Micro-Raman studies on 50 keV electron irradiated silicate glass

A potassium–lime-silicate glass was irradiated with a 50 keV electron beam. The impact of irradiation conditions on the glass structure (beam diameter, current, and irradiation time) was studied by Micro-Raman spectroscopy. For irradiation time less than the incubation time (around 360 s), structural evolutions are attributed to a glass densification. Irradiations longer than the incubation period led to a precipitation of supposed calcium enriched phase and formation of a more depolymerized silicate phase. A non-homogeneous irradiated glass structure was observed with the existence of an area (along the electron beam border) composed by a mixture of a concentrated Ca phase diluted into the amorphous silicate phase.     

Oxygen depletion in electron beam bombarded glass surfaces studied by XPS

XPS has been utilized to study the compositional changes which occur in glass after electron beam irradiation. In the bombarded surfaces a reduction in Na and O signals is observed, while Ca signal shows negligible variations. Two O_1s signals, assigned to bridging and non-bridging oxygen were found. Irradiation causes a decrease of these two types of oxygen. This is at variance with Lineweaver's mechanism which accounts for the decrease of the non-bridging oxygens only. After irradiation a second component in the Si_2p line is found. It has been attributed to the formation of SiSi bonds induced by oxygen outgassing. The formation of these bonds leads to a more compact structure and this might explain the observed density change in irradiated glass.     

Low energy and low dose electron irradiation of potassium–lime–silicate glass investigated by XPS. I. Surface composition

X-ray induced photoelectron spectroscopy has been used to study the influence of low-energy electron beam on the pristine potassium–lime–silicate glass surface prepared by fracturing in situ under ultrahigh vacuum. Relatively low-energy electron beam of 1600 eV with low-electron beam current density of 0.02–0.22 A/m² and low-electron dose of 29–5200 C/m² was used. The expected modified near-surface region thickness is in this case comparable with the mean sampling depth of the analytical tool. Therefore, possible changes and modifications due to electron irradiation could be recorded with high sensitivity. The freshly fractured glass surface was found to be significantly enriched with potassium, and slightly with calcium. As a consequence of the lowest electron dose irradiation used, the potassium signal substantially increased by a factor 1.24 relative to the value found for the fresh surface. For higher doses used, the potassium signal continuously increased with the dose to a maximum and decreased thereafter. This variation was accompanied with the qualitative opposite behaviour of calcium signal. The concentrations of the other elements present in the glass, oxygen and silicon, varied only slightly with the electron dose. They can be considered to be constant within experimental uncertainty. In agreement with experimental results, a model assuming mobility of only two most mobile cations, potassium and calcium, was suggested. The models assuming one layer and two layers on the bulk were developed. Their results reproduce well experimental findings: (i) the formation of a potassium-rich surface layer, and (ii) the opposite-like signal variation of calcium in comparison with potassium.     

Investigation of alkali borosilicate glass durability using tritium tracing, β-autoradiography, scanning electron microscopy and ion beam analysis

A Li-Na-containing borosilicate glass was submitted to aqueous corrosion in static mode in tritiated solutions of various pH at room temperature and 90 °C. Tritium counting, β-autoradiography, scanning electron microscopy (SEM) and ion beam analysis (IBA) techniques have been used to investigate the composition variations of the leached glass surfaces. In an acidic medium, the glass surface is covered by a thick hydrated silica layer; mobile elements like Li, Na and B and transition elements like Fe and Mo are strongly depleted. Near pH 7, relative enrichments of aluminium and iron are shown together with strong Li, Na and B depletions. In a basic medium, the glass surface exhibits iron and molybdenum enrichments whereas mobile elements seem to be kept at their nominal concentration level at the glass surface. The tritium activity and distribution on the leached glass surface is shown to depend strongly on the pH of the tritiated solutions. These observations are correlated with the observed changes of the surface morphology and chemistry characterized by IBA and SEM analysis. Elemental solubility versus pH of various chemical species have been calculated for comparison purpose with the experimental observations.     

