Probing the diffusion of vacuum ultraviolet (λ = 172 nm) induced oxidants by nanoparticles immobilization

Vacuum ultraviolet (VUV, λ = 172 nm) patterning of alkyl monolayer on silicon surface has been demonstrated with emphasis on the diffusion of VUV induced oxygen-derived active species, which are accountable for the pattern broadening. The VUV photons photo-dissociates the atmospheric oxygen and water molecules into the oxygen-derived active species (oxidants). These oxidants photo-oxidize the hexadecyl (HD) monolayer in VUV irradiated regions (Khatri et al., Langmuir. 24 (2008) 12077), as well as the little concentration of oxidants diffuses towards the masked areas. In this study, we performed VUV patterning at a vacuum pressure of 10 Pa to track the diffusion pathways for the oxidants with help of gold nanoparticles (AuNPs; ? = 10 nm) immobilization. At VUV irradiated sites AuNPs are found as uniformly distributed, but adjacent to the pattern boundary we observed quasi-linear arrays of AuNPs, which are determined by diffusion pathways of the oxidants. The diffusion of oxidants plays vital role in pattern broadening. The site selective anchoring of AuNPs demonstrates the utility of VUV photons for the construction of functional materials with microstructural architecture.     

Photoluminescence and Raman studies of Xe ion-implanted diamonds: Dependence on implantation dose

We report on photoluminescence and Raman studies of Xe ion-implanted diamond. Several natural and high-purity artificial diamonds implanted within the wide dose range of 10¹⁰-5×10¹⁴ ion/cm² were studied. The room temperature luminescence of the Xe center consists of two zero phonon lines, at 813 nm (strong) and 794 nm (weak). The dose dependences of photoluminescence and Raman spectra were studied. For doses less than 10¹³ ion/cm², the luminescence intensity grows with the implantation dose linearly. The defect-induced photoluminescence quenching was observed for doses equal or more than 10¹³ ion/cm². Possible models of the Xe center will be discussed. The nature of damages induced by ion implantation at different doses was analyzed using micro-Raman spectroscopy.     

Mass spectrometric study of photo dissociation of organic molecules by vacuum-ultraviolet irradiation for development of analysis technique

We have observed the photo-chemical reaction process of organic molecules in gas phase induced by vacuum ultraviolet (VUV) radiation. We chose hydrocarbons that contain five carbons in a molecule as samples. To observe the wavelength dependence, three kinds of excimer lamps (Ar₂*-126 nm, Kr₂*-147 nm and Xe₂*-172 nm) were used as light sources of the VUV radiation. Vaporized organic molecular compounds were irradiated by the VUV at a pressure of 12 Pa and detected by means of mass spectrometry. Change of the mass spectra with the irradiation period was measured. As a result, we found that different reaction rates were observed for the different compounds. In particular, 1-pentene and cyclopentane, which have the same molecular weight, have very different decomposition speeds for the irradiation of 172-nm radiation. The facts observed in this work are considered to be very promising for developing a technique to distinguish the targeted compound from others that have similar structures.     

Tunable VUV light generation for resonance ionization mass spectrometry of Krypton

Tunable coherent VUV radiation from 115.8 to 116.9 nm has been produced by non-linear four-wave sum frequency mixing in a xenon-argon mixture. 116.5 nm light generated by this means has been used as the first step in a three color, doubly resonant ionization scheme for Kr. In the process of validating the system the xenon refractive index per atom (STP) at 116.5 nm has been determined to be (n_(Xe) − 1)/N_Xe = −6.8(±0.8) × 10⁻²³ cm³.     

Enhanced luminescence and degradation resistance in Tb modified Yttrium Borate core-nano silica shell phosphor under UV and VUV excitation

Composition variation in optimized solid state reaction conditions has been done to achieve intense green emission in YTb_xBO₃ phosphor under UV and VUV (147 nm resonant Xe*, 172 nm Xe₂* excimer band) excitation. Inert interface layer created by fabricating a shell of silica nanoparticles over individual phosphor grain protected the phosphor surface from deterioration and oxidation of luminescent ion (Tb³⁺) thus completely arresting phosphor degradation. At optimum Tb content of 20 mol%, integrated photoluminescence intensity of developed YTb_xBO₃ phosphor is four times higher than commercial green YBT. With short decay time of 4 ms, YTb_xBO₃ core-nano silica shell green emitting phosphor has great application potential in PDP panel and phosphor coated Xe lamps.     

