Experimental and theoretical studies of spectral properties of chalcogenide Ge-S and As-Ge-S glasses and fibers are performed. A broad infrared (IR) luminescence band which covers the 1.2-2.3~$μ$m range with a lifetime about 6~$μ$s is discovered. Similar luminescence is also present in optical fibers drawn from these glasses. Arsenic addition to Ge-S glass significantly enhances both its resistance to crystallization and the intensity of the luminescence. Computer modeling of Bi-related centers shows that interstitial Bi$^+$ ions adjacent to negatively charged S vacancies are most likely responsible for the IR luminescence.
This thesis focuses on two different, but complementary, aspects of the modification of gallium lanthanum sulphide (GLS) glasses. Firstly the addition of transition metal ions as dopants is examined and their potential for use as active optical materials is explored. It is also argued that the spectroscopic analysis of transition metal ions is a useful tool for evaluating the local environment of their host. Secondly femtosecond (fs) laser modification of GLS is investigated as a method for waveguide formation.
First-principle study of bismuth-related oxygen-deficient centers ($=$Bi$\cdots$Ge$\equiv$, $=$Bi$\cdots$Si$\equiv$, and $=$Bi$\cdots$Bi$=$ oxygen vacancies) in Bi$_2$O$_3$-GeO$_2$, Bi$_2$O$_3$-SiO$_2$, Bi$_2$O$_3$-Al$_2$O$_3$-GeO$_2$, and Bi$_2$O$_3$-Al$_2$O$_3$-SiO$_2$ hosts is performed. A comparison of calculated spectral properties of the centers with the experimental data on luminescence emission and excitation spectra suggests that luminescence in the 1.2-1.3 $μ$m and 1.8-3.0 $μ$m ranges in Bi$_2$O$_3$-GeO$_2$ glasses and crystals is likely caused by $=$Bi$\cdots$Ge$\equiv$ and $=$Bi$\c…
Absorption, luminescence and Raman spectra of interstitial bismuth atoms, $\mathrm{Bi}^{0}$, and negatively charged dimers, $\mathrm{Bi}^{2-}$, in alumosilicate, germanosilicate, phosphosilicate and phosphogermanate glasses networks are calculated by time-dependent density functional method. On grounds of this calculation an extension of our previously suggested model of broadband near-IR luminescence in bismuth-doped glasses is put forward.
Near-bandgap Raman scattering was used to induce and study photostructural changes in AsxS100-x bulk glasses revealing a new photoinduced polymerization effect. Raman spectra were recorded also in off-resonant conditions allowing for a detailed comparison between the equilibrium glass structure and the metastable one induced by illumination. It is shown that in S-rich glasses structural changes involve the athermal scission of S8 rings and their polymerization to Sn chains. The fraction of bonds involved in this effect is surprisingly high, being one order of magnitude higher than the correspo…
Many properties of alloyed chalcogenide glasses can be closely correlated with the average coordination of these compounds. This is the case, for example, of the ultrasonic constants, dilatometric softening temperature and the vibrational densities of states. What is striking, however, is that these properties are nevertheless almost independent of the composition at given average coordination. Here, we report on some numerical verification of this experimental rule as applied to vibrational density of states.
A structural study is presented of ab-initio molecular dynamics simulations of Ge-As-Se calcogenide glasses performed at the same mean coordination number but differing stoichiometry ranging between Se rich and Se poor glasses. Starting configurations are generated via Reverse Monte Carlo (RMC) simulations of Extended X-ray Absorption Fine Structure (EXAFS) measurements of experimental samples. Structural analysis is presented illustrating the bonding trends found with changing stoichiometry.
Chalcogenide glasses possess several outstanding properties that enable several ground breaking applications, such as optical discs, infrared cameras, and thermal imaging systems. Despite the ubiquitous usage of these glasses, the composition property relationships in these materials remain poorly understood. Here, we use a large experimental dataset comprising approx 24000 glass compositions made of 51 distinct elements from the periodic table to develop machine learning models for predicting 12 properties, namely, annealing point, bulk modulus, density, Vickers hardness, Littleton point, You…
Er-doped phosphate glasses were fabricated by melt-quenching technique. The changes in their thermal, structural and luminescence properties with the addition of Al2O3, TiO2 or ZnO were studied. Physical and thermal properties were investigated through density measurement and differential thermal analysis. Structural characterization was performed using the Raman and Infrared spectroscopy. In order to study the influence of the composition on the luminescence properties of the glasses, the refractive index, the luminescence spectra and the lifetime values were measured. The results show that w…
In this paper, we present new models of germanium selenide chalcogenide glasses heavily doped with silver. The models were readily obtained with ab initio molecular dynamics and their structure agrees closely with diffraction measurements. Thermal molecular dynamics simulation reveals the dynamics of Ag+ ions and the existence of trapping centers as conjectured in other theory work. We show that first principles simulation is a powerful tool to reveal the motion of ions in glass.
