Influence of UV irradiation and heat treatment on the luminescence of molecular silver clusters in photo-thermo-refractive glasses

The luminescence spectra of photo-thermo-refractive (PTR) glasses containing cerium, silver, and antimony ions before and after UV irradiation and after heat treatment have been thoroughly investigated for the first time. It is shown that silver is present in the initial PTR glass in the form of ions and positively charged molecular clusters. After UV irradiation into the absorption band of cerium ions, silver partially passes to the neutral state in the form of atoms and neutral molecular clusters Ag₂, Ag₃, and Ag₄, which exhibit bright luminescence in the visible spectral range. Subsequent heat treatment at a temperature below the glassformation temperature leads to an increase in the luminescence intensity due to the increase in the concentration of neutral molecular clusters. Heat treatment at a temperature above the glass-formation temperature leads to the formation of silver nanocrystals and luminescence quenching. It is proposed to use PTR glasses with molecular silver clusters as phosphors for converting UV radiation into the visible range for solar power engineering and white LEDs.     

Influence of halogenides on luminescence from silver molecular clusters in photothermorefractive glasses

It is shown experimentally that a rise in the sodium halogenide (NaCl, NaBr) concentration in photothermorefractive glasses increases the intensity of luminescence from silver neutral molecular clusters. Substitution of NaBr for NaCl with their concentration being the same shifts the luminescence band toward longer waves and raises its intensity. These findings can be explained by the formation of molecular clusters of type Ag _n -Hal (Hal = Cl, Br) in photothermorefractive glass.     

The influence of low-temperature silver-ion exchange on the spectral-luminescent properties of fluorophosphate glasses doped with PbSe

Changes in the absorption and luminescence spectra of fluorophosphate glasses doped with PbSe caused by low-temperature Ag⁺–Na⁺ ion exchange are considered. It is found that the silver distribution gradient in a near-surface layer about 16 μm thick leads to two different processes of interaction between metal and semiconductor nanoparticles. PbSe molecular clusters and quantum dots more efficiently grow in deep layers with a low silver concentration. The near-surface glass layers with a high silver concentration exhibit formation of Ag metal nanoparticles, on the surface of which interaction with PbSe molecular clusters leads to the formation of Ag–Se–Pb bonds, which transform into Ag₂Se layers in the process of heat treatment. The appearance of the new phase is confirmed by X-ray diffraction.     

Formation of silver nanoparticles on the silicate glass surface after ion exchange

It has been experimentally shown that water vapor thermal treatment of silicate glasses with silver ions introduced by ion exchange leads to the formation of a silver nanoparticle layer with a high packing density on the glass surface. The results of studying the morphology of samples by atomic force and electron microscopy and X-ray spectral analysis of the composition of nanoparticles, as well as the optical density and luminescence spectra in different stages of the treatment, are presented. Mechanisms explaining the processes responsible for silver nanoparticle formation upon water vapor thermal treatment on the glass surface after ion exchange are proposed.     

The effect of Ce3+ ions on the spectral and decay characteristics of luminescence phosphate-borate glasses doped with rare-earth ions

The luminescent characteristics of Li₂O-B₂O₃-P₂O₅-CaF₂ (LBPC) glasses doped with Gd³⁺ and Tb³⁺ ions and codoped with Ce³⁺ are studied by pulsed optical spectrometry under electron beam excitation. It is found that in glass with Ce³⁺ and Gd³⁺ ions a decrease in the decay time of gadolinium luminescence in the 312-nm band (⁶ P _J → ⁸ S _7/2) was observed. It is shown that in the glass LBPC: Tb, Ce, an increase in the emission intensity in the main radiative transitions in terbium ion was observed. In the kinetics of luminescence band 545 nm of LBPC: Tb, Ce glasses, is present stage of buildup, the character of which changes with the doped of Ce³⁺ ions. The mechanism of energy transfer in LBP glasses doped with rare elements is discussed.     

Effect of the chemical state of silver on the luminescence properties of GeO<Subscript>2</Subscript>-Eu<Subscript>2</Subscript>O<Subscript>3</Subscript>-Ag films

A sol-gel method is used to prepare GeO₂-Eu₂O₃-Ag films in which the luminescence efficiency of Eu³⁺ ions during UV excitation is comparable to that in films activated by organic europium complexes. The luminescence spectra of these films are recorded, and the films are also studied using EPR and x-ray diffraction. The main origin of this effect is found to be complex Eu-Ag centers with a high quantum yield of the intracenter transfer of excitations to the rare-earth activator from silver ions and Ag _m ⁿ⁺ oligomer clusters located on the surface of silver nanoparticles.     