Observation of micropores in hard-carbon using Xe NMR porosimetry

The existence of micropores and the change of surface structure in pitch-based hard-carbon in xenon atmosphere were demonstrated using ¹²⁹Xe NMR. For high-pressure (4.0 MPa) ¹²⁹Xe NMR measurements, the hard-carbon samples in Xe gas showed three peaks at 27, 34 and 210 ppm. The last was attributed to the xenon in micropores (<1 nm) in hard-carbon particles. The NMR spectrum of a sample evacuated at 773 K and exposed to 0.1 MPa Xe gas at 773 K for 24 h showed two peaks at 29 and 128 ppm, which were attributed, respectively, to the xenon atoms adsorbed in the large pores (probably mesopores) and micropores of hard-carbon. With increasing annealing time in Xe gas at 773 K, both peaks shifted and merged into one peak at 50 ppm. The diffusion of adsorbed xenon atoms is very slow, probably because the transfer of molecules or atoms among micropores in hard-carbon does not occur readily. Many micropores are isolated from the outer surface. For that reason, xenon atoms are thought to be adsorbed only by micropores near the surface, which are easily accessible from the surrounding space.     

Light induced adsorption of Si nano-composites in LiF crystals at 157 nm

Si nano-composites were precipitated on LiF crystals following ablation from Si targets with laser light at 157 nm. The LiF/Si interface was analyzed with scanning electron microscopy, atomic force microscopy and energy dispersive X-ray microanalysis. It was found that Si composites were strongly attached to LiF ionic sites to form inhomogeneous structures consisted of small isotropic crystals 0.1-1 μm long, rich in Si and fluorine, which eventually further agglomerate to form larger structures. The thickness of the LiF/Si interface was increased from 50 nm to 2 μm following laser irradiation at 157 nm, due to accelerated adsorption of Si in the LiF interface by VUV light.     

Development of ultra-short pulse VUV laser system for nanoscale processing

We have developed intense vacuum ultraviolet (VUV) radiation sources for advanced material processing, such as photochemical surface reactions and precise processing on a nanometer scale. We have constructed a new VUV laser system to generate sub-picosecond pulses at the wavelength of 126 nm. A seed VUV pulse was generated in Xe as the 7th harmonic of a 882-nm Ti:sapphire laser. The optimum conversion was achieved at the pressure of 1.2 Torr. The seed pulse will be amplified by the Ar₂^*\mathrm{Ar}_{2}^{*} media generated by an optical-field-induced ionization Ar plasma produced by the Ti:sapphire laser. We have obtained a gain coefficient of g=0.16 cm⁻¹. Our developing system will provide VUV ultra-short pulses with sub-μJ energy at a repetition rate of 1 kHz.     

The luminescent properties of CaYBO4:Ln(Ln=Eu, Tb) under UV-VUV range

The luminescent properties of CaYBO₄:Ln(Ln=Eu³⁺, Tb³⁺) were investigated under ultraviolet (UV) and vacuum ultraviolet (VUV) region. The CT band of Eu³⁺ at about 245 nm blue-shifted to 230 nm in VUV excitation spectrum; the band with the maximum at 183 nm was considered as the host lattice absorption. For the sample of CaYBO₄:0.08Tb³⁺, the bands at about 235 and 263 nm were assigned to the f-d transitions of Tb³⁺ and the CT band of Tb³⁺ was calculated according to Jφrgensen's theory. Under UV and VUV excitation, the main emission of Eu³⁺ corresponding to the ⁵D₀-⁷F₂ transition located at about 610 nm and two intense emission of Tb³⁺ from the ⁵D₄-⁷F₅ transition had been observed at about 542 and 552 nm, respectively. With the incorporation of Gd³⁺ into the host lattice of CaYBO₄, the luminescence of Tb³⁺ was enhanced while that of Eu³⁺ was decreased because of their different excitation mechanism.     

A novel green phosphor GdCaAlO4:Tb for PDP application

A novel green-emitting nano-sized phosphor, Tb³⁺-doped GdCaAlO₄ was synthesized with a precursor prepared by citrate sol-gel method at relatively low temperature. Powder X-ray diffraction (XRD) analysis confirmed the formation of GdCaAlO₄. Field-emission scanning electron microscopy (FE-SEM) observation indicated a narrow size-distribution of about ∼100 nm for the particles with a spherical shape. Upon excitation with near UV and vacuum ultraviolet (VUV) light, the phosphor showed strong green-emission peaked at around 546 nm, corresponding to the ⁵D₄→⁷F₅ transition of Tb³⁺, and the highest photoluminescence (PL) intensity at 546 nm was found at a content of about 12 mol% Tb³⁺. As the Tb³⁺ concentration increases, the fast diffusion of energy among terbium ions toward traps or impurities resulting in a decrease of the lifetime. The optical properties study suggests that it is a potential candidate for plasma display panels (PDPs) application.     

