Formation of Ohmic contacts to n-GaAs using ion beam mixing of Tellurium

Ohmic contacts were formed on n-GaAs using thin evaporated layers of Te followed by bombardment of 100 keV Ar⁺ ions. The specific contact resistance _c showed a strong dependence on the ion dose in the range 10¹⁴ to 10¹⁶ ions cm^–2, with higher doses leading to progressively lower specific contact resistance. The substrate temperature during ion bombardment was varied in the range from 25 to 200° C and was found to have only a minor effect on the resultant values of _c. Elevated temperature aging of the Ohmic contacts at 200° C resulted in a progressive increase in the specific contact resistance, independent of either the ion dose or the substrate temperature used for ion beam mixing. Rutherford backscattering studies (RBS) indicate that the Ohmic contact behaviour was due to the in-diffusion of Te and subsequent formation of a heavily doped n ⁺ layer at the Te-GaAs interface.     

Formation of copper/gold solid solutions by ion beam mixing

The formation of copper/gold solid solutions due to ion beam mixing was studied by Rutherford backscattering, high-voltage electron microscopy and transmission high-energy electron diffraction. Irradiation of multilayered Cu/Au thin films were performed with Xe⁺ ions or Ar⁺ ions at room temperature to doses ranging from 5×10¹⁵ to 2.5×10¹⁶ ions/cm² and energies from 100 to 300 keV. The ion beam mixing leads to uniformly mixed metal layers. The grain size of mixed layers is pronounced increase. It was found that Cu/Au solid solutions are formed with different composition in dependence on itinial composition and implantation dose. Cu-rich and Au-rich solid solutions are induced by ion beam mixing at an initial composition Cu _x Au_100–x withx70. In addition to these solid solutions, a solid solution of middle composition Cu₆₀...₄₀Au₄₀...₆₀ is formed for an initial composition withx<70. The kinetics of formation of solid solution is discussed as a function of the initial composition and implantation dose. Post-annealing experiments of mixed Cu₅₀Au₅₀ multilayers lead to lattice transformations and provide a superlattice structure CuAuI of the L1₀-type. With this process of ordering is associated the formation of dislocation loops.     

The Influence of Ion – Neutral Collisions in the Plasma Sheath on the Ion Current to an Electrostatic Probe: Monte Carlo Simulation

We have carried out Monte Carlo simulation of the motion of Ar⁺ ions in the space charge sheath surrounding a cylindrical Langmuir probe. From these simulations the percentage of ions crossing the sheath boundary that are collected by the probe have been determined and thus the ion currents to the probe have been calculated. It is shown that the collisions of ions with neutral helium gas atoms in the sheath increase the percentage of ions collected by the probe above that predicted by collisionless orbital motion limited current (OMLC) theory and that the exponent, χ, of the power law dependence, i₊～U, of the ion current, i₊, on the probe voltage, U_p, increases above the value 0.5 predicted by OMLC theory. The results of the simulations are compared with recent Langmuir probe measurements made in flowing afterglow plasmas.     

Two-body correlations and pair formation in the two-dimensional Coulomb gas

We investigate pair correlations in the two-dimensional Coulomb gas made up of two species of point ions carrying electric charges Z₁ e(>0) and Z₂ e(<0), and interaction by the logarithmic Coulomb potential. This system is known to be classically stable for couplings=e ²/k _BTc=2/¦Z₁Z₂¦ (whereT is the temperature). Correlations between equally charged ions are shown to be greatly modified at short distances, in the range _c/2<< _c, due to gradual ion condensation. The usual integral equations for the pair correlation functions admit no solutions in that range. Preliminary Monte Carlo simulations for the symmetric case (Z₁=–Z₂) reveal a striking chemical equilibrium between tightly bound ion pairs and free ions, which is reasonably well described by a simple Bjerrum model.     

