Processing for optically active erbium in silicon by film co-deposition and ion-beam mixing

Techniques of film deposition by co-evaporation, ion-beam assisted mixing, oxygen ion implantation, and thermal annealing were been combined in a novel way to study processing of erbium-in-silicon thin-film materials for optoelectronics applications. Structures with erbium concentrations above atomic solubility in silicon and below that of silicide compounds were prepared by vacuum co-evaporation from two elemental sources to deposit 200-270 nm films on crystalline silicon substrates. Ar⁺ ions were implanted at 300 keV. Oxygen was incorporated by O⁺-ion implantation at 130 keV. Samples were annealed at 600 °C in vacuum. Concentration profiles of the constituent elements were obtained by Rutherford backscattering spectrometry. Results show that diffusion induced by ion-beam mixing and activated by thermal annealing depends on the deposited Si-Er profile and reaction with implanted oxygen. Room temperature photoluminescence spectra show Er³⁺ transitions in a 1480-1550 nm band and integrated intensities that increase with the oxygen-to-erbium ratio.     

Temperature behaviour of optical properties of Si+-implanted SiO2

Silicon nanocrystals were prepared by Si⁺-ion implantation and subsequent annealing of SiO₂ films thermally grown on a c-Si wafer. Different implantation energies (20-150 keV) and doses - cm ^-2 ) were used in order to achieve flat implantation profiles (through the thickness of about 100 nm) with a peak concentration of Si atoms of 5, 7, 10 and 15 atomic%. The presence of Si nanocrystals was verified by transmission electron microscopy. The samples exhibit strong visible/IR photoluminescence (PL) with decay time of the order of tens of μs at room temperature. The changes of PL in the range 70-300 K can be well explained by the exciton singlet-triplet splitting model. We show that all PL characteristics (efficiency, dynamics, temperature dependence, excitation spectra) of our Si⁺-implanted SiO₂ films bear close resemblance to those of a light-emitting porous Si and therefore we suppose similar PL origin in both materials. Received 1st September 1998 and Received in final form 7 September 1999     

Optical channel waveguides with trapezoidal-shaped cross sections in KTiOPO4 crystal fabricated by ion implantation

Optical channel waveguides were fabricated in KTiOPO₄ crystal by He⁺-ion implantation using photoresist masks with wedged-shaped cross sections. Semi-closed barrier walls with reduced refractive indices inside the crystal constructed the enclosed regions to be channel waveguides with trapezoidal-shaped cross sections. The m-line as well as end-fire coupling arrangements were performed to characterize the waveguides with light at wavelength of 632.8 nm. The propagation loss of the channel waveguides was determined to be as low as ∼2 dB/cm after simple post-irradiation thermal annealing treatment in air.     

Synthesis and characterization of lithium ferrite by oxalate precursor route

Nanocrystalline lithium ferrite (LiFe₅O₈) powders have been synthesized by oxalate precursor route. The effects of Fe³⁺/Li⁺ mole ratio, and annealing temperature on the formation, crystalline size, morphology and magnetic properties were systematically studied. The Fe³⁺/Li⁺ mole ratio was controlled from 5 to 3.33 while the annealing temperature was controlled from 600 to 1100 °C. The resultant powders were investigated by differential thermal analyzer (DTA), X-ray diffractometer (XRD), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). DTA results showed that LiFe₅O₈ phase started to form at around 520 °C. XRD indicated that LiFe₅O₈ phase always contained α-Fe₂O₃ impurity and the hematite phase formation increased by increasing the annealing temperature ?850 °C for different Fe³⁺/Li⁺ mole ratios 5, 4.55 and 3.85. Moreover, lithium ferrite phase was formed with high conversion percentage at critical annealing temperature 750–800 °C. Single well crystalline LiFe₅O₈ phase was obtained at Fe³⁺/Li⁺ mole ratio 3.33 and annealing temperatures from 800 to 1000 °C. Maximum saturation magnetization (68.7 emu/g) was achieved for the formed lithium ferrite phase at Fe³⁺/Li⁺ mole ratio 3.33 and annealing temperature 1000 °C.     

