A Comparison of Structure, Stability of Neutral and Cationic Vanadium-doped Germanium Clusters GenV0/+ (n = 2 - 8) by using Density Function Theorym clusters GenV0/+ (n = 2 - 8) by using density function theory

The geometries, stabilities and electronic properties of vanadium-doped germanium clusters GenV0/+ (n=2-8) were systematically investigated by using density functional theory (DFT) at the PBE level and the 6-311+G(d) basis set. The results show that the geometries of lowest-energy structures of the cationic clusters are only significant different from those of the neutral at n = 6 or 7. The ground state of neutral clusters is a doublet, except Ge2V which is a quartet while that of cationic clusters is a triplet, except Ge8V+, which is a singlet. The average binding energy values generally increase with increasing cluster size. The results from average binding energies showed that it is more stable for the cationic than neutral clusters at the same size. Furthermore, the calculated values of fragmentation energy, second-order energy difference, HOMO-LUMO gap and adiabatic ionization potential suggest that the neutral clusters possess higher stability when n = 2, 5, 8 and the cations are more stable when n = 2, 3, 5 and 6.

(thf)2Ln(Ge9{Si(SiMe3)3}3)2 (Ln = Eu, Sm): the first coordination of metalloid germanium clusters to lanthanides

We report the synthesis, structure and magnetic properties of the first rare earth complexes of metalloid group 14 clusters [(thf)2Ln(Ge9Hyp3)2] (Ln = Eu, Sm, Hyp = Si(SiMe3)3). X-ray crystallographic analysis...

Формирование аморфных нанокластеров и нанокристаллов германия в пленках GeSi-=SUB=-x-=/SUB=-O-=SUB=-y-=/SUB=- на кварцевой подложке с использованием печных и импульсных лазерных отжигов

Nonstoichiometric GeO_0.5[SiO_2]_0.5 and GeO_0.5[SiO]_0.5 germanosilicate glassy films are produced by the high-vacuum coevaporation of GeO_2 and either SiO or SiO_2 powders with deposition onto a cold fused silica substrate. Then the films are subjected to furnace or laser annealing (a XeCl laser, λ = 308 nm, pulse duration of 15 ns). The properties of the samples are studied by transmittance and reflectance spectroscopy, Raman spectroscopy, and photoluminescence spectroscopy. As shown by analysis of the Raman spectra, the GeO[SiO] film deposited at a substrate temperature of 100°C contains amorphous Ge clusters, whereas no signal from Ge–Ge bond vibrations is observed in the Raman spectra of the GeO[SiO_2] film deposited at the same temperature. The optical absorption edge of the as-deposited GeO[SiO_2] film corresponds to ~400 nm; at the same time, in the GeO[SiO] film, absorption is observed right up to the near-infrared region, which is apparently due to absorption in Ge clusters. Annealing induces a shift of the absorption edge to longer wavelengths. After annealing of the GeO[SiO_2] film at 450°C, amorphous germanium clusters are detected in the film, and after annealing at 550°C as well as after pulsed laser annealing, germanium nanocrystals are detected. The crystallization of amorphous Ge nanoclusters in the GeO[SiO] film requires annealing at a temperature of 680°C. In this case, the size of Ge nanoclusters in this film are smaller than that in the GeO[SiO_2] film. It is not possible to crystallize Ge clusters in the GeO[SiO] film. It seems obvious that the smaller the semiconductor nanoclusters in an insulating matrix, the more difficult it is to crystallize them. In the low-temperature photoluminescence spectra of the annealed films, signals caused by either defects or Ge clusters are detected.

Проявление квантоворазмерных эффектов в нанокристаллах и аморфных нанокластерах германия в плeнках GeSixOy

The non-stoichiometric germanosilicate films of two types GeOx[SiO](1-x) and GeOx [SiO2](1-x) were obtained by high-vacuum evaporation of GeO2 and either SiO or SiO2 powders and sputtering on a cold Si (001) substrate. The as-deposited and annealed (550 and 650 oC, 1 hour) samples were studied by IR spectrocopy, electron microscopy, Raman spectroscopy and photoluminescence (PL). From an analysis of Raman spectra, it was found that the as-deposited GeO[SiO2] film did not contain germanium clusters, and the as-deposited GeO[SiO] film contained amorphous germanium clusters; according to electron microscopy, it’s size was ~3 nm. According to IR spectroscopy, the films contained Si-O, Ge-O, and Si-O-Ge bonds. After annealing at 550 °C, amorphous germanium clusters were detected in both films, and after annealing at 650 °C, germanium nanocrystals were observed. A wide PL band with a maximum of 1050 nm was found in the as-deposited films at low temperatures. PL is probably due to defects, presumably oxygen vacancies and excess germanium atoms. Annealing causes a transformation of both film structure and PL spectra. In films containing germanium nanoclusters, PL is observed with a maximum of 1500–1600 nm. In this case, the PL signal from defects decreased. The temperature dependence of the intensity of the PL peaks was studied; it decreased with increasing temperature but remained at temperatures up to 200 K. The contribution to the PL from germanium nanocrystals formed during annealing is discussed.