Electron beam induced surface modification of amorphous Sb2Se3 thin film

The change in the surface morphology of amorphous Sb₂Se₃ thin films during the electron beam irradiation has been studied mainly by atomic force microscopy (AFM). Electron beam at accelerating voltages 30 kV is focused onto the surface of the specimens of 100-μm thickness, and then the surface morphology of each specimen has been observed by AFM in air. The modification of the film surface includes lateral and vertical resizing which is typically in the micrometer and sub-micrometer range. Protrusions above the surface as high as 90 nm are observed at 180 pA electron beam current, whilst trenches as deep as 97 nm are observed at 800 pA electron beam current (total thickness of thin film is 100 nm). The dependence of patterns characteristics on irradiation parameters such as exposure time and beam current has also been studied. Physical mechanisms for trench and mound formation are proposed.     

Changes in surface morphology of silicate glass induced by fast electron irradiation

Binary potassium-silicate glass was irradiated with a defocused electron beam. During the irradiation the alkali ions migrate from the surface into the depth and alkali ions depleted layer is created near the surface. Such changes in the chemical composition are also accompanied with changes of the glass structure and finally result in the volume changes of the irradiated glass. This was directly studied using atomic force microscope (AFM). A series of exposures with energy of electrons of 7–50 keV and with different doses were performed. For low doses the irradiated glass is continuously depressed with the increasing dose, indicating this way the structural changes leading to the volume compaction. It is suggested the compaction is caused by the relaxation processes of the silica subnetwork. A further increase of the electron dose causes a formation of the small bump inside the center of the depression. The bump arises with the dose and finally exceeds the surrounding surface. It is suggested that the expansion is connected with the migration of alkali ions and the formation of Si–O–O–Si bonds which result in the formation of new rings with new space requirements.     

On the limitation of quantitative measurements using transmission electron microscopy

This work discussed the limitation of (scanning) transmission electron microscopy (TEM/STEM) techniques in quantitative measurements in electron-beam-sensitive silicate glasses and glass ceramics. Electron beam induced damages in the silicate glasses containing Na and the glass ceramics containing fluorite nanocrystals were demonstrated. The damages were mainly caused by preferentially removing Na and decomposing CaF₂ into Ca. All the damage phenomena were observed under electron beam intensities, which were much weaker than the intensities used in the conventional high-resolution electron microscopy (HREM) and microanalysis in STEM. Therefore, although the advanced TEM/STEM techniques are very promising in the precise measurement of local composition at ultra-high spatial resolution in some materials, they may not be applicable to Na-containing silicate glasses and glass ceramics containing fluorite nanocrystals.     

Ion implantation effects in heavy metal fluoride glasses

Samples of a heavy metal fluoride glass (BInZnYbTGa) were subjected to argon and nitrogen irradiations of energies of 50 and 100 keV and fluences of 5×10¹⁶ and 1×10¹⁷ ions/cm². A 10 keV Ar irradiation at the ion dose of 1×10¹⁷/cm² was also performed. Modifications induced by the implants were characterized by nuclear microanalysis, electron spectroscopy, scanning electron microscopy and optical techniques. Surface precipitation of Th and Ba, as well as F and In depletion, were detected. Correlated modifications of the optical transmittance and reflectance were observed.     

Surface plasmon excited infrared-to-visible upconversion in Er-doped transparent glass ceramics

The surface plasmon (SP) excited infrared-to-visible upconversion luminescence has been studied in the oxyfluoride glass ceramics containing Er³⁺-doped fluoride nano-crystals. Upconversion luminescence was observed at glass ceramics. Quantum yield of upconversion luminescence increased with increasing heat-treatment temperature. The transparent glass ceramics heat-treated at 700 °C was covered with a 50 nm gold film, and then attached to an SF10 prism with index-matching oil to make an attenuated total reflection (ATR) illumination. The intense upconversion luminescence bands at 540 and 660 nm were observed at the SP resonance angle by using p-polarized laser beam. The apparent dependences of the upconversion efficiency on laser polarization and on incident angle demonstrated the SP excited upconversion of Er³⁺.     