Monolithic electrochromic devices using lithium ion conducting perovskite-type oxides

The electrical conductivities of several perovskite-type lithium ion conductors in the Li-Sr-Nb-Ta-Ti-O system have been investigated. The Li⁺-ion conductivities of the Ta-compounds were found to be higher than those of the corresponding Nb-compounds, i.e., Li_0.3Sr_0.6Ta_0.5Ti_0.5O₃ exhibits a bulk ionic conductivity of 1.7×10⁻⁴ S/cm at 30 °C, while Li_0.3Sr_0.6Nb_0.5Ti_0.5O₃ shows a value of 5.4×10⁻⁶ S/cm at the same temperature. Substitution of Fe in Li_0.3Sr_0.6Ta_0.5Ti_0.5O₃ decreases the Li⁺-ion conductivity slightly. The operation of a monolithic (single element) electrochromic devices was demonstrated using perovskite-type Li_0.3Sr_0.6B_0.5Ti_0.5O₃ (B=Nb, Ta). The tantalum compound exhibited the largest coloration at the positive electrode side by the application of a voltage of 1.5 V and was bleached under short-circuit conditions at 350 °C. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15–21, 2002.     

Flash – lamp annealing of phosphorus and antimony implanted silicon

The structure and electrophysical properties of a silicon layers after P⁺ and Sb⁺ ion implantation and subsequent pulse annealing of millisecond lengths have been investigated by the transmission electron microscopy and four-point probe measurements. It has been demonstrated, that for certain implantation and annealing conditions the epitaxially grown layers can involve the microtwins and dislocation loops. The impurity redistribution under the pulse annealing depends on the implantation dose and rather weaker the light irradiation energy density.     

Silicon nanocrystals in silica—Novel active waveguides for nanophotonics

Nanophotonic structures combining electronic confinement in nanocrystals with photon confinement in photonic structures are potential building blocks of future Si-based photonic devices. Here, we present a detailed optical investigation of active planar waveguides fabricated by Si⁺-ion implantation (400 keV, fluences from 3 to 6×10¹⁷ cm⁻²) of fused silica and thermally oxidized Si wafers. Si nanocrystals formed after annealing emit red-IR photoluminescence (PL) (under UV-blue excitation) and define a layer of high refractive index that guides part of the PL emission. Light from external sources can also be coupled into the waveguides (directly to the polished edge facet or from the surface by applying a quartz prism coupler). In both cases the optical emission from the sample facet exhibits narrow polarization-resolved transverse electric and transverse magnetic modes instead of the usual broad spectra characteristic of Si nanocrystals. This effect is explained by a theoretical model which identifies the microcavity-like peaks as leaking modes propagating below the waveguide/substrate boundary. We present also permanent changes induced by intense femtosecond laser exposure, which can be applied to write structures like gratings into the Si-nanocrystalline waveguides. Finally, we discuss the potential for application of these unconventional and relatively simple all-silicon nanostructures in future photonic devices.     

Mössbauer characterization of LixFe3O4

Mössbauer spectra of lithium intercalated Fe₃O₄, have been recorded at 300 K and 4.2 K. It has been observed that lithium can be incorporated and/or extruded at room temperature. The coexistence of lithiated and unlithiated particles after exposure of the sample to air, is interpreted in terms of the Li⁺-ion mobility. The results are compared with those obtained from X-Ray diffraction data and magnetization measurements.     

Impurity effect on the creation of point-defects in GaAs and InP investigated by a slow positron beam

The impurity effect on the creation of point-defects in 60-keV Be⁺-ion implanted GaAs and InP has been studied by a slow positron beam. Vacancy-type defects introduced by ion implantation were observed in n-type GaAs. For p-type GaAs, however, this was not the case. This can be attributed to the recombination of vacancy-type defects with pre-existing interstitial defects in p-type GaAs. In the case of InP, the vacancy-type defects were created by ion implantation and increased with the implantation dose. However, no significant doping effect was observed in InP.     