Harmonic generation in ZnO nanocrystalline laser deposited thin films

ZnO plasma produced by third harmonic 355 nm of Nd:YAG laser at various ambient pressures of oxygen was used for depositing quality nanocrystalline ZnO thin films. Time and space resolved optical emission spectroscopy is used to correlate the plasma properties with that of deposited thin films. The deposited films showed particle size of 8 and 84 nm at ambient oxygen pressure of 100 and 900 mTorr, respectively. Third harmonic generation observed in ZnO thin films deposited under 100 mTorr of ambient oxygen is reported.     

Passively Q-switched Nd:YAG pumped UV lasers at 280 and 374 nm

Pulsed UV lasers at the wavelengths of 374 and 280 nm are realized by cascaded second harmonic generation (SHG) and sum frequency generation (SFG) processes using a Nd:YAG laser at 1123 nm. The Nd:YAG laser is longitudinally pumped and passively Q-switched, and it has a high peak power of 3.2 kW. The UV peak powers at 280 and 374 nm are 100 and 310 W, with pulse lengths of 6 and 8 ns, respectively. Spectral broadening of 374 nm laser by stimulated Raman scattering is studied in single mode pure silica core UV fiber. Realizations of UV lasers enabling compact design at 280 and 374 nm wavelengths are demonstrated.     

Optimization of optical parametric chirped pulse amplification with different pump wavelengths

Optical parametric chirped pulse amplification with different pump wavelengths was investigated using LBO crystal, at signal central wavelength of 800 nm. According to our theoretical simulation, when pump wavelength is 492.5 nm, there is a maximal gain bandwidth of 190 nm centered at 805 nm in optimal noncollinear angle using LBO. Presently, pump wavelength of 492.5 nm can be obtained from second harmonic generation of a Yb:Sr₅(PO₄)₃F laser. The broad gain bandwidth can completely support ∼6 fs with a spectral centre of seed pulse at 800 nm. The deviation from optimal noncollinear angle can be compensated by accurately tuning crystal angle for phase matching. The gain spectrum with pump wavelength of 492.5 nm is much better than those with pump wavelengths of 400, 526.5 and 532 nm, at signal centre of 800 nm.     

Experimental determination of optical constants of MgF2 and AlF3 thin films in the vacuum ultra-violet wavelength region (60-124 nm), and its application to optical designs

The investigation of some solar radiations of interest for astrophysicists requires optics in the 80-130 nm vacuum ultra-violet spectral range (VUV). In this domain, where both transmittance and reflectance of most materials are very low, the measurement of optical constants is specifically difficult, and optical data are consequently often either inexistent or uncertain. Reliable modelling of optical components for VUV, like polarizing multi-layered mirrors, necessitates prior measurement of complex indices of the thin films involved in the coating. Fluorides like MgF₂ or AlF₃ are among the rare materials capable to contribute to multi-layer mirrors in the VUV.We have determined optical constants of thin films of these two materials by using a two media reflectance method at normal incidence and a graphical determination particularly suited to this VUV region, which we presented in a previous paper. Optical constants are determined in the range 60-124 nm with 2 nm step, and are compared to existing data. On the basis of these measured indices, polarizing mirrors for λ₁ = 121.6 nm or λ₂ = 103.2 nm have been modelled and fabricated. Their reflectance measured versus incidence angle by using monochromatized synchrotron radiation at the above wavelengths is found in agreement with the calculated predictions.     

XAFS at Eu-L3 edge and UV-VUV excited luminescence of europium doped strontium borophosphate prepared in air

The local structure and the valences of europium in SrBPO₅:Eu prepared in air were checked by means of XAFS at Eu-L₃ edge. From the EXAFS results, it was discovered that the doped europium atoms were nine-coordinated by oxygen atoms and the distances of bond Eu-O were 2.42 Å in the host. From the XANES data, it was found that the divalent and trivalent europium coexisted in the matrix. The emission spectra excited by VUV or UV exhibited a prominent broad band due to the 4f⁶5d-4f⁷ transition of Eu²⁺ ions, which indicated that the trivalent europium ions were reduced in air in the matrix at high temperature by the defects [V_Sr]″ formed by aliovalent substitution between Sr²⁺ and Eu³⁺ ions. The VUV excitation spectra in 100-200 nm range showed that the matrix had absorption bands with the maxima at about 130 and 150 nm, respectively.     

