Ion-beam induced mixing of Cu/Au bilayer thin film (kinematics and formation of solid solutions)

Ion-beam induced atomic mixing of Cu/Au bilayer thin film is studied using combined electrical resistivity measurements and Rutherford Backscattering Spectrometry (RBS). 400 keV Kr⁺ ion irradiation with fluences ranging from 3.3×10¹⁵ to 7.6×10¹⁶ ions/cm² at room temperature have been used. Ion beam mixing lead to a uniformly mixed metal alloy. The formation of Cu/Au solid solutions depends on the initial composition and on the fluence of irradiating ions. For an initial composition of Cu₄₂Au₅₈, a Cu-rich solid solution of composition Cu₇₂Au₂₈ is formed after irradiation with 7.6×10¹⁶ ions/cm². The kinematics of the intermixing process is also studied by in situ electrical resistivity measurements which confirmed the formation of the Cu/Au solid solutions.     

Nanoscale ion-beam mixing in Au–Si and Ag–Si eutectic systems

MeV ion induced mixing in the nanoscale regime for Au and Ag nanoislands on silicon substrates has been studied. Au and Ag nanoislands are grown on silicon substrates at room temperature and irradiated with 1.5-MeV Au²⁺ ions at various fluences. Cross-sectional high-resolution transmission electron microscopy and Rutherford backscattering spectrometry (RBS) are used to study the ion-beam mixing in Au/SiO_x/Si and Ag/SiO_x/Si systems. We observe a metastable mixed phase for the Au–Si system at a fluence of 1×10¹⁴ ionscm^-2, while no mixed phase is formed for the Ag–Si system. For both Au–Si and Ag–Si systems, a part of the islands is pushed into the substrate. The mixed phase of the Au–Si system is found to be crystalline in nature. The higher eutectic temperature and lower heat of mixing of the Ag–Si system compared to the Au–Si system could be responsible for the lack of mixing and silicide formation in the Ag–Si system. PACS 61.80.Jh; 61.82.Rx; 68.37.Lp; 64.75.+g; 61.46.+w     

TDPAC and emission Mössbauer spectroscopy of99Ru in YBa2Cu3O7−x

The hyperfine interactions of⁹⁹Ru(⁹⁹Rh) in YBa₂Cu₃O_7–x withx<0.2 andx1 were studied by means of TDPAC and emission Mössbauer spectroscopy. The superconductor YBa₂Cu₃O_7–x withx<0.2 was prepared by conventional heat treatment in oxygen, the semiconductor withx1 by heating the superconductor under a reduced pressure. The TDPAC and Mössbauer measurements show that Ru ions exclusively occupy the Cu-1 site, which forms one-dimensional Cu-O chains in the orthorhombic phase.     

Metallophilic Bond‐Induced Quenching of Delayed Fluorescence in Au25@BSA Nanoclusters

The metallophilic bond is a weak interaction between closed‐shell ions and has been widely used a probe for various sensing of toxic chemicals for environmental safety concerns. Here, the interaction between Au nanoclusters (NCs) and metallic ions (mercury (Hg²⁺) and copper (Cu²⁺) ions) is explored using steady‐state and time‐resolved luminescence and transient absorption measurements. For Hg²⁺ ions, the delayed fluorescence (DF) of bovine serum albumin (BSA) protected Au₂₅ (Au₂₅@BSA) NCs is quenched via an effective triplet state electron transfer through the metallophilic bond. However, the Cu²⁺ ions do not alter the DF in Au₂₅@BSA NCs because of the absence of the metallophilic interaction. Furthermore, for Au₈@BSA and Au₁₀@histidine, in which there are no Au⁺ ions on the surface, the fluorescence is not quenched by Hg²⁺ ions. Such a novel triplet electron transfer process through metallophilic bonds are observed and reported for the first time. The reduction of the reverse intersystem crossing is the crucial for Hg²⁺ ion sensing in the fluorescent Au₂₅@BSA NCs.     

SIMS direct surface imaging of Cu1−xCrx formation

Cu-Cr alloys, irradiated with a low-energy, high-current electron beam, are analyzed by high-resolution secondary ion mass spectrometry. Mass spectra and images of Cu⁺ and Cr⁺ surface distributions finely reveal the regions enriched in Cu and Cr. For electron beam energies above a threshold value, the formation of a non-equilibrium Cu_1−xCr_x solid solution, extending over sub-micrometer areas is highlighted for the first time. A discussion of the process leading to Cu_1−xCr_x formation is given.     