Gallium colloid formation during ion implantation of glass

Data are reported on the size and depth distribution of gallium colloids formed by gallium ion implantation at energies of 50 and 60 keV, and nominal doses up to 1.1 × 10¹⁷ ions/cm² into coverlip glass, float glass and white crown glass. Measurement techniques used to reveal colloid-induced changes include the wavelength dependence of optical reflectivity, transmission electron microscopy (TEM) and Rutherford backscattering (RBS). The reflectivity can be controlled by variations in ion dose, implant temperature and ion beam energy. The highest reflectivity is found after implants near 50°C and the level is extremely sensitive to the implant temperature. For controlled beam conditions, the reflectivity data are reproducible, despite there being variations in the colloid size and depth distributions as seen by TEM and RBS. The TEM data reveal that the depth distribution develops in two distinct regions, which at high concentration can precipitate into two layers of large colloids. Subsidiary experiments are reported to attempt to separate the effects of variations in the implant temperature and surface charging which influence the reflectivity, RBS and colloid formation.     

Sodium surface concentration analysis on glass by 23Na(p,α)20Ne nuclear reaction

The ²³Na(p, α)²⁰Ne nuclear reaction has been used to investigate the depth profile of Na near the surface of commercial soda-lime-silicate glasses. The depth profile of Na has been quantitatively determined (with a depth resolution of about 120 Å) without migration effects due to the measurement method. Such perturbations, which make other analysis techniques difficult to use, appear only with very high current densities of the incident beam. A brief review of the principles of nuclear reaction used to analyse the concentration profile near the surface of samples is presented. A comparison with the traditional methods is discussed.     

Electron irradiation‐induced effects on optical spectra of (NH4)2ZnCl4: x Sr2+ single crystals

The effect of electron‐beam irradiation with different doses on optical constants of (NH₄)₂ZnCl₄: x Sr²⁺ crystals with x=0.000, 0.020, 0.039, 0.087 or 0.144 wt% has been studied. The optical transmission in the energy range 3.4‐6.4 eV was measured hence the absorption coefficient was computed as a frequency function. The absorption coefficient was also calculated as a function of electron‐beam dose. Irradiation with e‐beam did not affect the allowed indirect type of transition responsible for interband transitions of (NH₄)₂ZnCl₄: x Sr²⁺ crystals. Values of the optical energy gap E_g and optical moment E_p for electronic interband transition of unexposed and (NH₄)₂ZnCl₄: x Sr²⁺ crystals after e‐beam exposure were deduced. The area under the absorption band at 5.30 eV was used to evaluate the effect of e‐irradiation on optical parameters of samples with x=0.00, 0.020 or 0.039. A shift in the position and a nonmonotonic change in the intensity of this band with increasing e‐beam dose was observed. Changes in the E_g value were used to evaluate the effect of e‐beam exposure dose on (NH₄)₂ZnCl₄: x Sr²⁺ samples with x=0.087 or 0.144. The obtained results were compared with those obtained for the same crystals after irradiation with different γ‐doses.     

On the growth of small crystals of Cd, Zn, Pt and Rh during electron microscope observations

The growth of small supported metal crystals under the influence of an electron beam has been studied in real-time using a 400 keV ultra-high-resolution electron microscope. Samples of Pt, Rh, Cd and Zn supported on amorphous C or Si films were prepared ex situ and crystal growth in situ was recorded directly using a TV imaging/video system attached to the microscope. The different types of observed crystal growth are reported: the fcc metals (Pt and Rh) grow by coalescence, or by the addition of atoms along the particle surface followed by structural rearrangements which result in approximately spherical particles. The hcp metals (Cd and Zn) grow in the form of long rafts along the surface of the substrate film.     