Desorption of cluster ions from adsorbed methane under cryogenic condition by low-energy ion irradiation

We have investigated ion desorption from adsorbed methane following keV He⁺ ion irradiation. The thickness of the adsorbed layer was precisely controlled. For mono-layered methane, only monomer ions (CH_x⁺) were desorbed by 1 keV He⁺ ion irradiation. On the other hand, a large number of cluster ions (C_nH_x⁺) up to n = 20 were desorbed from multi-layered film. Among cluster ions, molecular ions with CC bonds were found, which indicates that chemical bonds are newly formed by ion irradiation. Based on the results for thickness dependences of the mass spectral patterns, it was elucidated that the monomer ions are desorbed from the top surface layer through single electron excitation. While the cluster ions are formed mainly in the inside of the layers along the nuclear track due to the high-density electronic excitation, which is produced by nuclear collision between incident He⁺ ions and frozen molecules.     

Freezing-out of nuclear polarization in radioactive core ions of microclusters, “snowballs” in superfluid helium

A novel method was tried successfully to trap ions and to freeze out their nuclear polarization inside aggregates of helium atoms, snowballs, in superfluid helium. Spin polarized¹²B (T _1/2=20.4 ms) ions were introduced into superfluid helium and snowballs were created around the impinged impurity ions. Beta-ray asymmetry was measured to obtain the nuclear polarization of decaying¹²B. The comparison with the initial value of¹²B polarization produces that no relaxation in polarization was observed throughout lifetime of¹²B.     

Gas-phase vibrational spectroscopy and ab initio calculations of Rb(H2O)n and Rb(H2O)nAr cluster ions

The competition between ion–water electrostatic interactions and water–water hydrogen bonding in cluster ions depends on several factors, including charge density of the ion and temperature of the system. Infrared photodissociation spectra of Rb⁺(H₂O)_n=2–5 and Rb⁺(H₂O)_n=1–5Ar are presented here and compared to previous experiments involving potassium and cesium. The temperature, or internal energy, of hydrated rubidium cluster ions is controlled by varying the evaporative path available for cluster formation. Warmer clusters (with effective temperatures of 250–500 K) are formed by the evaporation of water, while colder clusters (40–120 K) can be formed by argon evaporation. Colder cluster ions tend to favor conformers with more hydrogen bonds compared to those cluster ions at warmer temperatures. Previous work from this laboratory has shown significant and dramatic differences between the spectra of hydrated potassium and cesium ions. With a charge density intermediate between that of K⁺ and Cs⁺, Rb⁺ plays an important role in bridging the gap in our previous studies.     

Nature of the transient species formed in the pulse radiolysis of 4‐hydroxybenzyl alcohol in aqueous solutions: observation of equilibrium in the reaction of OH‐adducts with HPO ions