Preparation of high J c YBa2Cu3O7−δ superconducting thin films by ion beam sputtering deposition

Preparation of high T _c and high J _c YBa₂Cu₃O_7– superconducting thin films by ion beam sputtering deposition is reported. The main factors affecting the composition of the films and the orientation of the crystal grains have been examined. Experimental results show that the Y, Ba and Cu composition of as-deposited films can be conveniently and accurately adjusted by a combined sputtering target which consists of a large sintered target of YBa₂Cu₃O_7– and a small one that is Ba and Cu rich (YBa_2.5Cu_3.3O_x). Fabrication conditions of highly oriented superconducting thin films are described. YBa₂Cu₃O_7– superconducting films with zero resistance at 88–90.5K and critical current density J _c (at 77K) of 1.5×10⁵ A/cm² are obtained.     

The effect of Ag substitution in the mixed conductor Cu7PSe6

Cu₇PSe₆ is a mixed conductor that crystallizes in the simple cubic structure at room temperature. Structural transitions above and below room temperature are accompanied by step-like changes in electrical conductivity. The substitution of Ag⁺ for Cu⁺ in Cu₇PSe₆ stabilized the simple cubic structure over a wider range of temperatures than is observed for the pure compound. A disproportionate decrease in electrical conductivity accompanies modest levels of silver substitution. The prominent step in electrical conductivity associated with the low-temperature crystallographic phase transition disappears in (Ag_xCu_1−x)₇PSe₆ solid solutions for a composition parameter x=0.20, replaced by two distinct changes in the slope of conductivity below room temperature.     

Fe57 Mössbauer study in cobalt substituted magnetite

The Mössbauer effect has been studied in the mixed ferrites Co _x Fe_3–x O₄ (forx=0.8, 0.9 and 1) with the spinel structure in the temperature range between 78 and 380 K. The composition withx=1, showed an expected Zeeman spectrum with two overlapping magnetic hyperfine patterns related to the Fe³⁺ ions in tetrahedral and octahedral sites. While for samples withx=0.8 and 0.9 the Mössbauer spectrum for each compound was successfully analysed into three different patterns corresponding to the ferric ions placed at the tetrahedral and octahedral sites and ferrous ions at the octahedral sites, indicating no electron transfer between Fe³⁺ and Fe²⁺, where the quantity of cobalt is sufficiently large to be located at the six nearest neighbours to ferrous ions. The Mössbauer effect parameters were calculated for these observed sites and their variation with temperature reported. The reduced hyperfine magnetic fields of the Fe³⁺ (B) ions were found to follow the Brillouin curve forS=5/2 and one third power law. The magnetic ordering temperature was determined to be 815 K and the possible magnetic interactions were discussed.     

Study of Au-Pd core-shell nanoparticles by using slow positron beam

Binary Au-Pd nanoparticles were synthesized by ultrasonic irradiation of solutions containing Au³⁺ and Pd²⁺ ions (the ion ratio from 0.3:0.7 to 0.9:0.1 mM) and cationic surfactant (SDS: sodium dodecyl sulfate). In each case the core-shell structure (Au core, Pd shell) was confirmed by scanning transmission electron microscopy (STEM). The mean diameters of them were all about 9 nm, and the thickness of the Pd shell depends on the ratio of Pd²⁺ and Au³⁺ ions in solution. In order to study the electronic states of core-shell nanoparticles and their dependence on shell thickness, Doppler broadening measurements were performed for Au-Pd core-shell nanoparticles by using slow positron beam technique. The ratio curves of Au-Pd particles did not match with those of pure Pd and pure Au, but a small difference in the low electron momentum region was observed among nanoparticles depending on Pd shell thickness.     

Effect of hole doping and antiferromagnetic coupling on the itinerant ferromagnetism of through Cu substitution at Ru site

Systematic studies on the structural, transport and magnetic properties of SrRu_1−xCu_xO₃ (x=0.0–0.2) compounds have been performed. SrRu_0.8Cu_0.2O₃ shows a tetragonal structure unlike the other compositions which exhibit a pseudo-cubic structure. Low temperature powder X-ray diffraction data of SrRu_0.8Cu_0.2O₃ collected at a synchrotron beam line reveals that the tetragonal structure is stable down to 8 K. Ferromagnetic transition temperatures (T_c) are significantly reduced from 160 to 34 K with Cu doping. All the compositions exhibit irreversibilities in M_ZFC(T) and M_FC(T) curves ascribable to the presence of domain structures. Magnetic susceptibility measurements show that the copper ions are anti-ferromagnetically coupled for concentrations higher than x=0.16. The antiparallel arrangement of Ru⁵⁺ ions with its neighboring cations also contributes to the large reduction in the observed magnetic moment. X-ray photoemission spectroscopy measurements show evidence for both tetravalent and pentavalent Ru ions while copper is in a divalent state. We conclude from our resistivity data that Cu²⁺ substitution promotes a polaronic type of conductivity.     

