Ternary chalcogenide As-S-Se glasses, important for optics, computers, material science and technological applications, are often made by pulsed laser deposition (PLD) technology but the plasma composition formed during the process is mostly unknown. Therefore, the formation of clusters in a plasma plume from different glasses was followed by laser desorption ionization (LDI) or laser ablation (LA) time-of-flight mass spectrometry (TOF MS) in positive and negative ion modes. The LA of glasses of different composition leads to the formation of a number of binary As(p)S(q), As(p)Se(r) and ternary As(p)S(q)Se(r) singly charged clusters. Series of clusters with the ratio As:chalcogen = 3:3 (As(3)S(3)(+), As(3)S(2)Se(+), As(3)SSe(2)(+)), 3:4 (As(3)S(4)(+), As(3)S(3)Se(+), As(3)S(2)Se(2)(+), As(3)SSe(3)(+), As(3)Se(4)(+)), 3:1 (As(3)S(+), As(3)Se(+)), and 3:2 (As(3)S(2)(+), As(3)SSe(+), As(3)Se(2)(+)), formed from both bulk and PLD-deposited nano-layer glass, were detected. The stoichiometry of the As(p)S(q)Se(r) clusters was determined via isotopic envelope analysis and computer modeling. The structure of the clusters is discussed.

Phosphorus nitride clusters generated during Laser Desorption Ionization (LDI) and Matrix-Assisted Laser Desorption Ionization (MALDI) of solid P(3) N(5) were analyzed via Time-of-Flight Mass Spectrometry (TOF MS). The LDI TOF mass spectra show the formation of series of clusters: P(m)N(n)(+) {(m=1; n=8-11), (m=4; n=3-4), (m=5; n=1-5), (m=6; n=1-3, 5-8), (m=2-7; n=1), (m=5-10; n=2), (m=4-6; n=3), (m=4,5; n=4), (m=5,6; n=5)}, and P(m)N(n)(-) (m=4,5; n=1). Using 3-hydroxypicolinic acid (HPA) as a matrix the P(m)N(n)(+) species (m=1-4, 6, 8) with a high nitrogen content (n=4, 5, 8, 10-12, 20) were identified. The formation of a N(6)(-) cluster was also detected using a C(60) matrix. Under various conditions singly charged P(m)(+) (m=2-7, 9, 13), P(m)(-) (m=3-11, 13, 15, 17), N(n)(+) (n=5, 9, 10, 12, 13), and N(n)(-) (n=6, 10-15) clusters were identified in the mass spectra. Such high nitrogen content clusters (up to N(15)(-)) generated by laser desorption from a solid material are described for the first time. The stoichiometry of the P(m)N(n) clusters was determined via isotopic envelope analysis and computer modelling. The composition of the clusters with respect to the crystalline structure of α-P(3)N(5) is discussed.

The local structure of Ga-Ge-Sb-S glasses is at least partly different from the structure of species identified in plasma by mass spectrometry, as deduced from Raman scattering spectroscopy analysis; these glasses are mainly formed by [GeS4/2]/[GaS4/2] tetrahedra and [SbS3/2] pyramids. Extended X-ray absorption fine structure measurements show that Er(3+) ions in Ga-Ge-Sb-S glasses are surrounded by 7 sulphur atoms.

Binary chalcogenide As-Se glasses and their thin films are important for optics, computers, materials science and technological applications. To increase understanding of the properties of thin films fabricated by plasma deposition techniques, more information concerning the physics of plasma plume is needed. In this study the formation of clusters in plasma plume from different As-Se glasses by laser desorption ionization (LDI) or laser ablation (LA) was studied by time-of-flight mass spectrometry (TOF MS) in positive and negative ion modes. Formation of a number of As(p)Se(q) singly charged clusters As(3)Se(q)(+) (q = 1-5), AsSe(q)(-) (q = 1-3), As(2)Se(q)(-) (q = 2-4), and As(3)Se(q)(-) (q = 2-5) was found from As-Se glasses with the molar ratio As:Se in the range from 1:2 to 7:3. The stoichiometry of the As(p)Se(q) clusters was determined via isotopic envelope analysis and computer modeling. The structure of the clusters is proposed and the relationship to the structure of the parent glasses, as also suggested by Raman scattering spectra, is discussed.

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