Reactions of ^. OH/O ^.? radicals, H‐atoms as well as specific oxidants such as N and Cl radicals with 4‐hydroxybenzyl alcohol (4‐HBA) in aqueous solutions have been investigated at various pH values using the pulse radiolysis technique. At pH 6.8, ^. OH radicals were found to react with 4‐HBA (k = 6 × 10⁹ dm³ mol^?1 s^?1) mainly by contributing to the phenyl moiety and to a minor extent by H‐abstraction from the ? CH₂OH group. ^. OH radical adduct species of 4‐HBA, i.e., ^. OH‐(4‐HBA) formed in the addition reaction were found to undergo dehydration to give phenoxyl radicals of 4‐HBA. Decay rate of the adduct species was found to vary with pH. At pH 6.8, decay was very much dependent on phosphate buffer ion concentrations. Formation rate of phenoxyl radicals was found to increase with phosphate buffer ion concentration and reached a plateau value of 1.6 × 10⁵ s^?1 at a concentration of 0.04 mol dm^?3 of each buffering ion. It was also seen that ^. OH‐(4‐HBA) adduct species react with HPO ions with a rate constant of 3.7 × 10⁷ dm³ mol^?1 s^?1 and there was no such reaction with H₂PO ions. However, the rate of reaction of ^. OH‐(4‐HBA) adduct species with HPO ions decreased on adding KH₂PO₄ to the solution containing a fixed concentration of Na₂HPO₄ which indicated an equilibrium in the H⁺ removal from ^. OH‐(4‐HBA) adduct species in the presence of phosphate ions. In the acidic region, the ^. OH‐(4‐HBA) adduct species were found to react with H⁺ ions with a rate constant of 2.5 × 10⁷ dm³ mol^?1 s^?1. At pH 1, in the reaction of ^. OH radicals with 4‐HBA (k = 8.8 × 10⁹ dm³ mol^?1 s^?1), the spectrum of the transient species formed was similar to that of phenoxyl radicals formed in the reaction of Cl radicals with 4‐HBA at pH 1 (k = 2.3 × 10⁸ dm³ mol^?1 s^?1) showing that ^. OH radicals quantitatively bring about one electron oxidation of 4‐HBA. Reaction of ^. OH/O ^.? radicals with 4‐HBA by H‐abstraction mechanism at neutral and alkaline pH values gave reducing radicals and the proportion of the same was determined by following the extent of electron transfer to methyl viologen. H‐atom abstraction is the major pathway in the reaction of O ^.? radicals with 4‐HBA compared to the reaction of ^. OH radicals with 4‐HBA. At pH 1, transient species formed in the reactions of H‐atoms with 4‐HBA (k = 2.1 × 10⁹ dm³ mol^?1 s^?1) were found to transfer electrons to methyl viologen quantitatively. Copyright © 2009 John Wiley & Sons, Ltd.     

Correlations between frequency of infra-red active vibrational modes and copper-oxygen distance in copper oxides. Application to superconductors

The infra-red spectra of a large number of ternary Cu(II) oxides with at least a quasi square-planar coordination of oxygen around the copper ions have been studied. The frequency of the bands with the highest frequency,v _max, is found to correlate extremely well with the shortest Cu–O distance.v _max increases at an impressive rate of 20 cm^–1 per 0.01 Å when the Cu–O distance becomes less than 1.97 Å, which is the Cu²⁺–O^2– distance in square-planar CuO₄ complexes as obtained from empirical ionic radii considerations. The marked sensitivity may be used as a titration procedure not only to assign bands but also to obtain diagnostic information about local coordination in compounds derived, for example, from the YBa₂Cu₃O_7–d structure such as LaCaBaCu₃O_7–d . The only example where this correlation fails is in the two-layer non-superconducting oxides derived from La₂(Ca, Sr)Cu₂O₆. The significance of this result is discussed. The marked dependence of frequency on the bond-distance is qualitatively examined in terms of an increased electron-phonon coupling to account for the observed tendency of the superconducting transition temperature to go through a maximum as the average basal plane Cu–O distance is decreased.     

The Influence of Collisions in the Space Charge Sheath on the Ion current Collected by a Langmuir Probe

The current/voltage characteristics of a cylindrical Langmuir probe have been studied in Ar⁺/electron afterglow plasmas in helium carrier gas under truly thermal conditions at 300 K using our flowing afterglow/Langmuir probe (FALP) apparatus. The orbital motion limited (oml) ion and electron current regions of the probe characteristics have been explored over a wide range of the reduced probe voltage (up to ～ 100) and over a wide range of electron (n_e) and ion (n₊) number densities (1.6 × 10⁷ to 1.5 × 10¹⁰ cm^?3) at a constant pressure of the He carrier gas of 1.2 Torr. The observed increase of the probe ion currents above those predicted by collisionless oml theory, resulting in an apparent increase of the measured ion number density above n_e in the plasma, is explained by the enhancement in the ion current collection efficiency due to collisions of ions with neutral gas atoms in the space charge sheath surrounding the probe. The continuous change in the exponent, χ, of the power-law dependence,i₊ ∞ V of the ion current, i₊, on the probe voltage, V_p from 0.5 at the highest n₊ (smallest sheath) towards 1.0 at the lowest n₊ (large sheath) indicates that the ion current collection from the plasma changes from the oml current regime at the high n₊ to the continuum regime at the low n₊ when the ions undergo multiple collisions with the helium atoms in the space charge sheath and thus “drift” towards the probe.     

