegration of bulk (e.g., chemical exfoliation) or the integration of atomic constituents (e.g., vapor phase growth) have been explored. Despite a large body of data available on the chemical synthesis of TMDCs, experimental strategies with high repeatability of control over film thickness, phase and compositional purity remain elusive, which calls for innovative synthetic concepts offering, for instance, self-limited growth in the z-direction and homogeneous lateral topography. This review summarizes the recent conceptual advancements in the growth of layered van der Waals TMDCs from both mixtures of metal and chalcogen sources (multi-source precursors; MSPs) and from molecular compounds containing metals and chalcogens in one starting material (single-source precursor; SSPs). The critical evaluation of the strengths, limitations and opportunities of MSP and SSP approaches is provided as a guideline for the fabrication of TMDCs from commercial and customized molecular precursors. For example, alternative synthetic pathways using tailored molecular precursors circumvent the challenges of differential nucleation and crystal growth kinetics that are invariably associated with conventional gas phase chemical vapor transport (CVT) and chemical vapor deposition (CVD) of a mixture of components. The aspects of achieving high compositional purity and alternatives to minimize competing reactions or side products are discussed in the context of efficient chemical synthesis of TMDCs. Moreover, a critical analysis of the potential opportunities and existing bottlenecks in the synthesis of TMDCs and their intrinsic properties is provided.

Magnetic nanoparticle-based amplification of microRNA detection in body fluids for early disease diagnosis.

Circulating biomarkers such as microRNAs (miRNAs), short noncoding RNA strands, represent prognostic and diagnostic indicators for a variety of physiological disorders making their detection and quantification an attractive approach for minimally invasive early disease diagnosis. However, highly sensitive and selective detection methods are required given the generally low abundance of miRNAs in body fluids together with the presence of large amounts of other potentially interfering biomolecules. Although a variety of miRNA isolation and detection methods have been established in clinics, they usually require trained personnel and often constitute labor-, time- and cost-intensive approaches. During the last years, nanoparticle-based biosensors have received increasing attention due to their superior detection efficiency even in very low concentration regimes. This is based on their unique physicochemical properties in combination with their high surface area that allows for the immobilization of multiple recognition sites resulting in fast and effective recognition of analytes. Among various materials, magnetic nanoparticles have been identified as useful tools for the separation, concentration, and detection of miRNAs. Here, we review state-of-the-art technology with regard to magnetic particle-based miRNA detection from body fluids, critically discussing challenges and future perspective of such biosensors while comparing their handling, sensitivity as well as selectivity against the established miRNA isolation and detection methods.

Molecular Routes to Two-Dimensional Metal Dichalcogenides MX2 (M = Mo, W; X = S, Se).

New synthetic access to two-dimensional transition metal dichalcogenides (TMDCs) is highly desired to exploit their extraordinary semiconducting and optoelectronic properties for practical applications. We introduce here an entirely novel class of molecular precursors, [MIV(XEtN(Me)EtX)2] (MIV = MoIV, WIV, X = S, Se), enabling chemical vapor deposition of TMDC thin films. Molybdenum and tungsten complexes of dianionic tridentate pincer-type ligands (HXEt)2NR (R = methyl, tert-butyl, phenyl) produced air-stable monomeric dichalcogenide complexes, [W(SEtN(Me)EtS)2] and [Mo(SEtN(Me)EtS)2], displaying W and Mo centers in an octahedral environment of 4 S and 2 N donor atoms. Owing to their remarkable volatility and clean thermal decomposition, both Mo and W complexes, when used in the chemical vapor deposition (CVD) process, produced crystalline MoS2 and WS2 thin films. X-ray diffraction analysis and atomic-scale imaging confirmed the phase purity and 2D structural characteristics of MoS2 and WS2 films. The new set of ligands presented in this work open ups convenient access to a scalable and precursor-based synthesis of 2D transition metal dichalcogenides.