Enhanced luminescence from spontaneously ordered Gd2O3:Eu based nanostructures

Nanostructured Gd₂O₃:Eu³⁺ and Li⁺ doped Gd₂O₃:Eu³⁺ thin films were prepared by pulsed laser ablation technique. The effects of annealing and Li⁺ doping on the structural, morphological, optical and luminescent properties are discussed. X-ray diffraction and Micro-Raman investigations indicate a phase transformation from amorphous to nanocrystalline phase and an early crystallization was observed in Li⁺ doped Gd₂O₃:Eu³⁺ thin films on annealing. AFM images of Li⁺ doped Gd₂O₃:Eu³⁺ films annealed at different temperatures especially at 973 K show a spontaneous ordering of the nanocrystals distributed uniformly all over the surface, with a hillocks (or tips) like self-assembly of nanoparticles driven by thermodynamic and kinetic considerations. Enhanced photoemission from locations corresponding to the tips suggest their use in high resolution display devices. An investigation on the photoluminescence of Gd_2−xEu_xO₃ (x=0.10) and Gd_2−x−yEu_xLi_yO₃ (x=0.10, y=0.08) thin films annealed at 973 K reveals that the enhancement in luminescence intensity of about 3.04 times on Li⁺ doping is solely due to the increase in oxygen vacancies and the flux effect of Li⁺ ions. The observed decrease in the values of asymmetric ratio from the luminescence spectra of Li⁺ doped Gd₂O₃:Eu³⁺ films at high temperature region is discussed in terms of increased EuO bond length as a result of Li⁺ doping.     

幻数尺寸Li-n-1,Lin,Li+ n+1(n=20,40)团簇的几何结构、电子与光学性质的第一性原理研究

基于密度泛函理论,采用第一性原理分子动力学模拟退火方法,对Li^-_n-1,Li_n,Li⁺_n+1 (n=20,40)的最低能量结构进行了全局搜索. 发现锂团簇的生长模式是以单个或多个嵌套的正多面体为核心,其余原子以五角锥为基本单元围绕核心生长. 基于最低能量结构的第一性原理电子结构计算得到锂团簇的分子轨道能级分布与无结构凝胶模型给出的电子壳层完全一致. 在总电 关键词： 团簇 电子结构 极化率 光吸收     

Au gettering by Ne and Ar implantation in silicon

The gettering efficiency for Au induced by Ne⁺ and Ar⁺ implantation has been studied. The depth distribution of gettered Au as a function of annealing temperature and dose of implanted Ne⁺ and Ar⁺ ions are presented. The experiment shows that the maximum efficiency of gettering occurs when the implantation doses are comparable with amorphization dose.     

Determination of migration of ion-implanted Ar and Zn in silica by backscattering spectrometry

It is well known that the refractive indices of lots of materials can be modified by ion implantation, which is important for waveguide fabrication. In this work the effect of Ar and Zn ion implantation on silica layers was investigated by Rutherford Backscattering Spectrometry (RBS) and Spectroscopic Ellipsometry (SE). Silica layers produced by chemical vapour deposition technique on single crystal silicon wafers were implanted by Ar and Zn ions with a fluence of 1–2?×10¹⁶ Ar/cm² and 2.5?×10¹⁶ Zn/cm², respectively. The refractive indices of the implanted silica layers before and after annealing at 300°C and 600°C were determined by SE. The migration of the implanted element was studied by real-time RBS up to 500°C. It was found that the implanted Ar escapes from the sample at 300°C. Although the refractive indices of the Ar-implanted silica layers were increased compared to the as-grown samples, after the annealing this increase in the refractive indices vanished. In case of the Zn-implanted silica layer both the distribution of the Zn and the change in the refractive indices were found to be stable. Zn implantation seems to be an ideal choice for producing waveguides.     