Complementary study of the internal porous silicon layers formed under high-dose implantation of helium ions

The surface layers of Si(001) substrates subjected to plasma-immersion implantation of helium ions with an energy of 2–5 keV and a dose of 5 × 10¹⁷ cm^–2 have been investigated using high-resolution X-ray reflectivity, Rutherford backscattering, and transmission electron microscopy. The electron density depth profile in the surface layer formed by helium ions is obtained, and its elemental and phase compositions are determined. This layer is found to have a complex structure and consist of an upper amorphous sublayer and a layer with a porosity of 30–35% beneath. It is shown that the porous layer has the sharpest boundaries at a lower energy of implantable ions.     

Decrease of the alkali signal during auger analysis of glasses

The decrease of the alkali signal during Auger electron spectroscopy (AES) has been studied on glasses with molar composition 20 M₂O · 80 SiO₂ and 20 M₂O · 10 CaO · 70 SiO₂, where M = Na and/or K. The samples were fractured in situ, and beam conditions in the region 1.5–3 keV and 1–40 μA were chosen. The K signal in 20 K₂O · 80 SiO₂ remained sufficiently constant to allow a reliable measurement. Its decrease showed an initial delay which can be explained by assuming a rapid decrease of the K concentration at some depth below the surface. The presence of CaO accelerates the migration of alkali during AES. This is not predicted by diffusion data.     

Electron Energy-Loss Spectroscopy Study of the Change in the Free-Electron Density in Thin Superconducting NbN Films under Ion-Beam Irradiation

The change in the free-electron density in ultrathin (5 nm) superconducting NbN films in the initial state and after irradiation by O⁺ ions to doses of (0.1–0.9) × 10¹⁷ cm^–2 has been studied by electron energy-loss spectroscopy (EELS). The analysis has been performed on cross section samples prepared by the focused ion beam method, using plasmon oscillations with energies up to 50 eV. The radiation-induced replacement of nitrogen atoms with oxygen atoms in niobium nitride is found to change the electrical properties of the material, which leads to a decrease in the free-electron density with an increase in the irradiation dose.     

电子辐照对VO2薄膜热致相变过程中光学性能的影响

利用能量为1.7MeV,注量分别为10^13-10^15/cm^2,的电子束辐照二氧化钒薄膜,对辐照及未辐照样品进行了UV－VIS,XPS参数测试,并测量900nm处光透射性能随温度的变化,发现电子辐照导致了VO2薄中的V离子价态由V^4向V^5 转变,薄膜热致相变前后的光透射比随注量增加变化较小,只在注量为10^14/cm^2时光透射比减小得较明显,相变温度点及热滞回线宽度随注量增加出现显著变化,并对有关的结果进行了讨论。     

Defect formation in subsurface Be+-and Se+-doped GaAs layers

The structure of subsurface Be⁺ and Se⁺ doped GaAs layers was studied by the X-ray diffraction technique. The implantation of Be⁺ ions into gallium arsenide substrates causes the formation of distorted layers with elastic strains. With an increase of the energy of implanted ions from 50 to 100 keV, the maximum distortion remains almost constant, whereas the thickness of the distorted layer, with a lattice constant which exceeds that of the host material, increases. At higher energies (≥150 keV), the thickness of the distorted layer continues increasing, but the maximum strain drops. The Se⁺ ions implantation into the GaAs substrates also provides the formation of layers distorted by positive tensile strain. The analysis of defect distributions and concentrations at various irradiation doses and the implanted-ion energies shows that the latter does not considerably affect these parameters. At the same time, an increase of the implanted-ion dose from 5 × 10¹⁴ to 5 × 10¹⁵ cm^?2 increases the strains observed. The role of the Frenkel-pair annihilation and ion channeling in the formation of a defect layer is also discussed.