Characterization of Standard Reference Material 2942, Ce-ion-doped glass, spectral correction standard for UV fluorescence

Standard Reference Material (SRM) 2942 is a cuvette-shaped, Ce-ion-doped glass, recommended for use for relative spectral correction of emission from 320 to 430 nm and day-to-day performance verification of steady-state fluorescence spectrometers. Properties of this standard that influence its effective use or contribute to the uncertainty in its certified emission spectrum were explored here. These properties include its photostability, absorbance, dissolution rate in water, anisotropy and temperature coefficient of fluorescence intensity. The expanded uncertainties in the certified spectrum are about 9% around the peak maximum at 330 nm, using an excitation wavelength of 310 nm. The SRM also exhibits a strong resistance to photodegradation, with no measurable decrease in fluorescence intensity even after 25 h of irradiation with UV light>280 nm from a Xe lamp.     

High luminance of new green emitting phosphor, Mg2SnO4:Mn

Mg₂SnO₄, which has an inverse spinel structure, was adopted as the host material of a new green emitting phosphor. Luminescence properties of the manganese-doped magnesium tin oxide prepared by the solid state reaction were investigated under vacuum ultraviolet (VUV) ray and low-voltage electron excitation. The Mg₂SnO₄:Mn phosphor exhibited green luminescence with the emission spectrum centered at 500 nm due to spin flip transition of the d-orbital electron associated with the Mn²⁺ ion. Optimum Mn concentration of Mg₂SnO₄:Mn under VUV excitation with 147 nm wavelength and electron beam excitation with 800 V excitation voltage are 0.25 and 0.6 mol%, respectively. The emission intensities of Mg₂SnO₄:Mn phosphors under the two excitation sources are higher than those of Zn₂SiO₄:Mn and ZnGa₂O₄:Mn phosphors. At 0.25 mol% of Mn concentration, on the other hand, the decay time is shorter than 10 ms.     

Synthesis and VUV spectral properties of nanoscaled Zn2SiO4:Mn green phosphor

Nanoscaled Zn₂SiO₄:Mn²⁺ green phosphor with regular and uniform morphology was synthesized by hydrothermal method at a low temperature of 140 °C. The structure and morphology of the phosphor was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of the hydrothermal temperature and the time on the crystallite structure and the vacuum ultraviolet (VUV) photoluminescence (PL) properties were evaluated. The as-synthesized nanoscaled Zn₂SiO₄:Mn²⁺ phosphor exhibited intensive broad emission around 523 nm, which was attributed to the ⁴T₁→⁶A₁ transition of Mn²⁺. The PL intensity increased along with the increasing hydrothermal temperature and time. The heat-treated phosphors exhibited higher PL intensity than the corresponding samples prepared using the conventional solid-state reaction.     

High-order harmonic generation in nitrogen molecules with subpicosecond visible dye-laser pulses

An experimental study of high-order harmonic generation in nitrogen molecules (N₂) has been made using intense visible (616 nm) dye-laser pulses, where the harmonic radiation up to the 21st order is observed. The harmonic distribution represents a plateau that is preceded by an intensity minimum at the 7th order. The harmonic generation characteristics were atomic-like. It has been found that there are some similarities in the high-order harmonic generation characteristics for N₂ and Ar, including the highest-order harmonics, harmonic distributions, and the influence of the multiphoton ionization on the high-order harmonic generation. These similarities are reasonably attributed to the energetic correspondence of excited levels and ionization potentials. It is pointed out that the ac Stark shift of excited levels and ionization potentials plays an important role also in the high-order harmonic generation in N₂.     

Upconverted VUV luminescence of Nd and Er doped into LiYF4 crystals under XeF-laser excitation

The upconverted VUV (185 nm) and UV (230 and 260 nm) luminescence due to 5d-4f radiative transitions in Nd³⁺ ions doped into a LiYF₄ crystal has been obtained under excitation by 351/353 nm radiation from a XeF excimer laser. The maximum upconversion efficiency, defined as the ratio of intensity for 5d-4f luminescence to overall intensity for 5d-4f and 4f-4f luminescence from the ⁴D_3/2 Nd³⁺ level, has been estimated to be about 70% under optimal focusing conditions for XeF laser radiation. A redistribution of intensity between three main components of 5d-4f Nd³⁺ luminescence is observed under changing the excitation power density, which favors the most long-wavelength band (260 nm) at higher excitation density level. The effect is interpreted as being due to excited state absorption of radiation emitted. The upconverted VUV and UV luminescence from the high-lying ²F(2)_7/2 4f level of Er³⁺ doped into a LiYF₄ crystal has also been obtained under XeF-laser excitation the most intense line being at 280 nm from the spin-allowed transition to the ²H(2)_11/2 4f level of Er³⁺, but the efficiency of upconversion for Er³⁺ emission is low, less than 5%.