Lithium mobility in the layered oxide Li1−xCoO2

The Li⁺-ion chemical diffusion coefficient in the layered oxide Li_0.65CoO₂ has been measured to be $\text{D}\text{?}\text{= 5 × 10}{}^{\mathrm{?12}}$ m² s^?1 by three independent techniques: (1) from the Warburg prefactor, (2) from the transition frequency for semi-infinite to finite diffusion lengths in steady-state ac-impedence measurements and (3) from a modified Tubandt method that uses ac-impedance data to distinguish interfacial and surface-layer resistances from the bulk resistance of the sample. This value and a small increase in D? with (1 ? x) in Li_1?xCoO₂, 0.45 < (1 ? x) < 0.80, compare favorably with the $\text{D}\text{?}\text{= 5}\text{to}\text{7 × 10}{}^{-12}\text{m}{}^2\text{s}{}^{-1}$ obtained by Honders for this system with pulse techniques. A qualitative discussion is presented as to why this composition dependence and why D? for this system is a factor of five larger than that for Li⁺-ion diffusion in Li_xTiS₂.     

Sputtering yields for light ions as a function of angle of incidence

The sputtering yield of Ni, Mo, and Au have been measured at oblique angles of incidence for H⁺-, D⁺-, and⁴He⁺-ion irradiation in the energy region from 1 to 8 keV. The yields were determined from the weight loss of the targets. For Ni and Mo the dependence of the sputtering yield on the angle of incidence was found to be much stronger for H⁺- and D⁺-ion than for⁴He⁺-ion irradiation. In all cases the maximum in the yield was found at angles of incidence ϑ≧80°, where ϑ is the angle measured from the surface normal. Furthermore the ratio of the maximum yield to the yeild at normal incidence increases with increasing surface binding energy of the target material as well as with increasing ion energy in the energy region inveestigated. The results are discussed qualitatively in view of a model for the sputtering mechanism for light ions.     

Multinuclear NMR Study of Structure and Mobility in Cyclic Model Lithium Conducting Systems

The transport of the lithium ions is the basis of lithium ion conductivity of currently used electrolytes. Understanding how the transport of lithium ions within the matrix is influenced by the interactions with solvating moieties is needed to improve their performance. Along these lines well-defined model compounds based on cyclotriphosphazene (CTP) and hexaphenylbenzene (HPB) cores, bearing side groups of ethylene carbonate, a common solvent for lithium salts used as electrolytes in Li-ion batteries (Thielen et al. Chem. Mater, 23, 2120, 2011) and blended with different amounts of Lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) have been studied by multinuclear nuclear magnetic resonance (NMR) spectroscopy. The local dynamics of the matrix was probed by ¹H and ³¹P NMR, while the local dynamics of the Li⁺ cations was unraveled by ⁷Li and ¹³C NMR. Transport of both ions was studied by pulsed-field gradient (PFG) NMR. Based on the different temperature dependences of the dynamics the bulk ion transport is not attributed to local dynamics, but to translational diffusion best characterized by PFG NMR. Although the glass transition temperatures of the blends are low, their conductivities are only in the range of typical polymer electrolytes. The results of NMR spectroscopy are in accord with the conjecture that the coordination between the cyclic carbonate functionality and the Li⁺-ion is too tight to allow for fast ion dynamics.     

Ion bombardment-induced charge state effects CaO single crystals: F+ and F centers

The effects of heavy-and light-ion bombardment on defect formation in CaO have been investigated by UV-absorption spectroscopy and volume measurements. While 500 keV Ar or Ca implantation produces only F⁺ centers, 240 keVH produces both F⁺ and F centers at a F⁺ to F ratio of 5.6 to 1. On the other hand, when an argon implanted sample is subsequently bombarded with hydrogen, about 30% of the F⁺ centers anneal during 1 ×10¹⁴ H/cm²; at higher H fluences, new F⁺ and F centers are produced. An effect of energy partition between ionization and nuclear/atomic collision processes for the incident ions on the charge state of the resulting defect is thus clearly demonstrated.