Density functional study of ternary AuxAgyCuz and AuxAgyCuz+ clusters (x + y+z = 5, 6)

ABSTRACT

We report a theoretical investigation of neutral Au_xAg_yCu_z and cationic Au_xAg_yCu_z⁺ ternary clusters, for x?+?y+z?=?5 and 6. Our study is performed within density functional theory at the TPSSTPSS/SDD level. The geometries, chemical order, binding energy, mixing energy, second difference in the energy, adiabatic ionisation potential of these clusters are evaluated as a function of the whole concentration range. The most probable dissociation channels and the corresponding dissociation energies for the most stable clusters are also determined and discussed.     

Ion beam mixing of Pt marker layers in Al

We have studied the ion beam mixing of Pt marker layers which were 1 nm thick and buried 55 nm deep in Al. The samples were irradiated with Ne, Ar, Kr, Xe, and Pb ions with ion energies ranging from 75 to 600 keV and damage energy densities from 0.17 to 2.0 keV/nm. The depth distributions of both the implanted ions and the marker atoms were measured with Rutherford backscattering spectrometry. The experimental mixing efficiency of = 0.856(24) nm⁵/keV is about ten times as high as was to be expected from the ballistic model and the local spike models. We suggest a connection between this unexpectedly high mixing efficiency and the vanishing primary solid solubility of the marker element in the host matrix.     

Materials modification at zirconium–silicon interface using swift heavy ions

The reactivity of the Zr/Si interface induced by swift heavy ion beams of Au has been investigated in the present work. Zirconium was evaporated on a clean silicon substrate in ultra high vacuum (UHV) at a pressure of 10^?8 Torr by the electron beam evaporation technique and the final layer was a thin film of Au to avoid oxidation of zirconium. The Zr/Si system was irradiated by 350 MeV Au²⁶⁺ ions at liquid nitrogen temperature at different fluences (0.46×10¹⁴, 1.85×10¹⁴ and 4.62×10¹⁴ ions/cm²). Rutherford back scattering (RBS) spectroscopy using 2 MeV He ions was used to monitor the Zr and Si concentration profiles and interdiffusion at the interfaces. The irradiation at the Zr/Si interface showed mixing. X-ray diffraction measurements confirmed the formation of the ZrSi₂ phase. Thermal spike formation and melting in the tracks was found to be the dominant process at the interfaces.     

Composition dependence on dispersion of Au/Cu bimetallic nanoparticles in nylon 11 thin films

Effect of composition on the dispersion of Au_xCu_1-x bimetallic nanoparticles into nylon 11 matrix has been investigated. TEM, EDX, and XPS depth profiling were used for characterizing the changes in the composition of the bimetallic particles and in the depth distribution of the particles in the nylon 11 layer caused by heat treatment in N₂ atmosphere. The island-like bimetallic particles were found to be formed on the nylon 11 surface before heat treatment. The results of XPS depth profiling revealed that, by the heat treatment, the Au_xCu_1-x bimetallic particles with x? 0.55 were not dispersed into the nylon 11 layer while those with x≥ 0.70 were homogeneously dispersed in the films, indicating the existence of critical composition for penetration of the bimetallic particles. By comparing the composition and structure of the bimetallic particles, the cause of these finding is discussed in terms of surface free energy of the particles. Received 29 November 2000     

Effect of interfacial alloying on the surface plasmon resonance of nanocrystalline Au-Ag multilayer thin films

Nanocrystalline Au and Ag in multilayer thin film form with Au/Ag/Au structure were prepared by high pressure (∼40 Pa) d.c. sputtering techniques. The Ag concentrations in Ag_xAu_1-x films were changed from x = 0 to 1. These multilayer films with varying Ag concentration showed significant changes in microstructures obtained from TEM and XRD analyses. The optical absorption spectra of these multilayer films showed a single plasmon band confirming the formation of Au-Ag alloy. We ascribe this alloying to the interfacial reactions in nanophase limited at the Au-Ag interface. The red-shift and broadening of the plasmon bands with the increase in silver concentration could be associated to the increase in size of the nanoparticles and its distribution. The observed red shift in the plasmon band may be associated with the change in electronic structure at the Au-Ag interface due to configuration mixing of the atomic energy levels of Au and Ag. Received 17 October 2002 / Received in final form 26 February 2003 Published online 23 May 2003 RID="a" ID="a"e-mail: msakp@mahendra.iacs.res.in     

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.     