Angular distribution of electron emission from atomic hydrogen by bare ion impact

A series of silver nanoparticle embedded in erbium-doped tellurite glasses were synthesized using a one step melt-quenching method. Density and refractive index of glasses were measured. Thermal and optical characterizations were performed and plasmon bands of elliptical nanoparticles were observed. An enhancement of green (525 and 550 nm) and red (632 nm) lines in luminescence spectra of Er³⁺-doped silver-embedded tellurite glass was recorded and explained by energy transfer mechanism from silver nanoparticles to erbium ion in addition to enhanced local field in vicinity of metallic nanoparticles in the glass. The presence of nanoparticles was confirmed by transmission electron microscopy imaging and reduction of silver ions to silver neutral particles discussed through the redox potential estimation in probable reactions. Silver-erbium co-doped tellurite glass exhibits strong novel optical properties which nominate it as the promising glass for laser, color displays, and photonic applications.     

Influence of silver on the Sm<Superscript>3+</Superscript> luminescence in “Aerosil” silica glasses

The introduction of silver into the samarium-containing silica glasses prepared by the original solgel method leads to the formation of complex optical centers involving samarium ions and simple and/or complex silver ions. These centers are characterized by the effective sensitization of Sm³⁺ luminescence by Ag⁺, (Ag₂)⁺, and (Ag⁺)₂ ions according to the exchange mechanism for, at least, Sm³⁺-Ag⁺ centers. The formation of Sm-Ag centers is accompanied by an increase in the concentration of nonbridging oxygen ions, which prevent the reduction of silver ions by hydrogen. Silver nanoparticles formed in small amounts upon this reduction are effective quenchers of luminescence from the corresponding excited states of Sm³⁺ ions.     

The influence of silver ion exchange on the formation and luminescent properties of lead sulfide molecular clusters and quantum dots

PbS molecular clusters and quantum dots are formed by heat treatment in fluorophosphate glasses of the Na₂O₃–Р₂O₅–Ga₂O₃–AlF₃–ZnO(S)–PbF₂ system with different lead concentrations. PbS molecular clusters are characterized by optical absorption in the range of 300–800 nm and low quantum yields, which decrease from 8.9 to 2.7% with a semiconductor component concentration. It is shown that the parameters of formation of quantum dots luminescing in the wavelength range of 1000–1500 nm are considerably different at different semiconductor component concentrations. The influence of silver ion exchange on the formation of PbS nanoparticles is studied. Introduction of silver stimulates the growth of molecular clusters, which is seen in the absorption spectra. A possible mechanism of interaction of silver nanoparticles with PbS quantum dots is presented.     

Effect of the photoinduced charge exchange of Ag+ ions on the sensitized luminescence of Eu3+ in oxide films

It has been found that the excitation of silver ions by ultraviolet radiation in GeO₂-Eu₂O₃-Ag and SiO₂-Eu₂O₃-Ag films is accompanied by the weakening of silver-ion-sensitized luminescence of Eu³⁺ ions. The degree and rate of such weakening vary in wide ranges depending on the nature of the matrix, thermal treatment temperature, and energy of an exciting photon. The revealed effect has been explained by the photoinduced charge exchange of silver ions in complex Ag-Eu centers.     

Specific features of thermal dissolution of silver and gold thin films in silicate glass

It has been shown experimentally that the thermal dissolution of silver and gold thin films in silicate glass is accompanied by the formation of a monolayer of silver and gold micro- and nanocrystals, respectively, on the surface of the glass. These processes occur at temperatures well below the melting temperature of the metal. Microcrystals are formed predominantly at the edges of islands of the metal film, where there is a sufficient amount of the material for their growth. Silver and gold nanocrystals are formed in the case when atoms of the metal dissolved in the glass repeatedly emerge on the glass surface. Silver and gold dissolved in the glass exist not only in the form of atoms and ions but also in the form of charged and neutral molecular clusters.

     

The mechanism of sensitized anti-stokes luminescence in crystals with adsorbed dyes

We have analyzed regular features of sensitization processes of crystals AgCl, AgCl_0.95I_0.05, and Zn_0.6Cd_0.4S to processes of a low-threshold (10^?3–10^?4 W/cm²) two-quantum excitation of anti-Stokes luminescence by adsorbed molecules and by J and H aggregates of dyes of different classes. The excitation centers of this luminescence are complex and consist of dye molecules and few-atom silver clusters adsorbed nearby. Luminescence-excitation processes involve stages of photoexcitation of adsorbed dye molecules; resonance transfer of electronic excitation energy to adsorbed atoms and few-atom silver clusters, levels of which lie near the middle of the band gap; and their subsequent photoionization.     

A Mechanism of the influence of Gd(III) and other Ln(III) ions on sensitized luminescence of Eu(III) and Tb(III) ions in aqueous and ethanol solutions: The role of hydroxyl bridges