Carrier-type reversal to enable the formation of semiconductor p-n junctions is a prerequisite for many electronic applications. Chalcogenide glasses are p-type semiconductors and their applications have been limited by the extraordinary difficulty in obtaining n-type conductivity. The ability to form chalcogenide glass p-n junctions could improve the performance of phase-change memory and thermoelectric devices and allow the direct electronic control of nonlinear optical devices. Previously, carrier-type reversal has been restricted to the GeCh (Ch=S, Se, Te) family of glasses, with very high…
In this chapter, by using ab-initio molecular dynamics, we introduce the latest simulation results on two materials for flash memory devices: Ge2Sb2Te5 and Ge-Se-Cu-Ag. This chapter is a review of our previous work including some of our published figures and text in Cai et al. (2010) and Prasai & Drabold (2011) and also includes several new results.
Due to their unique optical and electronic functionalities, chalcogenide glasses are materials of choice for numerous microelectronic and photonic devices. However, to extend the range of compositions and applications, profound knowledge about composition-property relationships is necessary. To this end, we collected a large quantity of composition-property data on chalcogenide glasses from SciGlass database regarding glass transition temperature ($T_g$), Young's modulus ($E$), coefficient of thermal expansion (CTE), and refractive index ($n_D$). With these data, we induced predictive models u…
Melt-fragility index (m) and glass molar volumes (Vm) of binary Ge-Se melts/glasses are found to change reproducibly as they are homogenized. Variance of Vm decreases as glasses homogenize, and the mean value of Vm increases to saturate at values characteristic of homogeneous glasses. Variance in fragility index of melts also decreases as they are homogenized, and the mean value of m decreases to acquire values characteristic of homogeneous melts. Broad consequences of these observations on physical behavior of chalcogenides melts/glasses are commented upon. The intrinsically slow kinetics of …
Photoluminescence (PL) and Raman spectra of sol-gel-derived silica glasses were studied in course of the consolidation of xerogel to dense glass. A number of ultraviolet PL bands in 3 eV - 4 eV region were found, which have not been observed in pure silica glasses not exposed to carbon compounds. Such PL bands, some of which exhibit distinct vibronic structures at room temperature, have been persistently reported in various high-surface porous or nanoparticle forms of SiO2. Based on their spectral shapes and decay kinetics properties, the structured PL bands in the 3.7-3.8 eV and 3.1-3.3 eV re…
A synopsis of the various photoinduced changes of rheological, mechanical and elastic properties is presented in the first part of the article. After a critical appraisal of a large body of experimental data it suggested that the photoviscous effect, that is, the athermal decrease of viscosity of a non-crystalline chalcogenide upon illumination is the key for a plethora of photoinduced effects reported so far in the literature under different names. Morphic effects (shape or surface morphology) may ap-pear either in the presence or absence of external mechanical stimuli leading to the fabricat…
We synthesize and study the properties of praseodymium doped fluoroindate glasses. Glass compositions with praseodymium molar concentrations up to 5% were obtained with good optical quality. Thermal, optical, and luminescence properties are investigated. Judd-Ofelt analysis is used to determine radiative lifetime and emission cross-section of the orange transition originating from the 3P0 level. We find that these glasses are good candidates for the realization of blue diode laser pumped orange lasers for quantum information processing applications.
The purpose of this work is to study the change in the structure of the Ge-Se network upon doping with Ag. The total structure factor S(Q) for two samples has been measured by neutron diffraction using the two-axis diffractometer dedicated to structural studies of amorphous materials, D4, at the Institut Laue Langevin. We have derived the corresponding radial distribution functions for each sample and each temperature, which gives us an insight about the composition and temperature dependence of the correlation distances and coordination numbers in the short-range. Our results are compatible w…
Preparation technology, the structure determination, multiband luminescence and nonlinear optical properties of the chalcogenide glasses are subject of present work. The glass samples with two different Er content were prepared by classical two-stage melt-quenching method. Glass state and morphology were confirmed by X-ray and EDS techniques. Influence of the Erbium doping on the luminescence and NLO properties was investigated.
Emerging technologies are demanding innovative properties of glasses. In this work, Cerium Oxide is used as a dopant in Zinc-Tellurite samples and its effects on the properties of the glass are investigated. Thermal analysis and x-ray diffraction confirmed the amorphous nature of all samples. The bivalent nature of Cerium is investigated spectroscopically and a strong redshift induced by the dopant is attributed to charge transfers O$^{2-}{\rightarrow}$Ce$^{4+}$, while the 4f-5d transition of Ce$^{3+}$ could not be identified in absorption or luminescence measurements. Yellow/red (570/650 nm) …
The photoluminescence of oxidized and fluorinated nominally pure silica glasses, which have good optical transparency in the optical gap, has been investigated under excitation by excimer lasers. The data are compared with the data for chlorinated silica glass, as well as glass containing OH. The excitation of localized states provides the release and capture of charge carriers, despite the low absorption coefficient. Holes are self-trapped. The recombination in the thermally activated or tunnel process creates luminescence of oxygen-deficient centers. It is concluded that oxidation and fluori…
We determine the electronic density of states for computationally-generated bulk samples of amorphous chalcogenide alloys As$_{x}$Se$_{100-x}$. The samples were generated using a structure-building algorithm reported recently by us ({J. Chem. Phys.} ${\bf 147}$, 114505). Several key features of the calculated density of states are in good agreement with experiment: The trend of the mobility gap with arsenic content is reproduced. The sample-to-sample variation in the energies of states near the mobility gap is quantitatively consistent with the width of the Urbach tail in the optical edge obse…
A structure of germanium selenide glasses is simulated by the featured clusters built from the tetrahedral GeSe4 units up to the clusters with six germanium atoms (Ge6Se16H4 and Ge6Se16H8). Quantum chemical calculations at the DFT level with effective core potentials for Ge and Se atoms for the clusters of different composition reveal their relative stability and optical properties.