Iodine laser production of highly charged Ta ions

The results of systematic studies of multiply charged Ta ion production with the fundamental frequency of an iodine laser (=1.315m), and its 2nd (0.657m) and 3rd (0.438m) harmonics are summarized and discussed. Short laser pulse (350 ps) and a focus spot diameter of 100m allowed for the laser power densities in the range of 5×10¹³–1.5×10¹⁵ W/cm². Corpuscular diagnostics were based on time-of-flight methods; two types of ion collectors and a cylindrical electrostatic ion energy analyzer were used. The Ta ions with charge state up to 55+ were registered in the distance of 210 cm; the maximum amplitude of the signal of a high energy ion group was found to belong to the ions with the charge state around 43+, depending on the laser power density. The ion energy distribution was measured for all three wavelengths, however, in a different energy range; the maximum registered ion energy was 8.8 MeV. The occurrence of highly charged ions in the far expansion zone is discussed in view of the mechanism of charge distribution freezing during two-temperature isothermal plasma expansion.The work was performed in a partial fulfillment of the research grant project No. A1010525 sponsored by the Academy of Sciences of the Czech Republic and grant project No. 202/95/0039 sponsored by the Grant Agency of the Czech Republic.     

Studies of the spin-Hamiltonian parameters, d–d transitions and defect structures for two tetragonal Cu centers in Ba2ZnF6:Cu crystal

Two theoretical methods, the perturbation theory method (PTM) and the complete diagonalization (of energy matrix) method (CDM), are applied to calculate the spin-Hamiltonian parameters (g-factors g, g and hyperfine structure constants A, A, obtained from electron paramagnetic resonance (EPR) spectra) and d–d transitions (obtained from optical spectra) for two tetragonal Cu²⁺ centers in Ba₂ZnF₆:Cu²⁺ crystals. The Cu²⁺(I) ion replaces the Zn²⁺ ion at tetragonally compressed octahedral coordination and has the ground state ²A₁(|d_z²), whereas the Cu²⁺(II) ion is at an interstitial site with a square-planar F⁻coordination and has the ground state ²B₂(|d_x²-y²). The calculated spin-Hamiltonian parameters and d–d transitions from the PTM and CDM coincide and are in reasonable agreement with the experimental values. This suggests that both methods are effective for the theoretical studies of EPR and optical spectral data for 3d⁹ ions in tetragonal symmetry with different ground states. The defect structures of the two Cu²⁺ centers in Ba₂ZnF₆:Cu²⁺ are also estimated.     

The Dependence of Benzo-15-Crown-5 Ether-Containing Oligo Paraphenylene Vinylene (CE-OPV) Emission Upon Complexation with Metal Ions in Solution

The effects of metal salts (NaCl, CaCl₂·2H₂O, EuCl₃·6H₂O and Eu(OAc)₃) on the steady state and time resolved fluorescence behaviour of poly(para phenylene vinylene) oligomers containing benzo-15-crown-5 ether units (CE-OPV) have been investigated. The presence of EuCl₃ causes a significant (8–9 fold) increase in the fluorescence emission intensity of the OPV segments, as compared to pure CE-OPV, in 99:1 methanol/chloroform solution and a small (9 nm) red shift in the emission maximum. The presence of Na⁺ or Ca²⁺ results in less marked increases in fluorescence intensity compared to Eu³⁺. In the presence of Eu³⁺ and Na⁺, the fluorescence intensity increases approximately linearly with metal ion concentration up to a metal ion/CE-OPV molar ratio of 10. The emission enhancement is not related to a simple 1:1 (CE-OPV:metal ion) complex formation process. In contrast, in acetonitrile, CE-OPV shows complex fluorescence quenching behaviour as a function of EuCl₃ concentration. This solvent dependence suggests that the emission changes with metal concentration are related to the formation of charge-transferred complexes. The marked changes in fluorescence quantum yield of the PPV backbone due to complexation with metal ions makes CE-OPV a sensitive fluorescent probe for metal ions, or may be exploited for improving the quantum yield of PPV-based devices.     