We studied sensitization of Eu(III) and Tb(III) ions by molecules of 1,10-phenanthroline and 2,2-bipyridil in D₂O and d ₆-ethanol and the influence of Nd(III), Pr(III), Sm(III), Gd(III), and Ho(III) ions on the luminescence intensity I _lum and lifetime τ_lum of Eu(III) and Tb(III) in solutions. The stability constants of complexes of Eu(III) and Gd(III) with 2,2′-bipyridil are measured by spectrophotometric and luminescence methods. It is shown that luminescence of Eu(III) is quenched by Gd(III) ions at the ion concentration equal to 10^?2–10^?1 M, which is caused by competing between these ions for a sensitizer. At the concentration of Ln(III) ions equal to 10^?6?10^?3 M, the sensitized luminescence of Eu(III) and Tb(III) was quenched and τ_lum decreased in the presence of Nd(III) ions, whereas in the presence of Gd(III) the luminescence intensity increased. It is proved that a bridge that connects the two ions upon energy transfer is formed by hydroxyl groups. The intensity of luminescence of Eu(III) and Tb(III) in aqueous solutions and its lifetime decreased in the presence of hydroxyl groups, while upon addition of Gd(III) to these solutions these quantities were restored. We also found that the addition of Gd(III) to deoxygenated ethanol solutions of 2,2′-bipyridil and Eu(III) slows down photochemical and thermal reactions between bipyridil and Eu(III), resulting in the increase in the luminescence intensity of Eu(III).     

Electronic Absorption Spectra of Neutral and Charged Silver Molecular Clusters

The structural, energy, and optical properties of charged and neutral molecular clusters (MCs) of silver Ag_n (n = 2–5) have been simulated within the density functional theory (DFT). It has been shown that the electronic absorption spectrum of neutral MCs is shifted toward lower energies compared to the charged ones. The strengths of the oscillators of neutral MCs are mainly larger than the ones of charged MCs. A comparison of the simulation results with the previously obtained experimental ones for glasses with silver MCs has been carried out.     

Luminescence of molecular silver clusters in oxyfluoride glasses

Luminescence spectra of silver-containing oxyfluoride glasses have been investigated in the excitation spectral range of 360–480 nm. Analysis of the luminescence spectra shows that silver in oxyfluoride glasses that contain no strong reducers and were subjected to heat treatment affecting redox processes exists in the form of neutral atoms and neutral molecular Ag₂, Ag₃, and Ag₄ clusters.     

Magnetic phase diagram of a random mixture of Jahn-Teller ions

A magnetic model of a random mixture containing Jahn-Teller ions, in which several kinds of exchange interactions between the Jahn-Teller ions and between the Jahn-Teller and non-Jahn-Teller ions are assumed, is proposed and studied by using the distribution function method. It is shown that a spin glass phase occurs when these exchange interactions have different signs. Our model would be applicable to a mixture Rb₂Cr_xMn_1-xCl₄ in which the spin glass phase has been observed.     

Spectral and luminescent study of reduced forms of Pd-octaethylporphin

It is shown by electron absorption spectroscopy methods that the reduction of Pd-octaethylporphin does not touch the unfilled d _x ²-_y ² orbitals of metal. In the reduction products (mono-and dianions), excess electrons are distributed on the lowest vacant molecular e _g (π*) orbital of the ligand. This does not contradict the results of the quantum-chemical calculation of electronic states of neutral Pd-porphyrins by the extended Hückel method that are presented in the literature. Differences in electronic absorption spectra of π-anions of Pd and Zn complexes are attributed to the distortion of the plane geometry of the tetrapyrrole skeleton due to the displacement of the Pd(II) ion from the macrocycle plane. Mono-and dianions of their Pd complex lose the ability to be luminescent. The emissive capacity is reconstructed in the product of π-dianion protonation, which is called phlorin-anion (π-monoanion of Pd-octaethylporphin phlorin). As the temperature is decreased from room temperature to 77 K, the fluorescence spectrum of this product becomes narrower, its peak shifts to the blue region, and the quantum yield of luminescence increases. Specific features of the spectral properties of phlorin-anion are described by conformational changes in the excited state. Phlorin-anion was found to quench luminescence of neutral Pd-octaethylporphin molecules at room temperature.     

Formation of silver thin films and nanoparticles inside and on the surface of silver-containing glasses by electron irradiation

It is shown experimentally that irradiation of silver-ion-containing glasses by 5–7-keV electrons with doses of 20–50 mC/cm² results in the formation of a silver thin film and nanoparticles on the surface. If the concentration of silver ions in the glass is high, a subsurface film arises as well. These effects are due to a negative space charge region forming under the surface. As a result, silver ions migrate in the resulting field from the volume of the glass toward the negative space charge region and the surface and thermalized electrons reduce the ions to neutral atoms.     

The effect of codopants on spectral-kinetic characteristics of luminescence of scintillation glasses doped with terbium ions

The effect of Ce³⁺ and Pr³⁺ ions on spectral-kinetic characteristics of luminescence of lithium–phosphate–borate glasses is studied. It is shown that terbium ion luminescence caused by transitions from ⁵D₃ and ⁵D₄ multiplets to the ground 7FJ term is detected in samples containing Tb³⁺/Ce³⁺ and Tb³⁺/Pr³⁺. It has been found that an increase in the concentration of cerium ions from 0.2 to 1 wt % leads to an increase in the intensity of main luminescence bands of terbium ions. In Tb³⁺/Pr³⁺ glasses, a decrease in the relative light yield is observed with an increase in the concentration of Pr³⁺ ions. Processes of energy transfer between Tb³⁺/Ce³⁺ and Tb³⁺/Pr³⁺ ions are discussed.