The axiomatic theory of ideally glassy networks, which has proved effective in describing phase diagrams and many properties of chalcogenide, oxide, and even molecular glasses, is here broadened to describe both geometrical properties, such as the first sharp diffraction peak, and kinetic properties, such as the nonreversible enthalpy of the glass transition, as measured by modulated differential scanning calorimetry. The discussion shows why the latter is such an effective tool for identifying strong glasses.
First-principle study of possible bismuth-related centers in SiO2 and GeO2 hosts is performed and the results are compared with the experimental data. The following centers are modeled: trivalent and divalent Bi substitutional centers; BiO interstitial molecule; interstitial ion, Bi^+, and atom, Bi^0; Bi...Si-Si and Bi...Ge-Ge complexes formed by interstitial Bi atoms and glass intrinsic defects, Si-Si or Ge-Ge oxygen vacancies; interstitial dimers, Bi0 and Bi_2^-. Experimental data available on bismuth-related IR luminescence in SiO2:Bi and GeO2:Bi glasses, visible (red) luminescence in SiO2:…
The development of enhanced optical devices relies on key materials properties. In this context, researchers have investigated the effects of metal nanoparticles incorporation in active rare-earth materials. Here, we discuss the effects of Silver nitrate addition 0.5%, 1.0% and 2.0% mol%) into a Pr3+ doped tellurite-tungstate glasses (TWNN) formed by the conventional melt-quenching technique. The XRD curves confirmed the amorphous structural nature of TWNN glasses. The FTIR spectra identified the presence of different vibrational groups. DSC curves verified the increase around 70 oC for therma…
Transition metal perovskite chalcogenides (TMPCs) are explored as stable, environmentally friendly semiconductors for solar energy conversion. They can be viewed as the inorganic alternatives to hybrid halide perovskites, and chalcogenide counterparts of perovskite oxides with desirable optoelectronic properties in the visible and infrared part of the electromagnetic spectrum. Past theoretical studies have predicted large absorption coefficient, desirable defect characteristics, and bulk photovoltaic effect in TMPCs. Despite recent progresses in polycrystalline synthesis and measurements of th…
Little is known about the role of network rigidity in light-induced structural rearrangements in network glasses due to a lack of supporting experiments and theories. In this report, we demonstrate for the first time the ultrafast structural rearrangements manifested as induced absorption (IA) over a broad spectral range in a-GexAs35-xSe65 thin films above the mean-field rigidity percolation transition, quantified by the mean coordination number <r> = 2.40. The IA spectrum arising from self-trapped excitons, induced structural rearrangements by softening the glass network that strikingly revea…
Raman and calorimetric studies on Ge_xSe_{1-x} glasses have provided evidence for the existence of the intermediate phase (IP) in chalcogenide and other glasses. Here, we present X-Ray Absorption Near Edge Structure (XANES) measurements on germanium selenide glasses in the IP composition range, and detect an electronic signature of the IP. Ab initio molecular dynamics (MD) based models of these glasses are discussed, and an atomistic picture of the IP, based upon the models and available experiments is presented. We show that these models reproduce detailed composition-dependent structure in t…
Semiconductor glasses exhibit many unique optical and electronic anomalies. We have put forth a semi-phenomenological scenario (J. Chem. Phys. 132, 044508 (2010)) in which several of these anomalies arise from deep midgap electronic states residing on high-strain regions intrinsic to the activated transport above the glass transition. Here we demonstrate at the molecular level how this scenario is realized in an important class of semiconductor glasses, namely chalcogen and pnictogen containing alloys. Both the glass itself and the intrinsic electronic midgap states emerge as a result of the f…
The photophysical properties of Bi82+ and Bi53+ polycations stabilized by [AlCl4]- have been studied experimentally and theoretically. The obtained product was thoroughly evaluated by powder X-ray diffraction and photoluminescence spectroscopy, making it clear that both Bi82+ and Bi53+ contribute to the observed broad near-infrared emission. Furthermore, it was revealed that Bi82+ polycation mainly results in the emission peaking at ca. 1180 nm, while Bi53+ the longer-wavelength emission. The following quantum chemistry calculation on Bi82+ polycation helps us attribute some observed excitatio…