Mixed valence states in cobalt iron cyanide

Cobalt iron cyanide with both Co and Fe in mixed valence states were prepared and characterized. In this mixed valence system the cobalt atom is found both as high spin Co(2+) and low spin Co(III) while iron always appears in low spin state to form two solid solutions: Co(2+)Co(III) hexacyanoferrates (II,III), and Co(2+)Co(III) hexacyanoferrate (II). Such solid solutions have the following formula units: (Co²⁺)_x(Co^III)_1−xK[(Fe^II)_1−x(Fe^III)_x(CN)₆]·H₂O and (Co²⁺)_1.5x(Co^III)_1−xK[Fe^II(CN)₆]·yH₂O (0?x?1, 1?y?14). Compounds within these two series were characterized from Infrared, Mössbauer, X-ray diffraction and thermo-gravimetric data, and magnetic measurements at low temperature. A model for their crystal structure is proposed and the structure for a representative composition refined from XRD powder patterns using the Rietveld method. A simple and reproducible procedure to prepare these solid solutions is provided. Within hexacyanoferrates, such mixed valence states system in both metal centres shows unique features, which are discussed from the obtained data.     

Features of the absorption spectra of thin films of M 2Ag1 − x CuxI3 solid solutions (M = Rb, Cs)

The absorption spectra of thin films of (MI)_{1 ? y} (Ag_{1 ? x} Cu_xI)_y solid solutions (M = Rb, Cs) with the initial molar concentration y = 0.33 have been investigated. It is established that, at low concentrations x, a local exciton band due to Cu⁺ ions is split off from the main long-wavelength exciton bands. In Rb₂Ag_{1 ? x} Cu_xI₃ solutions, the concentration shift of exciton bands indicates the formation of a persistent-type exciton spectrum. However, in Rb₂Ag_{1 ? x} Cu_xI₃ with x ≥ 0.5 and in Cs₂Ag_{1 ? x} Cu_xI₃ with x > 0.2, exciton spectra of amalgamation type are observed, which are related to the formation of more stable M ₃Ag_{2 ? 2x} Cu_2x I₅ solid solutions. The formation of these solutions leads to broadening of the exciton bands and to the concentration transition from persistent-to amalgamation-type exciton spectra.     

Thiolated cyclodextrin self-assembled monolayer-like characterized with secondary ion mass spectrometry

In the work the focus is on the preparation of self-assembled monolayer-like films consisting of thiolated cyclodextrin on gold substrate and a characterization by using secondary ion mass spectrometry. The short (1 min) and long (1 h) time preparations of self-assembled monolayer-like films, resulting in submonolayer and monolayer regimes, are investigated, respectively. The observed species of thiolated cyclodextrin (M as molecular ion) self-assembled monolayer-like films are assigned to three groups: Au_xH_yS_z clusters, fragments with origin in cyclodextrin molecule associated with Au, and molecular ions. The group of Au_xH_yS_z (x = 2-17, y = 0-2, z = 1-5) clusters have higher intensities than other species in the positive and even more in negative mass spectra. Interestingly, the dependence between the number of Au and S atoms shows that with the increasing size of Au_xH_yS_z clusters up to 11 Au atoms, the number of associated S atoms is also increasing and then decreasing. Molecular species as (M−S+H)Na⁺, (M+H)Na⁺, AuMNa⁺, (M₂−S)Na⁺, and M₂Na⁺ are determined, and also in cationized forms with K⁺. The intensities of thiolated cyclodextrin fragments at the long time preparation are approximately 10 times higher than the intensities of the same fragments observed at the short time. The largest observed ions in thiolated cyclodextrin self-assembled monolayer-like films are AuM₂ and Au₂M. The thiolated cyclodextrin molecular ions are compared with hexadecanethiol molecular ions in the form of Au_xM_w where the values of x and w are smaller for thiolated cyclodextrin than for hexadecanethiol. This result is supported with larger, more compact, and more stabile thiolated cyclodextrin molecule.     

Structural and optical properties of ZnSe x Te1−-x solid solutions in thin-film form

Solid solutions of ZnSe _x Te_1–x (0. 1 x 1) were synthesized by vacuum fusion of stoichiometric proportions of ZnSe and ZnTe. X-ray diffraction data revealed that they have polycrystalline cubic zinc-blende structure. The calculated unit cell lattice constant (a) for the different compositions in powder form vary linearly, with molecular fractionx following Vegard's law:a(x) = 6.165 – 0.485x. Thin films of ZnSe _x Te_1–x (0.1 x 1) solid solutions deposited onto glass or quartz substrates by thermal evaporation in a vacuum of 10^–4 Pa were found to be polycrystalline with a preferred (1 1 1) orientation. The obtained data were confirmed by electron diffraction. The optical studies showed that ZnSe _x Te_1–x polycrystalline films of different compositions have two direct transitions with corresponding energy gapsE _g andE _g + _so The variations in bothE _g andE _g + _so, withx indicate that ZnSe _x Te_1–x solid solution belongs to an amalgamation-type following quadratic equations with bowing parameters 1.251 and 1.275, respectively.