Rational Development of Guanidinate and Amidinate Based Cerium and Ytterbium Complexes as Atomic Layer Deposition Precursors: Synthesis,Modeling, and Application

Owing to the limited availability of suitable precursors for vapor phase deposition of rare-earth containing thin-film materials, new or improved precursors are sought after. In this study, we explored new precursors for atomic layer deposition (ALD) of cerium (Ce) and ytterbium (Yb) containing thin films. A series of homoleptic tris-guanidinate and tris-amidinate complexes of cerium (Ce) and ytterbium (Yb) were synthesized and thoroughly characterized. The C-substituents on the N-C-N backbone (Me, NMe₂, NEt₂, where Me=methyl, Et=ethyl) and the N-substituents from symmetrical iso-propyl (iPr) to asymmetrical tertiary-butyl (tBu) and Et were systematically varied to study the influence of the substituents on the physicochemical properties of the resulting compounds. Single crystal structures of [Ce(dpdmg)₃] 1 and [Yb(dpdmg)₃] 6 (dpdmg=N,N'-diisopropyl-2-dimethylamido-guanidinate) highlight a monomeric nature in the solid-state with a distorted trigonal prismatic geometry. The thermogravimetric analysis shows that the complexes are volatile and emphasize that increasing asymmetry in the complexes lowers their melting points while reducing their thermal stability. Density functional theory (DFT) was used to study the reactivity of amidinates and guanidinates of Ce and Yb complexes towards oxygen (O₂) and water (H₂O). Signified by the DFT calculations, the guanidinates show an increased reactivity toward water compared to the amidinate complexes. Furthermore, the Ce complexes are more reactive compared to the Yb complexes, indicating even a reactivity towards oxygen potentially exploitable for ALD purposes. As a representative precursor, the highly reactive [Ce(dpdmg)₃] 1 was used for proof-of-principle ALD depositions of CeO₂ thin films using water as co-reactant. The self-limited ALD growth process could be confirmed at 160 °C with polycrystalline cubic CeO₂ films formed on Si(100) substrates. This study confirms that moving towards nitrogen-coordinated rare-earth complexes bearing the guanidinate and amidinate ligands can indeed be very appealing in terms of new precursors for ALD of rare earth based materials.     

The Effect of Vibratory Grinding Time on Moisture Sorption,Particle Size Distribution,and Phenolic Bioaccessibility of Carob Powder

Carob pod powder, an excellent source of health-promoting substances, has found its use in a wide range of food products. Grinding conditions affect the physical and chemical properties of the powder, but their influence on the bioaccessibility of phenolic compounds in carob pod powder has not yet been determined. The carob pods were ground for 30–180 s in a vibratory grinder. The median values (D₅₀) of particle size decreased after 60 s of grinding (87.9 μm), then increased to 135.1 μm. Lightness showed a negative correlation with D₅₀ and a_w, while the values of redness and yellowness decreased with the reduction in particle size and water activity. The smaller the value of D₅₀, the higher the equilibrium moisture content of carob powder. Phenolic acids (vanillic, ferulic, cinnamic) and flavonoids (luteolin, naringenin, apigenin) were found in all samples of carob powder. The grinding time influenced their content in carob powder, with maximum values at 180 s. Similar observations were made when assessing antioxidant capacity. The in vitro digestion process only improved the bioaccessibility of catechin content in all samples. However, the bioaccessibility of the phenolic compounds and the total phenolic and flavonoid contents decreased with the increase in grinding time. Our findings revealed that the grinding of carob pods for 180 s improved the extractability of phenolics; however, their bioaccessibility was reduced. It is sufficient to ground the carob pod for 30 s, ensuring good availability of nutraceuticals and lower energy cost for grinding.     

Impact of random-field-type disorder on nematic liquid crystalline structures

The European Physical Journal E - In the nanoscale regime, flow behaviors for liquids show qualitative deviations from bulk expectations. In this work, we reveal by molecular dynamics simulations...