Mössbauer spectroscopy of a semiconductive phosphate glass (10V2O5 30Fe2O3 60P2O5 at low temperature

In order to clarify the difference between the local structures of Fe³⁺ and those of Fe²⁺ ions in a semiconductive phosphate (10V₂O₅-30Fe₂O₃-60P₂O₅) glass, the temperature dependencies of the isomer shift (IS), quadrupole splitting (QS) and absorption area (AR) for Fe³⁺ and Fe²⁺ ions were measured. Debye temperatures ( _D) for Fe³⁺ and Fe²⁺ ions were determined to be 318 ± 29 K and 223 ± 18 K, respectively, from the temperature dependence of the absorption area (AR). From the temperature dependence of the quadrupole splitting(QS), B strength parameters for Fe³⁺ and Fe²⁺ ions, which are the coefficients for theT ^3/2 term, were deduced. It was found that in this phosphate glass, Debye temperatures _D(AR) were consistent with those obtained using the relation of the B parameter to Debye temperature described in the literature. Also from the temperature dependence of the isomer shift, the difference between the thermal effects except the second-order Doppler shift for Fe³⁺ ions and those for Fe²⁺ ions was compared.     

Vibrational study of the superprotonic phase transition in the mixed crystal Rb2(HSeO4)(H2PO4)

Raman spectra (10–1200 cm⁻¹) of polycrystalline samples of Rb₂(HSeO₄)(H₂PO₄) were studied at temperatures ranging from 300 to 423 K. An assignment of most of the observed bands is proposed. The first‐order phase transition previously detected at 382 K was characterized as: This superionic‐protonic transition is believed to be governed by librations of the HSe/PO₄²⁻ ion and the A OH (A = Se, P) stretching mode. It corresponds to the weakening of  Se(P) O H˙˙˙ H O Se(P) hydrogen bonds and to the melting of the proton sublattice into a quasi‐liquid state in which the protons and the HSe/PO₄²⁻ ions contribute to the unusually high conductivity. The activation energy that was determined from the plot Δν_1/2 versus temperature for the ν (A OH) band has the same order of magnitude as that determined from conductivity measurements. Copyright © 2006 John Wiley & Sons, Ltd.     

Ion mixing in Al,Si, and their oxides

The redistribution of thin metallic markers due to ion irradiation was studied by backscattering spectrometry in Al, Al₂O₃, Si, and SiO₂. Marker species were selected for their similar masses and different chemical reactivities with the host media and included Ti, Fe, W, Pt, and Au. It was found that the marker signals are Gaussian and that the variance ² of the marker atom distributions increases linearly with the dose of the irradiation, is insensitive to the temperature of irradiation in the range of 80–300 K, and depends linearly on the nuclear stopping power of the incident ions. The absolute values of ² for Ti, Fe, W, Pt, and Au markers in Al and Al₂O₃, W, and Pt in SiO₂ and W in Si is, within±50 %, of 6.5×10³Å² for 300 keV, 8×10¹⁵ Xe ions/cm². These observations suggest that collisional cascade mixing is a dominant mechanism in this type of impurity-matrix combinations. Only Au and Pt in Si mix at a larger rate: ² for Pt is about 3 and for Au about 5 times larger than ² for all other markers. Lower threshold displacement energies and/or the contribution of processes other than cascade mixing are possible considered reasons. In polycrystalline Al, a rapid migration of Au and Pt atoms throughout the Al layer, similar to grain boundary diffusion, is observed.     