The formation and annealing of these defects are accompanied by volume changes in the ion implanted surface layer which can be monitored in sltu with a cantilever beam technique. The measurements show volume expansion of the order of 1.5% following 10¹⁶ 500 keV Ar implantation; subsequent implantation of 10¹⁸ 240 keV H compacts the previously expanded material by 25 %. These results are in qualitative agreement with the optical data and seem to indicate that volume changes are associated with the formation and annealing of F⁺ centers.     

Investigation of interaction between lithium and tantalum under a silicon film coating by electron-stimulated desorption technique

The electron-stimulated desorption of Li⁺ ions from lithium layers adsorbed on the tantalum surface coated with a silicon film has been investigated. The measurements are performed using a static magnetic mass spectrometer equipped with an electric field-retarding energy analyzer. The threshold of the electron-stimulated desorption of lithium ions is close to the ionization energy of the Li 1s level. The secondary thresholds are observed at energies of about 130 and 150 eV. The threshold at an energy of 130 eV is approximately 30 eV higher than the ionization energy of the Si 2p level and can be associated with the double ionization. The threshold at 150 eV can be caused by the ionization of the Si 2s level. It is demonstrated that the yield of Li⁺ ions does not correlate with the silicon amount in near-the-surface region of the tantalum ribbon and drastically increases at high annealing temperatures. The dependence of the current of Li⁺ desorption on the lithium concentration upon annealing of the tantalum ribbon at T>1800 K exhibits two maxima. The ions desorbed by electrons with energies higher than 130 and 150 eV make the largest contribution to the current of lithium ions after the annealing. The yield of lithium ions upon ionization of the Li 1s level at an energy of 55 eV is considerably lesser, but it is observed at higher concentrations of deposited lithium. The results obtained can be interpreted in the framework of the Auger-stimulated desorption model with allowance made for relaxation of the local surface field.     

Defects formation in the dual B+ and N+ ions implanted silicon

Silicon wafers were implanted with 40 keV B⁺ ions (to doses of 1.2×10¹⁴ or 1.2×10¹⁵ cm^–2) and 50 or 100 keV N⁺ ions (to doses from 1.2×10¹⁴ to 1.2×10¹⁵ cm^–2). After implantations, the samples were furnace annealed at temperatures from 100 to 450 °C. The depth profiles of the radiation damages before and after annealing were obtained from random and channeled RBS spectra using standard procedures. Two damaged regions with different annealing behaviour were found for the silicon implanted with boron ions. Present investigations show that surface disordered layer conserves at the annealing temperatures up to 450 °C. The influence of preliminary boron implantation on the concentration of radiation defects created in subsequent nitrogen implantation was studied. It was shown that the annealing behaviour of the dual implanted silicon layers depends on the nitrogen implantation dose.The authors would like to thank the members of the INP accelerator staff for the help during the experiments. The work of two authors (V.H. and J.K.) was partially supported by the Internal Grant Agency of Academy of Science of Czech Republic under grant No. 14805.     

Lithium Distribution in Red Blood Cells and Plasma: NMR Studies of Rat Blood

To understand the interaction of lithium (Li⁺) with a coadministered drug in both the blood and the brain, we have treated rats with either Li⁺ alone or Li⁺ and a codrug. In this paper we address the important problem of quantitation of intra and extracellular Li⁺ ion contents in blood by the ⁷Li-NMR technique and the use of a shift reagent (SR). Although Li⁺ can be studied by atomic absorption techniques, these techniques involve tedious separation of intra- and extracellular components prior to chemical analysis. Magnetic resonance studies on rat blood, in the dose range of 0.5 to 10 meq/kg, indicate that the intracellular red blood cell Li⁺ predominates in the lower dose range of 0.5–1.0 meq/kg. As the lithium dose increases, a significantly larger amount of Li⁺ accumulates in the extracellular volume. Our studies on a number of animals at various doses of LiCl indicate that ⁷Li-NMR of blood samples provide a reliable, noninvasive quantification of red blood cell and plasma Li⁺ concentrations. The NMR method was further used to study the effect of coadministered drugs such as thioridazine on the intra- and extracellular Li⁺ concentration of RBCs.