Secondary effects on solid surfaces stimulated by the cathode plasma flux in vacuum arcs

The conducting plasma region between the electrodes of a vacuum arc contains single-and multiple-charged ions of the cathode material. Investigation into the behaviour of this flux when it impinges upon a surface should take into account secondary processes. From among various processes on the surface in vacuum arc, particular attention is paid to the sputtering of the surface and to the secondary electron emission by positive ions emitted from the cathode spots. On the basis of the sputtering yield characteristicsS _r as a function of ion kinetic energyE _i and their energy distribution in the cathode flux, the total sputtering yieldsS _re for atomicaly clean surface have been determined. Experimental verification ofS _re was performed by measuring the ratio of mass deposited on the collectors to mass carried by the particle incident flux. It was found that the calculated value ofS _re is comparable to the evaluated one from the experiments. The emission of secondary electrons from clean metal surfaces due to a bombardment by multiple-charged ions is considered. The secondary electron emission _c depends on excess energyE _ex of incident ion and its average value _av for multiple-charged ions depends both on the fractional distribution of ion flux _zi and on the excess energyE _ex of each ion. It is proposed that the relationship derived is applicable to most combinations of atomic ions and pure metal surfaces.Presented at 17^th Symposium Plasma Physics and Technology, Prague, June 13–16, 1995.This work was supported by the State Committee for Scientific Research within the research project No. 3P40101507.     

Über die Energieabhängigkeit von Ionen-Molekül-Reaktionen mit negativen Ionen

Some ion-molecule reactions with negative ions (OH^? and NH ₂ ^? ) have been studied using a primary ion source, in which the negative ions were produced by electron impacts with electron resonance capture, and a secondary ion source, in which the primary negative ions produced ion-molecule reactions with formation of secondary negative ions. The secondary ions were magnetically analyzed and registered by a multiplier. Cross sections of the reactions in function of the energy of the primary ions were measured in the region of low energies up to about 20 eV. In the low energy region the cross sections rapidly decrease with increasing energy ～E ^?1/2 as it has been the case with the energy dependence of the cross section of charge transfer reactions with negative ions at the same energies.     

Ion aging effects on the dissociative-attachment instability in CO2 lasers

Onset of the dissociative-attachment instability requires that the rate coefficient for electron detachment (k _d) from negative ions be below a critical value. The predominant negative and positive ions in a CO₂N₂He gas-discharge plasma are known to change with time. As secondary by-products form and the predominant negative-ion species changes from CO ₃ ^– to NO ₂ ^– , a decrease ink _d occurs destabilizing the discharge. Since NO ₂ ^– and NO ₃ ^– are largely unreactive with respect to associative detachment,k _d depends in a sensitive fashion on the concentration of certain minority negative ions (O^–, O ₂ ^– ) and neutrals (CO, O, N). The sufficient conditions for the dissociative-attachment instability are much less sensitive to changes in the electron-ion and ion-ion recombination rate coefficients resulting from the ion aging process.     

Hyperthermal surface-collisions of water cluster cations

Size-selected, protonated water cluster cations (H₂O)_nH⁺, 4 n 32, are scattered at normal incidence from the surface of a diamond-coated silicon wafer at collision energies 0 E _coll 500 eV. The size distribution of collision-induced fragment-ions and the ion yield of scattered particles are analyzed, using a secondary time-of-flight mass spectrometer, as a function of the cluster size, n, and the collision energy, E _coll. Even at low impact energies only very small fragment-ions can be detected, with a maximum fragment size of 35% of the colliding parent cluster ions. For clusters consisting of more than 10 molecules, the protonated water dimer (H₂O)₂H⁺ becomes the predominant fragment-ion. The total charge survival yield obeys a nonlinear increase with cluster size; for the largest clusters investigated, more than 35% of the impacting ions survive the surface collision in the cationic charge state.